JPH06248116A - Rubber composition for tire - Google Patents
Rubber composition for tireInfo
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- JPH06248116A JPH06248116A JP3361593A JP3361593A JPH06248116A JP H06248116 A JPH06248116 A JP H06248116A JP 3361593 A JP3361593 A JP 3361593A JP 3361593 A JP3361593 A JP 3361593A JP H06248116 A JPH06248116 A JP H06248116A
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- silica
- rubber
- formula
- chemical
- chemical formula
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、タイヤ用、特にトレッ
ドに好適な補強性を有するゴム組成物に関し、特に耐摩
耗性および低発熱性が改良されたタイヤ用ゴム組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition having a reinforcing property suitable for a tire, particularly a tread, and more particularly to a rubber composition for a tire having improved wear resistance and low heat buildup.
【０００２】[0002]
【従来の技術】トラック、バス用タイヤのような、かな
り高い耐久性、低発熱性が要求されるゴム組成物では、
従来からＩＳＡＦのような高補強性のカーボンブラック
が使用されてきたが、充填剤としてカーボンブラックは
耐摩耗性が優れていることが認められているが、耐摩耗
性を向上させるためカーボンブラック量を増加させると
発熱性が悪化する。近年市場の経済性要求が高まるにつ
れ、更に低発熱性、耐燃費性を得ることが商品価値を決
定する重要なポイントとなって来た。2. Description of the Related Art For rubber compositions such as truck and bus tires, which require considerably high durability and low heat buildup,
Although carbon black having a high reinforcing property such as ISAF has been used so far, it is recognized that carbon black as a filler has excellent wear resistance. However, in order to improve wear resistance, the amount of carbon black must be increased. Is increased, the exothermicity deteriorates. As the market demand for economy has increased in recent years, obtaining low heat generation and fuel consumption resistance have become important points in determining product value.
【０００３】このためには充填剤として、カーボンブラ
ックの単独使用では限度があった。このため従来から用
いられた低発熱性向上の手法としては、カーボンブラッ
ク配合量の減少、シリカ配合量の増加というような配合
量の変更が行なわれている。To this end, carbon black alone has a limit as a filler. Therefore, as a conventional method for improving the low heat buildup, the blending amount is changed such that the blending amount of carbon black is decreased and the blending amount of silica is increased.
【０００４】ゴムの充填剤補強は補強性カーボンブラッ
クのような表面活性の高い微細粒子でストラクチャーが
発達したものでは、粒子表面とゴムとの界面接着力も大
きいので、分子鎖に加わっている張力分担をミクロに平
均化することも可能であるが、表面活性度が小さい充填
剤では、応力平均化に対する張力分担を受けもつ前に、
粒子表面とゴム分子との間の界面破壊を起こし、補強効
果を示さない。In the case of reinforcing the filler of rubber, fine particles having a high surface activity, such as reinforcing carbon black, having a developed structure have a large interfacial adhesive force between the particle surface and the rubber. It is also possible to micro-average, but in the case of fillers with low surface activity, before taking charge of the tension share for stress averaging,
It causes interfacial failure between the particle surface and rubber molecules, and does not show a reinforcing effect.
【０００５】粒子表面へのゴム分子の凝着更には化学的
結合は、引張応力の向上や引裂強さ、耐摩耗性などの補
強に有利に作用することになり、高補強性を与えるに
は、粒子表面でのゴム分子との化学結合は重要な因子
で、かかる化学結合に関与する官能基の粒子表面におけ
る存在とその種類について充分な考慮が払われなければ
ならない。Adhesion of rubber molecules to the surface of particles and further chemical bonding have an advantageous effect on enhancement of tensile stress, reinforcement of tear strength, abrasion resistance and the like, and in order to provide high reinforcement. The chemical bond with the rubber molecule on the particle surface is an important factor, and the existence and kind of the functional group involved in such chemical bond on the particle surface must be carefully considered.
【０００６】カーボンブラック粒子表面には、ゴム分子
と化学的結合をもたらすような官能基が存在することは
知られており、多くの研究により、カルボキシル基、水
酸基 It is known that the surface of carbon black particles has a functional group capable of chemically bonding with a rubber molecule, and many studies have shown that a carboxyl group and a hydroxyl group are present.
【０００７】シラノール基は親水性を有する−ＯＨ基の
ためにゴム分子とのぬれ性が良くなく、分散効果が悪い
という問題があり、このためγメルカプトプロピルトリ
メトキシシランのような所謂シランカップリング剤によ
り、分子鎖の一方の端はトリメトキシシラン基の加水分
解により、シリカ粒子のシラノール基と縮合反応により
結合し、即ちシリカ表面に結合し、他方の端末は、混練
時の機械的切断で生成したゴムのエラストマーラジカル
に官能基（−ＳＨ）が反応し、残りの水素ラジカルはエ
ラストマーラジカルにターミネートされて安定化され
る。このようにしてシラン粒子のまわりにベンゼンなど
の溶剤に不溶の所謂バウンドラバーが、シラン無添加の
場合より１．５倍に増加することが知られ、この充填剤
粒子周辺に形成する非運動的なゴム層は未架橋の運動し
易いゴム分子部分よりも高密度のいわゆる稠密構造とな
り、これが弾性率を高めると共に応力均一化に働き補強
することが知られている。Since the silanol group has a hydrophilic --OH group, it does not have good wettability with rubber molecules and has a poor dispersion effect. Therefore, so-called silane coupling such as γ-mercaptopropyltrimethoxysilane is required. Depending on the agent, one end of the molecular chain is bonded to the silanol group of the silica particles by a condensation reaction by hydrolysis of the trimethoxysilane group, that is, bonded to the silica surface, and the other end is mechanically cut during kneading. The functional group (-SH) reacts with the produced elastomer radical of the rubber, and the remaining hydrogen radical is terminated by the elastomer radical and stabilized. Thus, it is known that the so-called bound rubber around the silane particles, which is insoluble in a solvent such as benzene, is increased by 1.5 times as compared with the case where no silane is added. It is known that such a rubber layer has a so-called dense structure having a higher density than the uncrosslinked rubber molecule portion that is easy to move, and this increases the elastic modulus and also functions to equalize and reinforce the stress.
【０００８】しかし、このようなシランカップリング剤
をシリカと併用してシリカの補強性を向上させる手段に
よっても、シランカップリング剤は、シリカ中の不純物
であるアルミニウム等の影響で、その効果は低下する。
またＳｉに−ＯＨが２個ついた基も存在し、これもまた
カップリング効率の低下の原因の一つとなっている。従
って、シリカにシランカップリング剤を併用しても、カ
ーボンブラックの補強性には及ばないという問題があっ
た。However, even by a means for improving the reinforcing property of silica by using such a silane coupling agent in combination with silica, the effect of the silane coupling agent is aluminum due to impurities such as aluminum in the silica. descend.
There is also a group in which two -OH are attached to Si, which is also one of the causes of the decrease in coupling efficiency. Therefore, there is a problem that even if a silane coupling agent is used in combination with silica, it does not reach the reinforcing property of carbon black.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、天然
ゴムおよび／またはジエン系合成ゴムに配合するカーボ
ンブラックの一部をシリカで置き換え、低発熱性にする
と共にカーボンブラックだけの充填剤の場合と同等以上
の耐摩耗性を保持させたタイヤ用ゴム組成物を提供する
ことである。SUMMARY OF THE INVENTION An object of the present invention is to replace a part of carbon black compounded in a natural rubber and / or a diene-based synthetic rubber with silica so that the carbon black has a low exothermic property and a filler containing only carbon black. It is to provide a rubber composition for a tire that retains abrasion resistance equal to or higher than the case.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、前記の課
題を解決するため鋭意研究を行った結果、特定のシリカ
に対し、シランカップリング剤を組み合わすことによっ
て、有効に解決し得ることを見出して、本発明を完成す
るに至ったのである。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention can effectively solve the problem by combining a specific silica with a silane coupling agent. By finding this, the present invention has been completed.
【００１１】すなわち、本発明は、 天然ゴムおよび／またはジエン系合成ゴム１００重
量部に対して、カーボンブラック５〜６０重量部、有機
ケイ素化合物からなる疎水性化剤をシリカ量の１〜２０
重量％表面処理したシリカ５〜８０重量部、シランカッ
プリング剤をシリカ配合量の２〜１５重量％配合混練し
てなるタイヤ用ゴム組成物である。That is, in the present invention, 5 to 60 parts by weight of carbon black and 100 to parts by weight of natural rubber and / or diene-based synthetic rubber are used as the hydrophobic agent consisting of an organic silicon compound, and a silica amount of 1 to 20.
A rubber composition for a tire is obtained by compounding and kneading 5 to 80 parts by weight of surface-treated silica and 2 to 15% by weight of a silane coupling agent based on the amount of silica.
【００１２】 有機ケイ素化合物からなる疎水性化剤
が、下記化学式〔化６〕のシリコーンオイルよりなる群
から選ばれた少なくとも１種である前項記載のタイヤ
用ゴム組成物である。The rubber composition for a tire according to the above item, wherein the hydrophobizing agent composed of an organosilicon compound is at least one selected from the group consisting of silicone oils represented by the following chemical formula [Chemical Formula 6].
【化６】 [Chemical 6]
【００１３】 シランカップリング剤が下記化学式
〔化７〕、〔化８〕、〔化９〕および〔化１０〕よりな
る群から選ばれた 少なくとも１種である前項記載の
タイヤゴム組成物である。The tire rubber composition according to the preceding paragraph, wherein the silane coupling agent is at least one selected from the group consisting of the following chemical formulas [Chemical formula 7], [Chemical formula 8], [Chemical formula 9] and [Chemical formula 10].
【化７】 [Chemical 7]
【化８】 [Chemical 8]
【化９】 [Chemical 9]
【化１０】 [Chemical 10]
【００１４】以下、本発明の内容を詳細に説明する。本
発明における、ゴム成分としては天然ゴムまたは合成ゴ
ムを単独またはこれらをブレンドして使用することがで
きる。この合成ゴムとしては、合成ポリイソプレンゴ
ム、ポリブタジエンゴムやスチレンブタジエンゴム等が
例示できる。カーボンブラックとしては、ＩＳＡＦ、Ｈ
ＡＦ等が好ましく使用できるが、特に限定されるもので
はない。シリカとしては、合成無水微粉ケイ酸が好まし
いが特に限定するものではない。シランカップリング剤
としては、例えば、前記化学式〔化７〕、〔化８〕、
〔化９〕および〔化１０〕よりなる群から選ばれた各化
合物が挙げられる。これらの化合物は、単独に又は併用
して使用することができる。The contents of the present invention will be described in detail below. As the rubber component in the present invention, natural rubber or synthetic rubber can be used alone or in a blend thereof. Examples of this synthetic rubber include synthetic polyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber. As carbon black, ISAF, H
AF and the like can be preferably used, but are not particularly limited. As silica, synthetic anhydrous fine silicic acid is preferable, but it is not particularly limited. Examples of the silane coupling agent include those represented by the chemical formulas [Chemical formula 7], [Chemical formula 8],
Examples include each compound selected from the group consisting of [Chemical Formula 9] and [Chemical Formula 10]. These compounds can be used alone or in combination.
【００１５】一般に、シリカ表面には、種類により、そ
の程度は異なるが、多数のシラノール基が存在する。シ
ラノール基は親水性であり、前記の如くゴムとのぬれ性
が悪く、ゴムとの相互作用は弱い。このシラノール基と
ゴムポリマーの両方に作用して補強性を向上させるのが
前記の如くシランカップリング剤の役割である。しか
し、このシランカップリング剤は、シリカ中の不純物で
あるアルミニウム 不純物が表面にある場合、＝Ａｌ−ＯＨとなる。 これもまたカップリング効率の低下の原因の１つとなっ
ている。In general, a large number of silanol groups are present on the surface of silica, although the degree varies depending on the type. The silanol group is hydrophilic, has poor wettability with rubber as described above, and has weak interaction with rubber. It is the role of the silane coupling agent that acts on both the silanol group and the rubber polymer to improve the reinforcing property, as described above. However, this silane coupling agent does not contain aluminum, which is an impurity in silica. If the impurities are on the surface, then = Al-OH. This is also one of the causes of the decrease in coupling efficiency.
【００１６】本発明は有機ケイ素化合物からなる疎水性
化剤、特にシリコーンオイルをシリカ表面に処理するこ
とによりシリカ表面のこれらカップリング効率を低下さ
せる末端の−ＯＨを覆ってしまい、シランカップリング
剤の反応を促進させる。また同時に親水性であったシリ
カ表面を疎水性とし、ポリマーとの親和性を高める働き
も有する。The present invention treats the surface of silica with a hydrophobizing agent composed of an organosilicon compound, particularly silicone oil, to cover the terminal --OH which reduces the coupling efficiency on the surface of silica, and thus the silane coupling agent. Promote the reaction of. At the same time, the surface of the silica, which was hydrophilic, is made hydrophobic so that the affinity with the polymer is increased.
【００１７】このような作用を有する有機ケイ素化合物
からなる疎水性化剤は、例えば、前記化学式〔化６〕で
示されるシリコーンオイル（メチルハイドロジエンポリ
シロキサン）よりなる群から選ばれた少なくとも１種で
あり、例えば、下記構造式The hydrophobizing agent made of an organosilicon compound having such an action is, for example, at least one selected from the group consisting of silicone oil (methylhydrogenpolysiloxane) represented by the chemical formula [Chemical Formula 6]. And, for example, the following structural formula
【化１１】 [Chemical 11]
【化１２】 [Chemical 12]
【化１３】 等が挙げられる。また、流動性に影響がなければ、分岐
していてもかまわない。 [Chemical 13] Etc. Further, if it does not affect the liquidity, it may be branched.
【００１８】表面処理は、例えば、所定量のシリカとシ
リコーンオイルをブレンドした後、２５０℃で１時間熱
処理することにより行うことができる。前記化学式〔化
７〕、〔化８〕、〔化９〕又は〔化１０〕で示したシラ
ンカップリング剤を使用したとき、特に相乗効果がある
ため、このシリカを充填剤として使用することによっ
て、ゴムをカーボンブラック単独充填の時と同等かそれ
以上の耐摩耗性を保持させることができる。The surface treatment can be carried out, for example, by blending a predetermined amount of silica and silicone oil and then heat-treating at 250 ° C. for 1 hour. When the silane coupling agent represented by the chemical formula [Chemical formula 7], [Chemical formula 8], [Chemical formula 9] or [Chemical formula 10] is used, there is a particularly synergistic effect. Therefore, by using this silica as a filler, It is possible to maintain abrasion resistance equal to or higher than that when the rubber is filled with carbon black alone.
【００１９】カーボンブラックの使用量は５重量部未満
では、補強効果が十分でなく、６０重量部超では、高発
熱性となるばかりか、耐摩耗性もかえって低下する。表
面処理シリカ使用量は５重量部未満では、置換による低
発熱性のメリットが小さく、８０重量部超では作業性の
悪化をもたらす。表面処理シリカは２０〜５０重量部が
好ましい。If the amount of carbon black used is less than 5 parts by weight, the reinforcing effect is not sufficient, and if it exceeds 60 parts by weight, not only high heat build-up but also abrasion resistance deteriorates. If the amount of surface-treated silica used is less than 5 parts by weight, the merit of low heat generation due to substitution is small, and if it exceeds 80 parts by weight, workability is deteriorated. The surface-treated silica is preferably 20 to 50 parts by weight.
【００２０】シランカップリング剤の使用量は、シリカ
重量に対し、２重量％未満ではカップリング効果が小さ
く、１５重量％超ではポリマーのゲル化を引き起こす。
有機ケイ素化合物からなる疎水性化剤の処理量は、シリ
カ量に対し１〜２０重量％である。１重量％未満では目
的とする表面処理の効果が見られず、２０重量％超では
シランカップリング剤が反応するＳｉ−ＯＨサイトまで
覆いつくしてましいカップリング剤の効果を妨げる。ま
た、処理量は使用するシリカの表面積、すなわちＳｉ−
ＯＨサイト数によって適宜調整されることが好ましい。If the amount of the silane coupling agent used is less than 2% by weight based on the weight of silica, the coupling effect is small, and if it exceeds 15% by weight, gelation of the polymer occurs.
The treatment amount of the hydrophobizing agent composed of an organosilicon compound is 1 to 20% by weight based on the amount of silica. If it is less than 1% by weight, the desired effect of the surface treatment is not observed, and if it exceeds 20% by weight, the Si—OH site where the silane coupling agent reacts is covered and the effect of the desired coupling agent is hindered. Further, the treatment amount is the surface area of silica used, that is, Si-
It is preferably adjusted appropriately depending on the number of OH sites.
【００２１】なお、本発明のタイヤ用ゴム組成物には、
ゴム工業で通常使用される配合剤、例えば、他の補強性
充填剤、加硫剤、加硫促進剤、老化防止剤、軟化剤等を
適宜配合することができるのは勿論のことである。The tire rubber composition of the present invention contains
It goes without saying that the compounding agents usually used in the rubber industry, for example, other reinforcing fillers, vulcanizing agents, vulcanization accelerators, antioxidants, softening agents and the like can be appropriately compounded.
【００２２】[0022]
【実施例】以下に実施例により、本発明を更に具体的に
説明するが、本発明は、この実施例により限定されるも
のではない。 （実施例１〜９および比較例１〜５）下記表１〜表３
に、天然ゴムおよび／またはジエン系合成ゴム１００重
量部にカーボンブラックの配合量、表面処理シリカの種
類及びその配合量、シランカップリング剤の配合量を変
えた実施例、比較例の組成物について、耐摩耗性及び発
熱性を測定した結果を示す。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Examples 1 to 9 and Comparative Examples 1 to 5) Tables 1 to 3 below
The compositions of Examples and Comparative Examples in which 100 parts by weight of natural rubber and / or diene-based synthetic rubber were mixed with different amounts of carbon black, the type of surface-treated silica and its amount, and the amount of silane coupling agent. The results of measurement of wear resistance and heat generation are shown below.
【００２３】なお、耐摩耗性及び発熱性の測定法は下記
のとおりである。 （ゴム物性測定法） （１） 耐摩耗性 耐摩耗性を表す耐摩耗指数はランボーン試験機を用いて
摩耗損失量を測定し、次式により算出した。 (耐摩耗指数)＝(対照物の容量損失量)×１００／(供試
試験片の容量損失量) この指数が大きい程、耐摩耗性が良好なことを示す。The methods of measuring wear resistance and heat generation are as follows. (Rubber physical property measuring method) (1) Abrasion resistance The abrasion resistance index showing abrasion resistance was calculated by the following formula by measuring the amount of abrasion loss using a Lambourn tester. (Abrasion resistance index) = (capacity loss amount of control) × 100 / (capacity loss amount of test specimen) The larger this index, the better the abrasion resistance.
【００２４】（２） 発熱性 発熱性を表す tanδ値は、岩本製作所（株）製の粘弾性
スペクトロメーターを使用し、引張りの動歪１％、周波
数５０Ｈｚ、２５℃の条件で測定した。なお、試験片
は、厚さ２mm、幅５mmのスラブシートを用い、試料挟み
間距離２cmとして初期荷重を１００ｇとした。対照物と
対比した指数で表し、指数の値の低いほど、低発熱性を
示す。(2) Exothermicity The tanδ value representing the exothermicity was measured by using a viscoelasticity spectrometer manufactured by Iwamoto Seisakusho Co., Ltd. under the conditions of a tensile dynamic strain of 1%, a frequency of 50 Hz and 25 ° C. As the test piece, a slab sheet having a thickness of 2 mm and a width of 5 mm was used, and the initial load was 100 g with the distance between the samples being 2 cm. It is expressed by an index in comparison with the control product, and the lower the index value, the lower the heat buildup.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】また、図１及び図２に上記表１〜表３の測
定値であるtanδ値と耐摩耗性との関係をまとめたもの
を示す。上記表１〜表３並びに図１及び図２から明らか
なように、本発明のタイヤ用ゴム組成物（実施例１〜
９）は、比較例１〜５に較べ耐摩耗性は同等またはそれ
以上であり、一方低発熱性であることが判る。Further, FIGS. 1 and 2 show a summary of the relationship between the tan δ value which is the measured value in Tables 1 to 3 and the wear resistance. As is clear from Tables 1 to 3 and FIGS. 1 and 2, the rubber composition for a tire of the present invention (Examples 1 to 1)
It can be seen that in 9), the wear resistance is equal to or higher than that of Comparative Examples 1 to 5, while the heat generation is low.
【００２９】[0029]
【発明の効果】本発明の天然ゴムおよび／またはジエン
系合成ゴムに配合するカーボンブラックの一部を有機ケ
イ素化合物からなる疎水性化剤によって表面処理したシ
リカに置換し、シランカップリング剤を配合したタイヤ
用ゴム組成物は、加硫物において、耐摩耗性を、カーボ
ンブラック単独配合した場合と較べて、同等程度かそれ
以上に保持しながら、低発熱性にすることができる。従
って、近年省エネルギーを目指した低燃費性が要求され
ている時、製品の性能向上に大きく寄与することができ
る。EFFECT OF THE INVENTION A part of the carbon black blended in the natural rubber and / or the diene-based synthetic rubber of the present invention is replaced with silica surface-treated with a hydrophobizing agent composed of an organosilicon compound, and a silane coupling agent is blended. The rubber composition for a tire can have low heat build-up while maintaining the wear resistance of the vulcanized product at the same level or higher as compared with the case where only carbon black is blended. Therefore, when low fuel consumption aiming at energy saving is demanded in recent years, it can greatly contribute to the performance improvement of the product.
【図１】実施例１〜７及び比較例１〜２における 発熱
性を表すtanδ値と耐摩耗性との関係を示す図面であ
る。FIG. 1 is a drawing showing a relationship between a tan δ value representing heat generation and wear resistance in Examples 1 to 7 and Comparative Examples 1 and 2.
【図２】実施例８〜９及び比較例３〜５における 発熱
性を表すtanδ値と耐摩耗性との関係を示す図面であ
る。FIG. 2 is a drawing showing the relationship between tan δ value representing heat generation and wear resistance in Examples 8 to 9 and Comparative Examples 3 to 5.
Claims (3)
ム１００重量部に対して、カーボンブラック５〜６０重
量部、有機ケイ素化合物からなる疎水性化剤をシリカ量
の１〜２０重量％表面処理したシリカ５〜８０重量部、
シランカップリング剤をシリカ配合量の２〜１５重量％
配合混練してなるタイヤ用ゴム組成物。1. A surface treatment of 100 parts by weight of natural rubber and / or diene-based synthetic rubber with 5 to 60 parts by weight of carbon black and 1 to 20% by weight of silica of a hydrophobizing agent comprising an organic silicon compound. 5 to 80 parts by weight of silica,
Silane coupling agent is 2 to 15% by weight of silica compounding amount
A rubber composition for a tire obtained by compounding and kneading.
が、下記化学式〔化１〕のシリコーンオイルよりなる群
から選ばれた少なくとも１種である請求項１記載のタイ
ヤ用ゴム組成物。 【化１】 2. The rubber composition for a tire according to claim 1, wherein the hydrophobizing agent made of an organosilicon compound is at least one selected from the group consisting of silicone oils represented by the following chemical formula [Chemical formula 1]. [Chemical 1]
２〕、〔化３〕、〔化４〕および〔化５〕よりなる群か
ら選ばれた少なくとも１種である請求項１記載のタイヤ
用ゴム組成物。 【化２】 【化３】 【化４】 【化５】 3. The tire according to claim 1, wherein the silane coupling agent is at least one selected from the group consisting of the following chemical formulas [Chemical formula 2], [Chemical formula 3], [Chemical formula 4] and [Chemical formula 5]. Rubber composition. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03361593A JP3403747B2 (en) | 1993-02-23 | 1993-02-23 | Rubber composition for tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03361593A JP3403747B2 (en) | 1993-02-23 | 1993-02-23 | Rubber composition for tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06248116A true JPH06248116A (en) | 1994-09-06 |
| JP3403747B2 JP3403747B2 (en) | 2003-05-06 |
Family
ID=12391363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03361593A Expired - Fee Related JP3403747B2 (en) | 1993-02-23 | 1993-02-23 | Rubber composition for tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3403747B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08176462A (en) * | 1994-12-22 | 1996-07-09 | Nippon Silica Ind Co Ltd | Partially hydrophobic precipitated silicic acid |
| EP0721971A1 (en) * | 1995-01-13 | 1996-07-17 | Bridgestone Corporation | Pneumatic tires |
| EP0731133A2 (en) * | 1995-03-09 | 1996-09-11 | Sumitomo Chemical Company, Limited | Rubber composition |
| WO1996029364A1 (en) | 1995-03-17 | 1996-09-26 | Nippon Zeon Co., Ltd. | Rubber composition |
| EP0784072A1 (en) | 1996-01-11 | 1997-07-16 | COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN-MICHELIN & CIE | Silica-based composition for pneumatic tyre containing a reinforcing additive comprising a functionalized polyorganosiloxane and an organosilane |
| EP0795577A1 (en) * | 1996-03-11 | 1997-09-17 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| WO1998011161A1 (en) * | 1996-09-11 | 1998-03-19 | The Yokohama Rubber Co., Ltd. | Polysiloxane-containing tire rubber composition |
| EP0864605A2 (en) * | 1997-03-10 | 1998-09-16 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| US6033597A (en) * | 1995-08-31 | 2000-03-07 | The Yokohama Rubber Co., Ltd. | Polysiloxane-containing rubber composition |
| JP2000109604A (en) * | 1998-08-06 | 2000-04-18 | Bridgestone Corp | Rubber composition and pneumatic tire made therefrom |
| US6075092A (en) * | 1996-04-17 | 2000-06-13 | Nippon Zeon Co., Ltd. | Rubber composition |
| US6172160B1 (en) | 1996-04-17 | 2001-01-09 | Nippon Zeon Co., Ltd. | Diene polymer composition, process for the preparation of the same, and rubber composition containing the same |
| JP2001192454A (en) * | 2000-01-14 | 2001-07-17 | Shin Etsu Chem Co Ltd | Organopolysiloxane, compounding agent for rubber, rubber composition containing the agent and tire |
| US6548573B1 (en) * | 1999-12-20 | 2003-04-15 | Caterpillar Inc | Composition and process for making a water and mud repellant rubber |
| JP2003113273A (en) * | 2001-07-06 | 2003-04-18 | Degussa Ag | Silane-modified oxide or silicate filler, method of producing the same and rubber compound including the filler and use thereof |
| WO2003097737A1 (en) * | 2002-05-17 | 2003-11-27 | Cabot Corporation | Elastomeric compositions containing surface-modified silica gels |
| US6689834B2 (en) | 2000-09-11 | 2004-02-10 | Bayer Aktiengesellschaft | Liquid sulfur-containing oligosiloxanes and their use in rubber mixtures |
| WO2005118705A1 (en) | 2004-06-01 | 2005-12-15 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire and pneumatic tire made therefrom |
| EP1634899A1 (en) | 2000-06-07 | 2006-03-15 | Zeon Corporation | Conjugated diene rubber gel, rubber compositions containing the same and process for production of conjugated diene rubber |
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1993
- 1993-02-23 JP JP03361593A patent/JP3403747B2/en not_active Expired - Fee Related
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| EP0721971A1 (en) * | 1995-01-13 | 1996-07-17 | Bridgestone Corporation | Pneumatic tires |
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| EP0731133B1 (en) * | 1995-03-09 | 2001-06-20 | Sumitomo Chemical Company Limited | Rubber composition |
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