JP4895576B2 - Rubber composition and high-performance tire using the same - Google Patents
Rubber composition and high-performance tire using the same Download PDFInfo
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本発明は、ゴム組成物に関し、詳細には、低温および高温条件下でのグリップ性能、持続性ならびに耐摩耗性を向上させた高性能タイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly to a rubber composition for a high-performance tire having improved grip performance, durability and wear resistance under low and high temperature conditions.
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、一般に、グリップ性能および耐摩耗性がともに優れたゴム組成物が要求される。従来、高いグリップ性能を得るために、たとえば、ガラス転移温度（Ｔｇ）の高いスチレンブタジエンゴム（ＳＢＲ）を使用する方法が知られているが、温度依存性が増大し、温度変化に対する性能変化が大きくなるといった問題があった。 In general, a rubber composition excellent in grip performance and wear resistance is required for tread rubber of racing tires and other racing tires. Conventionally, in order to obtain high grip performance, for example, a method using styrene butadiene rubber (SBR) having a high glass transition temperature (Tg) is known. However, the temperature dependency increases, and the performance change with respect to the temperature change occurs. There was a problem of getting bigger.
また、軟化点の高い樹脂を、プロセスオイルと置換して配合する方法も知られているが、置換量が多量であると、該樹脂の影響により、温度依存性が大きくなるという問題があった。 In addition, a method of blending a resin having a high softening point by replacing it with process oil is also known, but if the amount of substitution is large, there is a problem that temperature dependency becomes large due to the influence of the resin. .
さらに、軟化剤およびカーボンブラックを多量に配合する方法、または粒子径の小さいカーボンブラックを使用する方法も知られているが、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った。 Furthermore, a method of blending a large amount of softener and carbon black, or a method of using carbon black having a small particle size is also known, but the problem is that the dispersibility of carbon black is poor and wear resistance decreases. was there.
特許文献１には、ＳＢＲを含有するゴム成分に、所定の低分子量スチレンブタジエン共重合体、樹脂ならびに軟化剤および／または可塑剤を所定量配合することで、グリップ性能および耐摩耗性を向上させたタイヤトレッド用ゴム組成物が開示されているが、グリップ性能の温度依存性については開示されておらず、さらに、グリップ性能および耐摩耗性には、改善の余地がある。 Patent Document 1 improves grip performance and wear resistance by blending a predetermined amount of a low molecular weight styrene butadiene copolymer, a resin, and a softener and / or a plasticizer into a rubber component containing SBR. A tire tread rubber composition is disclosed, but the temperature dependence of grip performance is not disclosed, and there is room for improvement in grip performance and wear resistance.
本発明は、低温および高温条件下でのグリップ性能、持続性ならびに耐摩耗性を向上させたゴム組成物およびそれを用いた高性能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 having improved grip performance, durability and wear resistance under low and high temperature conditions, and a high-performance tire using the rubber composition.
本発明は、（Ａ）スチレンブタジエンゴムを含むゴム成分１００重量部に対して、（Ｂ）重量平均分子量が１０００〜５０００である液状スチレンブタジエンゴムを１０重量部以上、および（Ｃ）芳香族系石油樹脂を５重量部以上含むゴム組成物に関する。 The present invention relates to (A) 100 parts by weight of a rubber component containing styrene butadiene rubber, (B) 10 parts by weight or more of liquid styrene butadiene rubber having a weight average molecular weight of 1000 to 5000, and (C) an aromatic system. The present invention relates to a rubber composition containing 5 parts by weight or more of a petroleum resin.
芳香族系石油樹脂（Ｃ）は、フェノール系樹脂であることが好ましい。 The aromatic petroleum resin (C) is preferably a phenolic resin.
液状スチレンブタジエンゴム（Ｂ）の水素添加率が６０％以下であることが好ましい。 The hydrogenation rate of the liquid styrene butadiene rubber (B) is preferably 60% or less.
また、本発明は、前記ゴム組成物を用いた高性能タイヤに関する。 The present invention also relates to a high performance tire using the rubber composition.
本発明によれば、ＳＢＲを含むゴム成分に、低分子量の液状スチレンブタジエンゴムおよび芳香族系石油樹脂を配合することで、低温および高温条件下でのグリップ性能、持続性ならびに耐摩耗性を向上させたゴム組成物およびそれを用いた高性能タイヤを提供することができる。 According to the present invention, by combining a rubber component containing SBR with a low molecular weight liquid styrene butadiene rubber and an aromatic petroleum resin, grip performance, durability and wear resistance under low and high temperature conditions are improved. A rubber composition and a high-performance tire using the rubber composition can be provided.
本発明のゴム組成物は、（Ａ）ゴム成分、（Ｂ）液状スチレンブタジエンゴム（液状ＳＢＲ）、および（Ｃ）芳香族系石油樹脂からなる。 The rubber composition of the present invention comprises (A) a rubber component, (B) a liquid styrene butadiene rubber (liquid SBR), and (C) an aromatic petroleum resin.
ゴム成分（Ａ）は、スチレンブタジエンゴム（ＳＢＲ）を含む。 The rubber component (A) includes styrene butadiene rubber (SBR).
ゴム成分（Ａ）中のＳＢＲのスチレン含有率は、２５重量％以上が好ましく、３０重量％以上がより好ましい。ＳＢＲのスチレン含有率が２５重量％未満では、充分なグリップ性能が得られない傾向がある。また、ＳＢＲのスチレン含有率は、５０重量％以下が好ましく、４５重量％以下がより好ましい。ＳＢＲのスチレン含有率が５０重量％をこえると、耐摩耗性が低下するだけでなく、温度依存性が増大し、温度変化に対する性能変化が大きくなってしまう傾向がある。 The styrene content of SBR in the rubber component (A) is preferably 25% by weight or more, and more preferably 30% by weight or more. When the styrene content of SBR is less than 25% by weight, sufficient grip performance tends not to be obtained. The styrene content of SBR is preferably 50% by weight or less, and more preferably 45% by weight or less. When the styrene content of SBR exceeds 50% by weight, not only the wear resistance is lowered, but also the temperature dependency is increased and the performance change with respect to the temperature change tends to increase.
ゴム成分（Ａ）中のＳＢＲの含有率は、６０重量％以上が好ましく、８０重量％以上がより好ましく、１００重量％が最も好ましい。ＳＢＲの含有率が６０重量％未満では、グリップ性能が低下する傾向がある。 The content of SBR in the rubber component (A) is preferably 60% by weight or more, more preferably 80% by weight or more, and most preferably 100% by weight. If the SBR content is less than 60% by weight, the grip performance tends to decrease.
また、ゴム成分（Ａ）は、前記ＳＢＲ以外のゴム成分を含むことができる。他のゴムの成分としては、たとえば、シス−１，４−ポリイソプレン、低シス−１，４−ポリブタジエン、高シス−１，４−ポリブタジエン、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、ハロゲン化ブチルゴム（Ｘ−ＩＩＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、天然ゴム（ＮＲ）などが挙げられるが、特にこれらに限定されるものではない。これらの他のゴム成分は、本発明に使用されるゴム成分中に１種類または２種類以上含まれていてもよい。 The rubber component (A) can contain a rubber component other than the SBR. Examples of other rubber components include cis-1,4-polyisoprene, low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, ethylene-propylene-diene rubber (EPDM), and chloroprene rubber (CR ), Halogenated butyl rubber (X-IIR), acrylonitrile-butadiene rubber (NBR), natural rubber (NR), and the like, but are not particularly limited thereto. One or more kinds of these other rubber components may be contained in the rubber component used in the present invention.
液状ＳＢＲ（Ｂ）のガラス転移温度（Ｔｇ）は、−６０℃以上が好ましく、−５０℃以上がより好ましい。Ｔｇが−６０℃未満では、エネルギーロスが低く、所定のグリップが得られない傾向がある。また、液状ＳＢＲ（Ｂ）のＴｇは、−２０℃以下が好ましく、−３０℃以下がより好ましい。液状ＳＢＲ（Ｂ）のＴｇが−２０℃をこえると、低温で硬くなり低温でのグリップが得られない傾向がある。 The glass transition temperature (Tg) of the liquid SBR (B) is preferably −60 ° C. or higher, and more preferably −50 ° C. or higher. When Tg is less than −60 ° C., energy loss is low and a predetermined grip tends not to be obtained. Further, Tg of the liquid SBR (B) is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower. When the Tg of the liquid SBR (B) exceeds -20 ° C, it tends to be hard at low temperatures and a grip at low temperatures cannot be obtained.
液状ＳＢＲ（Ｂ）の重量平均分子量（Ｍｗ）は１０００以上、好ましくは１５００以上である。液状ＳＢＲ（Ｂ）のＭｗが１０００未満では、耐摩耗性が低下する。また、液状ＳＢＲ（Ｂ）のＭｗは５０００以下、好ましくは４０００以下である。液状ＳＢＲ（Ｂ）のＭｗが５０００をこえると、特に低温時のグリップ性能が低下する。 The weight average molecular weight (Mw) of the liquid SBR (B) is 1000 or more, preferably 1500 or more. When the Mw of the liquid SBR (B) is less than 1000, the wear resistance is lowered. Moreover, Mw of liquid SBR (B) is 5000 or less, Preferably it is 4000 or less. When the Mw of the liquid SBR (B) exceeds 5000, grip performance particularly at low temperatures is deteriorated.
液状ＳＢＲ（Ｂ）におけるブタジエン部の二重結合は水素添加されていることが好ましい。液状ＳＢＲ（Ｂ）におけるブタジエン部の二重結合に水素添加される場合、液状ＳＢＲ（Ｂ）の水素添加率は、２５％以上が好ましく、４０％以上がより好ましい。液状ＳＢＲ（Ｂ）の水素添加率が２５％未満では、液状ＳＢＲ（Ｂ）がマトリックスであるゴム成分（Ａ）に取り込まれ、充分なグリップ性能が得られない傾向がある。液状ＳＢＲ（Ｂ）の水素添加率は、６０％以下が好ましく、５０％以下がより好ましい。液状ＳＢＲ（Ｂ）の水素添加率が６０％をこえると、ゴム組成物が硬くなり、充分なグリップ性能および耐摩耗性が得られず、また、ブリードアウトしてしまう傾向がある。 It is preferable that the double bond of the butadiene part in liquid SBR (B) is hydrogenated. In the case where hydrogen is added to the double bond of the butadiene portion in the liquid SBR (B), the hydrogenation rate of the liquid SBR (B) is preferably 25% or more, and more preferably 40% or more. When the hydrogenation rate of the liquid SBR (B) is less than 25%, the liquid SBR (B) tends to be taken into the rubber component (A) as a matrix and sufficient grip performance cannot be obtained. The hydrogenation rate of the liquid SBR (B) is preferably 60% or less, and more preferably 50% or less. When the hydrogenation rate of liquid SBR (B) exceeds 60%, the rubber composition becomes hard, sufficient grip performance and wear resistance cannot be obtained, and there is a tendency to bleed out.
液状ＳＢＲ（Ｂ）の配合量は、ゴム成分（Ａ）１００重量部に対して１０重量部以上、好ましくは２０重量部以上である。液状ＳＢＲ（Ｂ）の配合量が１０重量部未満では、グリップ性能が低下する。また、液状ＳＢＲ（Ｂ）の配合量は、６０重量部以下が好ましく、５０重量部以下がより好ましい。液状ＳＢＲの配合量が６０重量部をこえると、耐摩耗性が低下する傾向がある。 The compounding quantity of liquid SBR (B) is 10 weight part or more with respect to 100 weight part of rubber components (A), Preferably it is 20 weight part or more. When the blending amount of the liquid SBR (B) is less than 10 parts by weight, the grip performance is lowered. Moreover, 60 weight part or less is preferable and, as for the compounding quantity of liquid SBR (B), 50 weight part or less is more preferable. When the blending amount of the liquid SBR exceeds 60 parts by weight, the wear resistance tends to decrease.
芳香族系石油樹脂（Ｃ）としては、フェノール系樹脂、クマロンインデン樹脂、スチレン樹脂、ロジン樹脂、ＤＣＰＤ樹脂などがあげられる。 Examples of the aromatic petroleum resin (C) include phenolic resins, coumarone indene resins, styrene resins, rosin resins, DCPD resins, and the like.
フェノール系樹脂としては、たとえばコレシン（ＢＡＳＦ社製）、タッキロール（田岡化学工業（株）製）などがあげられる。 Examples of the phenolic resin include colesin (manufactured by BASF), tackolol (manufactured by Taoka Chemical Industry Co., Ltd.), and the like.
また、クマロンインデン樹脂としては、たとえばエスクロン（新日鉄化学（株）製）、ネオポリマー（新日本石油化学（株）製）などがあげられる。 Examples of the coumarone indene resin include Esculon (manufactured by Nippon Steel Chemical Co., Ltd.), neopolymer (manufactured by Nippon Petrochemical Co., Ltd.), and the like.
芳香族系石油樹脂（Ｃ）としては、なかでも、高温でヒステリシスロスが大きいという理由から、フェノール系樹脂が好ましい。 As the aromatic petroleum resin (C), a phenolic resin is preferable because of high hysteresis loss at high temperatures.
芳香族系石油樹脂（Ｃ）の軟化点は、１００℃以上が好ましく、１１０℃以上がより好ましい。芳香族系石油樹脂（Ｃ）の軟化点が１００℃未満では、耐摩耗性が低下する傾向がある。また、芳香族系石油樹脂（Ｃ）の軟化点は、１６０℃以下が好ましく、１４０℃以下がより好ましい。芳香族系石油樹脂（Ｃ）の軟化点が１６０℃をこえると、グリップ性能が低下する傾向がある。 The softening point of the aromatic petroleum resin (C) is preferably 100 ° C. or higher, and more preferably 110 ° C. or higher. When the softening point of the aromatic petroleum resin (C) is less than 100 ° C., the wear resistance tends to decrease. Moreover, the softening point of the aromatic petroleum resin (C) is preferably 160 ° C. or less, and more preferably 140 ° C. or less. When the softening point of the aromatic petroleum resin (C) exceeds 160 ° C., the grip performance tends to be lowered.
芳香族系石油樹脂（Ｃ）の配合量は、ゴム成分（Ａ）１００重量部に対して５重量部以上、好ましくは１０重量部以上である。芳香族系石油樹脂（Ｃ）の配合量が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、芳香族系石油樹脂（Ｃ）の配合量は、２５重量部以下が好ましく、２０重量部以下がより好ましい。芳香族系石油樹脂の配合量（Ｃ）が２５重量部をこえると、温度依存性が増大し、温度変化に対する性能変化が大きくなる傾向がある。 The compounding amount of the aromatic petroleum resin (C) is 5 parts by weight or more, preferably 10 parts by weight or more with respect to 100 parts by weight of the rubber component (A). When the blending amount of the aromatic petroleum resin (C) is less than 5 parts by weight, the effect of improving the grip performance is small. Further, the blending amount of the aromatic petroleum resin (C) is preferably 25 parts by weight or less, and more preferably 20 parts by weight or less. When the blending amount (C) of the aromatic petroleum resin exceeds 25 parts by weight, the temperature dependency increases, and the performance change with respect to the temperature change tends to increase.
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、カーボンブラック、シリカ、炭酸カルシウム、アルミナ、クレー、タルクなど、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、主としてカーボンブラックが好ましい。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 rubber composition of the present invention preferably further contains a reinforcing filler. As the reinforcing filler, carbon black, silica, calcium carbonate, alumina, clay, talc, and the like can be arbitrarily selected from those conventionally used in rubber compositions for tires. preferable. The reinforcing fillers may be used alone or in combination of two or more.
補強用充填剤としてカーボンブラックを含む場合、カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ）は、１１０ｍ2／ｇ以上が好ましく、１３０ｍ2／ｇ以上がより好ましい。カーボンブラックのＮ2ＳＡが１１０ｍ2／ｇ未満では、グリップ性能および耐摩耗性がともに低下する傾向がある。また、カーボンブラックのＮ2ＳＡは、３００ｍ2／ｇ以下が好ましく、２８０ｍ2／ｇ以下がより好ましい。カーボンブラックのＮ2ＳＡが３００ｍ2／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。 When carbon black is included as the reinforcing filler, the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 110 m 2 / g or more, and more preferably 130 m 2 / g or more. When N 2 SA of carbon black is less than 110 m 2 / g, both grip performance and wear resistance tend to be lowered. Also, N 2 SA of the carbon black is preferably 300 meters 2 / g or less, more preferably 280m 2 / g. When the N 2 SA of the carbon black exceeds 300 m 2 / g, good dispersion is difficult to obtain and the wear resistance tends to decrease.
補強用充填剤として、カーボンブラックを含む場合、カーボンブラックの配合量は、ゴム成分（Ａ）１００重量部に対して５０重量部以上が好ましく、８０重量部以上がより好ましい。カーボンブラックの配合量が５０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配合量は、１５０重量部以下が好ましく、１３０重量部以下がより好ましい。カーボンブラックの配合量が１５０重量部をこえると、加工性が低下する傾向がある。 When carbon black is included as a reinforcing filler, the blending amount of carbon black is preferably 50 parts by weight or more, more preferably 80 parts by weight or more with respect to 100 parts by weight of the rubber component (A). When the blending amount of carbon black is less than 50 parts by weight, the wear resistance tends to decrease. The blending amount of carbon black is preferably 150 parts by weight or less, and more preferably 130 parts by weight or less. When the blending amount of carbon black exceeds 150 parts by weight, processability tends to decrease.
さらに、本発明のゴム組成物には、ゴム成分（Ａ）、液状ＳＢＲ（Ｂ）、芳香族系石油樹脂（Ｃ）および補強用充填剤のほかに、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、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。 In addition to the rubber component (A), liquid SBR (B), aromatic petroleum resin (C) and reinforcing filler, the rubber composition of the present invention includes various chemicals commonly used in the rubber industry. For example, additives such as vulcanizing agents such as sulfur, various vulcanization accelerators, various softening agents, various anti-aging agents, stearic acid, and ozone deterioration preventing agents can be blended.
本発明のゴム組成物は、空気入りタイヤのトレッド部に用いられることが好ましく、とくに、カート用タイヤなどの競技用タイヤのトレッド部に用いられることが好ましい。該空気入りタイヤは、通常の空気入りタイヤの製造方法により製造できる。すなわち、前記ゴム組成物を未加硫の段階でタイヤのトレッド部の形状に押し出し加工し、タイヤ成型機上で通常の方法により貼り合わせて未加硫タイヤを成形する。この未加硫タイヤを加硫機中で加熱、加圧して空気入りタイヤを得る。 The rubber composition of the present invention is preferably used for a tread portion of a pneumatic tire, and particularly preferably used for a tread portion of a racing tire such as a cart tire. The pneumatic tire can be manufactured by an ordinary pneumatic tire manufacturing method. That is, the rubber composition is extruded into the shape of a tread portion of a tire at an unvulcanized stage, and bonded together by a normal method on a tire molding machine to form an unvulcanized tire. This unvulcanized tire is heated and pressurized in a vulcanizer to obtain a pneumatic tire.
実施例に基づいて本発明を詳細に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be described in detail based on examples, but the present invention is not limited thereto.
次に、実施例および比較例で用いた薬品をまとめて説明する。
スチレンブタジエンゴム（ＳＢＲ）：旭化成工業（株）製のＴＵＦＤＥＮＥ４３５０（スチレン含有量：４０重量％、ＳＢＲ固形分１００重量部に対してオイル含有量５０重量部）
石油樹脂（１）：新日鐵化学（株）製のエスクロンＧ９０（クマロンインデン樹脂、軟化点：９０℃）
石油樹脂（２）：新日鐵化学（株）製のエスクロンＶ１２０（クマロンインデン樹脂、軟化点：１２０℃）
石油樹脂（３）：ＢＡＳＦ社製のコレシン（フェノール系樹脂、軟化点：１４０℃）
カーボンブラック（ＣＢ）：三菱化学（株）製のダイアブラックＡ（Ｎ１１０、Ｎ2ＳＡ：１４２ｍ2／ｇ）
アロマオイル：（株）ジャパンエナジー製のプロセスＸ−２６０
老化防止剤６ＰＰＤ：フレキシス（株）製のサントフレックス１３（Ｎ−フェニル−Ｎ’−（１，３−ジメチルブチル）−ｐ−フェニレンジアミン）
ステアリン酸：日本油脂（株）製のステアリン酸「桐」
酸化亜鉛：三菱金属工業（株）製の酸化亜鉛２種
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤ＣＢＳ：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド）
Next, the chemicals used in the examples and comparative examples will be described together.
Styrene butadiene rubber (SBR): TUFDEN 4350 manufactured by Asahi Kasei Corporation (styrene content: 40% by weight, oil content 50 parts by weight with respect to 100 parts by weight of SBR solid content)
Petroleum resin (1): Escron G90 (coumarone indene resin, softening point: 90 ° C.) manufactured by Nippon Steel Chemical Co., Ltd.
Petroleum resin (2): Escron V120 manufactured by Nippon Steel Chemical Co., Ltd. (coumarone indene resin, softening point: 120 ° C.)
Petroleum resin (3): Colesin manufactured by BASF (phenolic resin, softening point: 140 ° C.)
Carbon black (CB): Dia Black A (N110, N 2 SA: 142 m 2 / g) manufactured by Mitsubishi Chemical Corporation
Aroma oil: Process X-260 manufactured by Japan Energy Co., Ltd.
Anti-aging agent 6PPD: Santoflex 13 (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine) manufactured by Flexis Co., Ltd.
Stearic acid: Stearic acid “paulownia” manufactured by NOF Corporation
Zinc oxide: 2 types of zinc oxide manufactured by Mitsubishi Metal Industries, Ltd. Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. CBS: Noxeller CZ (N-cyclohexyl- manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. 2-Benzothiazylsulfenamide)
＜液状スチレンブタジエンゴム（１）（液状ＳＢＲ（１））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２．５ｇを加え、昇温条件下で１５分間重合し、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、液状ＳＢＲ（１）を合成した。（重量平均分子量（Ｍｗ）：７０００、ガラス転移温度：−４５℃、スチレン含有率：２５重量％、水素添加なし）
<Liquid Styrene Butadiene Rubber (1) (Synthesis of Liquid SBR (1))>
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, 2.5 g of n-butyllithium is added and polymerized for 15 minutes under elevated temperature conditions. (1) was synthesized. (Weight average molecular weight (Mw): 7000, Glass transition temperature: -45 ° C, Styrene content: 25% by weight, no hydrogenation)
＜液状スチレンブタジエンゴム（２）（液状ＳＢＲ（２））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３．０ｇを加え、昇温条件下で１０分間重合し、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、液状ＳＢＲ（２）を合成した（重量平均分子量（Ｍｗ）：３０００、ガラス転移温度：−４５℃、スチレン含有率：２５重量％、水素添加なし）。
<Liquid Styrene Butadiene Rubber (2) (Synthesis of Liquid SBR (2))>
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, 3.0 g of n-butyllithium is added and polymerized for 10 minutes under elevated temperature conditions. Thereafter, 1.5 g of 2,6-di-t-butyl-p-cresol is added as an anti-aging agent, and liquid SBR is added. (2) was synthesized (weight average molecular weight (Mw): 3000, glass transition temperature: −45 ° C., styrene content: 25% by weight, no hydrogenation).
＜液状スチレンブタジエンゴム（３）（液状ＳＢＲ（３））の合成）＞
耐熱容器に液状スチレンブタジエンゴム（２）を２００ｇ、ＴＨＦ３００ｇ、１０％パラジウムカーボン１０ｇを加え、窒素置換したのち、圧力が５．０ｋｇ／ｃｍ2となるように水素置換して、８０℃で反応させることで液状ＳＢＲ（３）を合成した。なお、水素添加率は四塩化炭素を溶媒として用い、１５質量％の濃度で測定した１００ＭＨｚのプロトンＮＭＲの不飽和結合部のスペクトルの減少から算出した（重量平均分子量（Ｍｗ）：３０００、スチレン含有率：２５重量％、水素添加率：５０％）。
<Liquid Styrene Butadiene Rubber (3) (Synthesis of Liquid SBR (3))>
Add 200 g of liquid styrene-butadiene rubber (2) to the heat-resistant container, 300 g of THF, 10 g of 10% palladium carbon, and after purging with nitrogen, purging with hydrogen so that the pressure becomes 5.0 kg / cm 2 and reacting at 80 ° C. As a result, liquid SBR (3) was synthesized. The hydrogenation rate was calculated from the decrease in the spectrum of the unsaturated bond portion of proton NMR at 100 MHz measured at a concentration of 15% by mass using carbon tetrachloride as a solvent (weight average molecular weight (Mw): 3000, containing styrene) Rate: 25% by weight, hydrogenation rate: 50%).
実施例３、５、参考例１、２、４、および比較例１〜４
硫黄および加硫促進剤以外の薬品を表１に示す配合処方にしたがって配合し、ＢＲ型バンバリーミキサーで５分間混練りした。その後、得られた混練物に硫黄および加硫促進剤を表１に示す配合処方にしたがって添加して、２軸オープンロールで温調８０℃で３分間混練りし、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物をトレッド形状に成形して、他のタイヤ部材と貼りあわせ、１７０℃で１５分間プレス加硫することにより、試験用カートタイヤ（タイヤサイズ：１１×７．１０−５）を製造し、以下の試験に用いた。
Examples 3, 5 , Reference Examples 1, 2, 4 and Comparative Examples 1-4
Chemicals other than sulfur and a vulcanization accelerator were blended according to the blending formulation shown in Table 1, and kneaded for 5 minutes with a BR type Banbury mixer. Thereafter, sulfur and a vulcanization accelerator were added to the obtained kneaded material according to the formulation shown in Table 1, and kneaded with a biaxial open roll at a temperature of 80 ° C. for 3 minutes to obtain an unvulcanized rubber composition. Obtained. The obtained unvulcanized rubber composition was molded into a tread shape, bonded to another tire member, and press vulcanized at 170 ° C. for 15 minutes to obtain a test cart tire (tire size: 11 × 7.10). -5) was produced and used for the following tests.
（グリップ性能）
カートに前記タイヤを装着し、１周約５ｋｍのサーキットコースを５周走行した際の官能評価によりグリップ性能を判定した。１００点満点で７０点以上が良好である。なお、低温グリップ性能は１５℃、高温グリップ性能は３０℃における測定値を示す。
(Grip performance)
The tire was mounted on the cart, and the grip performance was judged by sensory evaluation when the circuit course of one lap of about 5 km was run five laps. A score of 70 out of 100 is good. The low temperature grip performance is measured at 15 ° C., and the high temperature grip performance is measured at 30 ° C.
（持続性）
カートに前記タイヤを装着し、１周約５ｋｍのサーキットコースを５周走行した際の官能評価により持続性を判定した。１００点満点で７０点以上が良好である。
(Persistence)
The tire was mounted on the cart, and the sustainability was determined by sensory evaluation when the circuit course of one lap of about 5 km was run for five laps. A score of 70 out of 100 is good.
（耐摩耗性）
カートに前記タイヤを装着し、１周約５ｋｍのサーキットコースを５周走行した際の官能評価により耐摩耗性を判定した。１００点満点で７０点以上が良好である。
(Abrasion resistance)
The tire was mounted on the cart, and the wear resistance was determined by sensory evaluation when the circuit course of one lap of about 5 km was run for five laps. A score of 70 out of 100 is good.
以上の試験より得られた試験結果を表１に示す。 Table 1 shows the test results obtained from the above tests.
所定の液状スチレンブタジエンゴムおよび石油樹脂を所定量配合した実施例では、低温および高温条件下でのグリップ性能、持続性ならびに耐摩耗性が向上した。 In an example in which a predetermined amount of a predetermined liquid styrene butadiene rubber and a petroleum resin was blended, grip performance, durability and wear resistance under low and high temperature conditions were improved.
Claims (4)
（Ｂ）重量平均分子量が１０００〜５０００であり、水素添加率が４０〜６０％である液状スチレンブタジエンゴムを１０重量部以上、および
（Ｃ）芳香族系石油樹脂を５重量部以上含むゴム組成物。 (A) For 100 parts by weight of a rubber component containing styrene butadiene rubber,
(B) a weight average molecular weight of Ri der 1000-5000, liquid styrene-butadiene rubber 10 parts by weight or more hydrogenation ratio is 40% to 60%, and (C) a rubber containing aromatic petroleum resin 5 parts by weight or more Composition.
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| JP2007246625A (en) * | 2006-03-14 | 2007-09-27 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JP5363018B2 (en) * | 2007-07-13 | 2013-12-11 | 住友ゴム工業株式会社 | Rubber composition and studless tire made from the rubber composition |
| JP2009155428A (en) * | 2007-12-26 | 2009-07-16 | Toyo Tire & Rubber Co Ltd | Tread rubber composition for lacing tire |
| JP5216386B2 (en) * | 2008-03-27 | 2013-06-19 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| JP5446380B2 (en) * | 2009-03-30 | 2014-03-19 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP5616073B2 (en) * | 2010-01-27 | 2014-10-29 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| EP2742094B1 (en) | 2012-01-20 | 2017-06-21 | Daikin Industries, Ltd. | Fluororubber composition and method for producing same |
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| US11898661B2 (en) | 2012-02-24 | 2024-02-13 | Daikin Industries, Ltd. | Fluororubber composition |
| JP5868250B2 (en) * | 2012-04-12 | 2016-02-24 | 住友ゴム工業株式会社 | Rubber composition for tread of high performance tire and pneumatic tire using the same |
| CN103589014B (en) * | 2012-08-16 | 2016-01-20 | 山东玲珑轮胎股份有限公司 | Fully synthetic rubber tread rubber material of engineering tire |
| WO2016039008A1 (en) * | 2014-09-08 | 2016-03-17 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP6801183B2 (en) | 2014-09-08 | 2020-12-16 | 住友ゴム工業株式会社 | Pneumatic tires |
| JP6716942B2 (en) | 2016-02-18 | 2020-07-01 | 住友ゴム工業株式会社 | Pneumatic tire and method for manufacturing pneumatic tire |
| JP6862787B2 (en) | 2016-11-22 | 2021-04-21 | 住友ゴム工業株式会社 | Pneumatic tires |
| MY191032A (en) * | 2016-12-15 | 2022-05-30 | Toyo Tire Corp | Rubber composition for tire and pneumatic tire using same |
| CA3074360A1 (en) | 2017-09-01 | 2019-03-07 | Kuraray Co., Ltd. | Heavy-duty tire rubber compositions and tires |
| CA3074423A1 (en) | 2017-09-01 | 2019-03-07 | Kuraray Co., Ltd. | High-grip tire rubber compositions |
| EP3677634B1 (en) | 2017-09-01 | 2022-03-23 | Kuraray Co., Ltd. | Rubber composition for high grip tire |
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| JPH06104760B2 (en) * | 1986-10-17 | 1994-12-21 | 日本合成ゴム株式会社 | Rubber composition |
| JPH09278944A (en) * | 1996-04-09 | 1997-10-28 | Yokohama Rubber Co Ltd:The | Rubber composition having high hysteresis loss |
| JP2005154696A (en) * | 2003-11-28 | 2005-06-16 | Sumitomo Rubber Ind Ltd | Rubber composition for a tire tread |
| JP4113847B2 (en) * | 2004-02-12 | 2008-07-09 | 住友ゴム工業株式会社 | Rubber composition and tire using the same |
| JP2005220181A (en) * | 2004-02-04 | 2005-08-18 | Bridgestone Corp | Tire tread rubber composition and pneumatic tire using the same |
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