JP2009167238A - Rubber composition and tire using the same - Google Patents

Rubber composition and tire using the same Download PDF

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JP2009167238A
JP2009167238A JP2008004007A JP2008004007A JP2009167238A JP 2009167238 A JP2009167238 A JP 2009167238A JP 2008004007 A JP2008004007 A JP 2008004007A JP 2008004007 A JP2008004007 A JP 2008004007A JP 2009167238 A JP2009167238 A JP 2009167238A
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rubber
rubber composition
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silane coupling
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JP5414182B2 (en
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Masahiro Hojo
将広 北條
Akira Tsufuku
亮 津布久
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Bridgestone Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition achieving both of hysteresis loss characteristics-improving effect and improvement of reinforcing property without causing deterioration of scorch time, and to provide a tire using the composition. <P>SOLUTION: The rubber composition contains (B) 10-140 pts.mass inorganic filler based on (A) 100 pts.mass natural rubber and/or diene synthetic rubber, and further contains (C) a silane coupling agent containing a thioester group in combination with (D) a silane coupling agent containing a thiol group regulated so that the molar ratio of the components (C)/(D) may be from 99/1 to 70/30, and the total content of the components (C) and (D) may be 1-20 mass% based on the component (B). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立したゴム組成物及びそれを用いたタイヤに関する。   The present invention relates to a rubber composition that achieves both an improvement effect of hysteresis loss characteristics and an improvement in reinforcement without causing deterioration of scorch time, and a tire using the rubber composition.

従来より、無機充填剤であるシリカを配合したゴム組成物は、転がり抵抗とウェット性能の改善に効果的であるため、多用されている。シリカを配合したゴム組成物において、転がり抵抗とウェット性能の改善を効果的に発揮させるためには、シランカップリング剤を配合すると共に、配合するシランカップリング剤の反応を高精度に制御することが必要とされている。   Conventionally, rubber compositions containing silica as an inorganic filler have been widely used because they are effective in improving rolling resistance and wet performance. In order to effectively improve rolling resistance and wet performance in a rubber composition containing silica, a silane coupling agent should be blended and the reaction of the blended silane coupling agent must be controlled with high accuracy. Is needed.

例えば、メルカプト官能基の水素原子が置換されている保護化メルカプトシラン(商品名:NXTシラン)のようなS1(化合物中の硫黄原子の数1個)のシランカップリング剤は、比較的高温域で混合が可能であり、且つ、シリカの分散性改良による配合ゴムのヒステリシスロス低減に優れるものである(例えば、特許文献1参照)。
しかしながら、補強性の観点からみると、ビス(トリエトキシシリルプロピル)テトラスルフィドのようなS4(化合物中の硫黄原子の数4個、例えば、商品名:Si69)のカップリング剤に対して劣ると言う問題点がある他、配合ゴムのヒステリシスロス低減についても、更なる改良が望まれているのが現状である。
For example, a silane coupling agent of S1 (number of sulfur atoms in a compound) such as protected mercaptosilane (trade name: NXT silane) in which a hydrogen atom of a mercapto functional group is substituted is a relatively high temperature range. And is excellent in reducing the hysteresis loss of the compounded rubber by improving the dispersibility of silica (see, for example, Patent Document 1).
However, from the viewpoint of reinforcement, it is inferior to the coupling agent of S4 (number of four sulfur atoms in the compound, for example, trade name: Si69) such as bis (triethoxysilylpropyl) tetrasulfide. In addition to the above-mentioned problems, the present situation is that further improvement is desired for reducing the hysteresis loss of the compounded rubber.

一方、保護化メルカプトシランの脱保護を促進し、シランカップリング剤を活性化させる方法としては、例えば、少なくとも一つのN−H結合を含んだアミン化合物を用いるもの(例えば、特許文献2参照)や、ジエン系ゴム100部に対し、シリカ10〜150部を密閉式の混合機で混合するに際し、特定の式で表わされるカップリング剤1〜20部とグアニジン基、スルフェンアミド基及びベンゾチアジル基の少なくとも一種の基を含む化合物0.5〜5部を同じ混合工程において混合するタイヤ用ゴム組成物及びその製法(例えば、特許文献3参照)が知られている。   On the other hand, as a method for accelerating the deprotection of protected mercaptosilane and activating the silane coupling agent, for example, an amine compound containing at least one NH bond is used (for example, see Patent Document 2). In addition, when mixing 10 to 150 parts of silica with 100 parts of diene rubber with a closed mixer, 1 to 20 parts of a coupling agent represented by a specific formula, a guanidine group, a sulfenamide group, and a benzothiazyl group There is known a tire rubber composition in which 0.5 to 5 parts of a compound containing at least one group is mixed in the same mixing step and a method for producing the same (for example, see Patent Document 3).

しかしながら、上記特許文献3に記載の化合物を用いると、スコーチタイムが大幅に低下してしまうという課題があり、また、上記特許文献1及び2では、加硫ゴムのヒステリシスロス特性向上効果が小さく、更に、上記特許文献3では、加硫ゴムにおけるシリカの分散性については何等記載されていないものである。
従って、無機充填剤であるシリカを配合したゴム組成物において、従来のシランカップリング剤ではスコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立できないのが現状ある。
特開2001−505225号公報(特許請求の範囲、実施例等) 国際公開WO2002/48256号公報(特許請求の範囲、実施例等) 特開2007−154130号公報(特許請求の範囲、実施例等)
However, when the compound described in Patent Document 3 is used, there is a problem that the scorch time is significantly reduced. In Patent Documents 1 and 2, the effect of improving the hysteresis loss characteristics of the vulcanized rubber is small. Furthermore, in the said patent document 3, nothing is described about the dispersibility of the silica in a vulcanized rubber.
Therefore, in a rubber composition containing silica as an inorganic filler, the conventional silane coupling agent is incapable of achieving both the improvement of the hysteresis loss characteristic and the improvement of the reinforcing property without causing deterioration of the scorch time.
JP 2001-505225 A (Claims, Examples, etc.) International Publication WO2002 / 48256 (Claims, Examples, etc.) JP 2007-154130 A (Claims, Examples, etc.)

本発明者は、上記従来の課題及び現状等に鑑み、これを解消しようとするものであり、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立したゴム組成物及びそれを用いたタイヤを提供することを目的とする。   The present inventor intends to solve this problem in view of the above-described conventional problems and the present situation, and has a rubber composition that achieves both an improvement in hysteresis loss characteristics and an improvement in reinforcement without incurring a deterioration in scorch time. And it aims at providing the tire using the same.

本発明者らは、上記従来の課題等について、鋭意検討した結果、天然ゴム及び/又はジエン系合成ゴム100質量部に対して、無機充填剤を10〜140質量部を含有し、更に特定のシランカップリング剤の2種を特定の比率で特定量を併用することにより、上記目的のゴム組成物及びそれを用いたタイヤが得られることを見い出し、本発明を完成するに至ったのである。   As a result of intensive studies on the above-described conventional problems, the present inventors contain 10 to 140 parts by mass of an inorganic filler with respect to 100 parts by mass of natural rubber and / or diene synthetic rubber, and further The inventors have found that the above-mentioned rubber composition and a tire using the same can be obtained by using a specific amount of two types of silane coupling agents in a specific ratio, and the present invention has been completed.

すなわち、本発明は、次の(1)〜(3)に存する。
(1) (A)天然ゴム及び/又はジエン系合成ゴム100質量部に対して、(B)無機充填剤10〜140質量部を含有し、更に下記一般式(I)で表される(C)シランカップリング剤と下記一般式(II)で表される(D)シランカップリング剤とをモル比(C)成分/(D)成分で99/1〜70/30の割合で併用し、かつ、(C)成分と(D)成分の合計含有量が(B)成分に対して1〜20質量%であることを特徴とするゴム組成物。

Figure 2009167238
Figure 2009167238
(2) 前記(B)成分の無機充填剤がシリカである上記(1)に記載のゴム組成物。
(3) 上記(1)又は(2)に記載のゴム組成物を用いたことを特徴とするタイヤ。 That is, the present invention resides in the following (1) to (3).
(1) (A) 10 to 140 parts by mass of (B) inorganic filler with respect to 100 parts by mass of natural rubber and / or diene synthetic rubber, and further represented by the following general formula (I) (C ) The silane coupling agent and the (D) silane coupling agent represented by the following general formula (II) are used in a molar ratio (C) component / (D) component in a ratio of 99/1 to 70/30, And the rubber content characterized by the total content of (C) component and (D) component being 1-20 mass% with respect to (B) component.
Figure 2009167238
Figure 2009167238
(2) The rubber composition according to (1), wherein the inorganic filler of the component (B) is silica.
(3) A tire using the rubber composition according to (1) or (2).

本発明によれば、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立したゴム組成物及びそれを用いたタイヤが提供される。   ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which improved the hysteresis loss characteristic improvement effect and reinforcement | strengthening property, and the tire using the same are provided, without causing deterioration of scorch time.

以下に、本発明の実施形態を詳しく説明する。
本発明のゴム組成物は、(A)天然ゴム及び/又はジエン系合成ゴム100質量部に対して、(B)無機充填剤0〜140質量部を含有し、更に下記一般式(I)で表される(C)シランカップリング剤と下記一般式(II)で表される(D)シランカップリング剤とをモル比(C)成分/(D)成分で99/1〜70/30の割合で併用し、かつ、(C)成分と(D)成分の合計含有量が(B)成分に対して1〜20質量%であることを特徴とするものである。

Figure 2009167238
Figure 2009167238
Hereinafter, embodiments of the present invention will be described in detail.
The rubber composition of the present invention contains (B) an inorganic filler in an amount of 0 to 140 parts by mass with respect to 100 parts by mass of (A) natural rubber and / or diene synthetic rubber, and is further represented by the following general formula (I). The (C) silane coupling agent represented and the (D) silane coupling agent represented by the following general formula (II) are 99/1 to 70/30 in a molar ratio (C) component / (D) component. It is used in combination at a ratio, and the total content of the component (C) and the component (D) is 1 to 20% by mass with respect to the component (B).
Figure 2009167238
Figure 2009167238

本発明に用いるゴム成分(A)としては、天然ゴム及び/又はジエン合成系ゴムが用いられ、例えば、天然ゴム、シス−1,4−ポリイソプレン、スチレン−ブタジエン共重合体、低シス−1,4−ポリブタジエン、イソプレン、高シス−1,4−ポリブタジエン、エチレン−プロピレン−ジエン共重合体、クロロプレンゴム、ハロゲン化ブチルゴム、アクリロニトリル−ブタジエンゴム等の少なくとも1種を使用することができる。   As the rubber component (A) used in the present invention, natural rubber and / or diene synthetic rubber is used. For example, natural rubber, cis-1,4-polyisoprene, styrene-butadiene copolymer, low cis-1 , 4-polybutadiene, isoprene, high cis-1,4-polybutadiene, ethylene-propylene-diene copolymer, chloroprene rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber and the like can be used.

本発明に用いる無機充填剤としては、例えば、シリカ、カーボンブラック、アミノケイ酸、ゼオライト、クレー、シリカが固定化されたカーボンブラック等を用いることができる。
好ましくは、シリカの使用が望ましく、沈降法によるシリカが好ましく用いられる。シリカは、特にBET比表面積が40〜350m/g、70〜300m/gであるものが望ましい。このようなシリカとしては、市販では東ソーシリカ社製の「ニップシールVN3」、「ニップシルAQ」、「ニプシルKQ」や、デグサ社製の「Ultrasil UN3」、「Ultrasil 7000GR」などを挙げることができるが、これらに限定されるものではない。更に好ましくは、上記のシリカが含まれれば、ゴム用無機充填剤として使用されるカーボンブラックを併用することもできる。
As the inorganic filler used in the present invention, for example, silica, carbon black, aminosilicic acid, zeolite, clay, carbon black on which silica is fixed can be used.
Preferably, the use of silica is desirable, and silica by precipitation is preferably used. Silica, especially BET specific surface area of 40~350m 2 / g, it it is desirable in 70~300m 2 / g. Examples of such silica include “Nippal VN3”, “Nipsil AQ”, “Nipsil KQ” manufactured by Tosoh Silica Co., “Ultrasil UN3”, “Ultrasil 7000GR” manufactured by Degussa, and the like. However, it is not limited to these. More preferably, if the silica is contained, carbon black used as an inorganic filler for rubber can be used in combination.

これらの(B)成分である無機充填剤の合計含有量は、ゴム成分100質量部に対して、10〜140質量部、好ましくは、20〜100質量部、更に好ましくは、25〜80質量部であることが望ましい。
この(B)無機充填剤の含有量が10質量部未満であると、無機充填剤を含有せしめる効果がなく、補強性が著しく低下し、一方、140質量部を越えると、無機充填剤同士の凝集などで分散が極度に悪化することとなる。
The total content of the inorganic filler as the component (B) is 10 to 140 parts by weight, preferably 20 to 100 parts by weight, more preferably 25 to 80 parts by weight with respect to 100 parts by weight of the rubber component. It is desirable that
When the content of the inorganic filler (B) is less than 10 parts by mass, there is no effect of containing the inorganic filler, and the reinforcing property is remarkably lowered. On the other hand, when the content exceeds 140 parts by mass, Dispersion is extremely deteriorated due to aggregation.

本発明に用いるシランカップリング剤は、下記一般式(I)で表される(C)シランカップリング剤と下記一般式(II)で表される(D)シランカップリング剤とが併用される。

Figure 2009167238
Figure 2009167238
As the silane coupling agent used in the present invention, (C) a silane coupling agent represented by the following general formula (I) and (D) a silane coupling agent represented by the following general formula (II) are used in combination. .
Figure 2009167238
Figure 2009167238

具体的に用いることができる(C)成分のシランカップリング剤としては、例えば、上記式(I)中、A、B、Dがエトキシ基であり、Xがプロピレン基であり、Xがヘプチル基である3−オクタノイルチオ−1−プロピルトリエトキシシラン、上記式(I)中、Aがエトキシ基であり、Bはなし、Dが2−メチル−1,3−プロパンジアルコキシ基であり、Xがプロピレン基であり、Xがヘプチル基である3−(2−メチル−1,3−プロパンジアルコキシエトキシシリル)−1−プロピルチオオクタノエート、上記式(I)中、A、、B、Dがエトキシ基であり、Xがプロピレン基であり、Xがヘプタテシル基である3−オクタノイルチオ−1−プロピルトリエトキシシランなどの少なくとも1種が挙げられる。
市販では、例えば、モメンティブ パーフォーマンス マテリアルズ社製の「NXT シラン」、「NXT−Low−V シラン」、「NXT Ultra Low−V シラン」などを挙げることができるが、これらに限定されるものではない。
Specific examples of the silane coupling agent of component (C) that can be used include, in the above formula (I), A, B, and D are ethoxy groups, X is a propylene group, and X 1 is heptyl. 3-octanoylthio-1-propyltriethoxysilane, which is a group, wherein A is an ethoxy group, B is none, D is a 2-methyl-1,3-propane dialkoxy group, and X is a propylene group, X 1 is a heptyl group 3- (2-methyl-1,3-propane dialkoxy triethoxysilyl) -1-propyl thio octanoate, in the above formula (I), a ,, B, Examples include at least one such as 3-octanoylthio-1-propyltriethoxysilane, in which D is an ethoxy group, X is a propylene group, and X 1 is a heptathecil group.
Examples of commercially available products include “NXT silane”, “NXT-Low-V silane”, and “NXT Ultra Low-V silane” manufactured by Momentive Performance Materials, but are not limited thereto. Absent.

また、(D)成分のシランカップリング剤としては、例えば、上記式(II)中、上記式(II)中、A、Bがエトキシ基、Dがメチル基であり、Xがプロピレン基である3−メルカプトプロピルジエトキシメチルシラン、上記式(II)中、A、Bがメチル基、Dがエトキシ基であり、Xがプロピレン基である3−メルカプトプロピルエトキシジメチルシランなどの少なくとも1種が挙げられる。
市販では、例えば、東京化成工業社製の3−メルカプトプロピルトリエトキシシラン、信越化学工業社製の商品名「KBM803」、「KBM802」、デグザ社製の商品名「VP Si363」などを挙げることができるが、これらに限定されるものではない。
Examples of the silane coupling agent of component (D) include, for example, in the above formula (II), in the above formula (II), A and B are ethoxy groups, D is a methyl group, and X is a propylene group. 3-mercaptopropyldiethoxymethylsilane, and at least one of 3-mercaptopropylethoxydimethylsilane in which A and B are methyl groups, D is an ethoxy group, and X is a propylene group in the above formula (II) It is done.
Examples of commercially available products include 3-mercaptopropyltriethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd., trade names “KBM803” and “KBM802” manufactured by Shin-Etsu Chemical Co., Ltd., and product names “VP Si363” manufactured by Degussa. However, it is not limited to these.

これらのシランカップリング剤の併用率、含有量は、モル比(C)成分/(D)成分で99/1〜70/30の割合で併用し、かつ、(C)成分と(D)成分の合計含有量が(B)成分に対して1〜20質量%である。
好ましくは、モル比(C)成分/(D)成分で97/3〜80/20の割合で併用し、(C)成分と(D)成分の合計含有量が(B)成分に対して3〜15質量%とすることが望ましい。
これらのシランカップリング剤の併用率がモル比(C)成分/(D)成分で99/1未満では、所望の効果が得られず、一方、70/30を超える併用率では、混合押し出しの工程で焼け(スコーチ)が生じ易くなり、好ましくない。
また、これらのシランカップリング剤の合計含有量が(B)成分に対して1質量%では、加工性や耐摩耗性を確保することが難しく、一方、20質量%を超えても、所望の効果が得られず、好ましくない。
The combined ratio and content of these silane coupling agents are used in a molar ratio (C) component / (D) component in a ratio of 99/1 to 70/30, and (C) component and (D) component. The total content of 1 to 20% by mass with respect to the component (B).
Preferably, the molar ratio (C) component / (D) component is used in a ratio of 97/3 to 80/20, and the total content of (C) component and (D) component is 3 with respect to (B) component. It is desirable to set it to -15 mass%.
When the combined ratio of these silane coupling agents is less than 99/1 in terms of the molar ratio (C) component / (D) component, the desired effect cannot be obtained, whereas when the combined ratio exceeds 70/30, mixed extrusion is not possible. Burning (scorch) is likely to occur in the process, which is not preferable.
In addition, when the total content of these silane coupling agents is 1% by mass with respect to the component (B), it is difficult to ensure workability and wear resistance. An effect is not acquired and it is not preferable.

本発明のゴム組成物には、上記ゴム成分、無機充填剤、シランカップリング剤2種の他に、ゴム業界で通常使用される配合剤を本発明の効果を阻害しない範囲で用いることができ、例えば、軟化剤、老化防止剤、加硫剤、加硫促進剤などを用途に応じて適宜配合することができる。   In the rubber composition of the present invention, in addition to the above rubber component, inorganic filler and silane coupling agent, compounding agents usually used in the rubber industry can be used as long as the effects of the present invention are not impaired. For example, a softener, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator and the like can be appropriately blended depending on the use.

本発明のゴム組成物は、上記各成分を、例えば、バンバリーミキサー、ニーダー等により混練りすることにより製造することができ、乗用車、トラック、バス、二輪車用等のタイヤのトレッド等、ほーす、ベルトアンドのゴム製品に好適に使用できる。
また、本発明のゴム組成物を用いてタイヤを製造する場合は、例えば、押し出し機カレンダー等により混練して押し出すことによってタイヤトレッド用ゴムを作製し、これらを成型ドラム上で他の部材と張り合わせること等でグリーンタイヤを作製し、このグリーンタイヤをタイヤモールドに収め、内側から圧を加えながら加硫する方法などにより行うことができる。また、本発明のタイヤの内部には、空気の他に窒素や不活性ガスを充填することができる。
The rubber composition of the present invention can be produced by kneading the above-mentioned components with, for example, a Banbury mixer, a kneader, etc., such as tire treads for passenger cars, trucks, buses, motorcycles, etc. It can be suitably used for belt-and-rubber products.
In the case of producing a tire using the rubber composition of the present invention, for example, a rubber for a tire tread is prepared by kneading and extruding with an extruder calendar or the like, and these are laminated with other members on a molding drum. Thus, a green tire can be produced by placing the green tire in a tire mold and vulcanizing while applying pressure from the inside. Further, the tire of the present invention can be filled with nitrogen or inert gas in addition to air.

このように構成される本発明では、(A)天然ゴム及び/又はジエン系合成ゴム100質量部に対して、(B)無機充填剤10〜140質量部を含有し、更に下記一般式(I)で表される(C)シランカップリング剤と下記一般式(II)で表される(D)シランカップリング剤とをモル比(C)成分/(D)成分で99/1〜70/30の割合で併用し、かつ、(C)成分と(D)成分の合計含有量が(B)成分に対して1〜20質量%含有せしめることにより、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立した上で、ウェット性能の更なる向上及び低い転がり抵抗を有するゴム組成物及びそれを用いたタイヤが得られることとなる。   In this invention comprised in this way, it contains 10-140 mass parts of (B) inorganic filler with respect to 100 mass parts of (A) natural rubber and / or diene type synthetic rubber, and also the following general formula (I) ) And (D) silane coupling agent represented by the following general formula (II) in a molar ratio (C) component / (D) component of 99/1 to 70 / Hysteresis without causing deterioration of the scorch time, when used in combination at a ratio of 30 and the total content of the component (C) and the component (D) is 1 to 20% by mass with respect to the component (B). A rubber composition having a further improvement in wet performance and a low rolling resistance and a tire using the rubber composition can be obtained while achieving both an improvement in loss characteristics and an improvement in reinforcement.

次に、本発明を実施例及び比較例に基づいて更に詳述するが、本発明は、これらの実施例に何ら限定されるものではない。   Next, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.

〔実施例1〜6及び比較例1〜4〕
下記表1〜4に示す配合処方のゴム組成物をバンバリーミキサーにて混練した。
得られた各ゴム組成物について、下記方法で未加硫物性となるスコーチタイムを測定し、加工安定性について評価した。
また、得られた各ゴム組成物を厚さ約2cmのシート状にした後、171℃で15分間プレス加硫した。この組成物について下記各方法にて加硫物性となる動的粘弾性試験(tanδ)、耐摩耗性について評価した。
これらの結果を下記表1〜4に示す。
[Examples 1 to 6 and Comparative Examples 1 to 4]
The rubber compositions having the formulation shown in Tables 1 to 4 below were kneaded with a Banbury mixer.
About each obtained rubber composition, the scorch time used as the unvulcanized physical property was measured by the following method, and processing stability was evaluated.
Further, each rubber composition obtained was formed into a sheet having a thickness of about 2 cm, and then press vulcanized at 171 ° C. for 15 minutes. The composition was evaluated for the dynamic viscoelasticity test (tan δ) and abrasion resistance, which are vulcanized physical properties by the following methods.
These results are shown in Tables 1 to 4 below.

(スコーチタイムの測定方法)
JIS K 6300−1:2001に準拠し、配合したゴム組成物を130℃で測定し、余熱を始めてからの値が最低値Vmより5単位上昇するまでの時間を測定した。
測定値は、各表の比較例の値を100として指数表示した。ムニースコーチタイムは、値が大きい程、加工安定性が良いことを示す。
(Scorch time measurement method)
In accordance with JIS K 6300-1: 2001, the blended rubber composition was measured at 130 ° C., and the time from the start of preheating until the value rose by 5 units from the minimum value Vm was measured.
The measured values were displayed as an index with the value of the comparative example in each table as 100. As the Moony coach time is larger, the processing stability is better.

〔動的粘弾性試験(tanδ)〕
上島製作所社製、スペクトロメーター(動的粘弾性動的粘弾性試験機)を用い、周波数52Hz、初期歪10%、測定温度60℃、動歪1%で測定し、tanδ(損失係数)の数値を、各表の比較例の値を100として指数表示した。tanδの指数値が小さいほど低発熱性であることを示す。
[Dynamic viscoelasticity test (tan δ)]
Using a spectrometer (dynamic viscoelastic dynamic viscoelasticity tester) manufactured by Ueshima Seisakusho Co., Ltd., measured at a frequency of 52 Hz, initial strain of 10%, measurement temperature of 60 ° C., dynamic strain of 1%, and a numerical value of tan δ (loss coefficient) Was expressed as an index with the value of the comparative example in each table as 100. A smaller index value of tan δ indicates a lower exothermic property.

(耐磨耗性の評価方法)
JIS K 6264−2:2005に準拠し、ランボーン摩耗試験機を用いて、室温下でスリップ率25%の条件で試験を行い、摩耗量の逆数を、各表の比較例を100として指数表示した。数値は大きいほど、耐摩耗性が良好であることを示す。
(Abrasion resistance evaluation method)
In accordance with JIS K 6264-2: 2005, a test was conducted using a Lambourne abrasion tester under the condition of a slip rate of 25% at room temperature, and the reciprocal of the abrasion amount was indicated as an index with the comparative example of each table as 100. . It shows that abrasion resistance is so favorable that a numerical value is large.

Figure 2009167238
Figure 2009167238

Figure 2009167238
Figure 2009167238

Figure 2009167238
Figure 2009167238

Figure 2009167238
Figure 2009167238

上記表1〜4の結果から明らかなように、本発明範囲となる実施例1〜6は、本発明の範囲外となる比較例1〜4に比べて、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果と補強性の向上を両立できることが判った。
本発明では、(C)成分のシランカップリング剤と(D)成分のメルカプト系シランカップリング剤とを特定の割合で併用を行うと、スコーチタイムの悪化を招くことなく、ヒステリシスロス特性向上効果の他、補強性も向上することができることが証明されることとなった。従来では、特許文献(FR−A−2094859号公報)に記載されるように、一般にメルカプト系シランを用いると、早期加硫(スコーチ)により加工性を著しく悪化してしまうが、メルカプト系シランの使用量等を調節することにより、加工性の悪化を回避できることが明らかとなった。
As is clear from the results of Tables 1 to 4, Examples 1 to 6, which are the scope of the present invention, are not compared with Comparative Examples 1 to 4 that are outside the scope of the present invention, without incurring deterioration of the scorch time. It was found that the hysteresis loss characteristic improving effect and the reinforcing property can be improved at the same time.
In the present invention, when the silane coupling agent of component (C) and the mercapto silane coupling agent of component (D) are used in a specific ratio, the effect of improving the hysteresis loss characteristic is brought about without deteriorating the scorch time. In addition, it was proved that the reinforcing property can be improved. Conventionally, as described in a patent document (FR-A-2094859), when a mercapto silane is generally used, workability is significantly deteriorated due to early vulcanization (scorch). It became clear that deterioration of workability can be avoided by adjusting the amount used.

本発明では、乗用車、トラック、バス、二輪車用等のタイヤのトレッド等に好適に使用できるゴム組成物及びそれを用いたタイヤが得られる。   In the present invention, a rubber composition that can be suitably used for treads of tires for passenger cars, trucks, buses, motorcycles, and the like and tires using the same are obtained.

Claims (3)

(A)天然ゴム及び/又はジエン系合成ゴム100質量部に対して、(B)無機充填剤10〜140質量部を含有し、更に下記一般式(I)で表される(C)シランカップリング剤と下記一般式(II)で表される(D)シランカップリング剤とをモル比(C)成分/(D)成分で99/1〜70/30の割合で併用し、かつ、(C)成分と(D)成分の合計含有量が(B)成分に対して1〜20質量%であることを特徴とするゴム組成物。
Figure 2009167238
Figure 2009167238
(A) 100 parts by mass of natural rubber and / or diene-based synthetic rubber, (B) 10 to 140 parts by mass of inorganic filler, and further represented by the following general formula (I) (C) Silane cup A ring agent and a (D) silane coupling agent represented by the following general formula (II) are used in a molar ratio (C) component / (D) component in a ratio of 99/1 to 70/30, and ( The rubber composition, wherein the total content of component (C) and component (D) is 1 to 20% by mass relative to component (B).
Figure 2009167238
Figure 2009167238
前記(B)成分の無機充填剤がシリカである請求項1に記載のゴム組成物。   The rubber composition according to claim 1, wherein the inorganic filler of the component (B) is silica. 請求項1又は2に記載のゴム組成物を用いたことを特徴とするタイヤ。   A tire using the rubber composition according to claim 1.
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