JP2006169464A - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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本発明は、ゴム組成物及びそれを用いた空気入りタイヤに関し、特にタイヤのトレッドに用いることにより、乾燥路面における高い操作性（ドライグリップ性）を低下させることなく、耐熱疲労性を向上させることが可能なゴム組成物に関するものである。 The present invention relates to a rubber composition and a pneumatic tire using the rubber composition, and particularly improves heat fatigue resistance without reducing high operability (dry grip performance) on a dry road surface by using the tire in a tire tread. The present invention relates to a rubber composition that can be used.
タイヤのトレッドには、乾燥路面における高い操縦安定性（ドライグリップ性）が要求される。従来から、ドライグリップ性を向上させるために、トレッド用ゴム組成物においては、ゴム組成物中の樹脂や、アロマチックオイル、液状ポリマー等のオイル成分を増量することが行われている。しかしながら、オイル成分を増量すると、耐熱性が低下し、走行中にタイヤ内部の発熱と変形とにより亀裂が発生しやすくなるという問題がある。 A tire tread is required to have high steering stability (dry grip performance) on a dry road surface. Conventionally, in order to improve dry grip properties, in a rubber composition for a tread, an amount of oil components such as a resin, an aromatic oil, and a liquid polymer in the rubber composition has been increased. However, when the oil component is increased, the heat resistance is lowered, and there is a problem that cracks are likely to occur due to heat generation and deformation inside the tire during running.
この問題に対して、主に架橋の熱的な安定性を向上させるために、モノスルフィドを増加させることが可能な加硫促進剤としてチウラム化合物、ジチオカルバミン酸金属塩、ジチオリン酸金属塩の適用が考えられる（特許文献１参照）。しかしながら、これらの化合物の配合量を増やし過ぎると、静的な耐熱性は向上するものの、耐疲労性が低下し、その結果、耐熱疲労性が向上しないという問題がある。 In response to this problem, thiuram compounds, dithiocarbamic acid metal salts, and dithiophosphoric acid metal salts have been used as vulcanization accelerators capable of increasing monosulfide mainly to improve the thermal stability of crosslinking. Possible (see Patent Document 1). However, when the compounding amount of these compounds is excessively increased, the static heat resistance is improved, but the fatigue resistance is lowered. As a result, there is a problem that the heat fatigue resistance is not improved.
また、フェニレンビスマレイミド、ＰＫ９００、１,６-ヘキサメチレンジチオ硫酸ナトリウム・２水和物等の耐熱架橋剤の使用も考えられるが（特許文献２参照）、これらの化合物は天然ゴム及びイソプレンゴムとの反応性に優れるものの、ビニル結合量の高いポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムとの反応性が低く、単独の配合では、これらビニル結合量の高いゴム成分に大量に配合しても耐熱疲労性が向上しないという問題があった。 In addition, the use of a heat-resistant cross-linking agent such as phenylene bismaleimide, PK900, 1,6-hexamethylenedithiosulfate sodium dihydrate, etc. is also considered (see Patent Document 2). These compounds include natural rubber and isoprene rubber. However, it has low reactivity with polybutadiene rubber and styrene-butadiene copolymer rubber with high vinyl bond. There was a problem that fatigue did not improve.
これに対し、ゴム組成物の耐熱疲労性を向上させる化合物として、１,６-ビス[Ｎ,Ｎ'-ジ(２-エチルヘキシル)チオカルバモイルジチオ]-ヘキサンが弊社にて開発されたが（特許文献３参照）、該化合物をもってしても依然として耐熱疲労性に改善の余地が有り、更なる性能向上が求められている。 On the other hand, 1,6-bis [N, N'-di (2-ethylhexyl) thiocarbamoyldithio] -hexane was developed by our company as a compound that improves the heat fatigue resistance of rubber compositions (patented) Even if it has this compound, there exists room for improvement in heat fatigue resistance, and further performance improvement is calculated | required.
そこで、本発明の目的は、上記従来技術の問題を解決し、タイヤのトレッドに用いることにより、高いグリップ性能を維持しながら、タイヤの耐熱疲労性を向上させることが可能なゴム組成物、及び該ゴム組成物をトレッドに用いた高性能タイヤを提供することにある。 Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and by using the tire tread, a rubber composition capable of improving the thermal fatigue resistance of the tire while maintaining high grip performance, and The object is to provide a high-performance tire using the rubber composition in a tread.
本発明者らは、上記目的を達成するために鋭意検討した結果、特定のゴム成分に対し、特定の加硫促進剤と特定の加硫剤とを組み合わせて配合することにより、高いグリップ性能を維持しつつ、タイヤの耐熱疲労性を向上させることが可能なゴム組成物が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a high grip performance by combining a specific rubber component with a specific vulcanization accelerator and a specific vulcanizing agent. It has been found that a rubber composition capable of improving the heat fatigue resistance of a tire can be obtained while maintaining the present invention, and the present invention has been completed.
即ち、本発明のゴム組成物は、（１）ビニル結合量が30％以上であるポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムの少なくとも一方を含むゴム成分に、（２）下記式(I)で表される化合物と、（３）下記式(II)で表される有機チオスルフェート化合物とを配合してなることを特徴とする。
［式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に炭素数３〜１２の直鎖若しくは分岐鎖アルキル基又は炭素数７〜１２のアラルキル基を示す。］
Ｍ1Ｏ3Ｓ−Ｓ−(ＣＨ2)n−Ｓ−ＳＯ3Ｍ1 ・・・ (II)
［式中、ｎは３〜１０を表し、Ｍ1はリチウム、カリウム、ナトリウム、マグネシウム、カルシウム、バリウム、亜鉛、ニッケル又はコバルトの１当量を表す。また、該化合物は、結晶水を含有していてもよい。］
That is, the rubber composition of the present invention comprises (1) a rubber component containing at least one of a polybutadiene rubber and a styrene / butadiene copolymer rubber having a vinyl bond amount of 30% or more, and (2) the following formula (I): And (3) an organic thiosulfate compound represented by the following formula (II).
[Wherein, R 1 , R 2 , R 3 and R 4 each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms. ]
M 1 O 3 S—S— (CH 2 ) n —S—SO 3 M 1 (II)
[Wherein, n represents 3 to 10, and M 1 represents one equivalent of lithium, potassium, sodium, magnesium, calcium, barium, zinc, nickel, or cobalt. Further, the compound may contain crystal water. ]
本発明のゴム組成物の好適例においては、前記式(I)で表される化合物のＲ1、Ｒ2、Ｒ3及びＲ4が、それぞれ独立に炭素数８〜１２の直鎖又は分岐鎖アルキル基である。ここで、該Ｒ1、Ｒ2、Ｒ3及びＲ4は、２-エチルヘキシル基であるのが特に好ましい。 In a preferred example of the rubber composition of the present invention, R 1 , R 2 , R 3 and R 4 of the compound represented by the formula (I) are each independently a linear or branched chain having 8 to 12 carbon atoms. It is an alkyl group. Here, it is particularly preferred that R 1 , R 2 , R 3 and R 4 are 2-ethylhexyl groups.
本発明のゴム組成物の他の好適例において、前記スチレン・ブタジエン共重合体ゴムは、結合スチレン含有率が20〜60質量％である。ここで、該結合スチレン含有率は、30〜45質量％であるのが更に好ましい。 In another preferred embodiment of the rubber composition of the present invention, the styrene / butadiene copolymer rubber has a bound styrene content of 20 to 60% by mass. Here, the bound styrene content is more preferably 30 to 45% by mass.
本発明のゴム組成物の他の好適例においては、前記ゴム成分中の前記スチレン・ブタジエン共重合体ゴムの含有率が50〜100質量％である。ここで、ゴム成分中の上記スチレン・ブタジエン共重合体ゴムの含有率は、70〜100質量％であるのが更に好ましい。 In another preferred embodiment of the rubber composition of the present invention, the content of the styrene / butadiene copolymer rubber in the rubber component is 50 to 100% by mass. Here, the content of the styrene / butadiene copolymer rubber in the rubber component is more preferably 70 to 100% by mass.
本発明のゴム組成物の他の好適例においては、前記式(II)で表される有機チオスルフェート化合物が１,６-ヘキサメチレンジチオ硫酸ナトリウム・２水和物である。 In another preferred embodiment of the rubber composition of the present invention, the organic thiosulfate compound represented by the formula (II) is 1,6-hexamethylenedithiosulfate sodium dihydrate.
本発明のゴム組成物の他の好適例においては、前記式(I)で表される化合物の配合量が、前記ゴム成分100質量部に対し0.1〜20質量部である。 In another preferred embodiment of the rubber composition of the present invention, the compounding amount of the compound represented by the formula (I) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
本発明のゴム組成物の他の好適例においては、前記式(II)で表される化合物の配合量が、前記ゴム成分100質量部に対し0.1〜20質量部である。 In another preferable example of the rubber composition of the present invention, the compounding amount of the compound represented by the formula (II) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
また、本発明の空気入りタイヤは、上記のゴム組成物をトレッドに使用したことを特徴とする。ここで、本発明のタイヤにおいて、タイヤ内に充填する気体としては、通常の若しくは酸素分圧を変えた空気、又は窒素等の不活性なガスが挙げられる。 The pneumatic tire of the present invention is characterized by using the above rubber composition in a tread. Here, in the tire of the present invention, examples of the gas filled in the tire include normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen.
本発明によれば、タイヤのトレッドに用いることにより、高いグリップ性能を維持しながら、タイヤの耐熱疲労性等の耐久性を向上させることが可能なゴム組成物を提供することができる。また、該ゴム組成物をトレッドに用いた高性能タイヤを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can improve durability, such as heat fatigue resistance of a tire, can be provided, maintaining a high grip performance by using for the tread of a tire. Moreover, the high performance tire which used this rubber composition for the tread can be provided.
以下に、本発明を詳細に説明する。本発明のゴム組成物は、（１）ビニル結合量が30％以上であるポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムの少なくとも一方を含むゴム成分に、（２）上記式(I)で表される化合物と、（３）上記式(II)で表される有機チオスルフェート化合物とを配合してなる。 The present invention is described in detail below. The rubber composition of the present invention includes (1) a rubber component containing at least one of a polybutadiene rubber and a styrene / butadiene copolymer rubber having a vinyl bond content of 30% or more, and (2) represented by the above formula (I). And (3) an organic thiosulfate compound represented by the above formula (II).
本発明のゴム組成物に用いるゴム成分は、耐熱性を向上させる観点から、ビニル結合量が30％以上、好ましくは40％以上であるポリブタジエンゴム(ＢＲ)及びスチレン・ブタジエン共重合体ゴム(ＳＢＲ)の少なくとも一方を含む。ここで、該スチレン・ブタジエン共重合体ゴムは、結合しているスチレン単位の含有率、即ち、結合スチレン含有率が20〜60質量％であるのが好ましい。スチレン・ブタジエン共重合体ゴムの結合スチレン含有率が20質量％未満では、低温域及び高温域における所望のグリップ力を得ることができず、60質量％を超えると、ブロック剛性が必要以上に高くなり、路面へのトレッドゴムの食い込み量が減少し、所望のグリップ力を得ることができない。また、これらの効果が顕著となることから、上記スチレン・ブタジエン共重合体ゴムは、結合スチレン含有率が30〜45質量％であるのがより好ましい。なお、ビニル結合量は、赤外法（モレロ法）でミクロ構造を分析することにより求めることができ、結合スチレン含有率は、1Ｈ-ＮＭＲでスペクトルの積分比を算出することにより求めることができる。該スチレン・ブタジエン共重合体ゴムは、乳化重合、溶液重合等の如何なる重合法によって合成したものであってもよい。また、上記ビニル結合量の高いポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムとしては、油展されているものを好適に使用することができる。高ビニル結合量のポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムが油展されていると、バンバリーミキサー等を用いて混練する際、滑りが生じず、容易且つ確実に混練を行うことができる。 From the viewpoint of improving heat resistance, the rubber component used in the rubber composition of the present invention has a polybutadiene rubber (BR) and a styrene / butadiene copolymer rubber (SBR) having a vinyl bond content of 30% or more, preferably 40% or more. ). Here, the styrene / butadiene copolymer rubber preferably has a content of bonded styrene units, that is, a content of bonded styrene of 20 to 60% by mass. If the styrene-butadiene copolymer rubber has a bound styrene content of less than 20% by mass, the desired grip strength in the low and high temperature ranges cannot be obtained, and if it exceeds 60% by mass, the block rigidity is unnecessarily high. Thus, the amount of tread rubber biting into the road surface is reduced, and a desired grip force cannot be obtained. Moreover, since these effects become remarkable, it is more preferable that the styrene / butadiene copolymer rubber has a bound styrene content of 30 to 45% by mass. The vinyl bond amount can be determined by analyzing the microstructure by the infrared method (Morero method), and the bound styrene content can be determined by calculating the integral ratio of the spectrum by 1 H-NMR. it can. The styrene / butadiene copolymer rubber may be synthesized by any polymerization method such as emulsion polymerization or solution polymerization. In addition, as the polybutadiene rubber and styrene / butadiene copolymer rubber having a high vinyl bond amount, oil-extended ones can be preferably used. When the polybutadiene rubber having a high vinyl bond amount and the styrene / butadiene copolymer rubber are oil-extended, slipping does not occur when kneading using a Banbury mixer or the like, and the kneading can be performed easily and reliably.
また、上記ゴム成分には、上記ビニル結合量の高いポリブタジエンゴム及びスチレン・ブタジエン共重合体ゴムの他、天然ゴム(ＮＲ)、イソプレンゴム(ＩＲ)、アクリロニトリルブタジエンゴム(ＮＢＲ)、エチレン・プロピレンゴム(ＥＰＭ)、エチレン・プロピレンターポリマー、ブチルゴム、アクリルゴム等をブレンドしてもよい。 In addition to the polybutadiene rubber and styrene / butadiene copolymer rubber having a high vinyl bond content, the rubber component includes natural rubber (NR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), and ethylene / propylene rubber. (EPM), ethylene / propylene terpolymer, butyl rubber, acrylic rubber or the like may be blended.
本発明のゴム組成物に用いる上記式(I)の化合物において、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に炭素数３〜１２の直鎖若しくは分岐鎖アルキル基又は炭素数７〜１２のアラルキル基を示し、炭素数３〜１２の直鎖若しくは分岐鎖アルキル基としては、２-エチルヘキシル基、イソプロピル基、イソブチル基、ドデシル基等が挙げられ、一方、炭素数７〜１２のアラルキル基としては、ベンジル基等が挙げられる。Ｒ1、Ｒ2、Ｒ3及びＲ4の炭素数が２以下ではゴム成分中への分散が悪くなり、耐熱性が悪化し、炭素数が１３以上では、加硫速度が非常に遅れる。具体的に、式(I)の化合物としては、１,１０-ビス[Ｎ,Ｎ'-ジベンジルチオカルバモイルジチオ]-デカン、１,１０-ビス[Ｎ,Ｎ'-ジ(２-エチルヘキシル)チオカルバモイルジチオ]-デカン等が挙げられる。 In the compound of the above formula (I) used in the rubber composition of the present invention, R 1 , R 2 , R 3 and R 4 are each independently a linear or branched alkyl group having 3 to 12 carbon atoms or 7 carbon atoms. Represents an aralkyl group having ˜12, and examples of the linear or branched alkyl group having 3 to 12 carbon atoms include 2-ethylhexyl group, isopropyl group, isobutyl group, dodecyl group, etc. Examples of the aralkyl group include a benzyl group. When the carbon number of R 1 , R 2 , R 3 and R 4 is 2 or less, the dispersion into the rubber component is deteriorated and the heat resistance is deteriorated. Specifically, the compound of formula (I) is 1,10-bis [N, N′-dibenzylthiocarbamoyldithio] -decane, 1,10-bis [N, N′-di (2-ethylhexyl) And thiocarbamoyldithio] -decane.
上記式(I)の化合物は、加硫促進剤として機能すると共に加硫剤としても機能する。そのため、ゴム組成物が、前述したビニル結合量の高いポリブタジエンゴム及び／又はスチレン・ブタジエン共重合体ゴムと式(I)の化合物とを含む場合、式(II)の化合物を更に配合しなくても、該ゴム組成物は、高いドライグリップ性と高い耐熱疲労性とを有する。 The compound of the above formula (I) functions not only as a vulcanization accelerator but also as a vulcanizing agent. Therefore, when the rubber composition contains the above-mentioned polybutadiene rubber and / or styrene-butadiene copolymer rubber having a high vinyl bond amount and the compound of the formula (I), the compound of the formula (II) may not be further blended. However, the rubber composition has high dry grip properties and high heat fatigue resistance.
上記式(I)の化合物の配合量は、前記ゴム成分100質量部に対し0.1〜20質量部である。該化合物の配合量が0.1質量部未満では、後述する有機チオスルフェート化合物を充分活性化させる効果が得られず、20質量部を超えると、ゴム組成物の破壊特性が低下する。 The compounding amount of the compound of the above formula (I) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component. When the compounding amount of the compound is less than 0.1 parts by mass, the effect of sufficiently activating the organic thiosulfate compound described later cannot be obtained, and when it exceeds 20 parts by mass, the fracture characteristics of the rubber composition are deteriorated.
本発明のゴム組成物は、加硫剤として硫黄と共に上記式(II)で表される有機チオスルフェート化合物を含有する。この混合物からなる加硫剤の総配合量は、前記ゴム成分100質量部に対して、合計量で0.1〜20.0質量部の範囲であり、好ましくは1.0〜10.0質量部の範囲である。加硫剤の総配合量が0.1質量部未満では、充分な弾性率を確保できず、20.0質量部を超えると、破断時伸びが低下し、耐リブ欠け性が著しく低下する。ここで、上記式(II)の化合物の配合量は、前記ゴム成分100質量部に対し0.1〜20.0質量部であるのが好ましく、2.0〜6.0質量部であるのが更に好ましい。式(II)の化合物の配合量が0.1質量部未満では、耐熱疲労性を充分に向上させることができず、20.0質量部を超えると、破断時伸びが低下し、耐リブ欠け性が著しく低下する。 The rubber composition of the present invention contains an organic thiosulfate compound represented by the above formula (II) together with sulfur as a vulcanizing agent. The total amount of the vulcanizing agent comprising this mixture is in the range of 0.1 to 20.0 parts by mass, preferably in the range of 1.0 to 10.0 parts by mass, with respect to 100 parts by mass of the rubber component. When the total amount of the vulcanizing agent is less than 0.1 parts by mass, a sufficient elastic modulus cannot be secured, and when it exceeds 20.0 parts by mass, the elongation at break is lowered and the rib chipping resistance is remarkably lowered. Here, the compounding amount of the compound of the above formula (II) is preferably 0.1 to 20.0 parts by mass, more preferably 2.0 to 6.0 parts by mass with respect to 100 parts by mass of the rubber component. If the compounding amount of the compound of formula (II) is less than 0.1 parts by mass, the heat fatigue resistance cannot be sufficiently improved, and if it exceeds 20.0 parts by mass, the elongation at break is lowered and the rib chipping resistance is remarkably lowered. To do.
上記式(II)において、ｎで示されるメチレン鎖の数は３〜１０であることが必要であり、２以下では、耐熱疲労性を向上させる効果が充分に得られず、１１以上では分子量が増えるわりに耐熱疲労性の向上効果が小さい。更に、分子内環化反応を抑制する観点から、該メチレン鎖の数は、３〜６であることが好ましい。また、Ｍ1はリチウム、カリウム、ナトリウム、マグネシウム、カルシウム、バリウム、亜鉛、ニッケル又はコバルトの１当量を表すが、入手の容易性と効果を勘案すると、カリウム、ナトリウム等が好ましい。この化合物は分子内に結晶水を有する水和物であってもよい。具体的に、式(II)の化合物としては、ナトリウム塩一水和物、ナトリウム塩二水和物等が挙げられ、経済的理由から、チオ硫酸ナトリウムからの誘導体、例えば１,６-ヘキサメチレンジチオ硫酸ナトリウム・２水和物が最も好ましい。 In the above formula (II), the number of methylene chains represented by n needs to be 3 to 10, and if it is 2 or less, the effect of improving heat fatigue resistance is not sufficiently obtained, and if it is 11 or more, the molecular weight is low. Although it increases, the effect of improving heat fatigue resistance is small. Furthermore, from the viewpoint of suppressing the intramolecular cyclization reaction, the number of the methylene chains is preferably 3-6. M 1 represents one equivalent of lithium, potassium, sodium, magnesium, calcium, barium, zinc, nickel, or cobalt, and potassium, sodium, and the like are preferable in consideration of availability and effects. This compound may be a hydrate having crystal water in the molecule. Specific examples of the compound of formula (II) include sodium salt monohydrate, sodium salt dihydrate and the like. For economic reasons, derivatives from sodium thiosulfate such as 1,6-hexamethylene Sodium dithiosulfate dihydrate is most preferred.
本発明のゴム組成物には、更に、充填剤として窒素吸着比表面積（Ｎ2ＳＡ）が80〜280m2/gであるカーボンブラックを配合するのが好ましい。カーボンブラックの窒素吸着比表面積が80m2/g未満では、充分な弾性率が得られず耐摩耗性が悪化し、280m2/gを超えると、グリップ力及び耐摩耗性の向上が望めない割りに混練作業性が悪化してしまう。該カーボンブラックとしては、ＨＡＦ、ＩＳＡＦ、ＳＡＦ等が挙げられ、市販品を使用することができる。これらの中でも、低温域のウェット路面でのグリップ力と、高温域のウェット路面又はセミウェット路面でのグリップ力との両立の観点から、ＳＡＦが好ましい。上記カーボンブラックは、一種単独で使用してもよいし、２種以上を併用してもよい。 The rubber composition of the present invention preferably further contains carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 80 to 280 m 2 / g as a filler. When the nitrogen adsorption specific surface area of carbon black is less than 80 m 2 / g, sufficient elastic modulus cannot be obtained and the wear resistance deteriorates, and when it exceeds 280 m 2 / g, the improvement in grip strength and wear resistance cannot be expected. In addition, the kneading workability is deteriorated. Examples of the carbon black include HAF, ISAF, SAF, and the like, and commercially available products can be used. Among these, SAF is preferable from the viewpoint of coexistence of grip force on a wet road surface in a low temperature region and grip force on a wet road surface or a semi-wet road surface in a high temperature region. The said carbon black may be used individually by 1 type, and may use 2 or more types together.
上記カーボンブラックの配合量は、前記ゴム成分100質量部に対し70〜200質量部が好ましく、90〜130質量部がより好ましい。該カーボンブラックの配合量が70質量部未満では、ゴム組成物のドライグリップ性及び弾性率が充分でなく、また強度等の一般的な特性も充分でなく、接地性が悪化する。一方、該カーボンブラックの配合量が200質量部を超えると、ゴム組成物が硬くなり過ぎ、かえって耐摩耗性が低下してしまい、更にゴム組成物の加工性も極端に悪化する。 The compounding amount of the carbon black is preferably 70 to 200 parts by mass, more preferably 90 to 130 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount of the carbon black is less than 70 parts by mass, the dry grip property and elastic modulus of the rubber composition are not sufficient, and general characteristics such as strength are not sufficient, and the grounding property is deteriorated. On the other hand, when the blending amount of the carbon black exceeds 200 parts by mass, the rubber composition becomes too hard, and on the contrary, the wear resistance is lowered, and the processability of the rubber composition is extremely deteriorated.
本発明のゴム組成物には、更に、Ｃ9芳香族系石油樹脂及び／又はアルキルフェノール系樹脂を配合するのが好ましい。ここで、Ｃ9芳香族系石油樹脂とは、Ｃ9芳香族系モノマーの重合体をいい、Ｃ9芳香族系モノマーとしては、ビニルトルエン、α-メチルスチレン、クマロン、インデン等が挙げられる。該Ｃ9芳香族系モノマーは、一種単独で使用してもよいし、二種以上を併用してもよい。一方、アルキルフェノール系樹脂としては、ｐ-ｔ-ブチルフェノール-アセチレン等のアルキルフェノール-アセチレン系樹脂、並びにクレゾール類、キシレノール類、ｐ-ｔ-ブチルフェノール、ｐ-ｔ-オクチルフェノール類を含むアルキルフェノール-ホルムアルデヒド系樹脂が挙げられる。これらの樹脂は、軟化点が60〜150℃であるのが好ましい。該樹脂の軟化点が60℃未満では、高温域のウェット路面及びセミウェット路面における充分なグリップ力が得られず、150℃を超えると、混練の際に樹脂が均一に分散せず、耐摩耗性が著しく低下してしまう。これらＣ9芳香族系石油樹脂及びアルキルフェノール系樹脂は、一種単独で使用してもよいし、二種以上を併用してもよい。これらの樹脂の配合量は、前記ゴム成分100質量部に対し3〜120質量部であり、5〜70質量部であるのが好ましい。これらの樹脂の配合量が3質量部未満では、グリップ力等のウェット性能における添加効果が充分に得られず、120質量部を超えると、ゴム組成物の混練における作業性が著しく悪化する。 The rubber composition of the present invention further preferably blended the C 9 aromatic petroleum resin and / or alkylphenol resin. Here, the C 9 aromatic petroleum resin means a polymer of C 9 aromatic monomer, as the C 9 aromatic monomer, vinyl toluene, alpha-methyl styrene, coumarone, indene, and the like. The C 9 aromatic monomer may be used alone or in combination of two or more. On the other hand, alkylphenol-based resins include alkylphenol-acetylene resins such as pt-butylphenol-acetylene, and alkylphenol-formaldehyde resins including cresols, xylenols, pt-butylphenol, and pt-octylphenols. Can be mentioned. These resins preferably have a softening point of 60 to 150 ° C. If the softening point of the resin is less than 60 ° C, sufficient grip on the wet and semi-wet road surfaces in the high temperature range cannot be obtained, and if it exceeds 150 ° C, the resin is not evenly dispersed during kneading and wear resistance The performance is significantly reduced. These C 9 aromatic petroleum resins and alkylphenol resins may be used alone or in combination of two or more. The compounding quantity of these resin is 3-120 mass parts with respect to 100 mass parts of said rubber components, and it is preferable that it is 5-70 mass parts. If the blending amount of these resins is less than 3 parts by mass, the effect of addition in wet performance such as grip strength cannot be obtained sufficiently.
本発明のゴム組成物は、加硫後のアセトン・クロロホルム抽出分が前記ゴム成分100質量部に対し30〜270質量部であることを必要とする。該抽出分が30質量部未満又は270質量部を超えると、グリップ力や耐摩耗性の向上が望めない割りに、混練作業性が悪化してしまう。該抽出分は、グリップ力及び耐摩耗性と混練作業性との両立の観点から、30〜200質量部であるのが好ましい。 The rubber composition of the present invention requires that the acetone / chloroform extract after vulcanization is 30 to 270 parts by mass with respect to 100 parts by mass of the rubber component. When the extracted amount is less than 30 parts by mass or exceeds 270 parts by mass, the kneading workability is deteriorated although the improvement in gripping force and wear resistance cannot be expected. The extracted amount is preferably 30 to 200 parts by mass from the viewpoints of both grip strength and wear resistance and kneading workability.
本発明のゴム組成物には、上記ゴム成分、式(I)の化合物、式(II)の有機チオスルフェート化合物、硫黄、カーボンブラック、Ｃ9芳香族系石油樹脂、アルキルフェノール系樹脂の他、ゴム業界で通常使用される各種配合剤、例えば、プロセスオイル等の油分、無機充填剤、軟化剤、ジベンゾチアジルジスルフィド、４,４'-ジメチルジベンゾチアジルジスルフィド、Ｎ-シクロヘキシル-２-ベンゾチアジル-スルフェンアミド、Ｎ-ｔ-ブチル-２-ベンゾチアジル-スルフェンアミド、Ｎ-ｔ-ブチル-２-ベンゾチアジル-スルフェンイミド、Ｎ-オキシジエチレン-ベンゾチアジル-スルフェンアミド、Ｎ,Ｎ'-ジシクロヘキシル-２-ベンゾチアジル-スルフェンアミド等の加硫促進剤、加硫助剤、老化防止剤、酸化亜鉛、ステアリン酸、オゾン劣化防止剤、着色剤、帯電防止剤、滑剤、酸化防止剤、カップリング剤、発泡剤、発泡助剤等を、本発明の目的を害しない範囲で適宜配合することができる。これら配合剤としては、市販品を好適に使用することができる。 In the rubber composition of the present invention, the rubber component, a compound of formula (I), an organic thiosulfate compound of formula (II), sulfur, carbon black, C 9 aromatic petroleum resin, other alkylphenol-based resins, Various compounding agents commonly used in the rubber industry, such as oils such as process oils, inorganic fillers, softeners, dibenzothiazyl disulfide, 4,4'-dimethyldibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazyl- Sulfenamide, Nt-butyl-2-benzothiazyl-sulfenamide, Nt-butyl-2-benzothiazyl-sulfenimide, N-oxydiethylene-benzothiazyl-sulfenamide, N, N'-dicyclohexyl- Vulcanization accelerators such as 2-benzothiazyl-sulfenamide, vulcanization aids, anti-aging agents, zinc oxide, stearic acid, antiozonants, colorants Antistatic agents, lubricants, antioxidants, coupling agents, foaming agents, a foaming aid, etc., may be appropriately blended within the range not damaging the object of the present invention. As these compounding agents, commercially available products can be suitably used.
上記プロセスオイル等の油分としては、特に制限はなく、目的に応じて適宜選択することができるが、アロマチックオイル、ナフテン系オイル、パラフィン系オイル、エステル系オイル、溶液状共役ジエンゴム、溶液状水素添加共役ジエンゴム等が好ましい。プロセスオイル等の油分が上記ゴム組成物に含まれていると、該ゴム組成物の流動性をコントロールすることができ、該ゴム組成物の加硫前の粘度を低下させ、その流動性を高めることができるため、極めて良好に押出しを行うことができる。 The oil content of the process oil and the like is not particularly limited and may be appropriately selected depending on the intended purpose. However, aromatic oil, naphthenic oil, paraffin oil, ester oil, solution conjugated diene rubber, solution hydrogen Addition conjugated diene rubber and the like are preferable. When the oil composition such as process oil is contained in the rubber composition, the fluidity of the rubber composition can be controlled, the viscosity of the rubber composition before vulcanization is lowered, and the fluidity is increased. Therefore, extrusion can be performed very well.
上記プロセスオイル等の油分の上記ゴム組成物における含有量は、前記ポリブタジエンゴム及び／又はスチレン・ブタジエン共重合体ゴムが油展されている場合は、これらの油展分も含めて、前記ゴム成分100質量部に対し35〜200質量部であるのが好ましく、40〜150質量部であるのがより好ましい。プロセスオイル等の油分の含有量が35質量部未満では、未加硫ゴム組成物のムーニー粘度が極端に高くなって加工性が悪化したり、ドライグリップ性が悪化し、200質量部を超えると、未加硫ゴム組成物のムーニー粘度が極端に低くなって加工性が悪化したり、加硫後のゴムが軟らかくなり過ぎて、耐摩耗性が悪化する。 When the polybutadiene rubber and / or styrene / butadiene copolymer rubber is oil-extended, the content of oil such as the process oil in the rubber composition includes the oil component and the rubber component. The amount is preferably 35 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass. When the content of oil such as process oil is less than 35 parts by mass, the Mooney viscosity of the unvulcanized rubber composition becomes extremely high, the workability deteriorates, the dry grip property deteriorates, and the content exceeds 200 parts by mass. Further, the Mooney viscosity of the unvulcanized rubber composition becomes extremely low and the processability deteriorates, or the rubber after vulcanization becomes too soft and the wear resistance deteriorates.
本発明のゴム組成物は、前記ゴム成分、式(I)の化合物及び式(II)の有機チオスルフェート化合物と、必要に応じて適宜選択した各種配合剤とを、混練り、熱入れ、押出し、加硫等して製造される。 The rubber composition of the present invention, the rubber component, the compound of formula (I) and the organic thiosulfate compound of formula (II), and various compounding agents appropriately selected as necessary are kneaded, heated, Manufactured by extrusion or vulcanization.
前記混練りの条件としては、特に制限はなく、混練装置への投入体積、ローターの回転速度、ラム圧、混練温度、混練時間、混練装置の種類等の諸条件について目的に応じて適宜選択することができる。前記混練装置としては、例えば、通常ゴム組成物の混練に用いるバンバリーミキサー、インターミックス、ニーダー等が挙げられる。 The kneading conditions are not particularly limited, and various conditions such as the input volume to the kneading apparatus, the rotational speed of the rotor, the ram pressure, the kneading temperature, the kneading time, and the type of the kneading apparatus are appropriately selected according to the purpose. be able to. Examples of the kneading apparatus include a Banbury mixer, an intermix, and a kneader that are usually used for kneading a rubber composition.
前記熱入れの条件としては、特に制限はなく、熱入れ温度、熱入れ時間、熱入れ装置等の諸条件について目的に応じて適宜選択することができる。前記熱入れ装置としては、例えば、通常ゴム組成物の熱入れに用いるロール機等が挙げられる。 The heating conditions are not particularly limited, and various conditions such as the heating temperature, the heating time, and the heating apparatus can be appropriately selected according to the purpose. Examples of the heating device include a roll machine ordinarily used for heating a rubber composition.
前記押出しの条件としては、特に制限はなく、押出時間、押出速度、押出装置、押出温度等の諸条件について目的に応じて適宜選択することができる。前記押出装置としては、例えば、通常タイヤ用ゴム組成物の押出しに用いる押出機等が挙げられる。前記押出温度は、適宜決定することができる。 The conditions for the extrusion are not particularly limited, and various conditions such as an extrusion time, an extrusion speed, an extrusion apparatus, and an extrusion temperature can be appropriately selected according to the purpose. As said extrusion apparatus, the extruder etc. which are normally used for extrusion of the rubber composition for tires are mentioned, for example. The extrusion temperature can be appropriately determined.
前記加硫を行う装置、方式、条件等については、特に制限はなく、目的に応じて適宜選択することができる。前記加硫を行う装置としては、例えば、通常タイヤ用ゴム組成物の加硫に用いる金型による成形加硫機等が挙げられる。前記加硫の条件として、その温度は、通常100〜190℃程度である。 There is no restriction | limiting in particular about the apparatus, system, conditions, etc. which perform the said vulcanization | cure, According to the objective, it can select suitably. Examples of the vulcanizing apparatus include a molding vulcanizer using a mold usually used for vulcanizing a rubber composition for tires. As the vulcanization conditions, the temperature is usually about 100 to 190 ° C.
上述のように、本発明のゴム組成物は、高いグリップ性能を維持しつつ、耐熱疲労性等の耐熱性が向上しているため、高性能タイヤのトレッドに好適である。 As described above, the rubber composition of the present invention is suitable for a tread of a high-performance tire because heat resistance such as heat fatigue resistance is improved while maintaining high grip performance.
本発明の空気入りタイヤは、前記本発明のゴム組成物をトレッドに使用してなることを特徴とする。本発明のタイヤは、前記ゴム組成物をトレッドに用いること以外は、特に制限はなく、公知のタイヤの構成をそのまま採用することができる。 The pneumatic tire of the present invention is characterized by using the rubber composition of the present invention as a tread. There is no restriction | limiting in particular except for using the said rubber composition for a tread, and the tire of this invention can employ | adopt the structure of a well-known tire as it is.
本発明の空気入りタイヤの一例としては、一対のビード部と、一対のサイド部と、トレッド部と、上記ビード部間にトロイド状に延在させたカーカスと、該カーカスのクラウン部に配したベルトとを備えたタイヤ等が好適に挙げられる。該タイヤは、ラジアル構造であっても、バイアス構造であってもよい。 As an example of the pneumatic tire of the present invention, a pair of bead portions, a pair of side portions, a tread portion, a carcass extending in a toroid shape between the bead portions, and a crown portion of the carcass are arranged. A tire provided with a belt is preferably exemplified. The tire may have a radial structure or a bias structure.
前記トレッドの構造としては、特に制限はなく、一層構造であっても、多層構造であってもよく、直接路面に接地する上層のキャップ部と、このキャップ部のタイヤ径方向内側に隣接して配置される下層のベース部とから構成される、いわゆるキャップ・ベース構造を有していてもよい。本発明においては、少なくとも前記キャップ部が前記本発明のゴム組成物で形成されているのが好ましい。 The structure of the tread is not particularly limited, and may be a single layer structure or a multilayer structure. An upper cap portion that directly contacts the road surface and an inner side in the tire radial direction of the cap portion are adjacent to each other. You may have what is called a cap base structure comprised from the base part of the lower layer arrange | positioned. In the present invention, it is preferable that at least the cap portion is formed of the rubber composition of the present invention.
本発明の空気入りタイヤは、その製造方法に特に制限はないが、例えば、前記本発明のゴム組成物を調製し、該ゴム組成物を生タイヤケースのクラウン部に予め貼り付けられた未加硫のベース部の上に貼り付け、所定のモールドで所定温度・所定圧力の下で加硫成形することにより製造することができる。 The production method of the pneumatic tire of the present invention is not particularly limited. For example, the rubber composition of the present invention is prepared, and the rubber composition is not added to the crown portion of the raw tire case in advance. It can be manufactured by pasting on a sulfur base and vulcanization molding with a predetermined mold at a predetermined temperature and pressure.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
表１に示す配合処方に従い、バンバリーミキサーを用いて、各種ゴム組成物を調製した。得られたゴム組成物を160℃で15分間加硫した後、ＪＩＳ Ｋ６２６５に記載のフレクソメーターによる定応力測定を行い、サンプル内部に亀裂が発生するまでの時間を耐熱疲労時間とし、比較例１を100として指数表示した。結果を表１に示す。なお、指数値が大きい程、耐熱疲労時間が長く、耐熱疲労性が良好であることを示す。 Various rubber compositions were prepared using a Banbury mixer according to the formulation shown in Table 1. After the obtained rubber composition was vulcanized at 160 ° C. for 15 minutes, a constant stress measurement was performed with a flexometer described in JIS K6265, and the time until cracks occurred inside the sample was defined as the heat fatigue time. The index is shown with 1 being 100. The results are shown in Table 1. In addition, it shows that heat resistance fatigue time is so long that an index value is large, and heat fatigue resistance is favorable.
ビニル結合量が30％以上のスチレン・ブタジエン共重合体ゴムをゴム成分とし、式(I)で表される化合物と式(II)で表される化合物とを配合してなる実施例１〜２のゴム組成物は耐熱疲労時間が非常に長かった。一方、本願請求項１に規定する条件を満たさない比較例２〜１０のゴム組成物は、比較例１と比べて耐熱疲労時間の向上が不充分であった。特に、実施例１及び２と、比較例９及び１０との比較から、１,６-ビス[Ｎ,Ｎ'-ジ(２-エチルヘキシル)チオカルバモイルジチオ]-ヘキサンに代えて１,１０-ビス[Ｎ,Ｎ'-ジ(２-エチルヘキシル)チオカルバモイルジチオ]-デカンを用いることで、ゴム組成物の耐熱疲労性が大幅に向上することが分る。 Examples 1-2 in which a styrene / butadiene copolymer rubber having a vinyl bond content of 30% or more is used as a rubber component, and a compound represented by the formula (I) and a compound represented by the formula (II) are blended This rubber composition had a very long heat fatigue time. On the other hand, the rubber compositions of Comparative Examples 2 to 10 that did not satisfy the conditions defined in claim 1 of the present application were insufficient in improving the heat fatigue time compared with Comparative Example 1. In particular, from comparison between Examples 1 and 2 and Comparative Examples 9 and 10, 1,10-bis instead of 1,6-bis [N, N′-di (2-ethylhexyl) thiocarbamoyldithio] -hexane It can be seen that the use of [N, N′-di (2-ethylhexyl) thiocarbamoyldithio] -decane significantly improves the heat fatigue resistance of the rubber composition.
Claims (9)
（２）下記式(I)で表される化合物と、
（３）下記式(II)で表される有機チオスルフェート化合物と
を配合してなるゴム組成物。
［式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に炭素数３〜１２の直鎖若しくは分岐鎖アルキル基又は炭素数７〜１２のアラルキル基を示す。］
Ｍ1Ｏ3Ｓ−Ｓ−(ＣＨ2)n−Ｓ−ＳＯ3Ｍ1 ・・・ (II)
［式中、ｎは３〜１０を表し、Ｍ1はリチウム、カリウム、ナトリウム、マグネシウム、カルシウム、バリウム、亜鉛、ニッケル又はコバルトの１当量を表す。また、該化合物は、結晶水を含有していてもよい。］ (1) A rubber component containing at least one of a polybutadiene rubber and a styrene / butadiene copolymer rubber having a vinyl bond amount of 30% or more,
(2) a compound represented by the following formula (I):
(3) A rubber composition comprising an organic thiosulfate compound represented by the following formula (II).
[Wherein, R 1 , R 2 , R 3 and R 4 each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms. ]
M 1 O 3 S—S— (CH 2 ) n —S—SO 3 M 1 (II)
[Wherein, n represents 3 to 10, and M 1 represents one equivalent of lithium, potassium, sodium, magnesium, calcium, barium, zinc, nickel, or cobalt. Further, the compound may contain crystal water. ]
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| KR20110081321A (en) * | 2008-10-30 | 2011-07-13 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Thiocarbamoyldisulfanyl-functional cycloaliphatic compound, process for its preparation, filled sulfur-vulcanizable elastomer composition containing same and articles fabricated therefrom |
| US7987880B2 (en) | 2006-10-30 | 2011-08-02 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for tire base tread |
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| JP2001288297A (en) * | 2000-02-04 | 2001-10-16 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2004043640A (en) * | 2002-07-11 | 2004-02-12 | Bridgestone Corp | Tire, retreaded tire and rubber composition for mending vulcanized rubber product |
| JP2004256792A (en) * | 2003-02-06 | 2004-09-16 | Bridgestone Corp | Rubber composition and pneumatic tire given by using the same |
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| JP2001288297A (en) * | 2000-02-04 | 2001-10-16 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2004043640A (en) * | 2002-07-11 | 2004-02-12 | Bridgestone Corp | Tire, retreaded tire and rubber composition for mending vulcanized rubber product |
| JP2004256792A (en) * | 2003-02-06 | 2004-09-16 | Bridgestone Corp | Rubber composition and pneumatic tire given by using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7987880B2 (en) | 2006-10-30 | 2011-08-02 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for tire base tread |
| KR20110081321A (en) * | 2008-10-30 | 2011-07-13 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Thiocarbamoyldisulfanyl-functional cycloaliphatic compound, process for its preparation, filled sulfur-vulcanizable elastomer composition containing same and articles fabricated therefrom |
| JP2012507559A (en) * | 2008-10-30 | 2012-03-29 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Thiocarbamoyl disulfanyl functional alicyclic compound, process for its preparation, filled sulfur vulcanizable elastomeric composition containing it, and articles made therefrom |
| KR101671230B1 (en) | 2008-10-30 | 2016-11-01 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Thiocarbamoyldisulfanyl-functional cycloaliphatic compound, process for its preparation, filled sulfur-vulcanizable elastomer composition containing same and articles fabricated therefrom |
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