JP3403747B2 - Rubber composition for tire - Google Patents
Rubber composition for tireInfo
- Publication number
- JP3403747B2 JP3403747B2 JP03361593A JP3361593A JP3403747B2 JP 3403747 B2 JP3403747 B2 JP 3403747B2 JP 03361593 A JP03361593 A JP 03361593A JP 3361593 A JP3361593 A JP 3361593A JP 3403747 B2 JP3403747 B2 JP 3403747B2
- Authority
- JP
- Japan
- Prior art keywords
- chemical
- rubber
- silica
- weight
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
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、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
からなる化合物をシリカ量の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, the present invention is based on 100 parts by weight of natural rubber and / or diene-based synthetic rubber, 5 to 60 parts by weight of carbon black, and at least one selected from the group consisting of silicone oils represented by the following chemical formula. A rubber composition for a tire, which is obtained by kneading 5 to 80 parts by weight of silica obtained by surface-treating a compound of 1 type in an amount of 1 to 20% by weight of silica, and a silane coupling agent in an amount of 2 to 15% by weight of a silica content. .
【化６】 [Chemical 6]
【００１２】[0012]
【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種である上記記載のタ
イヤ用ゴム組成物である。The tire rubber composition as described above, 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]. is there.
【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、上記構成のシリコーンオイルを
シリカ表面に表面に処理することによりシリカ表面のこ
れらのカップリング効率を低下させる末端−ＯＨ基を覆
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をも有する。In the present invention, by treating the surface of the silicone oil having the above-mentioned constitution on the surface of silica, the terminal --OH groups which reduce the coupling efficiency of these on the surface of silica are covered and the reaction of the silane coupling agent is promoted. Let At the same time, the surface of the silica, which has been 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）は、前記〔化
６〕で示される化合物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 silicone oil (methylhydrogenpolysiloxane) having such an action is at least one selected from the group consisting of the compounds represented by the above-mentioned [Chemical formula 6].
【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 tan δ value representing exothermicity was measured 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。EFFECTS OF THE INVENTION The rubber composition for a tire of the present invention has low heat build-up while maintaining the wear resistance of the vulcanized product to the same extent or more as compared with the case where carbon black is blended alone. You can 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.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 7/00 - 21/00 C08K 3/00 - 3/04 C08K 3/34 - 3/36 C08K 9/04 - 9/06 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C08L 7 /00-21/00 C08K 3/00-3/04 C08K 3/34-3/36 C08K 9 / 04-9/06
Claims (2)
ム１００重量部に対して、カーボンブラック５〜６０重
量部、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種からなる化合物をシリカ
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。 【化１】 1. At least one selected from the group consisting of 5 to 60 parts by weight of carbon black and 100 parts by weight of natural rubber and / or diene-based synthetic rubber, and a silicone oil represented by the following chemical formula [Formula 1]. A rubber composition for a tire obtained by compounding and kneading 5 to 80 parts by weight of silica obtained by surface-treating a compound in an amount of 1 to 20% by weight, and 2 to 15% by weight of a silane coupling agent in an amount of silica. [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】 2. 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 JPH06248116A (en) | 1994-09-06 |
| JP3403747B2 true 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) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3534464B2 (en) * | 1994-12-22 | 2004-06-07 | 東ソー・シリカ株式会社 | Partially hydrophobized precipitated silica |
| EP0721971B1 (en) * | 1995-01-13 | 2000-09-13 | Bridgestone Corporation | Process for preparing pneumatic tires |
| DE69613417T2 (en) * | 1995-03-09 | 2002-05-29 | Sumitomo Chemical Co | rubber compound |
| US6015850A (en) * | 1995-03-17 | 2000-01-18 | Nippon Zeon Co., Ltd. | Rubber composition |
| DE69632512T2 (en) * | 1995-08-31 | 2005-05-25 | The Yokohama Rubber Co., Ltd. | Polysiloxane-containing rubber composition |
| FR2743564A1 (en) * | 1996-01-11 | 1997-07-18 | Michelin & Cie | RUBBER COMPOSITIONS FOR SILICA-BASED TIRE CASINGS CONTAINING A REINFORCING ADDITIVE BASED ON A FUNCTIONALIZED POLYORGANOSILOXANE AND AN ORGANOSILANE COMPOUND. |
| US5914364A (en) * | 1996-03-11 | 1999-06-22 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| US5780538A (en) * | 1996-03-11 | 1998-07-14 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| WO1997039056A1 (en) | 1996-04-17 | 1997-10-23 | Nippon Zeon Co., Ltd. | Diene polymer composition, process for the preparation of the same, and rubber composition containing the same |
| US6075092A (en) * | 1996-04-17 | 2000-06-13 | Nippon Zeon Co., Ltd. | Rubber composition |
| KR100281944B1 (en) * | 1996-09-11 | 2001-02-15 | 하기와라 세이지 | Tire Rubber Compositions Containing Polysiloxanes |
| JP4950370B2 (en) * | 1998-08-06 | 2012-06-13 | 株式会社ブリヂストン | Method for reducing variation in manufacturing pneumatic tires |
| US6548573B1 (en) * | 1999-12-20 | 2003-04-15 | Caterpillar Inc | Composition and process for making a water and mud repellant rubber |
| 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 |
| EP1634899B1 (en) | 2000-06-07 | 2009-07-29 | Zeon Corporation | Conjugated diene rubber gel, rubber compositions containing the same and process for production of conjugated diene rubber |
| DE10044989A1 (en) | 2000-09-11 | 2002-03-21 | Bayer Ag | Liquid sulfur-containing oligosiloxanes and their use in rubber compounds |
| DE10132943A1 (en) * | 2001-07-06 | 2003-01-23 | Degussa | Silane-modified oxidic or silicate filler, process for its production and its use |
| EP2223958B1 (en) | 2001-10-05 | 2011-12-28 | Bridgestone Corporation | Rubber composition |
| US20030216489A1 (en) * | 2002-05-17 | 2003-11-20 | Meng-Jiao Wang | Elastomeric compositions containing surface-modified silica gels |
| JP4810798B2 (en) | 2004-06-01 | 2011-11-09 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| CN1308401C (en) * | 2004-10-14 | 2007-04-04 | 武汉理工大学 | Method for preparing hydrophobic inorganic and organic composite corpuscle |
| JP4726507B2 (en) * | 2005-02-04 | 2011-07-20 | 株式会社ブリヂストン | Rubber masterbatch and production method thereof, and rubber composition and tire using the same |
| JP2007216829A (en) * | 2006-02-16 | 2007-08-30 | Bridgestone Corp | Tire for construction vehicle, and its manufacturing method |
| KR101247858B1 (en) | 2008-01-18 | 2013-03-26 | 가부시키가이샤 브리지스톤 | Rubber composition and tire |
| EP2272909B1 (en) | 2008-04-30 | 2015-11-25 | Bridgestone Corporation | Tire prepared by using rubber composition containing modified polymer |
| JP5323424B2 (en) * | 2008-09-02 | 2013-10-23 | 東洋ゴム工業株式会社 | Pneumatic tire |
| CN102459445B (en) | 2009-04-28 | 2014-02-05 | 株式会社普利司通 | Pneumatic tire |
| JP5545619B2 (en) | 2009-07-22 | 2014-07-09 | 株式会社ブリヂストン | tire |
| JPWO2012165543A1 (en) | 2011-06-01 | 2015-02-23 | 竹本油脂株式会社 | Dispersant for inorganic filler and method for producing the same |
| US10017625B2 (en) | 2012-05-08 | 2018-07-10 | Bridgestone Corporation | Rubber composition, crosslinked rubber composition and tire |
| EP3042764B1 (en) | 2013-09-03 | 2018-03-28 | NOK Corporation | Silicone rubber-fluorine resin laminate |
| JP6624059B2 (en) | 2014-08-27 | 2019-12-25 | 日本ゼオン株式会社 | Cyclic olefin rubber and method for producing the same, and rubber composition, cross-linked rubber and tire |
| JP7010284B2 (en) | 2017-03-24 | 2022-01-26 | 日本ゼオン株式会社 | Cyclopentene ring-opening copolymer and its production method |
| JP2018203970A (en) | 2017-06-09 | 2018-12-27 | 株式会社ブリヂストン | Rubber composition, method for producing rubber composition and tire |
| KR20210005567A (en) | 2018-04-24 | 2021-01-14 | 니폰 제온 가부시키가이샤 | Ring-opening copolymer |
| JP7359148B2 (en) | 2018-07-13 | 2023-10-11 | 日本ゼオン株式会社 | Ring-opened copolymer composition |
| US20210301053A1 (en) | 2018-08-17 | 2021-09-30 | Zeon Corporation | Copolymer formed by ring-opening copolymerization of cycloolefin, production method therefor, rubber composition, and crosslinked rubber object |
| US20220380522A1 (en) | 2019-12-17 | 2022-12-01 | Zeon Corporation | Ring-opened copolymer |
-
1993
- 1993-02-23 JP JP03361593A patent/JP3403747B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06248116A (en) | 1994-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3403747B2 (en) | Rubber composition for tire | |
| JP3103153B2 (en) | Rubber composition | |
| KR100357504B1 (en) | Rubber composition | |
| EP1958984B1 (en) | Rubber composition | |
| JP3792830B2 (en) | Rubber composition for tire sidewall and tire | |
| JP4157608B2 (en) | Rubber composition | |
| EP0803535B1 (en) | Rubber composition for tyre sidewall and tyre | |
| JP3363539B2 (en) | Rubber composition for tire tread | |
| JP3442113B2 (en) | Rubber composition for tire tread | |
| JP4321894B2 (en) | Pneumatic tire | |
| JP5442489B2 (en) | Rubber composition for tire and pneumatic tire | |
| JP5562799B2 (en) | Rubber composition and pneumatic tire | |
| JPH08245838A (en) | Pneumatic tire | |
| JP6033633B2 (en) | Surface-treated silica, rubber composition using the same, and pneumatic tire | |
| JPH1095204A (en) | Pneumatic tire | |
| JP3808515B2 (en) | Rubber composition | |
| JP6451265B2 (en) | Rubber composition for tire | |
| JPH11263882A (en) | Rubber composition | |
| JP4790147B2 (en) | Rubber composition for tire tread | |
| JPH11255964A (en) | Rubber composition | |
| JP3530088B2 (en) | Rubber composition and method for producing the same | |
| JP3996696B2 (en) | Rubber composition | |
| JP3494575B2 (en) | Rubber composition for tire tread | |
| JP4076611B2 (en) | Rubber composition | |
| JPH1159116A (en) | Heavy load pneumatic tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080229 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090228 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100228 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100228 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110228 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |