JP2006232916A - Rubber composition for tire tread - Google Patents
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本発明はタイヤトレッド用ゴム組成物に関し、更に詳しくはシリカと特定のシランカップリング剤との反応生成物を含む、氷上性能を損なうことなく、ウェット性能及びタイヤ耐久性を改良することができるタイヤトレッド用ゴム組成物及びそれをキャップトレッド部に用いた空気入りタイヤに関する。 The present invention relates to a rubber composition for a tire tread, and more specifically, a tire including a reaction product of silica and a specific silane coupling agent, which can improve wet performance and tire durability without impairing performance on ice. The present invention relates to a rubber composition for a tread and a pneumatic tire using the rubber composition for a cap tread portion.
スタッドレスタイヤの分野では、氷上性能向上のため、低温でも十分低い硬度を示す天然ゴム（ＮＲ）／ポリブタジエンゴム（ＢＲ）の配合が好んで用いられ、これにオイルや可塑剤を多量に配合することが行われている。しかしながら、ＢＲを配合すること及び低硬度であることのために、ウェット性能は十分であるとは言いがたかった。そこで、ウェット性能向上のためにシリカを配合することが好まれるが（例えば特許文献１及び２参照）、シリカを配合するとムーニースコーチが早くなるなどの加工性の悪化を招く場合がある。 In the field of studless tires, natural rubber (NR) / polybutadiene rubber (BR), which has a sufficiently low hardness even at low temperatures, is preferably used to improve performance on ice, and a large amount of oil or plasticizer should be added to this. Has been done. However, due to the blending of BR and low hardness, it was difficult to say that the wet performance was sufficient. Therefore, it is preferred to add silica for improving wet performance (see, for example, Patent Documents 1 and 2). However, when silica is added, workability may be deteriorated such that Mooney scorch is accelerated.
氷上性能の改良のために、熱膨張カプセルや発泡剤を配合してゴム中に中空部位を作ることによって吸水効果を狙う方法も提案されているが（例えば特許文献３参照）、これらは中空部位を有するために、耐摩耗性低下やスタッドレスタイヤ特有のサイプが多いブロックパターンに起因してサイプ底にクラックが発生しやすく、耐久性の悪化を招くという問題がある。 In order to improve the performance on ice, a method of aiming at a water absorption effect by blending a thermally expandable capsule or a foaming agent to create a hollow portion in rubber has also been proposed (see, for example, Patent Document 3). Therefore, there is a problem in that cracks are likely to occur at the bottom of the sipe due to a decrease in wear resistance and a block pattern having many sipe unique to studless tires, leading to deterioration of durability.
従って、本発明は、前述の従来技術の問題点を改善して、氷上性能を損なうことなく、ウェット性能向上とタイヤ耐久性向上を達成しうるタイヤトレッド用ゴム組成物を得ることを目的とする。 Accordingly, an object of the present invention is to obtain a rubber composition for a tire tread that can improve the wet performance and the tire durability without impairing the performance on ice, by improving the above-described problems of the prior art. .
本発明に従えば、天然ゴム（ＮＲ）又は天然ゴム（ＮＲ）／ポリブタジエンゴム（ＢＲ）を含むゴム分１００重量部、式：
Ｙ3ＳｉＣ3Ｈ6ＳＣ（＝Ｏ）Ｒ
（式中、Ｙは独立にメトキシ、エトキシ、プロポキシ、イソプロポキシ、イソブトキシ、アセトキシ又はオキサマート基を示し、Ｒは環式又は分岐アルキル基、アルケニル基、アリール基及びアラルキル基から選ばれるＣ1〜Ｃ18の炭化水素基を示す。）
で表される少なくとも１種のシランカップリング剤Ｘとシリカとの反応生成物であって、その反応量がシリカ重量に対しシランカップリング剤Ｘが１〜２５重量％である反応生成物１０〜３０重量部並びに平均粒径Ｄ５０が３〜１５μｍでアスペクト比が１０〜２５のウォラストナイト３〜７重量部を含んでなる０℃のＪＩＳ硬度が５２以下であるタイヤトレッド用ゴム組成物及びそれをキャップトレッドに用いた空気入りタイヤが提供される。
According to the present invention, natural rubber (NR) or natural rubber (NR) / polybutadiene rubber (BR) containing 100 parts by weight of rubber, formula:
Y 3 SiC 3 H 6 SC (═O) R
(In the formula, Y independently represents a methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, acetoxy or oxamate group, and R represents a C 1 to C selected from a cyclic or branched alkyl group, an alkenyl group, an aryl group and an aralkyl group. 18 hydrocarbon groups are shown.)
A reaction product of at least one silane coupling agent X and silica represented by the formula: wherein the reaction amount is 10 to 25% by weight of the silane coupling agent X with respect to the silica weight. A rubber composition for tire treads having a JIS hardness of 52 or less and a JIS hardness of 52 or less, comprising 30 parts by weight and 3-7 parts by weight of wollastonite having an average particle diameter D50 of 3-15 μm and an aspect ratio of 10-25 A pneumatic tire using a cap tread is provided.
本発明によればＮＲ又はＮＲ／ＢＲ系のゴム組成物において、シリカを特定のシランカップリング剤Ｘで処理したシランカップリング剤処理シリカ及び特定のウォラストナイトを配合することによって、氷上性能を損なうことなく、ウェット性能及びタイヤ耐久性の更なる改良が達成できる。 According to the present invention, in a rubber composition based on NR or NR / BR, the performance on ice can be improved by blending a silane coupling agent-treated silica obtained by treating silica with a specific silane coupling agent X and a specific wollastonite. Further improvements in wet performance and tire durability can be achieved without loss.
空気入りタイヤのウェット性能向上の方法として、ヒステリシス摩擦向上や凝着摩擦向上が効果があるらしいことが分かってきており、本発明者は、凝着摩擦の向上を図るために、低温時の貯蔵弾性率（Ｅ’）を低下させるべく、特定のシランカップリング剤で処理したシリカを配合することを検討した。その結果、シリカ配合に比して、特定のシランカップリング剤で処理した処理シリカ配合ではムーニースコーチが早くなることはなく、さらにシリカ配合よりもＥ’を低下させることができることから、加工性の悪化を引き起こすことなく、シリカ配合以上のウェット性能の向上が達成できることと見出した。また前記シランカップリング剤処理シリカとウォラストナイトとを組合せて配合することにより、耐クラック性を向上させることもでき、サイプ欠損を大幅に低減することができ、耐久性の向上も図ることができることを見出した。 As a method of improving the wet performance of pneumatic tires, it has been found that hysteresis friction improvement and adhesion friction improvement seem to be effective, and the present inventor has proposed that storage at low temperatures is performed in order to improve adhesion friction. In order to lower the elastic modulus (E ′), it was studied to blend silica treated with a specific silane coupling agent. As a result, the Mooney scorch is not accelerated in the treated silica compound treated with a specific silane coupling agent compared to the silica compound, and E 'can be lowered more than in the silica compound. It has been found that the wet performance can be improved more than silica blending without causing deterioration. Also, by combining the silane coupling agent-treated silica and wollastonite, crack resistance can be improved, sipe defects can be greatly reduced, and durability can be improved. I found out that I can do it.
即ち、本発明は、ＮＲ又はＮＲ／ＢＲを含むタイヤ用ゴム組成物において、下記式で表される少なくとも１種のシランカップリング剤Ｘとシリカとを、シリカ重量に対し１〜２５重量％（好ましくは５〜２０重量％）の反応量で反応させて得られる反応生成物１０〜３０重量部（好ましくは１５〜２５重量部）並びに平均粒径Ｄ５０が３〜１５μｍ（好ましくは５〜１５μｍ）でアスペクト比が１０〜２５（好ましくは１０〜２０）のウォラストナイト３〜７重量部を配合することによって得られる、０℃のＪＩＳ硬度が５２以下（好ましくは４８〜５２）であるタイヤトレッド用ゴム組成物に関する。 That is, the present invention relates to a tire rubber composition containing NR or NR / BR, wherein at least one silane coupling agent X represented by the following formula and silica are contained in an amount of 1 to 25% by weight based on the silica weight ( 10 to 30 parts by weight (preferably 15 to 25 parts by weight) of a reaction product obtained by reacting with a reaction amount of preferably 5 to 20% by weight) and an average particle diameter D50 of 3 to 15 μm (preferably 5 to 15 μm) Tire tread having a JIS hardness of 52 or less (preferably 48 to 52) obtained by blending 3 to 7 parts by weight of wollastonite having an aspect ratio of 10 to 25 (preferably 10 to 20) The present invention relates to a rubber composition.
シランカップリング剤Ｘ
Ｙ3ＳｉＣ3Ｈ6ＳＣ（＝Ｏ）Ｒ
（式中、Ｙは独立にメトキシ、エトキシ、プロポキシ、イソプロポキシ、イソブトキシ、アセトキシ及びオキサマート基、の中から選ぶことができ、Ｒは環式又は分岐アルキル基、アルケニル基、アリール基及びアラルキル基から選ばれるＣ1〜Ｃ18の炭化水素基を示す。）
Silane coupling agent X
Y 3 SiC 3 H 6 SC (═O) R
Wherein Y can be independently selected from methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, acetoxy and oxamate groups, and R can be selected from cyclic or branched alkyl groups, alkenyl groups, aryl groups and aralkyl groups. (C 1 -C 18 hydrocarbon group selected)
本発明に従ったゴム組成物に配合されるゴム分としては、天然ゴム又は天然ゴムと各種ポリブタジエンのブレンドをあげることができ、ＮＲ／ＢＲブレンド比には特に限定はないが、ＢＲの割合がゴム分合計量の８０重量％以下であることが好ましい。なお、ＮＲ，ＢＲ以外のゴムも必要に応じ少量成分として配合することができる。 The rubber component blended in the rubber composition according to the present invention can include natural rubber or a blend of natural rubber and various polybutadienes, and the NR / BR blend ratio is not particularly limited. It is preferably 80% by weight or less of the total rubber content. In addition, rubbers other than NR and BR can be blended as a minor component as required.
前記一般式で表わされるシランカップリング剤Ｘは公知の化合物であり、シランカップリング剤として、例えばＧＥ東芝シリコーン（株）より３−オクタノイルチオプロピルトリエトキシシランなどとして市販されており、本発明においてもこれらを使用することができる。本発明によれば、予じめタイヤ配合用として使用できる任意のシリカをこのシランカップリング剤Ｘ（シリカ重量の１〜２５重量％）と反応させて（シリカの水酸基とシランカップリング剤Ｘのエトキシ基とが反応する）、ゴム組成物に配合する。この反応は、例えば乾式反応法としてヘンシェルミキサーなどの高速撹拌可能な装置にシリカ粒子を仕込み、撹拌しながらシランカップリング剤を滴下する方法によって容易に実施することができる。反応に使用するシランカップリング剤Ｘの量が少な過ぎると充分な表面処理量が得られないので好ましくなく、逆に多過ぎると表面処理が均一に行われずゴム中への分散性や加工性が十分でなくなるので好ましくない。シランカップリング剤Ｘで処理したシリカの配合量が少な過ぎるとＥ’の低減効果が小さく氷上制動、ウェット性能が良化しないので好ましくなく、逆に多過ぎるとＥ’の低減効果はあるものの、硬度も大きく低下してしまうので好ましくない。 The silane coupling agent X represented by the above general formula is a known compound, and is commercially available as, for example, 3-octanoylthiopropyltriethoxysilane from GE Toshiba Silicone, as a silane coupling agent. These can also be used in According to the present invention, any silica that can be used for pre-mixing tires is reacted with the silane coupling agent X (1 to 25% by weight of the silica weight) (the hydroxyl group of silica and the silane coupling agent X). It reacts with the ethoxy group) and is added to the rubber composition. This reaction can be easily carried out by, for example, a dry reaction method in which silica particles are charged in an apparatus capable of high-speed stirring such as a Henschel mixer and the silane coupling agent is dropped while stirring. If the amount of the silane coupling agent X used in the reaction is too small, it is not preferable because a sufficient surface treatment amount cannot be obtained. Conversely, if the amount is too large, the surface treatment is not uniformly performed and dispersibility in rubber and workability are poor. This is not preferable because it is not sufficient. If the amount of silica treated with the silane coupling agent X is too small, the effect of reducing E ′ is small, so it is not preferable because braking on ice and wet performance are not improved. Conversely, if too much, there is an effect of reducing E ′. This is not preferable because the hardness is greatly reduced.
本発明に従えば、前記ゴム組成物に平均粒径Ｄ５０（即ち粒径加積曲線から、通過重量百分率が５０％に対する粒径）が３〜１５μｍ、好ましくは５〜１５μｍで、アスペクト比（即ち長軸と短軸の比）が１０〜２５、好ましくは１０〜２０のウォラストナイトを、ゴム成分１００重量部に対し、３〜７重量部配合する。ウォラストナイトの平均粒径Ｄ５０が小さ過ぎると、耐久性向上など補強性の効果が得られないので好ましくなく、逆に大き過ぎると分散性が悪化し、結果として耐久性を悪化させるので好ましくない。ウォラストナイトのアスペクト比が小さ過ぎると耐久性向上など補強性の効果が得られないので好ましくなく、逆に大き過ぎると分散性が悪化し、結果として耐久性を悪化させるので好ましくない。ウォラストナイトの配合量が少な過ぎると耐久性向上など補強性の効果が得られないので好ましくなく、逆に多過ぎると分散性が悪化し、結果として、耐久性を悪化させるので好ましくない。 According to the present invention, the rubber composition has an average particle diameter D50 (that is, a particle diameter with respect to a passing weight percentage of 50% from the particle diameter accumulation curve) of 3 to 15 μm, preferably 5 to 15 μm, and an aspect ratio (that is, 3-7 parts by weight of wollastonite having a ratio of major axis to minor axis) of 10 to 25, preferably 10 to 20 is blended with respect to 100 parts by weight of the rubber component. If the average particle diameter D50 of wollastonite is too small, it is not preferable because the effect of reinforcing properties such as durability improvement cannot be obtained. Conversely, if it is too large, dispersibility deteriorates, and as a result, durability deteriorates. . If the wollastonite aspect ratio is too small, the reinforcing effect such as improvement in durability cannot be obtained. On the other hand, if the aspect ratio is too large, the dispersibility deteriorates, resulting in deterioration of durability. If the blending amount of wollastonite is too small, it is not preferable because a reinforcing effect such as improvement in durability cannot be obtained. On the contrary, if it is too much, dispersibility is deteriorated, and as a result, durability is deteriorated.
本発明において使用するウォラストナイト（Ｗｏｌｌａｓｔｏｎｉｔｅ）（珪灰石）は化学式ＣａＳｉＯ3で示される珪酸塩鉱物で、天然鉱物として産出されるウォラストナイとは、石灰石と花崗岩の接触部で変成作用を受けて発達した鉱物で、色はガラス光沢のある白色、帯灰色、帯褐色を呈し、結晶形態は針状、塊状をなしている。主成分はＳｉＯ2とＣａＯをほぼ等量含有し、微量成分としてＡｌ2Ｏ3，Ｆｅ2Ｏ3等を含有しており、天然に産出される低温型（β型）と合成の高温型（α型）がある。なお、ウォラストナイトは、例えば巴工業株式会社より各種グレードが市販されており、本発明においてはこれらの市販品のうち、前記平均粒径Ｄ５０及びアスペクト比のものを使用することができる。 Wollastonite (wollastonite) used in the present invention is a silicate mineral represented by the chemical formula CaSiO 3 , and wollastonite produced as a natural mineral is developed by undergoing metamorphism at the contact point between limestone and granite. The minerals are white, greyish, and brownish in color with a glass luster, and are in the form of needles and lumps. The main component contains almost equal amounts of SiO 2 and CaO, and contains trace amounts of Al 2 O 3 , Fe 2 O 3, etc., and the naturally produced low temperature type (β type) and synthetic high temperature type ( α type). For example, various grades of wollastonite are commercially available from Sakai Kogyo Co., Ltd., and among these commercially available products, those having the average particle diameter D50 and aspect ratio can be used.
本発明に係るゴム組成物には、前記した必須成分に加えて、カーボンブラックなどのその他の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混合して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the above-described essential components, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, Various additives that are generally blended for tires such as plasticizers and other general rubbers can be blended. These additives are mixed by a general method to form a composition, which is vulcanized or crosslinked. Can be used for The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜３及び比較例１〜８
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を２リットルの密閉型ミキサーで５分間混練し、１６５±５℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物を用いて以下に示す試験法で未加硫物性を評価した。結果は表Ｉに示す。
Examples 1-3 and Comparative Examples 1-8
Sample preparation In the formulation shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 2 liter closed mixer and released when the temperature reached 165 ± 5 ° C to obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition. Using this rubber composition, unvulcanized physical properties were evaluated by the following test methods. The results are shown in Table I.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で２０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
ムーニースコーチ：ＪＩＳ Ｋ６３００に基づき１２５℃にて粘度が５ポイント上昇する時間を測定した。この数値が大きいほど結果がよいことを示す。
Ｔ９５：ＪＩＳ Ｋ６３００に基づき１６０℃にて９５％の加硫度に達する時間を測定した。
硬度（０℃）：ＪＩＳ Ｋ６２５３に準拠して測定した０℃の硬度。
ｔａｎδ（０℃）：（株）東洋精機製作所製 粘弾性スペクトロメーターを用いて、０℃下、初期歪１０％、振幅±２％、周波数２０Hzで測定した。
Ｅ’（０℃）：（株）東洋精機製作所製 粘弾性スペクトロメーターを用いて、０℃下、初期歪１０％、振幅±２％、周波数２０Hzで測定した。
Rubber property evaluation test method Mooney scorch: Based on JIS K6300, the time required for the viscosity to rise by 5 points at 125 ° C. was measured. The larger this value, the better the result.
T95: Based on JIS K6300, the time required to reach a vulcanization degree of 95% at 160 ° C. was measured.
Hardness (0 ° C.): 0 ° C. hardness measured in accordance with JIS K6253.
tan δ (0 ° C.): Measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. at 0 ° C., initial strain 10%, amplitude ± 2%, and frequency 20 Hz.
E ′ (0 ° C.): Measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. at 0 ° C., initial strain 10%, amplitude ± 2%, and frequency 20 Hz.
氷上摩擦：加硫ゴムシートを偏平円柱状の台ゴムにはりつけ、インサイドドラム型氷上摩擦試験機にて、測定温度−１．５℃、荷重０．５４MPa、ドラム回転速度２５Km／ｈで測定した。数値が大きい程よい。
ウェットスキッド：英国式ポータブルスキッドレジスタンステスターを用いて、路面＃６０シリコンカーバイドクロス、水温２３±２℃における抵抗値を測定した。この数値が大きい程結果が良いことを示す。
Friction on ice: A vulcanized rubber sheet was attached to a flat cylindrical base rubber, and measured with an inside drum type on-ice friction tester at a measurement temperature of -1.5 ° C, a load of 0.54 MPa, and a drum rotation speed of 25 km / h. Larger numbers are better.
Wet skid: Using a British portable skid resistance tester, the resistance value was measured at a road surface of # 60 silicon carbide cloth at a water temperature of 23 ± 2 ° C. The larger this value, the better the result.
クラック成長：ＪＩＳ Ｋ６２６０に準拠して、デマチア屈曲試験機にて繰り返し屈曲による亀裂成長を測定した。ストローク５７mm、速度３００±１０rpm、屈曲回数１０万回での亀裂成長を比較例１を１００とする指数で示す。数値が大きい方がよい。
老化後クラック成長：ギャーオーブンで８０℃×１４４時間熱老化後、同様に亀裂成長を測定した。
Crack growth: Based on JIS K6260, crack growth due to repeated bending was measured with a Dematia bending tester. Crack growth at a stroke of 57 mm, a speed of 300 ± 10 rpm, and a number of flexions of 100,000 is shown by an index with Comparative Example 1 being 100. A larger number is better.
Crack growth after aging: Crack growth was measured in the same manner after heat aging in a GA oven at 80 ° C. for 144 hours.
表Ｉ脚注
＊１：天然ゴム（ＴＳＲ２０）
＊２：日本ゼオン（株）製ポリブタジエンゴムＢＲ１２２０
＊３：昭和キャボット（株）製カーボンブラックＮ２３４
＊４：ローディア（株）製シリカ１６５ＧＲ
Table I Footnote * 1: Natural rubber (TSR20)
* 2: Polybutadiene rubber BR1220 manufactured by Nippon Zeon Co., Ltd.
* 3: Carbon black N234 from Showa Cabot Co., Ltd.
* 4: Silica 165GR manufactured by Rhodia Co., Ltd.
＊５：シランカップリング剤Ｓｉ６９（デクッサ製）３３ｇをヘンシェルミキサーにて撹拌中のシリカ１６５ＧＲ２６７ｇ中にゆっくり添加して反応シリカ粒子を得た後、これを１５０℃×２時間乾燥させた処理したシリカ（処理シリカＡ）
＊６：３−オクタノイルチオプロピルトリエトキシシラン（ＧＥ東芝シリコーン（株）製）３３ｇをヘンシェルミキサーにて撹拌中のシリカ１６５ＧＲ２６７ｇ中にゆっくり添加して、反応シリカ粒子を得た後、これを１５０℃×２時間乾燥させて処理した処理シリカ（処理シリカＢ）
＊７：３−オクタノイルチオプロピルトリエトキシシラン（ＧＥ東芝シリコーン（株）製）９０ｇをヘンシェルミキサーにて撹拌中のシリカ１６５ＧＲ２１０ｇ中にゆっくり添加して、反応シリカ粒子を得た後、これを１５０℃×２時間乾燥させて処理した処理シリカ（処理シリカＣ）
* 5: 33 g of silane coupling agent Si69 (manufactured by Dexsa) was slowly added to 167 g of silica 165GR being stirred with a Henschel mixer to obtain reacted silica particles, which were then dried at 150 ° C. for 2 hours. (Processed silica A)
* 6: 33 g of 3-octanoylthiopropyltriethoxysilane (manufactured by GE Toshiba Silicone Co., Ltd.) was slowly added to 165 g of silica 165GR being stirred with a Henschel mixer to obtain reactive silica particles. Treated silica (treated silica B) dried and treated for 2 hours at ℃
* 7: 90 g of 3-octanoylthiopropyltriethoxysilane (manufactured by GE Toshiba Silicone Co., Ltd.) was slowly added to 210 g of silica 165GR being stirred with a Henschel mixer to obtain reacted silica particles. Treated silica treated by drying at ℃ x 2 hours (treated silica C)
＊８：巴工業（株）製ウォラストナイトＮＹＧＬＯＳ１２（Ｄ５０＝１２μｍ、アスペクト比＝１３）
＊９：デグッサ製Ｓｉ６９
＊１０：昭和シェル石油（株）製デソレックス３号
＊１１：松本油脂製薬（株）製マイクロスフェアーＦ１００
＊１２：鶴見化学工業（株）製油処理イオウ
＊１３：大内新興化学工業（株）製ノクセラーＣＺ−Ｇ
* 8: Sakai Kogyo Co., Ltd. Wollastonite NYGLOS12 (D50 = 12 μm, aspect ratio = 13)
* 9: Degussa Si69
* 10: Desolex No. 3 manufactured by Showa Shell Sekiyu K.K. * 11: Microsphere F100 manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
* 12: Oil-treated sulfur from Tsurumi Chemical Co., Ltd. * 13: Noxeller CZ-G from Ouchi Shinsei Chemical Co., Ltd.
比較例１は従来の典型的な配合であり、これを基準に各種比較実験を行なった。即ち、比較例２及び３は、従来の配合にシリカやシランカップリング剤Ｓｉ６９で処理したシリカを添加した場合で、低温Ｅ’が下がり、ウェット性能が向上するが、加硫速度が遅くなり、スコーチが速くなるため、加工性は悪くなった。これに比べて、本発明に従った実施例１ではシランカップリング剤Ｘで処理したシリカを配合し、シリカ単独配合よりもさらに低温Ｅ’が低下してウェット性能と氷上摩擦性能を向上させることができ、しかも、加硫速度が速くなりながら、スコーチ安全性が確保されているので、加工性も向上する。またゴム１００重量部に対し、ウォラストナイト５重量部を配合することにより、耐クラック成長性に優れている。このことは実施例２及び３においても同じである。 Comparative Example 1 is a conventional typical composition, and various comparative experiments were performed based on this. That is, Comparative Examples 2 and 3 are the cases where silica treated with silica or silane coupling agent Si69 is added to the conventional formulation, low temperature E ′ decreases, wet performance is improved, vulcanization speed is slow, As the scorch becomes faster, the workability deteriorated. Compared to this, in Example 1 according to the present invention, silica treated with the silane coupling agent X is blended, and the low temperature E ′ is further lowered and the wet performance and on-ice friction performance are improved as compared with the blend of silica alone. Moreover, since the scorch safety is ensured while the vulcanization speed is increased, the workability is also improved. Further, by blending 5 parts by weight of wollastonite with 100 parts by weight of rubber, the crack growth resistance is excellent. This also applies to Examples 2 and 3.
しかし、シランカップリング剤Ｘの処理量が３０重量％のシランカップリング剤処理シリカを用いた場合にはＥ’の低減効果に乏しく、氷上制動、ＷＥＴスキッドとも良化が認められない（比較例４）。また、シランカップリング剤Ｘで処理したシリカの配合量が、ゴム１００重量部に対し、１０重量部未満である時にはＥ’の低減効果が小さく、氷上制動、ウェットスキッドの向上度合が小さく好ましくない。一方配合量が３０重量部を超えるとＥ’の低減効果はあるものの、硬度も大きく低下してしまい、操縦安定性の悪化を引き起こすので好ましくない（比較例５及び６）。更に、ウォラストナイトの配合量が３重量部未満の時には耐クラック成長性に劣り、改善効果が認められず、逆にその配合量が８重量部を超えるとＥ’の低下が認められず、氷上制動、ウェットスキッドの向上が認められないので好ましくない（比較例７及び８）。 However, when silane coupling agent-treated silica having a treatment amount of silane coupling agent X of 30% by weight is used, the effect of reducing E ′ is poor, and neither braking on ice nor WET skid is observed (comparative example). 4). Further, when the amount of silica treated with the silane coupling agent X is less than 10 parts by weight with respect to 100 parts by weight of rubber, the effect of reducing E ′ is small, and the degree of improvement on ice braking and wet skid is small, which is not preferable. . On the other hand, if the blending amount exceeds 30 parts by weight, although there is an effect of reducing E ', the hardness is also greatly reduced, and the steering stability is deteriorated, which is not preferable (Comparative Examples 5 and 6). Furthermore, when the blending amount of wollastonite is less than 3 parts by weight, the crack growth resistance is inferior, and no improvement effect is observed. Conversely, when the blending amount exceeds 8 parts by weight, no decrease in E ′ is observed, It is not preferable because braking on ice and improvement of wet skid are not recognized (Comparative Examples 7 and 8).
以上の通り、本発明によれば、低温Ｅ’の低下によるウェット性能の向上、氷上摩擦性能の向上を図ることができ、クラック発生によるサイプ欠損を抑制でき、耐久性の向上、その他の性能の持続を図ることができるので、空気入りタイヤ、特にスタッドレスタイヤのキャップトレッド部に好適に用いることができる。 As described above, according to the present invention, it is possible to improve wet performance due to a decrease in low temperature E ′, improve friction performance on ice, suppress sipe loss due to crack generation, improve durability, and improve other performance. Since sustainability can be achieved, it can be suitably used for a cap tread portion of a pneumatic tire, particularly a studless tire.
Claims (2)
Ｙ3ＳｉＣ3Ｈ6ＳＣ（＝Ｏ）Ｒ
（式中、Ｙは独立にメトキシ、エトキシ、プロポキシ、イソプロポキシ、イソブトキシ、アセトキシ又はオキサマート基を示し、Ｒは環式又は分岐アルキル基、アルケニル基、アリール基及びアラルキル基から選ばれるＣ1〜Ｃ18の炭化水素基を示す。）
で表される少なくとも１種のシランカップリング剤Ｘとシリカとの反応生成物であって、その反応量がシリカ重量に対しシランカップリング剤Ｘが１〜２５重量％である反応生成物１０〜３０重量部並びに平均粒径Ｄ５０が３〜１５μｍでアスペクト比が１０〜２５のウォラストナイト３〜７重量部を含んでなる０℃のＪＩＳ硬度が５２以下であるタイヤトレッド用ゴム組成物。 100 parts by weight of rubber containing natural rubber (NR) or natural rubber (NR) / polybutadiene rubber (BR), formula:
Y 3 SiC 3 H 6 SC (═O) R
(In the formula, Y independently represents a methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, acetoxy or oxamate group, and R represents a C 1 to C selected from a cyclic or branched alkyl group, an alkenyl group, an aryl group and an aralkyl group. 18 hydrocarbon groups are shown.)
A reaction product of at least one silane coupling agent X and silica represented by the formula: wherein the reaction amount is 10 to 25% by weight of the silane coupling agent X with respect to the silica weight. A rubber composition for tire treads having a JIS hardness of 0 ° C. or less, comprising 30 parts by weight and 3 to 7 parts by weight of wollastonite having an average particle diameter D50 of 3 to 15 μm and an aspect ratio of 10 to 25.
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| JP2007031578A (en) * | 2005-07-27 | 2007-02-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
| WO2008087987A1 (en) * | 2007-01-17 | 2008-07-24 | Bridgestone Corporation | Rubber composition and pneumatic tire using the same |
| JP2008255156A (en) * | 2007-04-02 | 2008-10-23 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2009013307A (en) * | 2007-07-05 | 2009-01-22 | Sumitomo Rubber Ind Ltd | Rubber composition for cap tread of studless tire, and studless tire |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8067491B2 (en) | 2006-12-28 | 2011-11-29 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031578A (en) * | 2005-07-27 | 2007-02-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
| US8067491B2 (en) | 2006-12-28 | 2011-11-29 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8188174B2 (en) | 2006-12-28 | 2012-05-29 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US8501849B2 (en) | 2006-12-28 | 2013-08-06 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| JP2008174618A (en) * | 2007-01-17 | 2008-07-31 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| WO2008087987A1 (en) * | 2007-01-17 | 2008-07-24 | Bridgestone Corporation | Rubber composition and pneumatic tire using the same |
| JP2008255156A (en) * | 2007-04-02 | 2008-10-23 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2009013307A (en) * | 2007-07-05 | 2009-01-22 | Sumitomo Rubber Ind Ltd | Rubber composition for cap tread of studless tire, and studless tire |
| JP2021130442A (en) * | 2020-02-21 | 2021-09-09 | 住友ゴム工業株式会社 | tire |
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