JP2005126604A - Rubber composition and tire obtained by using the same - Google Patents
Rubber composition and tire obtained by using the same Download PDFInfo
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- JP2005126604A JP2005126604A JP2003364913A JP2003364913A JP2005126604A JP 2005126604 A JP2005126604 A JP 2005126604A JP 2003364913 A JP2003364913 A JP 2003364913A JP 2003364913 A JP2003364913 A JP 2003364913A JP 2005126604 A JP2005126604 A JP 2005126604A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
Description
本発明は、ゴム組成物および、それを用いたタイヤに関し、とりわけ優れた加工性および低減された転がり抵抗特性を有するゴム組成物、ならびにそれをトレッドに用いたタイヤに関する。 The present invention relates to a rubber composition and a tire using the rubber composition, and more particularly to a rubber composition having excellent processability and reduced rolling resistance characteristics, and a tire using the rubber composition.
従来、タイヤの転がり抵抗を低減させるために、ゴム成分として、溶液重合スチレンブタジエンゴム（Ｓ−ＳＢＲ）を用い、Ｓ−ＳＢＲの分子量を高く設定し、分子量分布をシャープにすることが行なわれてきた。また、シリカを補強剤として配合することにより、さらなる低燃費化が図られるようになった。しかし、シリカを配合すると、転がり抵抗の低減とウェットグリップ特性の向上を両立できるが、ゴム練り中にシリカがポリマーと結合してゲルを生成しやすく、ゲルが生成されると、練りゴムの粘度が上がるので、ゴム生地がわるくなるという工程上の問題が多発し、生産性が大きく低下した。 Conventionally, in order to reduce the rolling resistance of tires, solution-polymerized styrene butadiene rubber (S-SBR) is used as a rubber component, the molecular weight of S-SBR is set high, and the molecular weight distribution has been sharpened. It was. Further, by adding silica as a reinforcing agent, further reduction in fuel consumption has been achieved. However, when silica is blended, it is possible to achieve both reduction in rolling resistance and improvement in wet grip properties, but silica is likely to combine with the polymer during rubber kneading to form a gel. As a result, problems in the process of breaking the rubber fabric occurred frequently, and the productivity was greatly reduced.
また、ウェットグリップ特性の向上を目的として、低分子量および高分子量のポリマーを配合したゴム組成物について報告されている（特許文献１参照）。しかし、これらの技術によると、転がり抵抗が低減されない、または別々に配合する場合の低分子量ポリマーの分散性および加工性が悪化するという問題があった。 A rubber composition containing a low molecular weight polymer and a high molecular weight polymer has been reported for the purpose of improving wet grip characteristics (see Patent Document 1). However, according to these techniques, there has been a problem that the rolling resistance is not reduced, or the dispersibility and processability of the low molecular weight polymer when blended separately is deteriorated.
また、末端変性またはカップリングされたゴム成分と充填剤を使用し、ゴム組成物の性質を改善することも知られている（特許文献２参照）。しかし、これらの技術によると、アミンを末端に用いるため、シリカとの反応性が高くなく、ゴム組成物の性質改善効果が充分ではないという問題があった。 It is also known to improve the properties of a rubber composition by using a rubber component and a filler that are terminal-modified or coupled (see Patent Document 2). However, according to these techniques, since amine is used at the terminal, there is a problem that the reactivity with silica is not high and the property improving effect of the rubber composition is not sufficient.
本発明は、優れた加工性および低減された転がり抵抗を有するゴム組成物、およびそれをトレッドに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 having excellent processability and reduced rolling resistance, and a tire using the rubber composition.
すなわち、本発明は、溶液重合スチレン−ブタジエンゴム５０重量％以上、天然ゴム４０重量％以下、およびブタジエンゴム４０重量％以下からなるゴム成分、ならびに５５重量％以上のシリカおよびカーボンブラック４０重量％以下からなる補強剤からなるゴム組成物であって、該溶液重合スチレン−ブタジエンゴムは、（ａ）重量平均分子量が５０００以下の低分子量溶液重合スチレン−ブタジエンゴムを２５重量％以下、および（ｂ）ＳｎまたはＳｉでのカップリングにより高分子量溶液重合スチレン−ブタジエンゴムを含み、かつ該溶液重合スチレン−ブタジエンゴム全体の重量平均分子量が５０万以上であり、該カーボンブラックは、チッ素吸着比表面積が１４５ｍ2／ｇ以上であり、かつセチルトリメチルアンモニウムブロマイド吸着比表面積（ｍ2／ｇ）がヨウ素吸着量（ｍｇ／ｇ）に対して１．１倍以上であるゴム組成物に関する。 That is, the present invention relates to a rubber component composed of 50% by weight or more of solution-polymerized styrene-butadiene rubber, 40% by weight or less of natural rubber, and 40% by weight or less of butadiene rubber, and 40% by weight or less of silica and carbon black of 55% by weight or more. A rubber composition comprising a reinforcing agent comprising: (a) 25% by weight or less of a low molecular weight solution polymerized styrene-butadiene rubber having a weight average molecular weight of 5000 or less, and (b) Coupling with Sn or Si includes a high molecular weight solution-polymerized styrene-butadiene rubber, and the weight average molecular weight of the whole solution-polymerized styrene-butadiene rubber is 500,000 or more, and the carbon black has a nitrogen adsorption specific surface area. 145m and 2 / g or more, and cetyltrimethylammonium My Adsorption specific surface area (m 2 / g) is relates to a rubber composition is 1.1 times or more with respect to iodine adsorption (mg / g).
前記低分子量溶液重合スチレン−ブタジエンゴムは、アルキルシリル基で末端変性されていることが好ましい。 The low molecular weight solution polymerized styrene-butadiene rubber is preferably end-modified with an alkylsilyl group.
前記ゴム組成物のトルエン膨潤度は１８０〜３２０であることが好ましい。 The rubber composition preferably has a toluene swelling degree of 180 to 320.
シランカップリング剤はシリカ１００重量部に対して、２〜１２重量部配合され、１６０℃以上の温度で混練りされることが好ましい。 The silane coupling agent is preferably blended in an amount of 2 to 12 parts by weight with respect to 100 parts by weight of silica and kneaded at a temperature of 160 ° C. or higher.
また、本発明は、前記ゴム組成物をトレッドに用いたタイヤに関する。 The present invention also relates to a tire using the rubber composition in a tread.
本発明によれば、低分子量（５０００以下）および高分子量のＳ−ＳＢＲを混合することにより、混合時や押出し時のゴム生地を改善することができる。さらに、その低分子量ＢＲを末端変性することにより、シリカとの反応性を高め、混練り時の加工性の悪さを改善し、タイヤに用いた際の転がり抵抗を低減することができる。 According to the present invention, by mixing low molecular weight (5000 or less) and high molecular weight S-SBR, the rubber fabric at the time of mixing and extrusion can be improved. Furthermore, by terminal-modifying the low molecular weight BR, the reactivity with silica can be increased, the poor workability during kneading can be improved, and the rolling resistance when used in a tire can be reduced.
本発明のゴム組成物は、ゴム成分および補強剤からなる。 The rubber composition of the present invention comprises a rubber component and a reinforcing agent.
本発明で使用するゴム成分としては、溶液重合スチレン−ブタジエンゴム（Ｓ−ＳＢＲ）、天然ゴム（ＮＲ）およびブタジエンゴム（ＢＲ）を用いる。 As the rubber component used in the present invention, solution-polymerized styrene-butadiene rubber (S-SBR), natural rubber (NR) and butadiene rubber (BR) are used.
Ｓ−ＳＢＲの含有量は、ゴム成分中に５０重量％以上である。下限については、好ましくは６５重量％である。上限については好ましくは９０重量％、より好ましくは８０重量％である。前記Ｓ−ＳＢＲの含有量が５０重量％未満ではグリップ特性、特にウェットグリップ特性が低下する傾向がある。また、９０重量％をこえると、低温特性、例えば脆化特性やアイスウェットグリップ特性が劣る傾向がある。 The content of S-SBR is 50% by weight or more in the rubber component. The lower limit is preferably 65% by weight. The upper limit is preferably 90% by weight, more preferably 80% by weight. When the content of S-SBR is less than 50% by weight, grip characteristics, particularly wet grip characteristics tend to deteriorate. On the other hand, if it exceeds 90% by weight, the low temperature characteristics such as embrittlement characteristics and ice wet grip characteristics tend to be inferior.
Ｓ−ＳＢＲのスチレン単位量は５〜４５重量％であることが好ましい。下限については２０重量％であることが好ましい。また、上限については６５重量％であることが好ましい。スチレン単位量が５重量％未満でビニル単位量が６５重量％をこえると、ゴムの加硫特性が悪くなり、加硫時間が延びたり、加硫後の引き裂きや引っ張り特性が劣る傾向がある。また、ビニル単位量が２０重量％未満でスチレン単位量が４５重量％をこえると、転がり抵抗が低減されない傾向がある。 The amount of styrene unit in S-SBR is preferably 5 to 45% by weight. The lower limit is preferably 20% by weight. The upper limit is preferably 65% by weight. If the styrene unit amount is less than 5% by weight and the vinyl unit amount exceeds 65% by weight, the vulcanization characteristics of the rubber are deteriorated, the vulcanization time is prolonged, and the tearing and tensile properties after vulcanization tend to be inferior. On the other hand, when the vinyl unit amount is less than 20% by weight and the styrene unit amount exceeds 45% by weight, the rolling resistance tends not to be reduced.
Ｓ−ＳＢＲの重量平均分子量は５０万以上である。下限については８０万であることが好ましい。上限については２００万であることが好ましい。重量平均分子量が５０万未満では転がり抵抗が低減されない傾向がある。また、２００万をこえると生ゴムのムーニー粘度が上昇して、バンバリーでの混練り時にポリマー分散が悪くなったり、練りゴムの粘度が上昇しすぎる傾向がある。 The weight average molecular weight of S-SBR is 500,000 or more. The lower limit is preferably 800,000. The upper limit is preferably 2 million. If the weight average molecular weight is less than 500,000, the rolling resistance tends not to be reduced. On the other hand, if it exceeds 2 million, the Mooney viscosity of the raw rubber will increase, and there will be a tendency for the polymer dispersion to deteriorate during kneading in Banbury, or the viscosity of the kneaded rubber will increase too much.
また、Ｓ−ＳＢＲの分子量分布（Ｍｗ／Ｍｎ）は、１．５〜３．０であることが好ましい。 Moreover, it is preferable that the molecular weight distribution (Mw / Mn) of S-SBR is 1.5-3.0.
Ｓ−ＳＢＲは低分子量Ｓ−ＳＢＲおよび高分子量Ｓ−ＳＢＲを含む。 S-SBR includes low molecular weight S-SBR and high molecular weight S-SBR.
前記Ｓ−ＳＢＲは、低分子量Ｓ−ＳＢＲを２５重量％以下含む。下限については５重量％であることが好ましく、１０重量％であることがより好ましい。上限については２０重量％であることが好ましい。配合量が５重量％未満では、練りゴムの生地が悪くなる、あるいは粘度が上昇する。また、配合量が２５重量％をこえると、転がり抵抗が低減されない、あるいは生ゴムのフロー性が悪くなる。 The S-SBR contains 25% by weight or less of low molecular weight S-SBR. The lower limit is preferably 5% by weight, and more preferably 10% by weight. The upper limit is preferably 20% by weight. If the blending amount is less than 5% by weight, the kneaded rubber dough becomes worse or the viscosity increases. On the other hand, if the blending amount exceeds 25% by weight, the rolling resistance is not reduced or the raw rubber has poor flowability.
低分子量Ｓ−ＳＢＲの重量平均分子量は５０００以下である。下限については１０００であることが好ましく、２０００であることがより好ましい。上限については３５００であることが好ましく、３０００であることがより好ましい。１０００未満では、生地は良好であるが、転がり抵抗が低減される、発熱性が劣る、または耐摩耗性が劣る傾向がある。また、５０００をこえると、練りゴムの生地の改善がみられない。 The weight average molecular weight of the low molecular weight S-SBR is 5000 or less. The lower limit is preferably 1000, more preferably 2000. The upper limit is preferably 3500, and more preferably 3000. If it is less than 1000, the fabric is good, but the rolling resistance is reduced, the heat generation is inferior, or the wear resistance tends to be inferior. Moreover, when it exceeds 5000, the improvement of kneaded rubber dough is not seen.
シリカとの接着性を向上させるために、低分子量Ｓ−ＳＢＲは、末端変性されていることが好ましい。低分子量Ｓ−ＳＢＲに導入される官能基としては、アルキルシリル基、水酸基、エポキシ基などが導入される。なかでもシリカとの反応性や、ポリマー粘度の上昇が小さいという点から、アルキルシリル基が好ましい。 In order to improve the adhesion to silica, it is preferable that the low molecular weight S-SBR is terminal-modified. As the functional group introduced into the low molecular weight S-SBR, an alkylsilyl group, a hydroxyl group, an epoxy group, or the like is introduced. Of these, alkylsilyl groups are preferred from the standpoint of reactivity with silica and small increase in polymer viscosity.
高分子量Ｓ−ＳＢＲには、Ｓ−ＳＢＲをＳｎやＳｉでカップリングしたものを用いる。 As the high molecular weight S-SBR, one obtained by coupling S-SBR with Sn or Si is used.
Ｓ−ＳＢＲは高分子量Ｓ−ＳＢＲを７５〜９５重量％含む。下限については８０重量％であることが好ましい。上限については９０重量％であることが好ましい。配合量が７５重量％未満では、転がり抵抗が低減されない、または耐摩耗性が劣る傾向がある。また、配合量が９０重量％をこえると、低温脆性やアイスウェットグリップ特性が劣る傾向がある。 S-SBR contains 75-95 wt% of high molecular weight S-SBR. The lower limit is preferably 80% by weight. The upper limit is preferably 90% by weight. If the blending amount is less than 75% by weight, the rolling resistance tends not to be reduced or the wear resistance tends to be inferior. On the other hand, if the blending amount exceeds 90% by weight, the low temperature brittleness and ice wet grip characteristics tend to be inferior.
Ｓ−ＳＢＲのカップリング方法は、常法に従って、たとえば、Ｓ−ＳＢＲの分子鎖末端のアルカリ金属（Ｌｉなど）またはアルカリ土類金属（Ｍｇなど）を、たとえばハロゲン化スズまたはハロゲン化ケイ素と反応させることによって得ることができる。 The coupling method of S-SBR is performed by, for example, reacting an alkali metal (such as Li) or alkaline earth metal (such as Mg) at the molecular chain end of S-SBR with, for example, tin halide or silicon halide. Can be obtained.
本発明で使用するゴム成分としては、さらに、天然ゴム（ＮＲ）を用いる。ＮＲの含有量は、ゴム成分中に４０重量％以下、好ましくは３５重量％以下である。ＮＲの含有量が４０重量％をこえると転がり抵抗がより低減され、ゴムの生地も良好であるが、ウェットグリップ特性が劣る。 As the rubber component used in the present invention, natural rubber (NR) is further used. The content of NR is 40% by weight or less, preferably 35% by weight or less in the rubber component. When the NR content exceeds 40% by weight, the rolling resistance is further reduced and the rubber fabric is good, but the wet grip characteristics are inferior.
本発明で使用するゴム成分としては、さらに、ブタジエンゴム（ＢＲ）を用いる。ＢＲの含有量は、ゴム成分中に４０重量％以下、好ましくは２５重量％以下である。ＢＲの含有量が４０重量％をこえると転がり抵抗が低減され、耐摩耗性も優れるが、ウェットグリップ特性、ドライグリップ特性が劣る。 As the rubber component used in the present invention, butadiene rubber (BR) is further used. The content of BR is 40% by weight or less, preferably 25% by weight or less in the rubber component. When the content of BR exceeds 40% by weight, rolling resistance is reduced and wear resistance is excellent, but wet grip characteristics and dry grip characteristics are inferior.
つぎに、本発明では補強剤として、シリカおよびカーボンブラックを用いる。前記ゴム成分に対して、補強剤としてのシリカを多く用いることは、従来のカーボンブラック配合用のポリマーにシリカを用いることよりも効果的である。カーボンブラックと比較してシリカは表面活性が大きく、分子鎖末端などの変性による効果が生じやすい。したがって、シリカとカーボンブラックの比率は、シリカの比率を多くする必要がある。 Next, silica and carbon black are used as a reinforcing agent in the present invention. Using a large amount of silica as a reinforcing agent for the rubber component is more effective than using silica in a conventional polymer for blending carbon black. Silica has a higher surface activity than carbon black and is likely to have an effect due to modification of molecular chain ends and the like. Therefore, the ratio of silica to carbon black needs to be increased.
本発明では、補強剤としてシリカを用いる。シリカの含有量は、補強剤中に５５重量％以上である。下限については６０重量％であることが好ましい。上限については８０重量％であることが好ましい。シリカの含有量が５５重量％未満では、転がり抵抗が低減されない。 In the present invention, silica is used as a reinforcing agent. The content of silica is 55% by weight or more in the reinforcing agent. The lower limit is preferably 60% by weight. The upper limit is preferably 80% by weight. When the content of silica is less than 55% by weight, rolling resistance is not reduced.
さらに、本発明では、補強剤としてカーボンブラックを用いる。従来より、カーボンブラックをシリカと併用する場合には、シリカの電気抵抗の高さを考慮して表面積の大きな（粒子径の小さな）カーボンブラックを用いることが多い。この場合、転がり抵抗の増大が懸念されるので、分子鎖末端との反応性を高くするためにカーボンブラックの表面活性を高く（セチルトリメチルアンモニウムブロマイド吸着比表面積／ヨウ素吸着量の比を大きく）して、転がり抵抗値を低くする必要がある。 Furthermore, in the present invention, carbon black is used as a reinforcing agent. Conventionally, when carbon black is used in combination with silica, carbon black having a large surface area (small particle diameter) is often used in consideration of the high electric resistance of silica. In this case, since there is a concern about an increase in rolling resistance, the surface activity of carbon black is increased to increase the reactivity with the molecular chain end (the ratio of cetyltrimethylammonium bromide adsorption specific surface area / iodine adsorption amount is increased). Therefore, it is necessary to lower the rolling resistance value.
本発明で使用するカーボンブラックのチッ素吸着比表面積（Ｎ2ＳＡ）は、１４５ｍ2／ｇ以上である。下限については１６０ｍ2／ｇであることが好ましく、１７０ｍ2／ｇであることがより好ましい。また、上限については２２０ｍ2／ｇであることが好ましく、１９０ｍ2／ｇであることがより好ましい。Ｎ2ＳＡが１４５ｍ2／ｇ未満ではカーボンブラック比率を下げた場合の電気導電性が劣る。また、２２０ｍ2／ｇをこえると転がり抵抗が低減されない、または練りゴムの粘度が上昇しすぎる傾向がある。 The carbon black used in the present invention has a nitrogen adsorption specific surface area (N 2 SA) of 145 m 2 / g or more. The lower limit is preferably 160 m 2 / g, and more preferably 170 m 2 / g. The upper limit is preferably 220 m 2 / g, and more preferably 190 m 2 / g. When N 2 SA is less than 145 m 2 / g, the electrical conductivity when the carbon black ratio is lowered is inferior. Moreover, when it exceeds 220 m < 2 > / g, there exists a tendency for rolling resistance not to be reduced or for the viscosity of kneaded rubber to rise too much.
カーボンブラックのセチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）吸着比表面積は、１４０〜２００ｍ2／ｇであることが好ましい。ＣＴＡＢ吸着比表面積が１４０ｍ2／ｇ未満ではカーボンブラックの比率を下げた時の電気導電性が劣り、ドライグリップ特性の低下が大きくなる傾向がある。また、２００ｍ2／ｇをこえると、転がり抵抗が低減されない、または練りゴムの粘度が上昇しすぎる傾向がある。 The cetyltrimethylammonium bromide (CTAB) adsorption specific surface area of carbon black is preferably 140 to 200 m 2 / g. When the CTAB adsorption specific surface area is less than 140 m 2 / g, the electric conductivity when the ratio of carbon black is lowered tends to be inferior, and the dry grip characteristics tend to decrease greatly. Moreover, when it exceeds 200 m < 2 > / g, there exists a tendency for rolling resistance not to be reduced or the viscosity of kneaded rubber to rise too much.
カーボンブラックのヨウ素吸着量（ＩＡ）は、１４０〜２００ｍｇ／ｇであることが好ましい。ＩＡが１４０ｍｇ／ｇ未満ではカーボンブラックの比率を下げた時の電気導電性が劣り、ドライグリップ特性の低下が大きくなる傾向がある。また、２００ｍｇ／ｇをこえると転がり抵抗が低減されない、または練りゴムの粘度が上昇しすぎる傾向がある。 The iodine adsorption amount (IA) of carbon black is preferably 140 to 200 mg / g. If the IA is less than 140 mg / g, the electrical conductivity when the ratio of carbon black is lowered tends to be inferior, and the dry grip characteristics tend to decrease greatly. Moreover, when it exceeds 200 mg / g, there exists a tendency for rolling resistance not to be reduced or for the viscosity of kneaded rubber to rise too much.
ＣＴＡＢ（ｍ2／ｇ）のＩＡ（ｍｇ／ｇ）に対する比（ＣＴＡＢ／ＩＡ比）は、１．１以上である。下限については１．１５であることが好ましく、１．１８であることがより好ましい。上限については１．２９であることが好ましく、１．２５であることがより好ましい。ＣＴＡＢ／ＩＡ比が１．１未満では転がり抵抗の低減効果とドライグリップ特性のバランスが悪くなり、カーボンブラックの生産性が大きく劣る傾向がある。 The ratio of CTAB (m 2 / g) to IA (mg / g) (CTAB / IA ratio) is 1.1 or more. The lower limit is preferably 1.15, more preferably 1.18. The upper limit is preferably 1.29, and more preferably 1.25. If the CTAB / IA ratio is less than 1.1, the balance between the reduction effect of rolling resistance and the dry grip characteristics is poor, and the productivity of carbon black tends to be greatly inferior.
カーボンブラックの含有量は、補強剤中に４０重量％以下である。下限については２０重量％であることが好ましい。上限については３５重量％であることが好ましい。カーボンブラックの含有量が４０重量％をこえると転がり抵抗が低減されない。 The content of carbon black is 40% by weight or less in the reinforcing agent. The lower limit is preferably 20% by weight. The upper limit is preferably 35% by weight. When the content of carbon black exceeds 40% by weight, rolling resistance is not reduced.
前記ゴム成分と補強剤を混練りする際には、ゴム成分と補強剤との反応を効率よく行なうために、混練り機（バンバリーミキサーなど）中での反応温度を高く設定することが好ましい。具体的には、１６０℃以上、好ましくは１６０〜１８０℃に設定する。この場合、シリカ用のカップリング剤を従来のＳｉ６９（１分子中に硫黄原子４個）などからＳｉ２６６（１分子中に硫黄原子２個含む、高純度）などに変更して、耐熱性を向上させたうえで混練りすることが望ましい。 When kneading the rubber component and the reinforcing agent, it is preferable to set a high reaction temperature in a kneading machine (Banbury mixer or the like) in order to efficiently react the rubber component and the reinforcing agent. Specifically, it is set to 160 ° C. or higher, preferably 160 to 180 ° C. In this case, the coupling agent for silica is changed from conventional Si69 (four sulfur atoms in one molecule) to Si266 (two sulfur atoms in one molecule, high purity), etc. to improve heat resistance. It is desirable to knead after mixing.
シランカップリング剤は、シリカ１００重量部に対して２〜１２重量部使用することが好ましい。シランカップリング剤が２重量部未満ではシリカの性能を充分に引き出せずに、ウェットグリップ特性および耐摩耗性が劣る傾向がある。また、１２重量部をこえるとカップリング剤が過多でコスト高になり、耐摩耗性が劣る傾向がある。 The silane coupling agent is preferably used in an amount of 2 to 12 parts by weight based on 100 parts by weight of silica. When the silane coupling agent is less than 2 parts by weight, the performance of silica cannot be sufficiently obtained, and wet grip characteristics and wear resistance tend to be inferior. On the other hand, when the amount exceeds 12 parts by weight, the amount of the coupling agent is excessive and the cost becomes high, and the wear resistance tends to be inferior.
このようにして得られる本発明のゴム組成物は、トルエン膨潤度が１８０〜３２０％であることが好ましい。下限については２２０％であることがより好ましい。上限については３１０％であることがより好ましい。トルエン膨潤度が１８０％未満ではゴムの耐久性が劣り、耐摩耗性が悪化する傾向がある。また、３２０％をこえるとドライグリップ特性や転がり抵抗の低減効果が劣る傾向がある。ここで、トルエン膨潤度は、一辺が５ｍｍ程度に調整されたゴムの立方体を、トルエン中に２４時間浸漬したのち、浸漬後と浸漬前の重量比率を測定することにより求められる。 The rubber composition of the present invention thus obtained preferably has a toluene swelling degree of 180 to 320%. The lower limit is more preferably 220%. The upper limit is more preferably 310%. When the toluene swelling degree is less than 180%, the durability of the rubber is inferior and the wear resistance tends to deteriorate. Moreover, when it exceeds 320%, there exists a tendency for the dry grip characteristic and the reduction effect of rolling resistance to be inferior. Here, the degree of toluene swelling is determined by immersing a rubber cube whose side is adjusted to about 5 mm in toluene for 24 hours, and then measuring the weight ratio after immersion and before immersion.
本発明のゴム組成物は、タイヤに使用すると転がり抵抗が低減されているため、タイヤトレッドに好適に用いられる。 Since the rolling resistance of the rubber composition of the present invention is reduced when used in a tire, it is suitably used for a tire tread.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these.
以下に実施例および比較例で用いた材料をまとめて説明する。
ＮＲ：ＲＳＳ♯３
ポリマーＡ：日本ゼオン（株）製のＳＢＲ ＮＳ１１６（ＳｎでカップリングしたＳ−ＳＢＲ、スチレン単位量：２０重量％、ビニル単位量：６０重量％、末端基：カプロラクタム）
ポリマーＢ：試作ＳＢＲ（重量平均分子量：５０万、末端変性基として、アルキルシリル基を有し、１０重量％の分子量４８００のＳＢＲを含む）
ポリマーＣ：Ｓａｒｔｏｍｅｒ Ｃｏｍｐａｎｙ Ｉｎｃ製のライコン１００（液状ＳＢＲ、ビニル単位量：７５重量％、末端基：なし）
ポリマーＤ：日本ゼオン（株）製のリキッドＢＲ、ＰＯＬＹＯＩＬ１３０
シリカ：ローディア社製の１１５ＧＲ（Ｎ2ＳＡ：１１５ｍ2／ｇ）
シランカップリング剤：デグサ製のＳｉ２６６
カーボンブラックＮ１３４：三菱化学（株）製のＳＡＦ（Ｎ2ＳＡ：１４５ｍ2／ｇ、ＣＴＡＢ吸着比表面積：１３６ｍ2／ｇ、ＩＡ：１４２ｍｇ／ｇ）
アロマオイル：出光興産（株）製のＡＨ４０
硫黄：鶴見化学（株）製の粉末硫黄
加硫促進剤ＣＢＳ：鶴見化学工業（株）製のノクセラーＣＺ−Ｇ
加硫促進剤ＤＰＧ：住友化学工業（株）製のソクソシールＤ
The materials used in the examples and comparative examples will be described together below.
NR: RSS # 3
Polymer A: SBR NS116 manufactured by Nippon Zeon Co., Ltd. (S-SBR coupled with Sn, styrene unit amount: 20% by weight, vinyl unit amount: 60% by weight, end group: caprolactam)
Polymer B: Prototype SBR (weight average molecular weight: 500,000, including an alkylsilyl group as a terminal modification group, and containing 10% by weight of SBR having a molecular weight of 4800)
Polymer C: Rycon 100 manufactured by Sartomer Company Inc. (Liquid SBR, vinyl unit amount: 75% by weight, end group: none)
Polymer D: Liquid BR, POLYOIL130 manufactured by Nippon Zeon Co., Ltd.
Silica: 115GR manufactured by Rhodia (N 2 SA: 115 m 2 / g)
Silane coupling agent: Si266 from Degussa
Carbon black N134: SAF manufactured by Mitsubishi Chemical Corporation (N 2 SA: 145 m 2 / g, CTAB adsorption specific surface area: 136 m 2 / g, IA: 142 mg / g)
Aroma oil: AH40 made by Idemitsu Kosan Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator made by Tsurumi Chemical Co., Ltd. CBS: Noxeller CZ-G made by Tsurumi Chemical Co., Ltd.
Vulcanization accelerator DPG: Soxoseal D manufactured by Sumitomo Chemical Co., Ltd.
実施例１〜２および比較例１〜３
表１の配合にしたがって、硫黄および加硫促進剤以外の材料を１６０℃で１分間混練りした。さらに、硫黄および加硫促進剤を加えて１２０℃で１．５分間混練りした。つぎに、得られたゴム組成物を２５０ｋＰａ、１８０℃の条件で加硫した。得られた加硫ゴムについて、以下の試験を実施した。試験結果を表１に示す。
Examples 1-2 and Comparative Examples 1-3
According to the formulation in Table 1, materials other than sulfur and the vulcanization accelerator were kneaded at 160 ° C. for 1 minute. Furthermore, sulfur and a vulcanization accelerator were added and kneaded at 120 ° C. for 1.5 minutes. Next, the obtained rubber composition was vulcanized under the conditions of 250 kPa and 180 ° C. The following tests were performed on the obtained vulcanized rubber. The test results are shown in Table 1.
（ゴム硬度）
調製したゴム組成物の硬度（Ｈｓ）を、２５℃でＪＩＳ−Ａ硬度計で測定した。
(Rubber hardness)
The hardness (Hs) of the prepared rubber composition was measured with a JIS-A hardness meter at 25 ° C.
（損失正接）
（株）岩本製作所製のＶＥＳ−Ｆ−３を用いて、周波数１０Ｈｚ、初期歪み１０％、動歪み２％で６０℃における損失正接（ｔａｎδ）を測定した。このｔａｎδ値が小さいほど発熱しにくい。
(Loss tangent)
Using a VES-F-3 manufactured by Iwamoto Seisakusho, loss tangent (tan δ) at 60 ° C. was measured at a frequency of 10 Hz, an initial strain of 10%, and a dynamic strain of 2%. The smaller the tan δ value, the less heat is generated.
（練り生地）
１２０℃にて押し出し、トレッドを作製し、目視にて判断することにより、練り生地の状態を３段階で評価した。
○：滑らかな生地
△：サメ肌状の生地
×：でこぼこを多数有する生地
(Kneaded dough)
Extrusion was performed at 120 ° C., a tread was prepared, and the state of the kneaded dough was evaluated in three stages by visual judgment.
○: Smooth fabric △: Shark-like fabric ×: Fabric with many bumps
Claims (5)
該溶液重合スチレン−ブタジエンゴムは、（ａ）重量平均分子量が５０００以下の低分子量溶液重合スチレン−ブタジエンゴムを２５重量％以下、および（ｂ）ＳｎまたはＳｉでのカップリングにより高分子量溶液重合スチレン−ブタジエンゴムを含み、かつ該溶液重合スチレン−ブタジエンゴム全体の重量平均分子量が５０万以上であり、
該カーボンブラックは、チッ素吸着比表面積が１４５ｍ2／ｇ以上であり、かつセチルトリメチルアンモニウムブロマイド吸着比表面積（ｍ2／ｇ）がヨウ素吸着量（ｍｇ／ｇ）に対して１．１倍以上であるゴム組成物。 Solution polymerization styrene-butadiene rubber 50% by weight, natural rubber 40% by weight and butadiene rubber 40% by weight rubber component, and 55% by weight silica and carbon black 40% by weight reinforcing agent A rubber composition comprising:
The solution polymerized styrene-butadiene rubber comprises (a) a low molecular weight solution polymerized styrene-butadiene rubber having a weight average molecular weight of 5000 or less and 25% by weight or less, and (b) a high molecular weight solution polymerized styrene by coupling with Sn or Si. -Containing butadiene rubber, and the weight average molecular weight of the whole solution polymerized styrene-butadiene rubber is 500,000 or more,
The carbon black has a nitrogen adsorption specific surface area of 145 m 2 / g or more, and a cetyltrimethylammonium bromide adsorption specific surface area (m 2 / g) of 1.1 times or more with respect to the iodine adsorption amount (mg / g). A rubber composition.
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