JP2001172435A - Method for producing rubber composition and pneumatic tire - Google Patents
Method for producing rubber composition and pneumatic tireInfo
- Publication number
- JP2001172435A JP2001172435A JP35741299A JP35741299A JP2001172435A JP 2001172435 A JP2001172435 A JP 2001172435A JP 35741299 A JP35741299 A JP 35741299A JP 35741299 A JP35741299 A JP 35741299A JP 2001172435 A JP2001172435 A JP 2001172435A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- parts
- rubber composition
- kneading
- 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.)
- Granted
Links
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐破壊性、耐ティ
ア性を低下させることなく、低発熱性を向上させること
のできるゴム組成物の製造方法、およびこの方法により
製造したゴム組成物をトレッドゴムとして使用した空気
入りタイヤに関するものである。[0001] The present invention relates to a method for producing a rubber composition capable of improving low heat build-up without deteriorating fracture resistance and tear resistance, and a rubber composition produced by this method. It relates to a pneumatic tire used as tread rubber.
【０００２】[0002]
【従来の技術】空気入りタイヤのトレッド、特に、キャ
ップ／ベース構造のベース部に適用されるゴムには、低
発熱性のみならず耐破壊性および耐テア性が要求される
ため、従来より、弾性率を低下させて、ゴムの破断時伸
びを高くする方法がある。しかし、これは歪変形を大き
くするため、タイヤの低発熱性を悪化させる。2. Description of the Related Art Rubbers applied to treads of pneumatic tires, particularly to a base portion of a cap / base structure, are required to have not only low heat build-up but also fracture resistance and tear resistance. There is a method of lowering the elastic modulus and increasing the elongation at break of rubber. However, this increases the strain deformation, thereby deteriorating the low heat build-up of the tire.
【０００３】そこで、特定のヒドラジド化合物を配合し
て、ゴム組成物の低発熱化を図る技術がある（参照：特
開平１０−１３９９３４号公報および特開平１０−３３
０５４９号公報）。Therefore, there is a technique for blending a specific hydrazide compound to lower the heat generation of a rubber composition (see JP-A-10-139934 and JP-A-10-33).
No. 0549).
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記ヒドラジ
ド化合物は、ゴム混練り工程中、亜鉛華や練り温度の影
響を受けること、および、そのために所望の特性を備え
たゴム組成物を得るためには特定の製造方法が必要であ
ることが判明した。そこで、本発明は、ゴム発熱改良剤
として優れている特定のヒドラジド化合物を配合したゴ
ム組成物において、耐破壊性および耐ティア性を備え、
かつ低発熱性を十分に発揮できる、トレッド、特に、キ
ャップ／ベース構造のベース部のゴムに好適なゴム組成
物の製造方法を提供することを目的とする。However, the above-mentioned hydrazide compound is subject to the influence of zinc white and kneading temperature during the rubber kneading step, and in order to obtain a rubber composition having desired properties. Turned out to require a specific manufacturing method. Therefore, the present invention provides a rubber composition containing a specific hydrazide compound that is excellent as a rubber exothermic improver, and has fracture resistance and tear resistance,
It is an object of the present invention to provide a method for producing a rubber composition suitable for a tread, particularly a rubber for a base portion of a cap / base structure, which can sufficiently exhibit low heat build-up.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明は、以下の構成とする。 （１）本発明のゴム組成物の製造方法は、加硫剤投入前
のゴム混練り工程（いわゆるノンプロ練り工程）で、天
然ゴムおよびジエン系合成ゴムのうち少なくとも１種か
らなるゴム成分１００重量部に対して、下記の一般式
〔化２〕で表わされるヒドラジド化合物のうち少なくと
も１種を０．１〜５重量部と亜鉛華を０．２〜５重量部
とを同時に投入し、かつ最高温度（いわゆる落下温度）
を１３０℃〜１７０℃にして混練りすることを特徴とす
る。In order to achieve the above object, the present invention has the following arrangement. (1) In the method for producing a rubber composition according to the present invention, in a rubber kneading step (so-called non-pro kneading step) before the addition of a vulcanizing agent, a rubber component composed of at least one of natural rubber and diene-based synthetic rubber is used in an amount of 100% by weight. Parts by weight of at least one hydrazide compound represented by the following general formula [Formula 2] and 0.1-5 parts by weight of zinc white at the same time, and 0.2-5 parts by weight of zinc white. Temperature (so-called drop temperature)
At 130 ° C. to 170 ° C. and kneading.
【化２】 （式中、Ｒ1 およびＲ2 は炭素数１〜１８のアルキル
基、シクロアルキル基、またはアリール基をそれぞれ独
立に表し、Ｏ、Ｎ、Ｓのうち少なくとも１種のヘテロ原
子を含んでいてもよい。） 前記ゴム混練り工程で、カーボンブラックも投入、混練
りし、その配合量を、ゴム成分１００重量部に対して２
０〜６０重量部とすると、このゴム組成物をトレッドゴ
ムとしたとき、補強性等の点で好ましい。また、前記ゴ
ム混練り工程で、シリカも投入、混練りし、その配合量
は、ゴム成分１００重量部に対して２０重量部以下であ
ると、発熱耐久性等の点で好ましい。 なお、カーボン
ブラックやシリカの投入時期は、ヒドラジド化合物投入
時期に影響されない。 （２）本発明の空気入りタイヤは、上記各製造方法によ
り製造したゴム組成物をトレッドに適用したことを特徴
とする。トレッドがキャップ／ベース構造である場合に
は、ベース部に適用すると効果的である。Embedded image (In the formula, R 1 and R 2 each independently represent an alkyl group, a cycloalkyl group, or an aryl group having 1 to 18 carbon atoms, and may include at least one hetero atom of O, N, and S. In the rubber kneading step, carbon black is also charged and kneaded, and the compounding amount is 2 parts per 100 parts by weight of the rubber component.
When the amount is 0 to 60 parts by weight, when this rubber composition is used as a tread rubber, it is preferable in terms of reinforcing properties and the like. In the rubber kneading step, silica is also added and kneaded, and the amount of the silica is preferably 20 parts by weight or less based on 100 parts by weight of the rubber component, from the viewpoint of heat resistance and the like. The charging time of carbon black or silica is not affected by the charging time of the hydrazide compound. (2) The pneumatic tire of the present invention is characterized in that the rubber composition produced by each of the above production methods is applied to a tread. When the tread has a cap / base structure, it is effective to apply to the base portion.
【０００６】[0006]
【発明の実施の形態】本発明では、ヒドラジド化合物の
配合量を、ゴム成分１００重量部に対して、０．１〜５
重量部とするが、これは、０．１重量部未満では、目的
とする低発熱性が得られず、５重量部超過ではゴムの未
加硫粘度が上昇し好ましくないからである。同様の観点
がら、好ましくは、０．５〜３重量部である。本発明の
ヒドラジド化合物としては、１−ヒドロキシ−Ｎ′−
（１−メチルエチリデン）−２−ナフトエ酸ヒドラジ
ド、１−ヒドロシキ−Ｎ′−（１−メチルプロピリデ
ン）−２−ナフトエ酸ヒドラジド、１−ヒドロキシ−
Ｎ′−（１−メチルブチリデン）−２−ナフトエ酸ヒド
ラジド、１−ヒドロキシ−Ｎ′−（１，３−ジメチルブ
チリデン）−２−ナフトエ酸ヒドラジド、１−ヒドロキ
シ−Ｎ′−（２−フリルメチレン）−２−ナフトエ酸ヒ
ドラジド、３−ヒドロキシ−Ｎ′−（１−メチルエチリ
デン）−２−ナフトエ酸ヒドラジド、３−ヒドロキシ−
Ｎ′−（１−メチルプロピリデン）−２−ナフトエ酸ヒ
ドラジド、３−ヒドロキシ−Ｎ′−（１−メチルブチリ
デン）−２−ナフトエ酸ヒドラジド、３−ヒドロキシ−
Ｎ′−（１，３−ジメチルブチリデン）−２−ナフトエ
酸ヒドラジド、３−ヒドロキシ−Ｎ′−（２−フリルメ
チレン）−２−ナフトエ酸ヒドラジド等を例示でき、こ
れらのうち、好ましくは、１−ヒドロキシ−Ｎ′−（１
−メチルエチリデン）−２−ナフトエ酸ヒドラジド、１
−ヒドロシキ−Ｎ′−（１−メチルプロピリデン）−２
−ナフトエ酸ヒドラジド、１−ヒドロキシ−Ｎ′−
（１，３−ジメチルブチリデン）−２−ナフトエ酸ヒド
ラジド、１−ヒドロキシ−Ｎ′−（２−フリルメチレ
ン）−２−ナフトエ酸ヒドラジド、３−ヒドロキシ−
Ｎ′−（１−メチルエチリデン）−２−ナフトエ酸ヒド
ラジド、３−ヒドロキシ−Ｎ′−（１−メチルプロピリ
デン）−２−ナフトエ酸ヒドラジド、３−ヒドロキシ−
Ｎ′−（１，３−ジメチルブチリデン）−２−ナフトエ
酸ヒドラジド、３−ヒドロキシ−Ｎ′−（２−フリルメ
チレン）−２−ナフトエ酸ヒドラジドである。本発明の
ヒドラジド化合物は、単独でも、２種以上を組み合わせ
て使用しても良い。これらの化合物は、特開平１０−３
３０５４９号公報記載の合成法に準じて合成できる。ま
た、ヒドラジド化合物と同時に投入する亜鉛華は、ゴム
成分１００重量部に対して、０．２〜５重量部である
が、これは、０．２重量部未満ではゴムの弾性率が低下
し、目的とする低発熱性が得られず、５重量部超過では
ゴムがしゃっ解し、逆に低発熱性の悪化を生じてしまう
からである。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the amount of a hydrazide compound is 0.1 to 5 parts by weight based on 100 parts by weight of a rubber component.
If the amount is less than 0.1 part by weight, the desired low heat build-up cannot be obtained, and if it exceeds 5 parts by weight, the unvulcanized viscosity of the rubber increases, which is not preferable. From the same viewpoint, it is preferably 0.5 to 3 parts by weight. The hydrazide compound of the present invention includes 1-hydroxy-N'-
(1-methylethylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N '-(1-methylpropylidene) -2-naphthoic acid hydrazide, 1-hydroxy-
N '-(1-methylbutylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N'-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N '-(2- Furylmethylene) -2-naphthoic acid hydrazide, 3-hydroxy-N '-(1-methylethylidene) -2-naphthoic acid hydrazide, 3-hydroxy-
N '-(1-methylpropylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N'-(1-methylbutylidene) -2-naphthoic acid hydrazide, 3-hydroxy-
N '-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N'-(2-furylmethylene) -2-naphthoic acid hydrazide and the like can be exemplified, and among these, preferably, 1-hydroxy-N '-(1
-Methylethylidene) -2-naphthoic acid hydrazide, 1
-Hydroxy-N '-(1-methylpropylidene) -2
-Naphthoic acid hydrazide, 1-hydroxy-N'-
(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N '-(2-furylmethylene) -2-naphthoic acid hydrazide, 3-hydroxy-
N '-(1-methylethylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N'-(1-methylpropylidene) -2-naphthoic acid hydrazide, 3-hydroxy-
N '-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide and 3-hydroxy-N'-(2-furylmethylene) -2-naphthoic acid hydrazide. The hydrazide compounds of the present invention may be used alone or in combination of two or more. These compounds are described in JP-A-10-3
It can be synthesized according to the synthesis method described in Japanese Patent No. 30549. The zinc white added at the same time as the hydrazide compound is 0.2 to 5 parts by weight with respect to 100 parts by weight of the rubber component. This is because the desired low heat build-up cannot be obtained, and if the amount is more than 5 parts by weight, the rubber is sucked, and conversely, the low heat build-up is deteriorated.
【０００７】また、ゴム混練り中、系内温度は上昇する
ので、ある温度（落下温度）に達すると冷却して、系の
温度を下げるが、このときの温度を、本明細書中では、
「最高温度」と称する。この最高温度を、本発明では１
３０〜１７０℃とするが、これは、１３０℃未満では、
ヒドラジド化合物がカーボンブラックおよびゴムポリマ
ーと充分反応せず、目的とする低発熱性が得られず、１
７０℃を超えると、ゴムの耐破壊性の低下を招き好まし
くないからである。また、トレッドゴムとして、充分な
補強性を得るためには、カーボンブラックを２０重量部
以上配合した方が好ましく、さらに、低発熱性の点から
は、６０重量部以下が好ましい。シリカを配合した場合
には、低発熱性の点からは、２０重量部以下が好まし
い。During rubber kneading, the temperature inside the system rises, so that when the temperature reaches a certain temperature (drop temperature), the system is cooled to lower the temperature of the system.
Called "maximum temperature". According to the present invention, this maximum temperature is 1
30 to 170 ° C., which is lower than 130 ° C.
The hydrazide compound does not sufficiently react with the carbon black and the rubber polymer, and the desired low heat build-up cannot be obtained.
If the temperature is higher than 70 ° C., the rubber is likely to have a reduced fracture resistance, which is not preferable. Further, in order to obtain sufficient reinforcing properties as the tread rubber, it is preferable that carbon black is blended in an amount of 20 parts by weight or more, and from the viewpoint of low heat generation, it is preferably 60 parts by weight or less. When silica is blended, the amount is preferably 20 parts by weight or less from the viewpoint of low heat build-up.
【０００８】さらに、本発明の製造方法において、ヒド
ラジド化合物と亜鉛華とは、同時に投入する必要がある
が、投入前に、予め、ブレンダー等で混合しておき、こ
の混合物を投入してもよい。また、本発明に好適に使用
できるジエン系合成ゴムは、特に制限されないが、溶液
重合または乳化重合スチレン・ブタジエンゴム、ブタジ
エンゴム等を例示できる。本願発明の製造方法の使用に
際しては、通常、ゴム業界で使用する他の配合剤、例え
ば、加硫促進剤、加硫促進助剤、老化防止剤等を適宜、
常法により配合でき、混練り後の加硫も、常法により行
うことができる。Furthermore, in the production method of the present invention, the hydrazide compound and zinc white need to be charged at the same time, but before the charging, they may be mixed in a blender or the like in advance, and then the mixture may be charged. . The diene-based synthetic rubber that can be suitably used in the present invention is not particularly limited, and examples thereof include solution-polymerized or emulsion-polymerized styrene-butadiene rubber, butadiene rubber, and the like. When using the production method of the present invention, other compounding agents usually used in the rubber industry, for example, a vulcanization accelerator, a vulcanization accelerator, an antioxidant, etc.
It can be compounded by a conventional method, and vulcanization after kneading can be performed by a conventional method.
【０００９】[0009]
【実施例】以下に、本発明を実施例に基づいて具体的に
説明する。表１記載のように、ゴム混練り工程を、３つ
の混練り工程に分けて、ゴム成分と各配合剤とを混練り
した。第３混練り工程で加硫剤である硫黄を投入してお
り、本発明の「加硫剤投入前のゴム混練り工程」は、第
１混練り工程、および第２混練り工程が相当する。製造
された各ゴム組成物を、全トレッド部に適用して、常法
により、１１Ｒ２２．５のタイヤを作成し、以下の方法
で性能を測定した。 ＜低発熱性の評価＞各タイヤについて、一定速度および
ステップロードの条件下でドラムテストを実施し、各例
のゴム組成物からなるトレッド内部の一定深さ位置での
温度を測定し、比較例１の値を１００とし、指数表示し
た。数値が低い程、タイヤ温度が低く、低発熱性である
ことを示す。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. As shown in Table 1, the rubber kneading step was divided into three kneading steps, and the rubber component and each compounding agent were kneaded. In the third kneading step, sulfur as a vulcanizing agent is introduced, and the “rubber kneading step before the introduction of the vulcanizing agent” of the present invention corresponds to the first kneading step and the second kneading step. . Each of the manufactured rubber compositions was applied to all tread portions, and 11R22.5 tires were prepared by a conventional method, and the performance was measured by the following method. <Evaluation of low heat build-up> For each tire, a drum test was performed under the conditions of constant speed and step load, and the temperature at a constant depth position inside the tread made of the rubber composition of each example was measured. The value of 1 was set to 100, and the result was indicated by an index. The lower the numerical value, the lower the tire temperature and the lower the heat generation.
【００１０】＜耐破壊性、耐テア性の評価＞各タイヤ
を、実地使用し、残溝３mmまでタイヤ走行させ、タイヤ
のゴム表面３０cm周長当たりのゴム欠落部分の面積を求
め、比較例１の値を１００として指数表示した。数値が
大きい程、欠落面積が広く、耐破壊性、耐テア性が劣る
ことを示す。<Evaluation of fracture resistance and tear resistance> Each tire was used in practice and the tire was run to the remaining groove of 3 mm, and the area of the rubber missing portion per 30 cm circumference of the rubber surface of the tire was determined. The index value was expressed as an index with the value of 100 as 100. The larger the numerical value, the larger the missing area, indicating that the fracture resistance and tear resistance are inferior.
【００１１】[0011]
【表１】 （注）使用したヒドラジドは、下記の化学式［化３］で
表される。[Table 1] (Note) The hydrazide used is represented by the following chemical formula [Chemical Formula 3].
【化３】 第３混練り工程の最高温度は、いずれの例も、１１０℃
である。 カーボンブラック：Ｎ２２０ 加硫促進剤：ノクセラーＮＳEmbedded image The maximum temperature of the third kneading step is 110 ° C. in each case.
It is. Carbon black: N220 Vulcanization accelerator: Noxeller NS
【００１２】上記の結果から、ヒドラジドを配合した比
較例１は、それを配合しない比較例５に比べて、低発熱
性、耐破壊性、耐ティア性について効果は得られている
が、各実施例は、比較例１に比べても、各性能について
総合的に改良されていることがわかる。From the results described above, Comparative Example 1 in which hydrazide was blended exhibited lower heat generation, breakage resistance and tear resistance than Comparative Example 5 in which hydrazide was not blended. It can be seen that the example is comprehensively improved in each performance as compared with Comparative Example 1.
【００１３】[0013]
【発明の効果】以上説明したように、本発明の製造方法
によると、確実に、ヒドラジド化合物の低発熱性の効果
を得ることができ、この方法によるゴム組成物をトレッ
ドに適用した空気入りタイヤは、従来品に比べ、格段に
優れた低発熱性、耐破壊性、耐ティア性を有する。As described above, according to the production method of the present invention, the effect of low heat build-up of the hydrazide compound can be surely obtained, and the pneumatic tire in which the rubber composition according to this method is applied to the tread. Has remarkably low heat build-up, breakage resistance, and tear resistance compared to conventional products.
Claims (4)
ゴムおよびジエン系合成ゴムのうち少なくとも１種から
なるゴム成分１００重量部に対して、下記の一般式〔化
１〕で表わされるヒドラジド化合物のうち少なくとも１
種を０．１〜５重量部と亜鉛華を０．２〜５重量部とを
同時に投入し、かつ最高温度を１３０℃〜１７０℃にし
て混練りすることを特徴とするゴム組成物の製造方法。 【化１】 （式中、Ｒ1 およびＲ2 は炭素数１〜１８のアルキル
基、シクロアルキル基、またはアリール基をそれぞれ独
立に表し、Ｏ、Ｎ、Ｓのうち少なくとも１種のヘテロ原
子を含んでいてもよい。）In a rubber kneading step before a vulcanizing agent is added, 100 parts by weight of a rubber component composed of at least one of natural rubber and diene-based synthetic rubber are represented by the following general formula [Chemical Formula 1]. At least one of the hydrazide compounds
0.1 to 5 parts by weight of seed and 0.2 to 5 parts by weight of zinc white at the same time, and kneading at a maximum temperature of 130 to 170 ° C. and kneading. Method. Embedded image (In the formula, R 1 and R 2 each independently represent an alkyl group, a cycloalkyl group, or an aryl group having 1 to 18 carbon atoms, and may include at least one hetero atom of O, N, and S. Good.)
クも投入、混練りし、その配合量は、ゴム成分１００重
量部に対して２０〜６０重量部であることを特徴とする
請求項１記載のゴム組成物の製造方法。2. The method according to claim 1, wherein carbon black is added and kneaded in the rubber kneading step, and the compounding amount is 20 to 60 parts by weight based on 100 parts by weight of the rubber component. A method for producing a rubber composition.
混練りし、その配合量は、ゴム成分１００重量部に対し
て２０重量部以下であることを特徴とする請求項１また
は２記載のゴム組成物の製造方法。3. In the rubber kneading step, silica is also introduced.
The method for producing a rubber composition according to claim 1 or 2, wherein the compounding amount is 20 parts by weight or less based on 100 parts by weight of the rubber component.
の製造方法で製造したゴム組成物をトレッドに適用した
ことを特徴とする空気入りタイヤ。4. A pneumatic tire, wherein a rubber composition produced by the production method according to claim 1 is applied to a tread.
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| JP35741299A JP4541475B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing rubber composition and rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP35741299A JP4541475B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing rubber composition and rubber composition |
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| JP2001172435A true JP2001172435A (en) | 2001-06-26 |
| JP4541475B2 JP4541475B2 (en) | 2010-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP35741299A Expired - Fee Related JP4541475B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing rubber composition and rubber composition |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7073549B2 (en) | 2001-06-29 | 2006-07-11 | Sumitomo Rubber Industries Ltd. | Bus or truck tire having cap/base tread |
| WO2009057418A1 (en) * | 2007-10-30 | 2009-05-07 | Bridgestone Corporation | Modified natural rubber, process for production of the same, and rubber composition and tire each comprising the same |
| WO2009104555A1 (en) * | 2008-02-18 | 2009-08-27 | 株式会社ブリヂストン | Modified diene rubber, method for producing the same, rubber composition using the same, and tire |
| CN101921434A (en) * | 2010-09-19 | 2010-12-22 | 无锡宝通带业股份有限公司 | Preparation method of core rubber for high-temperature-resistant steel mesh conveying belt |
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| JP2014005381A (en) * | 2012-06-25 | 2014-01-16 | Bridgestone Corp | Production method of rubber composition |
| CN104277230A (en) * | 2013-07-12 | 2015-01-14 | 东洋橡胶工业株式会社 | Method for producing rubber master batch |
| DE102014110591A1 (en) | 2013-07-29 | 2015-01-29 | Toyo Tire & Rubber Co., Ltd. | Process for the preparation of a rubber composition |
| JP2015221901A (en) * | 2011-01-19 | 2015-12-10 | ブリヂストン アメリカズ タイヤ オペレイションズ エルエルシー | Rubber composition suitable for use as cap ply in tire |
| US9920184B2 (en) | 2013-11-08 | 2018-03-20 | Toyo Tire & Rubber Co., Ltd. | Production method for rubber composition |
| US10087292B2 (en) | 2014-09-19 | 2018-10-02 | Bridgestone Corporation | Method for producing rubber composition, and rubber composition |
| WO2021132496A1 (en) * | 2019-12-27 | 2021-07-01 | 横浜ゴム株式会社 | Rubber composition, method for preparing same, and tire for construction vehicle |
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| WO2009057418A1 (en) * | 2007-10-30 | 2009-05-07 | Bridgestone Corporation | Modified natural rubber, process for production of the same, and rubber composition and tire each comprising the same |
| JP2009108204A (en) * | 2007-10-30 | 2009-05-21 | Bridgestone Corp | Modified natural rubber and method for manufacturing it, as well as rubber composition and tire by using it |
| CN102099380A (en) * | 2008-02-18 | 2011-06-15 | 株式会社普利司通 | Modified diene rubber, method for producing the same, rubber composition using the same, and tire |
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| JPWO2009104555A1 (en) * | 2008-02-18 | 2011-06-23 | 株式会社ブリヂストン | Modified diene rubber, method for producing the same, rubber composition and tire using the same |
| US8389641B2 (en) | 2008-02-18 | 2013-03-05 | Bridgestone Corporation | Modified diene rubber, production method thereof, and rubber composition and tire using the rubber |
| CN102099380B (en) * | 2008-02-18 | 2014-03-12 | 株式会社普利司通 | Modified diene rubber, method for producing same, rubber composition using same, and tire |
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| JP2014005381A (en) * | 2012-06-25 | 2014-01-16 | Bridgestone Corp | Production method of rubber composition |
| CN104277230A (en) * | 2013-07-12 | 2015-01-14 | 东洋橡胶工业株式会社 | Method for producing rubber master batch |
| JP2015025093A (en) * | 2013-07-29 | 2015-02-05 | 東洋ゴム工業株式会社 | Method for producing rubber composition |
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| JP2021107528A (en) * | 2019-12-27 | 2021-07-29 | 横浜ゴム株式会社 | Rubber composition, method for manufacturing the same, and construction vehicle tire |
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