JP2013023651A - Rubber composition, production method thereof, and pneumatic tire - Google Patents
Rubber composition, production method thereof, and pneumatic tire Download PDFInfo
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本発明は、ゴム組成物及びその製造方法に関するものである。また、該ゴム組成物を用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition and a method for producing the same. The present invention also relates to a pneumatic tire using the rubber composition.
空気入りタイヤは、長期間使用中に、大気中の酸素やオゾンまた繰り返し屈曲や熱などにより劣化することで、サイドウォール部やトレッド部の溝底に亀裂が生じ、これが耐久性を悪化させる原因となる。そのため、耐屈曲疲労性、耐オゾン性、耐熱劣化性などを改良するために、タイヤ用ゴム組成物には、これらの性能に優れるアミン系老化防止剤が一般に配合されている。しかしながら、アミン系老化防止剤は、タイヤを茶色あるいは茶褐色に変色させていくため、その外観が悪くなり、タイヤの商品価値が低下するという問題がある。一方、ベンズイミダゾール系老化防止剤は、優れた耐熱性を有することから、防振ゴムに広く使用されているが、それをタイヤに使用することのよる外観性の向上効果については知られていなかった。 Pneumatic tires deteriorate due to atmospheric oxygen, ozone, repeated bending, heat, etc. during long-term use, causing cracks in the groove bottoms of the sidewalls and treads, which deteriorates durability. It becomes. Therefore, in order to improve bending fatigue resistance, ozone resistance, heat deterioration resistance, and the like, amine-based anti-aging agents having excellent performance are generally blended in the tire rubber composition. However, since the amine-based anti-aging agent discolors the tire to brown or brown, there is a problem that the appearance is deteriorated and the commercial value of the tire is lowered. On the other hand, benzimidazole anti-aging agents are widely used in anti-vibration rubbers because they have excellent heat resistance, but the effects of improving the appearance by using them in tires are not known. It was.
ベンズイミダゾール系老化防止剤をタイヤに用いた技術として、下記特許文献１には、アミン系老化防止剤などのプロトン供与型酸化防止剤とベンズイミダゾール系老化防止剤とを配合することにより、耐熱劣化性、耐酸化劣化性を向上したゴム組成物が開示されている。しかしながら、この文献では、ゴム組成物を調製する際に、アミン系老化防止剤とベンズイミダゾール系老化防止剤をそれぞれゴム成分に添加し混練するものであり、両者の事前混合物を用いる点については開示されておらず、またそれによる外観性の向上効果についても記載はない。 As a technique using a benzimidazole-based anti-aging agent for a tire, the following Patent Document 1 includes heat-resistant deterioration by incorporating a proton-donating antioxidant such as an amine-based anti-aging agent and a benzimidazole-based anti-aging agent. A rubber composition having improved properties and resistance to oxidation deterioration is disclosed. However, in this document, when preparing a rubber composition, an amine-based anti-aging agent and a benzimidazole-based anti-aging agent are respectively added to a rubber component and kneaded, and the point of using a premix of both is disclosed. No mention is made of the effect of improving the appearance.
下記特許文献２には、アミン系老化防止剤とベンズイミダゾール系老化防止剤と表面活性カーボンブラックを用いることにより、耐久性や耐熱性を向上した防振ゴム組成物が開示されている。しかしながら、この文献も、アミン系老化防止剤とベンズイミダゾール系老化防止剤を単純に配合するものであり、また外観性の向上効果についても開示されていない。 Patent Document 2 listed below discloses an anti-vibration rubber composition having improved durability and heat resistance by using an amine-based anti-aging agent, a benzimidazole-based anti-aging agent, and a surface-active carbon black. However, this document also simply mixes an amine-based anti-aging agent and a benzimidazole-based anti-aging agent, and does not disclose an effect of improving the appearance.
一方、下記特許文献３には、ベンズイミダゾール系老化防止剤とｐ−フェニレンジアミン系老化防止剤とを有機溶剤中で加熱することにより塩を形成し、この塩を老化防止剤としてゴム組成物に配合することにより、耐熱性、耐オゾン性及び耐屈曲疲労性を改良することが開示されている。しかしながら、粉末状のベンズイミダゾール系老化防止剤に対しアミン系老化防止剤を溶融させて混合してなる事前混合物については開示されておらず、また、外観性の改良を示唆する記載もない。 On the other hand, in Patent Document 3 below, a salt is formed by heating a benzimidazole anti-aging agent and a p-phenylenediamine anti-aging agent in an organic solvent, and this salt is used as an anti-aging agent in the rubber composition. It is disclosed to improve heat resistance, ozone resistance and bending fatigue resistance by blending. However, there is no disclosure of a pre-mixture obtained by melting and mixing an amine anti-aging agent with a powdered benzimidazole anti-aging agent, and there is no description suggesting an improvement in appearance.
なお、下記特許文献４には、ベンズイミダゾール化合物を用いることによりタイヤのグリップ性を向上することが開示されているが、この文献では、ベンズイミダゾールの２位の位置がメルカプト基以外の置換基で置換された化合物を用いており、ベンズイミダゾール系老化防止剤とアミン系老化防止剤との併用を開示するものではない。 In addition, Patent Document 4 below discloses that the grip property of a tire is improved by using a benzimidazole compound. In this document, the position of the 2-position of benzimidazole is a substituent other than a mercapto group. It uses a substituted compound and does not disclose the combined use of a benzimidazole antioxidant and an amine antioxidant.
本発明は、以上の点に鑑みてなされたものであり、耐熱劣化性を向上することができるとともに、ゴム表面の変色を抑制して外観性を改善することができるゴム組成物、及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above points, a rubber composition capable of improving heat resistance and improving appearance by suppressing discoloration of the rubber surface, and production thereof. It aims to provide a method.
本発明者は、上記課題に鑑み、鋭意検討していく中で、アミン系老化防止剤とベンズイミダゾール系老化防止剤を事前溶融混合した混合物を用いることにより、上記課題が解決できることを見出し、本発明を完成するに至った。 The present inventor has found that the above problems can be solved by using a mixture obtained by pre-melt mixing an amine-based anti-aging agent and a benzimidazole-based anti-aging agent in the intensive study in view of the above-mentioned problems, The invention has been completed.
本発明に係るゴム組成物は、粉末状のベンズイミダゾール系老化防止剤に対しアミン系老化防止剤を溶融させて混合してなる事前混合物と、ジエン系ゴムからなるゴム成分と、を配合してなり、前記ゴム成分１００質量部に対して、前記ベンズイミダゾール系老化防止剤を０．１〜４質量部、前記アミン系老化防止剤を０．５〜８質量部含有するものである。 The rubber composition according to the present invention comprises a premix obtained by melting and mixing an amine antioxidant to a powdered benzimidazole antioxidant and a rubber component made of a diene rubber. Thus, 0.1 to 4 parts by mass of the benzimidazole anti-aging agent and 0.5 to 8 parts by mass of the amine anti-aging agent are contained with respect to 100 parts by mass of the rubber component.
本発明に係るゴム組成物の製造方法は、粉末状のベンズイミダゾール系老化防止剤に対しアミン系老化防止剤を溶融させて混合することにより事前混合物を作製し、該事前混合物を、ジエン系ゴムからなるゴム成分１００質量部に対して、前記ベンズイミダゾール系老化防止剤が０．１〜４質量部、前記アミン系老化防止剤が０．５〜８質量部配合されるように、前記ゴム成分に添加し混練するものである。 The method for producing a rubber composition according to the present invention comprises preparing a premix by melting and mixing an amine anti-aging agent with a powdered benzimidazole anti-aging agent, and preparing the pre-mixture with a diene rubber. The rubber component is blended such that 0.1 to 4 parts by mass of the benzimidazole anti-aging agent and 0.5 to 8 parts by mass of the amine anti-aging agent are blended with respect to 100 parts by mass of the rubber component consisting of And kneaded.
上記事前混合物は、アミン系老化防止剤とベンズイミダゾール系老化防止剤を、前記アミン系老化防止剤の融点以上かつ前記ベンズイミダゾール系老化防止剤の融点未満の温度で、かつ無溶剤で加熱混合して得られたものであることが好ましい。 The premix is prepared by heating and mixing an amine anti-aging agent and a benzimidazole anti-aging agent at a temperature equal to or higher than the melting point of the amine anti-aging agent and lower than the melting point of the benzimidazole anti-aging agent and without solvent. It is preferable that it is obtained.
本発明に係る空気入りタイヤは、上記ゴム組成物を用いてなるものである。 The pneumatic tire according to the present invention is formed using the rubber composition.
本発明によれば、粉末状のベンズイミダゾール系老化防止剤に対してアミン系老化防止剤を溶融させて混合してなる事前混合物を、ゴム組成物に配合することにより、耐熱劣化性を向上させることができ、更に、タイヤの外観性を改善することができる。 According to the present invention, the heat deterioration resistance is improved by blending, in the rubber composition, a premix obtained by melting and mixing an amine anti-aging agent with a powdered benzimidazole anti-aging agent. In addition, the appearance of the tire can be improved.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係るゴム組成物は、ジエン系ゴムからなるゴム成分、及び、アミン系老化防止剤とベンズイミダゾール系老化防止剤との事前混合物、を含有するものである。 The rubber composition according to this embodiment contains a rubber component composed of a diene rubber and a premix of an amine-based antioxidant and a benzimidazole-based antioxidant.
上記ゴム成分となるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエンゴム（ＳＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体、スチレン−イソプレン−ブタジエン共重合体ゴム等が挙げられる。これらはそれぞれ単独で又は２種以上組み合わせて用いることができる。上記ゴム成分は、好ましくは、天然ゴム、ブタジエンゴム、スチレン−ブタジエンゴム、又はこれらの２種以上のブレンドである。 Examples of the diene rubber used as the rubber component include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber ( CR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer, styrene-isoprene-butadiene copolymer rubber, and the like. These can be used alone or in combination of two or more. The rubber component is preferably natural rubber, butadiene rubber, styrene-butadiene rubber, or a blend of two or more thereof.
上記事前混合物としては、粉末状のベンズイミダゾール系老化防止剤に対しアミン系老化防止剤を溶融させて混合してなる溶融混合物が用いられる。かかる事前混合物であると、溶融したアミン系老化防止剤が粉末状のベンズイミダゾール系老化防止剤の周りに付着し複合一体化した状態となっているので、ゴム組成物中において、アミン系老化防止剤はベンズイミダゾール系老化防止剤との相互作用により見かけ上高分子量化してゴム表面にブリードしにくくなるものと考えられ、そのため外観性が向上する。また、アミン系老化防止剤とベンズイミダゾール系老化防止剤とを併用することにより、両者の酸塩基相互作用により耐熱性が向上するが、本実施形態では事前溶融混合によりこの効果を高めることができるので、耐熱劣化性を一層向上することができる。 As the pre-mixture, a molten mixture obtained by melting and mixing an amine-based anti-aging agent with a powdered benzimidazole-based anti-aging agent is used. In such a premix, the melted amine-based anti-aging agent adheres around the powdered benzimidazole-based anti-aging agent and is in a state of being combined and integrated, so in the rubber composition, the amine-based anti-aging is prevented. It is considered that the agent becomes apparently high molecular weight due to the interaction with the benzimidazole anti-aging agent and becomes difficult to bleed on the rubber surface, and thus the appearance is improved. Further, by using an amine-based anti-aging agent and a benzimidazole-based anti-aging agent in combination, the heat resistance is improved by the acid-base interaction between them, but in this embodiment, this effect can be enhanced by pre-melt mixing. As a result, the heat deterioration resistance can be further improved.
上記アミン系老化防止剤としては、芳香族第２級アミンが好ましく用いられる。具体的には、Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、Ｎ−（３−メタクリロイルオキシ−２−ヒドロキシプロピル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ−シクロヘキシル−Ｎ’−フェニル−ｐ−フェニレンジアミンなどのｐ−フェニレンジアミン系老化防止剤、ｐ−（ｐ−トルエンスルホニルアミド）ジフェニルアミン、４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミン、オクチル化ジフェニルアミン、スチレン化ジフェニルアミンなどのジフェニルアミン系老化防止剤、Ｎ−フェニル−１−ナフチルアミン、Ｎ−フェニル−２−ナフチルアミン等のナフチルアミン系老化防止剤などが挙げられる。これらはそれぞれ単独で又は２種以上組み合わせて用いることができる。これらの中でも、ｐ−フェニレンジアミン系老化防止剤が好ましく、より好ましくはＮ−アルキル−Ｎ’−フェニル−ｐ−フェニレンジアミン（但し、アルキルとは炭素数３〜８のアルキル基）である。 As the amine-based antioxidant, an aromatic secondary amine is preferably used. Specifically, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N, N′-diphenyl-p-phenylene P-phenylenediamine-based antiaging agents such as diamine, N- (3-methacryloyloxy-2-hydroxypropyl) -N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, p- (p-toluenesulfonylamide) diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylated diphenylamine, styrenated diphenylamine and other diphenylamine-based antioxidants, N-phenyl-1-naphthylamine, Naphthyl such as N-phenyl-2-naphthylamine Examples include amine-based anti-aging agents. These can be used alone or in combination of two or more. Among these, p-phenylenediamine-based antioxidants are preferable, and N-alkyl-N′-phenyl-p-phenylenediamine (wherein alkyl is an alkyl group having 3 to 8 carbon atoms) is more preferable.
上記ベンズイミダゾール系老化防止剤としては、２−メルカプトベンズイミダゾール、芳香環に少なくとも１個のアルキル置換基（好ましくは炭素数１〜５のアルキル基）を有する２−メルカプトベンズイミダゾール、並びにそれらの金属塩が挙げられ、これらの少なくとも１種以上を用いることができる。具体的には、２−メルカプトベンズイミダゾール（ＭＢＩ）、２−メルカプトメチルベンズイミダゾール、２−メルカプトベンズイミダゾール亜鉛塩（ＺｎＭＢＩ）などが挙げられる。これらのベンズイミダゾール系老化防止剤は、一般に粉末状の形態で市販されており、そのような粉末状のベンズイミダゾール系老化防止剤を用いることができる。ここで、ベンズイミダゾール系老化防止剤の粒径は特に限定されないが、平均粒子径が１〜 ５００μｍであることが好ましい。ここで、平均粒子径は、走査型電子顕微鏡（ＳＥＭ）で観察して画像を得て、この画像を用いて、無作為抽出された５０個の粒子の直径（MediaCybernetics社の画像処理ソフト「Image-Pro Plus」を用いて、粒子の外周の２点を結び、かつ重心を通る径を２度刻みに測定した平均値）を計測することにより、その相加平均として求められる。 Examples of the benzimidazole anti-aging agent include 2-mercaptobenzimidazole, 2-mercaptobenzimidazole having an aromatic ring having at least one alkyl substituent (preferably an alkyl group having 1 to 5 carbon atoms), and metals thereof. A salt is mentioned, At least 1 or more types of these can be used. Specific examples include 2-mercaptobenzimidazole (MBI), 2-mercaptomethylbenzimidazole, and 2-mercaptobenzimidazole zinc salt (ZnMBI). These benzimidazole anti-aging agents are generally commercially available in powder form, and such powdery benzimidazole anti-aging agents can be used. Here, the particle size of the benzimidazole antioxidant is not particularly limited, but the average particle size is preferably 1 to 500 μm. Here, the average particle diameter is observed with a scanning electron microscope (SEM) to obtain an image. Using this image, the diameter of 50 particles randomly extracted (image processing software “ImageCyber of MediaCybernetics” “Image -Pro Plus "is used to determine the arithmetic mean of the two points on the outer circumference of the particle and the average value obtained by measuring the diameter passing through the center of gravity in increments of 2 degrees.
上記事前混合物は、アミン系老化防止剤を溶融させて、粉末状のベンズイミダゾール系老化防止剤と混合することにより得られる。より詳細には、アミン系老化防止剤とベンズイミダゾール系老化防止剤を、アミン系老化防止剤の融点以上かつベンズイミダゾール系老化防止剤の融点未満の温度で加熱攪拌して混合する。一般に、アミン系老化防止剤はベンズイミダゾール系老化防止剤に比べて融点が十分に低いので、混合時の加熱温度をアミン系老化防止剤の融点以上に設定することで、アミン系老化防止剤が溶融し、溶融したアミン系老化防止剤が粉末状のベンズイミダゾール系老化防止剤と複合一体化される。かかる混合時にアミン系老化防止剤やベンズイミダゾール系老化防止剤を溶解させる有機溶剤は不要である。すなわち、本実施形態では、無溶剤でベンズイミダゾール系老化防止剤とアミン系老化防止剤を溶融混合する。有機溶剤に溶解させて加熱混合すると、上記特許文献３のように塩が形成されてしまい、本実施形態特有の有利な効果が得られないためである。 The premix is obtained by melting an amine-based anti-aging agent and mixing it with a powdered benzimidazole-based anti-aging agent. More specifically, the amine-based anti-aging agent and the benzimidazole-based anti-aging agent are mixed by heating and stirring at a temperature not lower than the melting point of the amine-based anti-aging agent and lower than the melting point of the benzimidazole-based anti-aging agent. In general, amine-based anti-aging agents have a sufficiently low melting point compared to benzimidazole-based anti-aging agents, so by setting the heating temperature during mixing above the melting point of the amine-based anti-aging agent, the amine-based anti-aging agent When melted, the melted amine-based antioxidant is combined and integrated with the powdered benzimidazole-based antioxidant. An organic solvent that dissolves the amine-based anti-aging agent or the benzimidazole-based anti-aging agent during the mixing is unnecessary. That is, in this embodiment, the benzimidazole anti-aging agent and the amine anti-aging agent are melt-mixed without solvent. This is because, when dissolved in an organic solvent and heated and mixed, a salt is formed as in Patent Document 3, and advantageous effects peculiar to the present embodiment cannot be obtained.
ここで、事前混合の方法としては、例えば、アミン系老化防止剤を加熱溶融させ、この加熱溶融したアミン系老化防止剤に粉末状のベンズイミダゾール系老化防止剤を添加し攪拌混合してもよく、あるいは、ベンズイミダゾール系老化防止剤を攪拌しながら、加熱溶融したアミン系老化防止剤を添加し混合してもよく、あるいはまた、アミン系老化防止剤とベンズイミダゾール系老化防止剤をミキサーで攪拌混合しながら、混合時のせん断による摩擦熱やヒーターによる加熱でアミン系老化防止剤を溶融させてもよい。このようにして得られた事前混合物は、アミン系老化防止剤が溶融した状態のままゴム成分に添加混合してもよいし、一旦冷却してからゴム成分に添加混合してもよい。 Here, as a premixing method, for example, an amine anti-aging agent may be heated and melted, and a powdered benzimidazole anti-aging agent may be added to the heat-melted amine anti-aging agent, followed by stirring and mixing. Alternatively, while agitating the benzimidazole anti-aging agent, a heated and melted amine anti-aging agent may be added and mixed, or the amine anti-aging agent and the benzimidazole anti-aging agent may be stirred with a mixer. While mixing, the amine-based antioxidant may be melted by frictional heat due to shear during mixing or heating by a heater. The premix thus obtained may be added and mixed with the rubber component while the amine-based anti-aging agent is melted, or may be once cooled and then added and mixed with the rubber component.
事前混合物中におけるアミン系老化防止剤とベンズイミダゾール系老化防止剤との比率は、特に限定されないが、アミン系老化防止剤１００質量部に対して、ベンズイミダゾール系老化防止剤が１０〜１５０質量部であることが好ましく、より好ましくは２０〜１００質量部である。 The ratio of the amine-based anti-aging agent and the benzimidazole-based anti-aging agent in the premix is not particularly limited, but the benzimidazole-based anti-aging agent is 10 to 150 parts by mass with respect to 100 parts by mass of the amine-based anti-aging agent. It is preferable that it is 20-100 mass parts.
上記事前混合物のゴム成分に対する配合量は、次のように設定されることが好ましい。すなわち、事前混合物は、上記ゴム成分１００質量部に対してベンズイミダゾール系老化防止剤が０．１〜４質量部、アミン系老化防止剤が０．５〜８質量部となるように、ゴム成分に添加される。アミン系老化防止剤の含有量が０．５質量部未満であると、耐屈曲疲労性や耐オゾン性を確保することが困難になる。逆に、アミン系老化防止剤の含有量が８質量部を超えると、外観性を改善することが困難になる。アミン系老化防止剤の含有量は、より好ましくは１〜６質量部であり、更に好ましくは２〜５質量部である。一方、ベンズイミダゾール系老化防止剤の含有量が０．１質量部未満であると、上記事前混合による効果が不十分となり、逆に４質量部を超えると、外観性改良効果が小さくなる。ベンズイミダゾール系老化防止剤の含有量は、より好ましくは０．５〜３質量部である。 The blending amount of the premix with respect to the rubber component is preferably set as follows. That is, the pre-mixture has a rubber component such that the benzimidazole anti-aging agent is 0.1 to 4 parts by mass and the amine anti-aging agent is 0.5 to 8 parts by mass with respect to 100 parts by mass of the rubber component. To be added. If the content of the amine anti-aging agent is less than 0.5 parts by mass, it becomes difficult to ensure bending fatigue resistance and ozone resistance. On the other hand, when the content of the amine anti-aging agent exceeds 8 parts by mass, it becomes difficult to improve the appearance. The content of the amine anti-aging agent is more preferably 1 to 6 parts by mass, and further preferably 2 to 5 parts by mass. On the other hand, when the content of the benzimidazole anti-aging agent is less than 0.1 parts by mass, the effect of the pre-mixing becomes insufficient. Conversely, when the content exceeds 4 parts by mass, the appearance improving effect is reduced. The content of the benzimidazole anti-aging agent is more preferably 0.5 to 3 parts by mass.
本実施形態に係るゴム組成物には、カーボンブラックやシリカなどの一般にゴム組成物において配合される補強性充填剤を配合することができる。補強性充填剤の配合量は、特に限定されないが、ゴム成分１００質量部に対して１０〜２００質量部であることが好ましく、より好ましくは２０〜１００質量部である。 In the rubber composition according to the present embodiment, a reinforcing filler that is generally blended in a rubber composition such as carbon black or silica can be blended. Although the compounding quantity of a reinforcing filler is not specifically limited, It is preferable that it is 10-200 mass parts with respect to 100 mass parts of rubber components, More preferably, it is 20-100 mass parts.
本実施形態に係るゴム組成物には、上記した成分の他に、オイル等の軟化剤、ステアリン酸、亜鉛華、ワックス、加硫剤、加硫促進剤など、ゴム工業において一般に使用される各種添加剤を必要に応じて配合することができる。上記加硫剤としては、硫黄、硫黄含有化合物等が挙げられ、特に限定するものではないが、その配合量は上記ゴム成分１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。また、加硫促進剤の配合量としては、上記ゴム成分１００質量部に対して０．１〜７質量部であることが好ましく、より好ましくは０．５〜５質量部である。 In the rubber composition according to the present embodiment, in addition to the above-described components, various softeners such as oil, stearic acid, zinc white, wax, vulcanizing agent, vulcanization accelerator, and the like that are generally used in the rubber industry. An additive can be mix | blended as needed. Examples of the vulcanizing agent include sulfur and sulfur-containing compounds, and are not particularly limited. However, the blending amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 0.5-5 mass parts. Moreover, as a compounding quantity of a vulcanization accelerator, it is preferable that it is 0.1-7 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts.
該ゴム組成物は、通常のバンバリーミキサーやニーダーなどのゴム用混練機を用いて、常法に従い混練することで調製することができる。例えば、第１混練段階で、ゴム成分に対し、上記事前混合物とともに、加硫剤及び加硫促進剤を除く他の添加剤を加えて混練し、次いで、得られた混練物に、最終混練段階で、加硫剤と加硫促進剤を添加し混練することによりゴム組成物を得ることができる。 The rubber composition can be prepared by kneading according to a conventional method using a rubber kneader such as a normal Banbury mixer or kneader. For example, in the first kneading step, the rubber component is kneaded with the above premix and other additives excluding the vulcanizing agent and vulcanization accelerator, and then kneaded, and then the obtained kneaded product is subjected to the final kneading step. Thus, a rubber composition can be obtained by adding and kneading a vulcanizing agent and a vulcanization accelerator.
このようにして得られたゴム組成物は、例えば、トレッドやサイドウォール、ベルトやプライのトッピングゴム、ビードフィラー、リムストリップ等のタイヤ、コンベアベルト、防振ゴムなどの各種用途に用いることができるが、好ましくは、空気入りタイヤのゴム部分に用いることである。特には、空気入りタイヤのトレッドゴムやサイドウォールゴムとして用いることが好ましく、より好ましくはサイドウォールゴムに用いることであり、常法に従い、例えば１４０〜１８０℃で加硫成形することにより、空気入りタイヤを作製することができる。 The rubber composition thus obtained can be used for various applications such as treads and sidewalls, belts and ply topping rubbers, tires such as bead fillers and rim strips, conveyor belts, and vibration-proof rubbers. However, it is preferably used for a rubber portion of a pneumatic tire. In particular, it is preferably used as a tread rubber or a side wall rubber of a pneumatic tire, more preferably used as a side wall rubber, and in accordance with a conventional method, for example, by vulcanization molding at 140 to 180 ° C. Tires can be made.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
下記実施例及び比較例で使用した各成分の詳細は以下の通りである。 Details of each component used in the following examples and comparative examples are as follows.
・アミン系老化防止剤（６Ｃ）：Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、６ＰＰＤ、融点：４４℃、大内新興化学工業（株）製「ノクラック６Ｃ」
・ベンズイミダゾール系老化防止剤（ＭＢ）：２−メルカプトベンズイミダゾール、ＭＢＩ、融点：２８５℃、大内新興化学工業（株）製「ノクラックＭＢ」
・ベンズイミダゾール系老化防止剤（ＭＭＢ）：２−メルカプトメチルベンズイミダゾール、融点：２５０℃、大内新興化学工業（株）製「ノクラックＭＭＢ」
・天然ゴム：ＲＳＳ３号
・ブタジエンゴム：宇部興産（株）製「ＢＲ１５０Ｂ」
・カーボンブラック：ＨＡＦ、東海カーボン（株）製「シースト３」
・亜鉛華：三井金属鉱業（株）製「１号亜鉛華」
・ステアリン酸：花王（株）製「工業用ステアリン酸」
・硫黄：鶴見化学工業（株）製「５％油処理粉末硫黄」
・加硫促進剤：ＮＳ、大内新興化学工業株式会社製「ノクセラーＮＳ−Ｐ」
Amine-based antioxidant (6C): N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, 6PPD, melting point: 44 ° C., “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd. "
Benzimidazole anti-aging agent (MB): 2-mercaptobenzimidazole, MBI, melting point: 285 ° C., “NOCRACK MB” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Benzimidazole anti-aging agent (MMB): 2-mercaptomethylbenzimidazole, melting point: 250 ° C., “NOCRACK MMB” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Natural rubber: RSS No. 3 ・ Butadiene rubber: “BR150B” manufactured by Ube Industries, Ltd.
・ Carbon black: HAF, “Seast 3” manufactured by Tokai Carbon Co., Ltd.
・ Zinc flower: “No. 1 Zinc flower” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: "Industrial stearic acid" manufactured by Kao Corporation
・ Sulfur: “5% oil-treated powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator: NS, “Noxeller NS-P” manufactured by Ouchi Shinsei Chemical Co., Ltd.
評価方法は以下の通りである。 The evaluation method is as follows.
・外観性：試験片を屋外で日光に照射させ、照射前（屋外曝露０日）、２０日後（屋外曝露２０日）、及び４０日後（屋外曝露４０日）における試験片の表面を目視により観察して、下記の基準で外観性を評価した。
◎：表面が黒く、ほとんど変色なし
○：わずかに茶色または白色に変色している
△：やや茶色または白色に変色している
×：茶褐色または白色に変色している
Appearance: The test piece is exposed to sunlight outdoors, and the surface of the test piece is visually observed before irradiation (0 days outdoors), 20 days (20 days outdoors), and 40 days (40 days outdoors). The appearance was evaluated according to the following criteria.
◎: The surface is black and hardly discolored. ○: Slightly brown or white. △: Slightly brown or white. ×: Brown or white.
・耐熱劣化性（老化後の破断伸び保持率）：試験片を、９０℃に温度調節したギヤーオーブン中にて１９２時間加熱して熱履歴を与えた後、ＪＩＳ Ｋ６２５１に準拠した引張試験を行って破断伸びを測定し、老化前の破断伸びに対する老化後の破断伸びの保持率（＝１００×（老化後の破断伸び／老化前の破断伸び））を求めた。該保持率について、比較例１の値を１００とした指数で表示した。指数が大きいほど、耐熱劣化性に優れることを意味する。 ・ Heat-resistant deterioration (breaking elongation retention after aging): A test piece was heated in a gear oven adjusted to 90 ° C. for 192 hours to give a thermal history, and then subjected to a tensile test according to JIS K6251. Then, the elongation at break was measured, and the retention rate of the elongation after aging with respect to the elongation before aging (= 100 × (breaking elongation after aging / breaking elongation before aging)) was determined. The retention was expressed as an index with the value of Comparative Example 1 being 100. A larger index means better heat resistance.
実施例及び比較例で用いた事前混合物を以下のようにして調製した。 The premixes used in the examples and comparative examples were prepared as follows.
・事前混合物Ａ：アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）を、質量比で６Ｃ／ＭＢ＝３／１の割合で投入し、有機溶剤を添加することなく、マグネチックスターラーを用いてオイルバスにて１００℃で６時間加熱攪拌することにより、事前混合物Ａを得た。 Premix A: Amine-based anti-aging agent (6C) and benzimidazole-based anti-aging agent (MB) were added at a mass ratio of 6C / MB = 3/1, and without adding an organic solvent, Premix A was obtained by heating and stirring at 100 ° C. for 6 hours in an oil bath using a tic stirrer.
・事前混合物Ｂ：アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＭＢ）を、質量比で６Ｃ／ＭＭＢ＝３／１の割合で投入し、その他は事前混合物Ａと同様にして事前混合物Ｂを作製した。 Pre-mix B: Amine-based anti-aging agent (6C) and benzimidazole-based anti-aging agent (MMB) are added at a mass ratio of 6C / MMB = 3/1, and the others are the same as pre-mix A Premix B was made.
・事前混合物Ｃ：アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）の質量比を６Ｃ／ＭＢ＝３／３とし、その他は事前混合物Ａと同様にして事前混合物Ｃを作製した。 Premix C: Mass ratio of amine-based anti-aging agent (6C) and benzimidazole-based anti-aging agent (MB) was set to 6C / MB = 3/3, and pre-mix C was prepared in the same manner as pre-mix A. did.
・事前混合物Ｄ：アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）の質量比を６Ｃ／ＭＢ＝５／２とし、その他は事前混合物Ａと同様にして事前混合物Ｄを作製した。 Premix D: Premix D is prepared in the same manner as Premix A, except that the mass ratio of the amine antioxidant (6C) and the benzimidazole antioxidant (MB) is 6C / MB = 5/2. did.
・事前混合物Ｅ：アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）の質量比を６Ｃ／ＭＢ＝３／６とし、その他は事前混合物Ａと同様にして事前混合物Ｅを作製した。 Pre-mix E: Mass ratio of amine-based anti-aging agent (6C) and benzimidazole-based anti-aging agent (MB) is 6C / MB = 3/6, and pre-mix E is prepared in the same manner as pre-mix A. did.
バンバリーミキサーを使用し、下記表１に示す配合（質量部）に従って、常法に従いタイヤサイドウォール用ゴム組成物を調製した。詳細には、まず、ゴム成分に対し、硫黄及び加硫促進剤を除く他の配合剤を添加し混練し、次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して、実施例及び比較例の各ゴム組成物を調製した。その際、事前混合物については、溶融した状態のままゴム成分に添加した。 Using a Banbury mixer, a rubber composition for a tire sidewall was prepared according to a conventional method according to the formulation (parts by mass) shown in Table 1 below. Specifically, first, other compounding agents excluding sulfur and a vulcanization accelerator are added to the rubber component and kneaded, and then, in the final mixing stage, sulfur and a vulcanization accelerator are added to the obtained kneaded product. The rubber compositions of Examples and Comparative Examples were prepared by adding and kneading. At that time, the premix was added to the rubber component in a molten state.
なお、比較例３で用いたアミン系老防とベンズイミダゾールの塩は、上記特許文献３（特開昭５８−１２２９４６号公報）に記載の方法に従い、アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）を、メタノールとアセトンの混合溶媒中に溶解せしめ、９０〜１００℃で６時間加熱することにより沈殿物を得て、これを濾過、乾燥することにより作製したものである。但し、アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）は、質量比で６Ｃ／ＭＢ＝３／２の割合で投入した。 The amine-based antioxidant and benzimidazole salt used in Comparative Example 3 were prepared in accordance with the method described in Patent Document 3 (Japanese Patent Application Laid-Open No. 58-122946) and amine-based antioxidant (6C) and benzimidazole. A system anti-aging agent (MB) is dissolved in a mixed solvent of methanol and acetone and heated at 90 to 100 ° C. for 6 hours to obtain a precipitate, which is prepared by filtering and drying. . However, the amine-based antioxidant (6C) and the benzimidazole-based antioxidant (MB) were added at a mass ratio of 6C / MB = 3/2.
このようにして得られた各ゴム組成物について、１６０℃×３０分で加硫して厚さ２ｍｍの試験片を作製し、得られた試験片を用いて、外観性及び耐熱劣化性を評価した。 Each rubber composition thus obtained was vulcanized at 160 ° C. for 30 minutes to prepare a test piece having a thickness of 2 mm, and the obtained test piece was used to evaluate the appearance and heat resistance deterioration. did.
結果は、表１に示す通りであり、アミン系老化防止剤単独使用の比較例１に対し、アミン系老化防止剤とベンズイミダゾール系老化防止剤を単に併用した比較例２では、外観性と耐熱性が若干改良されたものの、まだ満足な結果ではなかった。 The results are as shown in Table 1. Compared with Comparative Example 1 in which an amine-based anti-aging agent is used alone, Comparative Example 2 in which an amine-based anti-aging agent and a benzimidazole-based anti-aging agent are simply used in combination, the appearance and heat resistance. Although the properties were slightly improved, the results were not yet satisfactory.
これに対し、アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＢ）の事前混合物を配合した実施例１であると、外観性と耐熱劣化性がともに大幅に改良されていた。アミン系老化防止剤（６Ｃ）とベンズイミダゾール系老化防止剤（ＭＭＢ）の事前混合物を配合した実施例２についても、実施例１と同様に、外観性と耐熱劣化性がともに大幅に改良されていた。実施例３では、事前混合物中のベンズイミダゾール系老化防止剤の量を増やしたことにより、耐熱劣化性は更に改良された。外観性については、比較例２に対しては改善効果があったものの、実施例１，２に比べてわずかに低下していた。 On the other hand, when it was Example 1 which mix | blended the pre-mixture of amine type anti-aging agent (6C) and benzimidazole type anti-aging agent (MB), both external appearance property and heat-resistant deterioration property were improved significantly. As in Example 1, both the appearance and the heat deterioration resistance were greatly improved in Example 2 in which a premixed mixture of amine-based anti-aging agent (6C) and benzimidazole-based anti-aging agent (MMB) was blended. It was. In Example 3, the heat deterioration resistance was further improved by increasing the amount of the benzimidazole anti-aging agent in the premix. The appearance was slightly reduced as compared with Examples 1 and 2 although there was an improvement effect with respect to Comparative Example 2.
一方、比較例３では、事前混合物を配合したものの、ベンズイミダゾール系老化防止剤の配合量が多すぎたため、耐熱劣化性は大幅に改良されたが、外観性改良効果がほとんどなくなっていた。比較例４は、上記特許文献３に記載された従来技術に相当するものであり、アミン系老化防止剤とベンズイミダゾール化合物との塩を使用した場合、外観性及び耐熱劣化性の点で、実施例１〜３よりも明らかに改良効果が劣るものであった。 On the other hand, in Comparative Example 3, although the premix was blended, the amount of the benzimidazole anti-aging agent was too large, so the heat deterioration resistance was greatly improved, but the effect of improving the appearance was almost lost. Comparative Example 4 corresponds to the prior art described in Patent Document 3 above, and in the case of using a salt of an amine-based antioxidant and a benzimidazole compound, it was carried out in terms of appearance and heat deterioration resistance. The improvement effect was clearly inferior to Examples 1-3.
また、アミン系老化防止剤の配合量を増やした系でも、比較例５，６及び実施例４を比較すると明らかなように、アミン系老化防止剤とベンズイミダゾール系老化防止剤の事前混合物を用いた実施例４であると、比較例５，６に対して、外観性と耐熱劣化性がともに大幅に改良されていた。 Further, even in a system in which the compounding amount of the amine-based anti-aging agent is increased, as is clear when Comparative Examples 5, 6 and Example 4 are compared, a pre-mix of the amine-based anti-aging agent and the benzimidazole-based anti-aging agent is used. In Example 4, the appearance and heat deterioration resistance were significantly improved compared to Comparative Examples 5 and 6.
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