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KR20040050040A - Rubber composition for tire tread - Google Patents

Rubber composition for tire tread Download PDF

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Publication number
KR20040050040A
KR20040050040A KR1020020077749A KR20020077749A KR20040050040A KR 20040050040 A KR20040050040 A KR 20040050040A KR 1020020077749 A KR1020020077749 A KR 1020020077749A KR 20020077749 A KR20020077749 A KR 20020077749A KR 20040050040 A KR20040050040 A KR 20040050040A
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South Korea
Prior art keywords
rubber
rubber composition
carbon black
tire tread
weight
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Korean (ko)
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박일용
원철연
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한국타이어 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016Compositions of the tread
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

본 발명은 타이어 트레드용 고무조성물에 관한 것으로서, 커플링제로서 디부틸 크산토겐 다이설파이드를 포함하는 카본블랙과 디엔계 고무 배합물로서, 이는 내마모성능, 회전저항 성능 및 젖음 주행성능 모두를 향상시킬 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for tire treads, comprising a carbon black and diene rubber compound containing dibutyl xanthogen disulfide as a coupling agent, which can improve both wear resistance, rolling resistance performance and wet running performance. have.

Description

타이어 트레드 고무조성물{Rubber composition for tire tread}Rubber composition for tire tread

본 발명은 타이어 트레드 고무조성물에 관한 것으로서, 더욱 상세하게는 카본블랙과 디엔계 고무 배합물에 커플링제로 디부틸 크산토겐 다이설파이드를 첨가함으로써 내마모성능, 회전저항 성능 및 젖음 주행성능 모두를 향상시킨 고무조성물에 관한 것이다.The present invention relates to a tire tread rubber composition, and more particularly, by adding dibutyl xanthogen disulfide as a coupling agent to a carbon black and diene rubber compound to improve both abrasion resistance, rolling resistance performance and wet running performance. It relates to a rubber composition.

일반적으로 지면에 직접 닿는 타이어 트레드의 물성 중 회전저항 성능, 내마모성능 및 젖음 주행 성능을 동시에 향상시키기는 어려운 것으로 알려져 있다. 즉, 한쪽 물성을 개선시키면 다른 2가지의 물성에 영향을 주어 대부분 나빠지는 현상이 있어 이들 세가지 물성의 균형은 최대의 과제 중 하나이다.In general, it is known that it is difficult to simultaneously improve the rolling resistance, wear resistance, and wet driving performance of physical properties of the tire tread directly in contact with the ground. In other words, if one of the physical properties is improved, the other two properties are affected, and most of them are deteriorated. Therefore, the balance of these three physical properties is one of the biggest problems.

타이어 트레드용 고무 조성물에 사용되는 원료 중 타이어의 물성을 좌우하는 가장 중요한 원료로는 고무와 보강제를 들 수 있다. 이 보강제는 충진 효과도 동시에 가지고 있으면 무기 충진제인 실리카와 유기 충진제인 카본블랙으로 대별될 수 있다. 이러한 보강제와 고무 사이에 물리/화학적 결합이 강할수록 물성이 좋아져 타이어가 제기능을 발휘하게 된다.Among the raw materials used in the rubber tread rubber composition, rubber and reinforcing agent are the most important raw materials that influence the physical properties of the tire. This reinforcing agent can be roughly divided into inorganic filler silica and organic filler carbon black as long as it has a filling effect. The stronger the physical / chemical bond between the reinforcing agent and the rubber, the better the physical properties of the tire will be.

종래의 타이어 기술에서는 고무와 보강제 사이에 황에 의한 가황 결합 외에 물리적 결합에 의해 보강효과를 나타내었다. 예를들면 타이어용 고무 배합 기술이 발달하면서 실리카 배합물을 사용하게 되었는데, 이 배합물 내의 고무와 실리카 사이의 결합력을 높이기 위해 실란 커플링제를 사용한다. 이러한 커플링제의 사용으로 인해 지구상에는 수십종의 실란 커플링제가 상품화되어 있다. 그러나, 이러한 실란 커플링제는 실리카를 사용하는 특정 조성물에 제한되어 있는 단점이 있다.In the conventional tire technology, the rubber and the reinforcing agent exhibited a reinforcing effect by physical bonding in addition to the vulcanized bond by sulfur. For example, the development of rubber compounding technology for tires has led to the use of silica blends, which use silane coupling agents to increase the bond between rubber and silica in the blends. Due to the use of such coupling agents, dozens of silane coupling agents have been commercialized on earth. However, these silane coupling agents have the disadvantage of being limited to certain compositions using silica.

따라서 현재 타이어 산업에서 보강제로 가장 일반적으로 사용되고 있는 카본블랙만을 사용하는 고무 조성물에서 고무와 카본블랙 사이의 결합력 향상에 대한 문제가 남아 있다.Therefore, there remains a problem of improving the bonding force between rubber and carbon black in a rubber composition using only carbon black, which is most commonly used as a reinforcement in the tire industry.

이를 위해 여러 화학회사에서는 여러 종류의 카본 커플링제를 상품화하여 고무와 카본블랙 사이의 결합력을 향상시키고자 하였다. 그러나 이때 사용되는 고무와 카본블랙 커플링제는 주로 발암물질로 알려진 니트로소 아민계 화합물을 포함한 것들로서, 타이어 업계를 포함한 대부분의 산업현장에서 현재 사용이 중지된 상태이다.To this end, various chemical companies have tried to commercialize various carbon coupling agents to improve the bonding force between rubber and carbon black. However, the rubber and carbon black coupling agents used are mainly those containing nitrosoamine compounds known as carcinogens, and are currently suspended in most industrial fields including the tire industry.

또는 커플링제 대신에 고무 말단기에 카본블랙과 결합할 수 있는 변성기를 도입한 새로운 고무들이 도입되었으나, 그 제조비용이 고가이며 첨가되는 변성기의 비율이 너무 낮으므로 그 특성을 뚜렷하게 나타내는 데는 다소 역부족이다. 미국특허 제4,614,771호에서 아미노알데히드, 아미노케톤, 아미노티오알데히드 및 아미노티오케톤 등으로 변성기를 도입하였다.In addition, new rubbers have been introduced in place of the coupling agent, and new rubbers having a modification group capable of bonding with carbon black have been introduced. However, the manufacturing cost is high and the ratio of the modification groups to be added is too low. . US Pat. No. 4,614,771 introduces a denaturation group into aminoaldehydes, aminoketones, aminothioaldehydes and aminothioketones.

최근에는 비발암성 물질로 이루어진 커플링제가 소개되어 카본블랙과 고무사이의 결합력을 상승시키고자 하는 노력이 있었으나(공개특허 제1999-24469호), 커플링제에 의한 물성 향상이 실리카 배합물보다 두드러지지 않았으며 커플링제가 소량만 첨가되어도 고무 무니점도 상승 및 스코치 문제를 야기시켜 현재까지도 실질적으로 적용이 어려운 실정이다.Recently, a coupling agent made of a non-carcinogenic substance has been introduced, and efforts have been made to increase the bonding force between carbon black and rubber (Public Patent No. 1999-24469), but the improvement of physical properties by the coupling agent was not as remarkable as that of the silica compound. In addition, even a small amount of coupling agent causes rubber Mooney viscosity to rise and the scorch problem is still practically difficult to apply.

이에 본 발명자들은 카본블랙을 보강제로 포함하는 고무 조성에 있어서 바람직한 커플링제를 찾기 위해 연구노력하던 중, 디부틸 크산토겐 다이설파이드를 커플링제로 사용한 결과 고무와 카본블랙 사이의 결합력이 향상되어 타이어의 회전저항 성능, 내마모성능 및 젖은 주행성이 모두 향상됨을 알게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors have been trying to find a suitable coupling agent in the rubber composition containing carbon black as a reinforcing agent, and as a result of using dibutyl xanthogen disulfide as the coupling agent, the binding force between the rubber and carbon black is improved and the tire It has been found that the rotational resistance performance, wear resistance and wet running performance are all improved to complete the present invention.

따라서, 본 발명은 인체에 무해한 커플링제 디부틸 크산토겐 다이설파이드를 사용함으로써 고무와 카본블랙 사이의 결합력을 높혀 타이어의 여러 물성을 향상시킨 타이어 트레드용 고무조성물을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a rubber composition for a tire tread, which improves various physical properties of a tire by increasing a bonding force between rubber and carbon black by using dibutyl xanthogen disulfide, which is harmless to a human body.

상기와 같은 목적을 달성하기 위한 본 발명의 타이어 트레드용 고무조성물은 카본블랙과 디엔계 고무 배합물로서, 이때 커플링제로 디부틸 크산토겐 다이설파이드를 원료고무 100중량부에 대하여 0.5∼5중량부로 포함하는 것임을 그 특징으로 한다.The rubber composition for tire treads of the present invention for achieving the above object is a carbon black and diene rubber compound, wherein 0.5 to 5 parts by weight of dibutyl xanthogen disulfide as a coupling agent based on 100 parts by weight of the raw material rubber. It is characterized by including.

이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명의 타이어 트레드용 고무조성물은 통상의 디엔계 카본블랙 배합고무로 된 타이어 트레드 고무 조성물 중에 커플링제로서 디부틸 크산토겐 다이설파이드를 사용한다.The rubber composition for tire treads of the present invention uses dibutyl xanthogen disulfide as a coupling agent in a tire tread rubber composition made of ordinary diene carbon black compounding rubber.

본 발명에서 원료고무는 용액중합 방법으로 제조된 스티렌 함량 20%이며 부타디엔 중에서 비닐함량이 60%인 스티렌-부타디엔 고무를 사용할 수 있다.In the present invention, the raw material rubber may be a styrene-butadiene rubber having a styrene content of 20% and a vinyl content of 60% in butadiene.

그리고, 보강제로서는 질소흡착 표면적이 70∼150㎡/g, 바람직하게는 90∼140㎡/g인 카본블랙을 사용하는 바, 그 함량은 원료고무 100중량부에 대하여 30∼100중량부, 바람직하게는 50∼80중량부이다.As the reinforcing agent, carbon black having a nitrogen adsorption surface area of 70 to 150 m 2 / g, preferably 90 to 140 m 2 / g is used, and the content thereof is 30 to 100 parts by weight, preferably 100 parts by weight of the raw material rubber. Is 50 to 80 parts by weight.

이같은 카본블랙과 고무의 결합력을 향상시키기 위한 본 발명의 커플링제인 디부틸 크산토겐 다이설파이드를 사용하면 놀랍게도 내마모성능, 트랙션 성능 및 저연비성능이 향상되는 결과를 보인다.The use of dibutyl xanthogen disulfide, which is a coupling agent of the present invention for improving the bonding strength of carbon black and rubber, surprisingly improves abrasion resistance, traction performance and low fuel efficiency.

그 함량은 원료고무 100중량부에 대하여 0.5∼5중량부, 바람직하게는 1∼3중량부이다.The content is 0.5-5 weight part with respect to 100 weight part of raw material rubbers, Preferably it is 1-3 weight part.

만일, 커플링제의 함량이 원료고무 100중량부에 대하여 5중량부 초과면 모듈러스나 내마모성능, 회전저항 성능 및 젖음 주행성은 높일 수 있으나 무니점도가 급격히 상승하게 되며 스코치 안정성이 크게 열악해질 수 있다. 반면에 그 함량이 0.5중량부 미만이면 물성 향상 효과는 있으나 그 효과가 크지 않으므로 바람직하지 않다.If the content of the coupling agent is greater than 5 parts by weight based on 100 parts by weight of the raw material rubber, modulus or wear resistance, rotational resistance and wet running performance may be increased, but the Mooney viscosity may increase rapidly, and scorch stability may be greatly deteriorated. On the other hand, if the content is less than 0.5 parts by weight, there is an effect of improving the physical properties, but the effect is not large, which is not preferable.

그밖에 본 발명의 고무조성물은 통상의 타이어 트레드 고무 조성에서와 같이연화제로서 아로마틱 오일, 산화아연, 스테아린산, 노화방지제, 가황제 및 가황촉진제 등을 포함함은 물론이다.In addition, the rubber composition of the present invention includes aromatic oils, zinc oxide, stearic acid, antioxidants, vulcanizing agents and vulcanization accelerators as softeners, as in the conventional tire tread rubber composition.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

실시예 1∼3 및 비교예 1∼3Examples 1-3 and Comparative Examples 1-3

다음 표 1에 나타낸 바와 같은 조성 및 배합비로 타이어 트레드용 고무조성물을 제조하였다. 제조된 고무 조성물을 시험 시편으로 제조하여 0℃tanδ(젖음 주행성), 60℃ tanδ 및 인장물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Next, a rubber composition for tire treads was prepared according to the composition and blending ratio as shown in Table 1 below. The rubber composition was prepared as a test specimen, and 0 ° C. tanδ (wet running property), 60 ° C. tanδ, and tensile properties were measured. The results are shown in Table 1 below.

여기서, 모듈러스, 신율은 인장시험기(ASTM D-638 방법)를 이용하여 측정하였고, 내마모성은 람본 마모시험기를 이용하여 측정하였고, tanδ는 점탄성 시험기를 사용하여 측정하였고, 스코치 안정성(t5)는 125℃에서 Min Torq. 대비 5 point torque가 올라갈때까지 걸리는 시간으로 측정한 것이다.Here, modulus and elongation were measured using a tensile tester (ASTM D-638 method), wear resistance was measured using a rambon wear tester, tanδ was measured using a viscoelastic tester, and scorch stability (t5) was 125 ° C. In Min Torq. This is a measure of how long it takes for the 5 point torque to rise.

실시예Example 비교예Comparative example 1One 22 33 1One 22 33 조성Furtherance s-SBR(스티렌 함량 20%, 부타디엔부의 비닐 함량 60%인 용액중합 SBR)s-SBR (Solution polymerization SBR with 20% styrene and 60% vinyl content in butadiene) 100100 100100 100100 100100 100100 100100 카본블랙(질소흡착 표면적 ---㎡/g)Carbon Black (Nitrogen Adsorption Surface Area --- ㎡ / g) 6565 6565 6565 6565 6565 6565 디부틸 크산토겐 다이설파이드Dibutyl Xanthogen Disulfide 0.50.5 22 44 -- 0.20.2 66 TBBSTBBS 1.251.25 1.251.25 1.251.25 1.251.25 1.251.25 1.251.25 sulfur 1.751.75 1.751.75 1.751.75 1.751.75 1.751.75 1.751.75 산화아연Zinc oxide 33 33 33 33 33 33 스테아린산Stearic acid 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5 아로마틱 오일Aromatic oils 1010 1010 1010 1010 1010 1010 노화방지제(6C)Antioxidant (6C) 1One 1One 1One 1One 1One 1One 물성Properties 무니점도Mooney viscosity 6666 7171 7676 6464 6565 8989 스코치(t5, min)Scorch (t5, min) 17:5517:55 17:0417:04 15:1115:11 18:2718:27 18:2218:22 12:1412:14 100% 모듈러스(지수)100% Modulus (Index) 103103 106106 111111 100100 100100 119119 300% 모듈러스(지수)300% modulus (index) 102102 107107 114114 100100 9999 128128 신율(지수)Elongation (index) 103103 104104 111111 100100 101101 8585 내마모성(지수)Wear Resistance (Index) 104104 111111 116116 100100 101101 102102 0℃tanδ0 ℃ tanδ 0.5420.542 0.5870.587 0.6220.622 0.4520.452 0.4610.461 0.6340.634 60℃tanδ60 ℃ tanδ 0.1240.124 0.1200.120 0.1150.115 0.1320.132 0.1290.129 0.1060.106

상기 표 1의 결과로부터, 고무와 카본블랙을 결합시켜주는 역할을 하는 디부틸 크산토겐 다이설파이드를 첨가하지 않은 경우에 비하여 첨가한 실시예 1 내지 3의 경우 타이어 트레드 성능에서 가장 중요한 내마모성능, 회전저항성능(60℃tanδ) 및 젖음 주행성(0℃ tanδ) 모두 향상되었으며, 무니점도 및 스코치 안정성(t5)도 크게 불리해지지 않음을 알 수 있다.From the results of Table 1, the most important wear resistance in the tire tread performance of Examples 1 to 3 added compared to the case of not adding dibutyl xanthogen disulfide that serves to bind the rubber and carbon black, Both the rotation resistance performance (60 ℃ tan δ) and the wet running (0 ℃ tan δ) was improved, it can be seen that the Mooney viscosity and scorch stability (t5) is also not very disadvantageous.

그러나, 디부틸 크산토겐 다이설파이드가 너무 소량 들어간 경우 물성 향상 효과는 있으나 그 효과가 크지 않음을 볼 수 있다(비교예 2).However, when too little dibutyl xanthogen disulfide enters the physical properties can be seen that the effect is not great (Comparative Example 2).

또한, 고무와 카본블랙을 결합시켜주는 디부틸 크산토겐 다이설파이드를 과량으로 사용하게 되면 모듈러스나 내마모성능, 회전저항성능 및 젖음 주행성을 높일 수는 있으나 무니점도가 급격히 상승하게 되며 스코치 안정성이 크게 열악해지므로 바람직하지 않다(비교예 3).In addition, excessive use of dibutyl xanthogen disulfide, which combines rubber and carbon black, can increase modulus, abrasion resistance, rotational resistance, and wet running performance, but the Mooney viscosity increases sharply and scorch stability is greatly increased. It is not preferable because it becomes poor (Comparative Example 3).

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 카본블랙을 보강제로 포함하는 디엔계 고무 조성에 커플링제로 디부틸 크산토겐 다이설파이드를 첨가한 경우 내마모성능, 회전저항 성능 및 젖음 주행성 모두를 향상시킬 수 있으면서 무니점도나 스코치 안정성을 해치지 않는 효과를 얻을 수 있다.As described in detail above, when dibutyl xanthogen disulfide is added as a coupling agent to a diene rubber composition including carbon black as a reinforcing agent according to the present invention, it is possible to improve both wear resistance, rolling resistance performance, and wet running performance. It is possible to obtain an effect that does not impair Mooney viscosity or scorch stability.

Claims (1)

카본블랙과 디엔계 고무 배합물로 이루어진 타이어 트레드 고무조성물에 있어서,In a tire tread rubber composition comprising a carbon black and a diene rubber compound, 용액중합 방법으로 제조된 스티렌 함량 20%이며 부타디엔부의 비닐 함량이 60%인 스티렌-부타디엔 고무 100중량부, 질소흡착 표면적 90∼140㎡/g인 카본블랙 50∼80중량부 및 커플링제 디부틸 크산토겐 다이설파이드 0.5∼5중량부를 포함하는 것임을 특징으로 하는 타이어 트레드 고무조성물.100 parts by weight of styrene-butadiene rubber having a styrene content of 20% and a vinyl content of 60% butadiene by the solution polymerization method, 50 to 80 parts by weight of carbon black having a nitrogen adsorption surface area of 90 to 140 m 2 / g, and a coupling agent dibutyl A tire tread rubber composition comprising 0.5 to 5 parts by weight of santogen disulfide.
KR1020020077749A 2002-12-09 2002-12-09 Rubber composition for tire tread Ceased KR20040050040A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01160809A (en) * 1987-12-17 1989-06-23 Mitsubishi Heavy Ind Ltd Production of sulfuric acid
JP2002146097A (en) * 2000-11-16 2002-05-22 Tokai Carbon Co Ltd Carbon black and its rubber composition
EP1221461A1 (en) * 2001-01-08 2002-07-10 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and article of manufacture
US6465581B1 (en) * 2001-01-24 2002-10-15 The Goodyear Tire & Rubber Company Silica reinforced rubber composition which contains stabilized unsymmetrical coupling agents and article of manufacture, including a tire, having at least one component comprised of such rubber composition
JP2002338750A (en) * 2001-05-15 2002-11-27 Sumitomo Rubber Ind Ltd Tread rubber composition and pneumatic tire using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01160809A (en) * 1987-12-17 1989-06-23 Mitsubishi Heavy Ind Ltd Production of sulfuric acid
JP2002146097A (en) * 2000-11-16 2002-05-22 Tokai Carbon Co Ltd Carbon black and its rubber composition
EP1221461A1 (en) * 2001-01-08 2002-07-10 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and article of manufacture
US6465581B1 (en) * 2001-01-24 2002-10-15 The Goodyear Tire & Rubber Company Silica reinforced rubber composition which contains stabilized unsymmetrical coupling agents and article of manufacture, including a tire, having at least one component comprised of such rubber composition
JP2002338750A (en) * 2001-05-15 2002-11-27 Sumitomo Rubber Ind Ltd Tread rubber composition and pneumatic tire using the same

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