JP5051938B2 - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
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- JP5051938B2 JP5051938B2 JP2000305263A JP2000305263A JP5051938B2 JP 5051938 B2 JP5051938 B2 JP 5051938B2 JP 2000305263 A JP2000305263 A JP 2000305263A JP 2000305263 A JP2000305263 A JP 2000305263A JP 5051938 B2 JP5051938 B2 JP 5051938B2
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- 0 CN(C(SSC(N**)=S)=S)I Chemical compound CN(C(SSC(N**)=S)=S)I 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、タイヤトレッド用ゴム組成物に関し、更に詳しくは、グリップ性能とグリップ持続性とをともに向上させることのできるタイヤトレッド用ゴム組成物に関する。
【０００２】
【従来の技術】
従来、タイヤのグリップ性能を向上させるために、タイヤトレッド用ゴム組成物として、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）を配合し、小粒系カーボンブラックを比較的多量配合するという手法が知られている。しかし、このタイヤトレッド用ゴム組成物を用いたタイヤでサーキットを高速度で周回するような過酷な条件で走行を行った場合に、ゴムが熱劣化や疲労劣化を起こし、グリップ力が低下してしまうという問題があった。
【０００３】
【発明が解決しようとする課題】
従って、本発明の課題は、グリップ性能とグリップ持続性とをともに向上させることのできるタイヤトレッド用ゴム組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明によれば、スチレン含量２０〜５０％のスチレン−ブタジエン共重合体ゴムを５０重量％以上含むゴム１００重量部に対し、さらに別の重量平均分子量が２０００〜５万のスチレン−ブタジエン共重合体ゴム５〜５０重量部、ＣＴＡＢ比表面積が１２０ｍ2／ｇ以上であるカーボンブラックを含む充填剤８０〜１８０重量部、下記式（１）に示すチウラム系化合物０．２〜３重量部と、さらに、ベンゾチアゾール系加硫促進剤を前記チウラム系化合物とベンゾチアゾール系加硫促進剤との重量比（チウラム系化合物／ベンゾチアゾール）が０．２〜２．０となるように含み、ジチオリン酸アンチモン加硫促進剤を含まない、タイヤトレッド用ゴム組成物が提供される。
【０００５】
【化２】
【０００６】
このように、スチレン含量２０〜５０％のスチレン−ブタジエン共重合体ゴムを含むタイヤトレッド用ゴム組成物に、上記式（１）のチウラム系化合物（以下、本発明のチウラム系化合物ともいう）を加硫促進剤として使用すると、ゴムポリマー間の架橋について、従来のチウラム系加硫促進剤に比べ、モノサルファイド結合やジサルファイド結合のように結合数の小さな硫黄結合が多くなり、結合数の大きな結合力の弱いポリサルファイド結合が少なくなるため、ポリサルファイド結合の切断による物性の低下が抑えられ、グリップ性能の低下が抑制されるので、グリップ性能とグリップ持続性をバランスよく向上させることができる。
【００１０】
【発明の実施の形態】
本発明のタイヤトレッド用ゴム組成物に配合するゴムとしては、スチレン含量２０〜５０％、好ましくは２５〜４０％のスチレン−ブタジエン共重合体ゴムを５０重量％以上、好ましくは、５０〜７０重量％使用し、このスチレン−ブタジエン共重合体ゴム単独でも他のゴムとのブレンドでもよい。このスチレン含量２０〜５０％のスチレン−ブタジエン共重合体ゴムを配合することで、グリップ性能を向上させることができる。
【００１１】
このスチレン−ブタジエン共重合体ゴム以外の他のゴムとしては、特に限定されないが、天然ゴム（ＮＲ）、ポリブタジエンゴム（ＢＲ）、ポリイソプレンゴム（ＩＲ）、上記以外のスチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム、クロロプレンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、イソプレン−ブタジエン共重合体ゴム等を挙げることができる。
【００１２】
さらには、重量平均分子量が２０００〜５万、さらには３０００〜４万の低分子量のスチレン−ブタジエン共重合体ゴムをゴム１００重量部に対し、５〜５０重量部配合するのが、グリップ性をさらに向上させるという点で好ましい。
【００１３】
また、本発明の充填剤は、ゴム１００重量部に対し、充填剤が８０〜１８０重量部、好ましくは、９０〜１４０重量部となるように配合される。充填剤量が８０重量部未満ではグリップ性能が低下してしまい、１８０重量部を超えると混合加工性が悪化してしまうからである。
【００１４】
充填剤としては、カーボンブラック、シリカ、シリカ表面処理カーボンブラック等の任意の充填剤が使用可能であり、２種以上の併用としてもよい。カーボンブラックとしては、ＣＴＡＢ比表面積が１２０ｍ2／ｇ以上、さらには１３０〜２５０ｍ2／ｇであるのが、充填剤のゴム補強性が向上し、グリップ性能をさらに改良することができるという点で好ましい。
【００１５】
本発明で使用するシリカとしては、通常この種のゴム組成物に配合使用される任意のシリカ、例えば、湿式法シリカ、乾式法シリカあるいは表面処理シリカなどを用いることができる。これらのシリカを用いるときには、ゴムとの補強性を高めるためにシランカップリング剤と併用することが好ましい。
【００１６】
本発明で使用するシリカ表面処理カーボンブラックは、カーボンブラックの表面にシリカを付着させたものであり、シリカに比べゴム中での分散性に優れ、未加硫ゴムの加工性を改良したものとして、特開平９−１１８７８０号公報等に記載されている。
【００１７】
本発明のチウラム系化合物は、下記式（１）に示す化合物である。
【００１８】
【化３】
式中、Ｒ1は炭素数１〜３のアルキレン基を表し、直鎖または分岐鎖でもよく、同じであっても異なっていてもよい。Ｒ2は、芳香族炭化水素基を表し、炭素数が６〜１４であるのが好ましく、種々の置換基を有する誘導体であってもよく、同じであっても異なっていてもよい。Ｒ3は、炭化水素基または水素基を表し、炭化水素基としては、Ｒ2と同様の芳香族炭化水素基や、直鎖または分岐鎖でもよい脂肪族炭化水素基若しくは脂環式炭化水素基であればよく、種々の置換基を有する誘導体であってもよく、同じであっても異なっていてもよい。脂肪族炭化水素基の炭素数は、１〜８であるのが好ましい。Ｒ3は全て芳香族炭化水素基であるのが特に好ましい。
【００２０】
芳香族炭化水素基としては、具体的には、例えば、フェニル基、ナフチル基、アントリル基等を挙げることができ、なかでも、フェニル基が好ましい。
【００２１】
この本発明のチウラム系化合物の配合量は、ジエン系ゴム１００重量部に対し、０．２〜３重量部、好ましくは０．２〜２．５重量部である。０．２重量部未満では、本発明の効果が十分でなく、３重量部を超えると焼け（早期加硫）が発生しやすくなってしまう。
【００２２】
本発明のタイヤトレッド用ゴム組成物では、ジエン系ゴム１００重量部に対し、さらにベンゾチアゾール系加硫促進剤を前記チウラム系化合物とベンゾチアゾール系加硫促進剤との重量比（チウラム系化合物／ベンゾチアゾール）が０．２〜２．０、さらには０．２〜１．５となるように含むのが、ゴムポリマー間の架橋のモノサルファイド結合の割合が増加するため、ポリサルファイド結合の切断による物性の低下を抑え、グリップ持続性をさらに向上させるという点で好ましい。
【００２３】
このベンゾチアゾール系加硫促進剤としては、メルカプトベンゾチアゾール（ＭＢＴ）、ジベンゾチアジルジスルフィド（ＭＢＴＳ）、Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド（ＴＢＢＳ）、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（ＣＢＳ）、Ｎ−オキシジエチレン−２−ベンゾチアゾリルスルフェンアミド（ＭＢＳ）、Ｎ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（ＤＣＢＳ）、メルカプトベンゾチアゾールの亜鉛塩、２−（４−モルフォリノジチオ）ベンゾチアゾール、２−（２，４−ジニトロ−フェニル）−メルカプトベンゾチアゾール、メルカプトベンゾチアゾールとシクロヘキシルアミンの塩、Ｎ，Ｎ−ジエチルチオカルバモイル−２−ベンゾチアゾリルスルフィド等が使用されるが、この中でも、スルフェンアミド系のものが好ましく用いられる。
【００２４】
本発明のゴム組成物には、上記各成分に加えて、さらに、硫黄、老化防止剤、軟化剤、可塑剤などのタイヤ用に一般に配合されている各種添加剤を配合することができ、かかる配合物は、一般的な方法で加硫してタイヤトレッドを製造することができる。これらの配合量も一般的な量とすることができる。例えば、硫黄の配合量は、ジエン系ゴム１００重量部当り１．０重量部以上とするのが好ましく、１．２〜２．５重量部とするのがさらに好ましい。
【００２５】
【実施例】
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。
実施例１、参考例１〜８及び比較例１〜４
下記表１に示す成分（重量部）のうち、チウラム系化合物、加硫促進剤および硫黄を除く成分を１．８リットルの密封型ミキサーで４〜５分間混練したマスターバッチに、加硫促進剤もしくはチウラム系化合物および硫黄を８インチのオープンロール混練したシリカ配合のゴム組成物を得た。次に、この組成物を１５×１５×０．２ｃｍの金型中で１６０℃、２０分間プレス加硫して目的とする試験片（ゴムシート）を調製し、これを以下のＭ３００変化率の測定に供し、その結果を表１に明記した。また、このゴム組成物をトレッドに用いて、１９５／５５Ｒ１５のサイズの乗用車用空気入りタイヤを作製し、以下のグリップ性、グリップ持続性の評価を行い表１に示した。
【００２６】
Ｍ３００変化率
ＪｌＳ Ｋ ６２５１に基づき、初期の３００％モジュラスと、１００℃、４８時間の条件で熱老化させた後の３００％モジュラスとを測定し、初期値に対する熱老化後の値の差を求め、その差を初期の値で除して変化率（％）とした。値が小さいほど、変化率が小さく耐熱老化性が良好であり、グリップ持続性の向上につながる。
グリップ性
作製したタイヤを１．６リットルクラスの国産乗用車に装着し、一周４．４１ｋｍのコースを走行した際のグリップ性能（グリップ感、ブレーキ性能、トラクション性能）について、以下の５段階のフィーリング評価を行った。値が大きいほどグリップ性に優れる。
５：非常に良好、４：良好、３：普通、２：やや劣る、１：非常に劣る
また、５は５-よりも、４+は４よりも、グリップ性が良好であることを示す。
グリップ持続性
作製したタイヤを１．６リットルクラスの国産乗用車に装着し、一周４．４１ｋｍのコースを５周連続走行した際の最速ラップタイムと最終（５周目）ラップタイムとのタイム差を算出し、各タイヤのグリップ持続性を以下の計算式にて求めた。
（比較例１のタイヤのタイム差）／（各タイヤのタイム差）×１００
この値が大きいほどグリップ持続性に優れる。
【００２７】
【表１】
【化４】
【００２９】
加硫促進剤ＣＢＳ：Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド加硫促進剤ＴＯＴ−Ｎ：ノクセラーＴＯＴ−Ｎ、テトラ（２−エチルヘキシル）老化防止剤６Ｃ：アンチゲン６Ｃ（Ｎ−フェニル−Ｎ′−（１，３−ジメチル）−ｐ−フェニレンジアミン）、住友化学社製
【００３０】
上記表１に示すように、本発明のチイラム系化合物を配合しなかった比較例１および比較例４については、Ｍ３００変化率が大きくなり耐熱老化性に劣るため、グリップ持続性が良好でない。また、スチレン含量２０〜５０％のスチレン−ブタジエン共重合体ゴムの量が少ない比較例２や全充填剤量が少ない比較例３については、グリップ性に劣るものであった。
【００３１】
それに対して、本発明のチウラム系化合物を配合した実施例１および参考例１〜８は、Ｍ３００変化率に優れ、グリップ性およびグリップ持続性ともにバランスよく向上させることができたが、本発明の実施例１では、Ｍ３００変化率、グリップ性およびグリップ持続性を最もバランスよく向上させることができた。
【００３２】
【発明の効果】
本発明に従って、所定のゴム成分と配合剤を所定量配合することによって、Ｍ３００変化率、グリップ性能およびグリップ持続性とを最もバランスよく向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber composition for tire treads, and more particularly to a rubber composition for tire treads that can improve both grip performance and grip durability.
[0002]
[Prior art]
Conventionally, in order to improve the grip performance of a tire, a styrene-butadiene copolymer rubber (SBR) having a high glass transition temperature (Tg) is blended as a rubber composition for a tire tread, and a relatively large amount of small-grain carbon black is contained. A method of blending is known. However, when the tire using the tire tread rubber composition is run under severe conditions such as going around the circuit at a high speed, the rubber deteriorates in heat and fatigue, and the gripping power is reduced. There was a problem that.
[0003]
[Problems to be solved by the invention]
Therefore, the subject of this invention is providing the rubber composition for tire treads which can improve both grip performance and grip sustainability.
[0004]
[Means for Solving the Problems]
According to the present invention, with respect to 100 parts by weight of a rubber containing 50% by weight or more of a styrene-butadiene copolymer rubber having a styrene content of 20 to 50%, another styrene-butadiene copolymer having a weight average molecular weight of 2000 to 50,000. 5 to 50 parts by weight of a combined rubber, 80 to 180 parts by weight of a filler containing carbon black having a CTAB specific surface area of 120 m 2 / g or more, 0.2 to 3 parts by weight of a thiuram compound represented by the following formula (1), Furthermore, a benzothiazole vulcanization accelerator is included so that the weight ratio of the thiuram compound to the benzothiazole vulcanization accelerator (thiuram compound / benzothiazole) is 0.2 to 2.0, and dithiophosphoric acid A rubber composition for a tire tread that does not contain an antimony vulcanization accelerator is provided.
[0005]
[Chemical formula 2]
[0006]
Thus, the thiuram compound of the above formula (1) (hereinafter also referred to as the thiuram compound of the present invention) is added to a tire tread rubber composition containing a styrene-butadiene copolymer rubber having a styrene content of 20 to 50%. When used as a vulcanization accelerator, compared to conventional thiuram vulcanization accelerators, there are more sulfur bonds with a small number of bonds, such as monosulfide bonds and disulfide bonds, and a larger number of bonds. Since polysulfide bonds with weak bonding strength are reduced, deterioration of physical properties due to cutting of polysulfide bonds is suppressed, and deterioration of grip performance is suppressed, so that grip performance and grip durability can be improved in a balanced manner.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
As a rubber compounded in the rubber composition for a tire tread of the present invention, a styrene-butadiene copolymer rubber having a styrene content of 20 to 50%, preferably 25 to 40%, is 50% by weight or more, preferably 50 to 70%. The styrene-butadiene copolymer rubber may be used alone or blended with other rubber. By blending the styrene-butadiene copolymer rubber having a styrene content of 20 to 50%, the grip performance can be improved.
[0011]
The rubber other than the styrene-butadiene copolymer rubber is not particularly limited, but natural rubber (NR), polybutadiene rubber (BR), polyisoprene rubber (IR), and other styrene-butadiene copolymer rubbers. (SBR), acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, isoprene-butadiene copolymer rubber, and the like.
[0012]
Further, the blending of 5 to 50 parts by weight of a low molecular weight styrene-butadiene copolymer rubber having a weight average molecular weight of 2000 to 50,000, more preferably 3000 to 40,000 with respect to 100 parts by weight of rubber improves the grip properties. This is preferable in terms of further improvement.
[0013]
The filler of the present invention is blended so that the filler is 80 to 180 parts by weight, preferably 90 to 140 parts by weight, with respect to 100 parts by weight of rubber. This is because when the amount of the filler is less than 80 parts by weight, the grip performance is deteriorated, and when it exceeds 180 parts by weight, the mixing processability is deteriorated.
[0014]
As the filler, any filler such as carbon black, silica, silica surface-treated carbon black can be used, and two or more kinds of fillers may be used in combination. The carbon black, CTAB specific surface area of 120 m 2 / g or more, further 130~250m 2 / g at and even improves the rubber reinforcing fillers, in that it can further improve the grip performance preferable.
[0015]
As the silica used in the present invention, any silica usually used in this type of rubber composition, for example, wet method silica, dry method silica, or surface-treated silica can be used. When these silicas are used, it is preferable to use them together with a silane coupling agent in order to enhance the reinforcement with rubber.
[0016]
The silica surface-treated carbon black used in the present invention is obtained by adhering silica to the surface of carbon black. It is superior in dispersibility in rubber compared to silica and improved in processability of unvulcanized rubber. JP-A-9-118780 and the like.
[0017]
The thiuram compound of the present invention is a compound represented by the following formula (1).
[0018]
[Chemical 3]
In the formula, R 1 represents an alkylene group having 1 to 3 carbon atoms, which may be linear or branched, and may be the same or different. R 2 represents an aromatic hydrocarbon group, preferably having 6 to 14 carbon atoms, may be a derivative having various substituents, and may be the same or different. R 3 represents a hydrocarbon group or a hydrogen group, and examples of the hydrocarbon group include an aromatic hydrocarbon group similar to R 2 , an aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may be linear or branched. As long as it is a derivative having various substituents, which may be the same or different. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1-8. R 3 is particularly preferably an aromatic hydrocarbon group.
[0020]
Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group. Among them, a phenyl group is preferable.
[0021]
The amount of the thiuram compound of the present invention is 0.2 to 3 parts by weight, preferably 0.2 to 2.5 parts by weight, based on 100 parts by weight of the diene rubber. If it is less than 0.2 parts by weight, the effect of the present invention is not sufficient, and if it exceeds 3 parts by weight, burning (early vulcanization) tends to occur.
[0022]
In the rubber composition for a tire tread of the present invention, the weight ratio of the thiuram compound to the benzothiazole vulcanization accelerator (thiuram compound / Benzothiazole) is contained in an amount of 0.2 to 2.0, more preferably 0.2 to 1.5, because the ratio of monosulfide bonds for crosslinking between rubber polymers is increased, so that polysulfide bonds are broken. It is preferable in terms of suppressing deterioration of physical properties and further improving grip sustainability.
[0023]
Examples of the benzothiazole vulcanization accelerator include mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), Nt-butyl-2-benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2- Benzothiazolylsulfenamide (CBS), N-oxydiethylene-2-benzothiazolylsulfenamide (MBS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS), mercaptobenzothiazole zinc Salt, 2- (4-morpholinodithio) benzothiazole, 2- (2,4-dinitro-phenyl) -mercaptobenzothiazole, mercaptobenzothiazole and cyclohexylamine salt, N, N-diethylthiocarbamoyl-2-benzo Thiazolyl sulfi Although like it is used, and among this, those sulfenamide are preferably used.
[0024]
In addition to the above components, the rubber composition of the present invention can further contain various additives that are generally compounded for tires, such as sulfur, anti-aging agents, softeners, and plasticizers. The compound can be vulcanized by a general method to produce a tire tread. These compounding amounts can also be set to general amounts. For example, the compounding amount of sulfur is preferably 1.0 part by weight or more per 100 parts by weight of diene rubber, and more preferably 1.2 to 2.5 parts by weight.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
Example 1, Reference Examples 1-8 and Comparative Examples 1-4
Among the components (parts by weight) shown in Table 1 below, a vulcanization accelerator was added to a master batch obtained by kneading the thiuram compound, the vulcanization accelerator and the components excluding sulfur with a 1.8 liter sealed mixer for 4 to 5 minutes. Or the rubber composition of the silica mixing | blending which kneaded the thiuram type compound and sulfur 8-inch open roll was obtained. Next, this composition was press vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a target test piece (rubber sheet), which was subjected to the following M300 change rate. It used for the measurement and the result was specified in Table 1. Moreover, using this rubber composition for a tread, a pneumatic tire for passenger cars having a size of 195 / 55R15 was produced, and the following grip properties and grip durability were evaluated.
[0026]
Based on M300 change rate JlS K 6251, the initial 300% modulus and the 300% modulus after heat aging at 100 ° C. for 48 hours were measured, and the difference between the initial value and the value after heat aging was determined. The difference was divided by the initial value to obtain the rate of change (%). The smaller the value, the smaller the rate of change and the better the heat aging resistance, leading to improved grip durability.
Grip performance Grip performance (grip feeling, brake performance, traction performance) when the produced tire is mounted on a 1.6 liter class domestic passenger car and traveled around a course of 4.41 km per cycle is as follows. A staged feeling evaluation was performed. The larger the value, the better the grip.
5: Very good, 4: Good, 3: Normal, 2: Slightly inferior, 1: Very inferior 5 indicates better grip than 4 − , 4 + indicates better grip than 4
Grip durability The time between the fastest lap time and the final (5th lap) lap time when the prepared tire is mounted on a 1.6 liter class domestic passenger car and the 4.41km course runs 5 laps continuously. The difference was calculated, and the grip durability of each tire was determined by the following formula.
(Time difference of tire of Comparative Example 1) / (Time difference of each tire) × 100
The larger this value, the better the grip durability.
[0027]
[Table 1]
[Formula 4]
[0029]
Vulcanization accelerator CBS: N-cyclohexyl-2-benzothiazylsulfenamide Vulcanization accelerator TOT-N: Noxeller TOT-N, tetra (2-ethylhexyl) antiaging agent 6C: Antigen 6C (N-phenyl-N '-(1,3-dimethyl) -p-phenylenediamine), manufactured by Sumitomo Chemical Co., Ltd.
As shown in Table 1 above, Comparative Example 1 and Comparative Example 4 in which the thiiram-based compound of the present invention was not blended had a high G300 change rate and poor heat aging resistance, and therefore the grip durability was not good. Further, Comparative Example 2 with a small amount of styrene-butadiene copolymer rubber having a styrene content of 20 to 50% and Comparative Example 3 with a small amount of total filler had poor grip properties.
[0031]
On the other hand, Example 1 and Reference Examples 1 to 8 in which the thiuram compound of the present invention was blended were excellent in M300 change rate and were able to improve both the grip properties and the grip sustainability in a balanced manner . In Example 1, it was possible to improve the M300 change rate, the grip performance, and the grip sustainability in the most balanced manner.
[0032]
【Effect of the invention】
According to the present invention, by blending a predetermined amount of a predetermined rubber component and a compounding agent, it is possible to improve the M300 change rate, grip performance, and grip sustainability in the most balanced manner .
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000305263A JP5051938B2 (en) | 2000-10-04 | 2000-10-04 | Rubber composition for tire tread |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000305263A JP5051938B2 (en) | 2000-10-04 | 2000-10-04 | Rubber composition for tire tread |
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| JP2002114871A JP2002114871A (en) | 2002-04-16 |
| JP5051938B2 true JP5051938B2 (en) | 2012-10-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4138729B2 (en) | 2004-11-01 | 2008-08-27 | 住友ゴム工業株式会社 | Rubber composition and tire comprising the same |
| JP4945084B2 (en) * | 2005-03-14 | 2012-06-06 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP4945083B2 (en) * | 2005-03-14 | 2012-06-06 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP4982973B2 (en) * | 2005-06-13 | 2012-07-25 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP5189253B2 (en) * | 2006-06-07 | 2013-04-24 | 株式会社ブリヂストン | Pneumatic tire |
| FR2967682B1 (en) * | 2010-11-23 | 2012-12-21 | Michelin Soc Tech | COMPOSITION CONTAINING A PARTICULAR DIENE ELASTOMER AND A SPECIFICALLY SPECIFIC SURFACE CARBON BLACK |
| JP6357880B2 (en) * | 2013-05-31 | 2018-07-18 | 三菱ケミカル株式会社 | Rubber masterbatch and manufacturing method thereof |
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| JP3717356B2 (en) * | 1999-12-15 | 2005-11-16 | 横浜ゴム株式会社 | Rubber composition for tire tread |
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