JP2007186030A - Rubber composition for clinch, its manufacturing method, and tire having clinch using rubber composition for clinch - Google Patents
Rubber composition for clinch, its manufacturing method, and tire having clinch using rubber composition for clinch Download PDFInfo
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Abstract
Description
本発明は、クリンチ用ゴム組成物およびその製造方法ならびに該クリンチ用ゴム組成物を用いたクリンチを有するタイヤに関する。 The present invention relates to a rubber composition for clinch, a method for producing the same, and a tire having clinch using the rubber composition for clinch.
リムとのチェーフィング部分であるクリンチは、走行時に重負荷および非常に強い熱履歴を受けるタイヤコンポーネットである。そのため、クリンチには重負荷に耐えうる強度および耐摩耗性を有するゴム組成物を用いる必要がある。 The clinch, which is a part of the chafing with the rim, is a tire component that receives a heavy load and a very strong thermal history during driving. Therefore, it is necessary to use a rubber composition having strength and abrasion resistance that can withstand heavy loads for clinch.
一般に、クリンチ用ゴム組成物には、ゴム成分としては耐摩耗性に優れるポリブタジエンゴムおよび補強剤としてはカーボンブラックが用いられている。しかし、近年環境問題が重視されるようになり、二酸化炭素の排出量の規制が強化され、また、石油現存量は有限であり、石油資源由来の原材料の使用には限界があるため、現在使用されている石油資源由来の原材料の一部または全てを石油外資源由来の原材料で代替したクリンチ用ゴム組成物の開発が求められている。さらに、クリンチ用ゴム組成物中に石油資源由来の原材料に代わり、天然ゴムやシリカなどの石油外資源由来の原材料を含有した場合、そのゴム強度、耐摩耗性などを向上させることができないという問題がある。 In general, a rubber composition for clinch uses a polybutadiene rubber having excellent wear resistance as a rubber component and carbon black as a reinforcing agent. However, in recent years, environmental issues have become more important, regulations on carbon dioxide emissions have been tightened, and the existing amount of petroleum is limited, so there are limits to the use of raw materials derived from petroleum resources. Development of a rubber composition for clinching in which some or all of the raw materials derived from petroleum resources are replaced with raw materials derived from non-petroleum resources is demanded. Furthermore, when the rubber composition for clinch contains raw materials derived from non-petroleum resources such as natural rubber and silica instead of the raw materials derived from petroleum resources, the rubber strength, wear resistance, etc. cannot be improved. There is.
特許文献１には、石油外資源由来の原材料として、天然ゴム、シリカ、セリサイトなどを使用することで、石油依存性を低減させたエコタイヤが開示されている。しかし、ゴム強度および耐摩耗性については考慮されておらず、いまだ改善の余地がある。 Patent Document 1 discloses an eco-tire in which dependence on petroleum is reduced by using natural rubber, silica, sericite, or the like as a raw material derived from resources other than petroleum. However, rubber strength and wear resistance are not considered, and there is still room for improvement.
本発明は、原材料の石油依存性が低減され、ゴム強度および耐摩耗性が改善されたクリンチ用ゴム組成物およびその製造方法ならびに該クリンチ用ゴム組成物を用いたクリンチを有するタイヤを提供することを目的とする。 The present invention provides a rubber composition for clinches in which the dependence of raw materials on petroleum is reduced, rubber strength and wear resistance are improved, a method for producing the same, and a tire having a clinching using the rubber composition for clinches. With the goal.
本発明は、天然ゴム３０〜９０重量％およびエポキシ化天然ゴム１０〜７０重量％を含むゴム成分１００重量部に対して、シリカ１５〜９０重量部を含むクリンチ用ゴム組成物に関する。 The present invention relates to a rubber composition for clinch containing 15 to 90 parts by weight of silica with respect to 100 parts by weight of a rubber component containing 30 to 90% by weight of natural rubber and 10 to 70% by weight of epoxidized natural rubber.
前記クリンチ用ゴム組成物の製造方法としては、（１）天然ゴムおよびシリカを混練りする工程、ならびに（２）工程（１）で排出された混練り物およびエポキシ化天然ゴムを混練りする工程を含むことが好ましい。 The method for producing the rubber composition for clinching includes (1) a step of kneading natural rubber and silica, and (2) a step of kneading the kneaded product discharged in step (1) and the epoxidized natural rubber. It is preferable to include.
また、本発明は、前記クリンチ用ゴム組成物を用いたクリンチを有するタイヤに関する。 The present invention also relates to a tire having a clinch using the rubber composition for clinch.
本発明によれば、天然ゴムおよびエポキシ化天然ゴムを所定含有率含むゴム成分およびシリカを所定量含有することで、原材料の石油依存性を低減し、ゴム強度および耐摩耗性を向上させたクリンチ用ゴム組成物およびその製造方法ならびに該クリンチ用ゴム組成物を用いたクリンチを有するタイヤを提供することができる。 According to the present invention, by including a predetermined amount of a natural rubber and a epoxidized natural rubber containing a rubber component and silica, the clinching is reduced in dependence on petroleum of raw materials and improved in rubber strength and wear resistance. A rubber composition having a clinching using the rubber composition for clinching and the rubber composition for clinching can be provided.
本発明のクリンチ用ゴム組成物は、ゴム成分およびシリカを含有する。 The rubber composition for clinch of the present invention contains a rubber component and silica.
前記ゴム成分は、天然ゴム（ＮＲ）およびエポキシ化天然ゴム（ＥＮＲ）を含む。 The rubber component includes natural rubber (NR) and epoxidized natural rubber (ENR).
ゴム成分中のＮＲの含有率は、３０重量％以上、好ましくは４０重量％以上である。ＮＲの含有率が３０重量％未満では、ゴム強度が充分でない。また、ＮＲの含有率は９０重量％以下、好ましくは８０重量％以下である。ＮＲの含有率が９０重量％をこえると、耐摩耗性が低下する。 The content of NR in the rubber component is 30% by weight or more, preferably 40% by weight or more. If the NR content is less than 30% by weight, the rubber strength is not sufficient. The NR content is 90% by weight or less, preferably 80% by weight or less. When the content of NR exceeds 90% by weight, the wear resistance decreases.
ＥＮＲとしては、市販のＥＮＲを用いてもよいし、ＮＲをエポキシ化して用いてもよい。ＮＲをエポキシ化する方法としては、とくに限定されるものではないが、クロルヒドリン法、直接酸化法、過酸化水素法、アルキルヒドロペルオキシド法、過酸法などの方法を用いて行うことができる。過酸法としてはたとえば、ＮＲに過酢酸や過蟻酸などの有機過酸を反応させる方法などがあげられる。 As ENR, commercially available ENR may be used, or NR may be epoxidized. The method for epoxidizing NR is not particularly limited, and can be carried out using a method such as a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, or a peracid method. Examples of the peracid method include a method of reacting NR with an organic peracid such as peracetic acid or performic acid.
ＥＮＲのエポキシ化率は、１２モル％以上が好ましく、１５モル％以上がより好ましい。ＥＮＲのエポキシ化率が１２モル％未満では、ＥＮＲがＮＲと相溶することによる改善効果が減少する傾向がある。また、ＥＮＲのエポキシ化率は、５０モル％以下が好ましく、４５モル％以下がより好ましい。ＥＮＲのエポキシ化率が５０モル％をこえると、ゴム強度が充分ではない傾向がある。 The epoxidation rate of ENR is preferably 12 mol% or more, and more preferably 15 mol% or more. When the epoxidation ratio of ENR is less than 12 mol%, the improvement effect due to the compatibility of ENR with NR tends to decrease. Further, the ENR epoxidation rate is preferably 50 mol% or less, more preferably 45 mol% or less. If the epoxidation rate of ENR exceeds 50 mol%, the rubber strength tends to be insufficient.
ゴム成分中のＥＮＲの含有率は１０重量％以上、好ましくは２０重量％以上である。ＥＮＲの含有率が１０重量％未満では、耐摩耗性が低下する。また、ＥＮＲの含有率は、７０重量％以下、好ましくは５０重量％以下である。ＥＮＲの含有率が７０重量％をこえると、得られたゴム組成物の強度が充分でない。 The content of ENR in the rubber component is 10% by weight or more, preferably 20% by weight or more. When the content of ENR is less than 10% by weight, the wear resistance is lowered. The ENR content is 70% by weight or less, preferably 50% by weight or less. When the content of ENR exceeds 70% by weight, the strength of the obtained rubber composition is not sufficient.
ＥＮＲは、ＮＲと混合することで、石油外資源由来の原材料を用いた海島構造を形成し、ゴム強度および耐摩耗性を向上させることができる。 When ENR is mixed with NR, it can form a sea-island structure using raw materials derived from non-petroleum resources, and can improve rubber strength and wear resistance.
ＮＲおよびＥＮＲ以外のゴム成分としては、スチレンブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム（Ｘ−ＩＩＲ）、イソモノオレフィンとｐ−アルキルスチレンとの共重合体のハロゲン化物などのゴムを含むこともできるが、これらのゴム成分は石油資源から得られるため、石油外資源の含有率を高めることで地球に優しく、将来の石油資源の減少に備えることができるという理由から、ＮＲおよびＥＮＲ以外のゴム成分は含まないことが好ましい。 Rubber components other than NR and ENR include styrene butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), halogenated butyl rubber (X-IIR), copolymer of isomonoolefin and p-alkylstyrene. However, these rubber components can be obtained from petroleum resources. Therefore, by increasing the content of non-oil resources, it is easy for the earth to prepare for the future reduction of petroleum resources. For this reason, it is preferable not to include rubber components other than NR and ENR.
シリカとしてはとくに制限はなく、湿式法または乾式法により調製され、タイヤ工業で一般的に使用されるものを用いることができる。 There is no restriction | limiting in particular as a silica, The thing prepared by the wet method or the dry method, and generally used in the tire industry can be used.
シリカの含有量は、ゴム成分１００重量部に対して１５重量部以上、好ましくは２０ 重量部以上である。シリカの含有量が１５重量部未満では、ゴム組成物の補強性が不足し、耐摩耗性が充分でない。また、シリカの含有量は、９０重量部以下、好ましくは８０重量部以下である。シリカの含有量が９０重量部をこえると、ゴム組成物の低発熱性が悪化する。 The content of silica is 15 parts by weight or more, preferably 20 parts by weight or more with respect to 100 parts by weight of the rubber component. When the silica content is less than 15 parts by weight, the rubber composition has insufficient reinforcement and wear resistance is not sufficient. The silica content is 90 parts by weight or less, preferably 80 parts by weight or less. When the silica content exceeds 90 parts by weight, the low heat build-up of the rubber composition is deteriorated.
本発明では、シリカとともにシランカップリング剤を併用することが好ましい。シランカップリング剤としては特に制限はなく、従来、タイヤ工業においてシリカと併用して用いられるものとすることができ、たとえば、ビス（３−トリエトキシシリルプロピル）ポリスルフィド、ビス（２−トリエトキシシリルエチル）ポリスルフィド、ビス（３−トリメトキシシリルプロピル）ポリスルフィド、ビス（２−トリメトキシシリルエチル）ポリスルフィド、ビス（４−トリエトキシシリルブチル）ポリスルフィド、ビス（４−トリメトキシシリルブチル）ポリスルフィドなどがあげられ、これらのシランカップリング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。 In the present invention, it is preferable to use a silane coupling agent in combination with silica. The silane coupling agent is not particularly limited, and can be conventionally used in combination with silica in the tire industry. For example, bis (3-triethoxysilylpropyl) polysulfide, bis (2-triethoxysilyl) Ethyl) polysulfide, bis (3-trimethoxysilylpropyl) polysulfide, bis (2-trimethoxysilylethyl) polysulfide, bis (4-triethoxysilylbutyl) polysulfide, bis (4-trimethoxysilylbutyl) polysulfide, etc. These silane coupling agents may be used alone or in combination of two or more.
シランカップリング剤を含有する場合、シランカップリング剤の含有量は、シリカ１００重量部に対して４重量部以上が好ましく、５重量部以上がより好ましい。シランカップリング剤の含有量が４重量部未満では、ゴム強度が劣る傾向がある。また、シランカップリング剤の含有量は２０重量部以下が好ましく、１８重量部以下がより好ましい。シランカップリング剤の含有量が２０重量部をこえると、ゴム強度が劣る傾向がある。 When the silane coupling agent is contained, the content of the silane coupling agent is preferably 4 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of silica. When the content of the silane coupling agent is less than 4 parts by weight, the rubber strength tends to be inferior. Further, the content of the silane coupling agent is preferably 20 parts by weight or less, and more preferably 18 parts by weight or less. When the content of the silane coupling agent exceeds 20 parts by weight, the rubber strength tends to be inferior.
カーボンブラックは、石油資源由来の原材料であり、含まないことが好ましい。 Carbon black is a raw material derived from petroleum resources and is preferably not contained.
本発明のクリンチ用ゴム組成物には、前記ゴム成分、シリカおよびシランカップリング剤のほかにも、シリカおよびカーボンブラック以外の補強剤、オイル、脂肪酸、酸化亜鉛、ワックス、各種老化防止剤、硫黄などの加硫剤、加硫促進剤などを適宜配合できる。 In addition to the rubber component, silica and silane coupling agent, the rubber composition for clinch of the present invention includes reinforcing agents other than silica and carbon black, oil, fatty acid, zinc oxide, wax, various anti-aging agents, sulfur Vulcanizing agents such as vulcanizing agents, vulcanization accelerators, and the like can be appropriately blended.
本発明のクリンチ用ゴム組成物の製造方法は、下記工程１および２を含むことが好ましい。 The manufacturing method of the rubber composition for clinch of the present invention preferably includes the following steps 1 and 2.
工程１では、ＮＲおよびシリカを混練りする。 In step 1, NR and silica are kneaded.
工程２では、工程１で排出された混練り物およびＥＮＲを混練りする。 In step 2, the kneaded material and ENR discharged in step 1 are kneaded.
工程１においては、シランカップリング剤、オイル、脂肪酸、酸化亜鉛、ワックス、各種老化防止剤などの配合剤も配合することができる。 In step 1, compounding agents such as a silane coupling agent, oil, fatty acid, zinc oxide, wax, and various anti-aging agents can be blended.
また、ＥＮＲを工程１ではなく、工程２で混練りすることで、天然ゴムとエポキシ化天然ゴムとの相溶性が良くなり、ゴム強度および耐摩耗性を向上させ、さらに、補強性も向上させることができるという効果が得られる。 Also, by kneading ENR in step 2 instead of step 1, compatibility between natural rubber and epoxidized natural rubber is improved, rubber strength and wear resistance are improved, and reinforcing properties are also improved. The effect that it can be obtained.
本発明のクリンチ用ゴム組成物は、重負荷に耐え得る充分なゴム強度および耐摩耗性を有しているという理由からクリンチとして使用される。 The rubber composition for clinch of the present invention is used as clinch because it has sufficient rubber strength and abrasion resistance to withstand heavy loads.
本発明のクリンチ用ゴム組成物を用いて、通常の方法により、本発明のタイヤを製造することができる。すなわち、必要に応じて前記配合剤を前記製造方法により配合した本発明のクリンチ用ゴム組成物を、未加硫の段階でタイヤのクリンチの形状にあわせて押出し加工し、タイヤ成型機上にて通常の方法で成形し、他のタイヤ部材とともに貼り合わせることにより、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することにより本発明のタイヤを得る。 Using the rubber composition for clinch of the present invention, the tire of the present invention can be produced by an ordinary method. That is, the rubber composition for clinch of the present invention, in which the compounding agent is blended according to the production method as necessary, is extruded in accordance with the shape of the tire clinch at an unvulcanized stage, on a tire molding machine An unvulcanized tire is formed by molding by a normal method and bonding together with other tire members. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain the tire of the present invention.
このようにして製造した本発明のタイヤは、本発明のクリンチ用ゴム組成物を用いることで、環境に配慮したエコタイヤとすることができる。 By using the rubber composition for clinch of the present invention, the tire of the present invention thus manufactured can be an eco-friendly tire that is environmentally friendly.
実施例に基づいて、本発明を具体的に説明するが、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 specifically described based on examples, but the present invention is not limited to these examples.
次に、実施例および比較例で用いた各種薬品をまとめて示す。
天然ゴム（ＮＲ）：ＫＲ７
エポキシ化天然ゴム（ＥＮＲ）：クランプリーガスリー製のＥＮＲ２５（エポキシ化率：２５モル％）
ブタジエンゴム（ＢＲ）：宇部興産（株）製のＢＲ１３０Ｂ
シリカ：デグッサ製のウルトラジルＶＮ３（ＢＥＴ：７５ｍ2／ｇ）
カーボンブラック：キャボットジャパン（株）製のＮ３５１Ｈ（ＣＴＡＢ：６６ｍ2／ｇ）
シランカップリング剤：デグッサ製のＳｉ２６６
オイル：出光興産（株）製のアロマチックオイル
ワックス：日本精鑞（株）製のオゾエース−０３５５
老化防止剤：住友化学（株）製のアンチゲン６Ｃ（Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン））
ステアリン酸：日本油脂（株）製の桐
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛
硫黄：軽井沢硫黄（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ＮＳ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド）
Next, various chemicals used in Examples and Comparative Examples are shown together.
Natural rubber (NR): KR7
Epoxidized natural rubber (ENR): ENR25 manufactured by Clampley Guthrie (epoxidation rate: 25 mol%)
Butadiene rubber (BR): BR130B manufactured by Ube Industries, Ltd.
Silica: Ultrazil VN3 manufactured by Degussa (BET: 75 m 2 / g)
Carbon black: N351H (CTAB: 66 m 2 / g) manufactured by Cabot Japan
Silane coupling agent: Si266 from Degussa
Oil: Aromatic oil wax manufactured by Idemitsu Kosan Co., Ltd .: Ozoace-0355 manufactured by Nippon Seiki Co., Ltd.
Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.)
Stearic acid: Tungsten zinc oxide manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide sulfur manufactured by Mitsui Mining & Smelting Co., Ltd .: Powdered sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd. Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide)
実施例１〜３および比較例１〜３
表１に示す配合処方にしたがい、硫黄および加硫促進剤およびＥＮＲ以外の薬品を、１．７Ｌのバンバリーミキサーを用いて、充填率５８％になるように投入し、８０ｒｐｍで１４０℃に到達するまで混練りし、混練り物１を得た（工程１）。次に、一度排出した後、１．７Ｌバンバリーミキサーを用いて、工程１で得られた混練り物１およびＥＮＲを、充填率が５８％になるように投入し、７０ｒｐｍで３分間混練りし、混練り物２を得た（工程２）。その後、オープンロールを用いて、工程２で得られた混練り物２、硫黄および加硫促進剤を８０℃の条件下で５分間混練りし、未加硫ゴム組成物を得た（工程３）。さらに、工程３で得られた未加硫ゴム組成物を１６０℃の条件下で２０分間プレス加硫することにより、実施例１〜３および比較例１〜３の加硫ゴム組成物を作製した。
Examples 1-3 and Comparative Examples 1-3
In accordance with the formulation shown in Table 1, chemicals other than sulfur, a vulcanization accelerator and ENR are charged to a filling rate of 58% using a 1.7 L Banbury mixer and reach 140 ° C. at 80 rpm. And kneaded product 1 was obtained (step 1). Next, after discharging once, using a 1.7 L Banbury mixer, the kneaded product 1 and ENR obtained in step 1 are charged so that the filling rate is 58%, kneaded at 70 rpm for 3 minutes, A kneaded product 2 was obtained (step 2). Then, using an open roll, the kneaded product 2, the sulfur and the vulcanization accelerator obtained in step 2 were kneaded for 5 minutes under the condition of 80 ° C. to obtain an unvulcanized rubber composition (step 3). . Furthermore, the vulcanized rubber compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared by press vulcanizing the unvulcanized rubber composition obtained in Step 3 for 20 minutes at 160 ° C. .
（ゴム強度）
前記加硫ゴム組成物から、３号ダンベル型試験片を作製し、ＪＩＳ Ｋ ６２５１「加硫ゴム及び熱可塑性ゴム―引張特性の求め方」に準じて、引張試験を実施し、試験片の破断強度（ＴＢ）および破断時伸び（ＥＢ）をそれぞれ測定した。そして、比較例１のゴム強度指数を１００として下記計算式によりゴム強度を指数表示した。ゴム強度指数が大きいほどゴム組成物の破壊強度が良好であることを示す。
（ゴム強度指数）＝（各配合の（ＴＢ×ＥＢ））
÷（比較例１の（ＴＢ×ＥＢ））×１００
(Rubber strength)
A No. 3 dumbbell-shaped test piece was prepared from the vulcanized rubber composition, and a tensile test was performed according to JIS K 6251 “Vulcanized rubber and thermoplastic rubber-Determination of tensile properties”. Strength (TB) and elongation at break (EB) were measured. The rubber strength index of Comparative Example 1 was taken as 100, and the rubber strength was displayed as an index according to the following formula. The larger the rubber strength index, the better the breaking strength of the rubber composition.
(Rubber strength index) = ((TB × EB) of each formulation)
÷ ((TB × EB) of Comparative Example 1) × 100
（ピコ摩耗試験）
ＪＩＳ Ｋ ６２６４「加硫ゴムおよび熱可塑性ゴム−耐摩耗性の求め方」に準じて、上島製作所（株）製のピコ摩耗試験機にて表面回転速度６０ｒｐｍ、負荷荷重４ｋｇ、試験時間１分間の条件で、摩耗させ、各実施例および比較例のゴム組成物からなる試験片の測定前後の重量変化を測定した。比較例１のピコ摩耗指数を１００とし、下記計算式で指数表示した。指数が大きいほど耐高シビアリティーが優れる。
（ピコ摩耗指数）＝（比較例１の重量変化）／（各配合の重量変化）×１００
上記の測定試験結果を表１に示す。
(Pico abrasion test)
In accordance with JIS K 6264 “Vulcanized rubber and thermoplastic rubber—How to determine wear resistance”, surface rotation speed 60 rpm, load load 4 kg, test time 1 minute with a pico abrasion tester manufactured by Ueshima Seisakusho Co., Ltd. The test piece was made to wear under the conditions, and the weight change before and after the measurement of the test piece made of the rubber composition of each example and comparative example was measured. The pico abrasion index of Comparative Example 1 was set to 100, and the index was expressed by the following formula. The higher the index, the better the resistance to high severity.
(Pico abrasion index) = (weight change of Comparative Example 1) / (weight change of each formulation) × 100
The measurement test results are shown in Table 1.
Claims (3)
シリカ１５〜９０重量部を含むクリンチ用ゴム組成物。 For 100 parts by weight of a rubber component containing 30 to 90% by weight of natural rubber and 10 to 70% by weight of epoxidized natural rubber,
A rubber composition for clinch containing 15 to 90 parts by weight of silica.
（２）工程（１）で排出された混練り物およびエポキシ化天然ゴムを混練りする工程
を含む請求項１記載のクリンチ用ゴム組成物の製造方法。 The rubber composition for clinch according to claim 1, comprising: (1) a step of kneading natural rubber and silica; and (2) a step of kneading the kneaded product discharged in step (1) and the epoxidized natural rubber. Production method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008297392A (en) * | 2007-05-30 | 2008-12-11 | Sumitomo Rubber Ind Ltd | Clinch rubber composition and pneumatic tire using the same |
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| JPH0790125A (en) * | 1990-03-28 | 1995-04-04 | Goodyear Tire & Rubber Co:The | Pneumatic tire with air-holding toe guard |
| JPH07149955A (en) * | 1993-09-17 | 1995-06-13 | Goodyear Tire & Rubber Co:The | Sulfur-vulcanized rubber composition containing epoxydated natural rubber and silica filler |
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| JP2005120147A (en) * | 2003-10-14 | 2005-05-12 | Sumitomo Rubber Ind Ltd | Rubber composition and pneumatic tire using the same |
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| JP2008297392A (en) * | 2007-05-30 | 2008-12-11 | Sumitomo Rubber Ind Ltd | Clinch rubber composition and pneumatic tire using the same |
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