JP2019026757A - Rubber composition for tire - Google Patents
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本発明は、廃ゴム製品からリサイクルによって回収された再生ゴムを使用したゴム組成物に関する。 The present invention relates to a rubber composition using recycled rubber recovered from waste rubber products by recycling.
近年、環境保護やコスト低減の観点から、タイヤ等の使用済みのゴム製品（廃ゴム製品）の一部を、例えば粉砕処理等によって再生ゴムに加工して、これを新ゴムに配合して再利用することが行われている。しかしながら、このような再生ゴムは加硫後の物性が新ゴムに比して劣るため、再生ゴムを含有するゴム組成物の加硫後の物性も悪くなり、実用に堪えなかったり、使用対象が制限されるという問題があった。また、再生ゴムによって加硫後の物性が低下するため、原料中の再生材料比率（再生ゴムの比率）を高めることが難しく、環境負荷を低減する効果が限定的であるという問題もあった。 In recent years, from the viewpoint of environmental protection and cost reduction, a part of used rubber products (waste rubber products) such as tires has been processed into recycled rubber by, for example, pulverization, etc., and this is blended with new rubber and recycled. It is being used. However, since such recycled rubber has inferior physical properties after vulcanization compared to the new rubber, the physical properties after vulcanization of the rubber composition containing the recycled rubber also deteriorated, and it is not practically used. There was a problem of being restricted. In addition, since the physical properties after vulcanization are lowered by recycled rubber, it is difficult to increase the ratio of recycled material in the raw material (the ratio of recycled rubber), and there is a problem that the effect of reducing environmental load is limited.
このような問題に対して、例えば、上述の粉砕処理の後、脱硫処理や官能化処理を施して再生ゴム自体の反応性を高めて、加硫後のゴム物性を良好にすることが検討されている（例えば、特許文献１を参照）。しかしながら、このような処理を行った再生ゴムを配合したゴム組成物であっても、例えば破断特性等の物性が充分に得られず、特に空気入りタイヤ等に用いる場合に加工性や加硫物性などの性能が充分に得られないという問題があった。そのため、廃ゴム製品からリサイクルによって回収された再生ゴムを使用したゴム組成物において、加工性及び加硫物性を向上しながら、原料中の再生材料比率を高める更なる改善が求められていた。 For such problems, for example, after the above-mentioned pulverization treatment, desulfurization treatment or functionalization treatment is performed to increase the reactivity of the recycled rubber itself to improve the rubber physical properties after vulcanization. (For example, refer to Patent Document 1). However, even a rubber composition containing a recycled rubber that has been subjected to such treatment does not provide sufficient physical properties such as breaking properties, and is particularly workable and vulcanized when used for pneumatic tires. There was a problem that performance such as the above could not be obtained sufficiently. For this reason, in rubber compositions using recycled rubber recovered from waste rubber products by recycling, further improvements have been demanded that increase the ratio of recycled materials in raw materials while improving processability and vulcanized physical properties.
本発明の目的は、廃ゴム製品からリサイクルによって回収された再生ゴムを使用したゴム組成物であって、加工性及び加硫物性を向上しながら、原料中の再生材料比率を高めることを可能にしたゴム組成物を提供することにある。 An object of the present invention is a rubber composition using recycled rubber recovered from waste rubber products by recycling, and it is possible to increase the ratio of recycled materials in raw materials while improving processability and vulcanization properties. An object of the present invention is to provide a rubber composition.
上記目的を達成する本発明のタイヤ用ゴム組成物は、イソプレン系ゴム３０質量部〜７０質量部およびスチレンブタジエンゴム３０質量部〜７０質量部からなるジエン系ゴム１００質量部に対して、ＣＴＡＢ吸着比表面積が１００ｍ2 ／ｇ〜２５０ｍ2 ／ｇであるシリカを３０質量部〜１５０質量部、粉末再生ゴムを５質量部〜１５０質量部、チウラムスルフィド系化合物で官能化された変性再生ゴムを５質量部〜１５０質量部を配合したことを特徴とする。 The rubber composition for tires of the present invention that achieves the above object is a CTAB adsorption with respect to 100 parts by mass of a diene rubber comprising 30 parts by mass to 70 parts by mass of isoprene rubber and 30 parts by mass to 70 parts by mass of styrene butadiene rubber. 30 parts by weight to 150 parts by mass of silica having a specific surface area of 100m 2 / g~250m 2 / g, 5 parts by weight to 150 parts by weight of powder reclaimed rubber, a functionalized modified recycled rubber thiuram sulfide-based compound 5 It is characterized by blending part by mass to 150 parts by mass.
本発明のタイヤ用ゴム組成物は、イソプレン系ゴムとスチレンブタジエンゴムとを主体として、粉末再生ゴムと変性再生ゴムとを併用し、且つ、上述の配合材を配合しているので、再生ゴムを配合したゴム組成物であっても、加工性および加硫物性を向上することができる。また、上述の配合によって加工性および加硫物性が改善するので、再生ゴムの配合量を従来に比べて多くすることができ、原料中の再生材料比率を高めることができる。 The rubber composition for tires of the present invention is mainly composed of isoprene-based rubber and styrene-butadiene rubber, and uses a combination of a powder regenerated rubber and a modified regenerated rubber, and the above compounding material is blended. Even with a blended rubber composition, processability and vulcanized physical properties can be improved. Moreover, since the processability and vulcanized physical properties are improved by the above-described blending, the blended amount of the recycled rubber can be increased as compared with the conventional one, and the ratio of the recycled material in the raw material can be increased.
本発明においては、粉末再生ゴムと変性再生ゴムとの配合量の比が１：１〜１：２であることが好ましい。これにより、粉末再生ゴムと変性再生ゴムとのバランスが良好になり、原料中の再生材料比率（再生ゴム比率）を高めながら、加工性および加硫物性を向上するには有利になる。 In the present invention, it is preferable that the ratio of the blended amount of the powder recycled rubber and the modified recycled rubber is 1: 1 to 1: 2. Thereby, the balance between the powdered recycled rubber and the modified recycled rubber becomes good, which is advantageous for improving processability and vulcanized physical properties while increasing the ratio of recycled material in the raw material (recycled rubber ratio).
本発明においては、粉末再生ゴムの粒径が８０メッシュ以上であることが好ましい。これにより、原料中の再生材料比率（再生ゴム比率）を高めながら、加工性および加硫物性を向上するには有利になる。尚、本発明において、粉末再生ゴムの粒径は、ＪＩＳ Ｋ６２２０に準拠して測定する。また、本発明において「粒径が８０メッシュ以上である」とは、粉末再生ゴムの７０質量％以上が８０メッシュを通過可能な粒径であることを意味し、３０質量％未満の割合であれば上記粒径の範囲外のものを含むことが許容されるものとする。 In the present invention, it is preferable that the particle diameter of the powder recycled rubber is 80 mesh or more. This is advantageous for improving processability and vulcanization properties while increasing the ratio of recycled material in the raw material (recycled rubber ratio). In the present invention, the particle diameter of the recycled powder rubber is measured according to JIS K6220. In the present invention, “the particle size is 80 mesh or more” means that 70% by mass or more of the powder recycled rubber is a particle size capable of passing through 80 mesh, and may be a ratio of less than 30% by mass. In other words, it is allowed to include those outside the above particle size range.
本発明においては、軟化点が６０℃〜１５０℃の石油系樹脂を前記ジエン系ゴム１００質量部に対して２質量部〜２０質量部配合することが好ましい。これにより粘着性を高めることができ、原料中の再生材料比率（再生ゴム比率）を高めながら、加工性および加硫物性を向上するには有利になる。 In the present invention, it is preferable to blend 2 to 20 parts by mass of a petroleum resin having a softening point of 60 to 150 ° C. with respect to 100 parts by mass of the diene rubber. Thereby, the adhesiveness can be increased, which is advantageous for improving processability and vulcanization properties while increasing the ratio of recycled material in the raw material (recycled rubber ratio).
本発明においては、スチレンブタジエンゴムにおけるスチレン含有量が２０質量％以上であることが好ましい。このようにスチレン含有量を設定することで、加工性を高めるには有利になる。 In the present invention, the styrene content in the styrene butadiene rubber is preferably 20% by mass or more. Setting the styrene content in this way is advantageous for improving workability.
本発明のタイヤゴム組成物は、空気入りタイヤのトレッド部に用いることが好ましく、本発明のタイヤ用ゴム組成物をトレッド部に用いた空気入りタイヤは、ゴム組成物中に再生ゴムが含まれていても、従来の新ゴムのみを用いた空気入りタイヤと同等の優れた走行性能を発揮することができる。 The tire rubber composition of the present invention is preferably used in the tread portion of a pneumatic tire, and the pneumatic tire using the tire rubber composition of the present invention in the tread portion includes a recycled rubber in the rubber composition. However, excellent running performance equivalent to that of a pneumatic tire using only a conventional new rubber can be exhibited.
本発明のタイヤ用ゴム組成物において、ゴム成分はジエン系ゴムであり、イソプレン系ゴムおよびスチレンブタジエンゴムを必ず含む。イソプレン系ゴムとしては、各種天然ゴム、エポキシ化天然ゴム、各種合成ポリイソプレンゴムを挙げることができる。イソプレン系ゴムおよびスチレンブタジエンゴムはそれぞれ、タイヤ用ゴム組成物に通常用いられるゴムを使用することができる。これらの配合量は、ジエン系ゴム全体を１００質量部としたとき、イソプレン系ゴムを３０質量部〜７０質量部、スチレンブタジエンゴムを３０質量部〜７０質量部、好ましくイソプレン系ゴムを４０質量部〜６０質量部、スチレンブタジエンゴムを４０質量部〜６０質量部である。これらゴムの配合量が上記範囲から外れると、本発明の所望の効果が充分に得られない。特に、本発明では、両者をバランスよく併用することが重要であり、イソプレン系ゴムの配合量が７０質量部を超えると（スチレンブタジエンゴムの配合量が３０質量部未満であると）、０℃におけるｔａｎδが悪化する。スチレンブタジエンゴムの配合量が７０質量部を超えると（イソプレン系ゴムの配合量が３０質量部未満であると）、ゴム組成物の粘度が悪化する。 In the rubber composition for tires of the present invention, the rubber component is a diene rubber and necessarily includes isoprene rubber and styrene butadiene rubber. Examples of the isoprene-based rubber include various natural rubbers, epoxidized natural rubber, and various synthetic polyisoprene rubbers. As the isoprene-based rubber and styrene-butadiene rubber, rubbers usually used in tire rubber compositions can be used. These compounding amounts are 30 parts by weight to 70 parts by weight of isoprene-based rubber, 30 parts by weight to 70 parts by weight of styrene-butadiene rubber, and preferably 40 parts by weight of isoprene-based rubber when the total amount of diene rubber is 100 parts by weight. -60 mass parts, styrene butadiene rubber is 40 mass parts-60 mass parts. If the blending amount of these rubbers is out of the above range, the desired effect of the present invention cannot be obtained sufficiently. In particular, in the present invention, it is important to use both in a balanced manner. When the blending amount of the isoprene-based rubber exceeds 70 parts by mass (when the blending amount of the styrene butadiene rubber is less than 30 parts by mass), 0 ° C. The tan δ becomes worse. When the blending amount of the styrene butadiene rubber exceeds 70 parts by mass (when the blending amount of the isoprene-based rubber is less than 30 parts by mass), the viscosity of the rubber composition is deteriorated.
本発明で使用するスチレンブタジエンゴムは、スチレン含有量が好ましくは２０質量％以上、より好ましくは２３質量％〜４０質量％であるとよい。スチレン含有量を設定することで加工性を高めるには有利になる。スチレン含有量が２０％未満であると、ゴム組成物の加工性が低下する。本発明において、スチレンブタジエンゴムのスチレン含有量はＪＩＳ Ｋ６２３９「原料ゴム‐溶液重合ＳＢＲのミクロ構造の求め方」という測定方法により求めることができる。 The styrene butadiene rubber used in the present invention preferably has a styrene content of 20% by mass or more, more preferably 23% by mass to 40% by mass. Setting the styrene content is advantageous for improving processability. If the styrene content is less than 20%, the processability of the rubber composition decreases. In the present invention, the styrene content of the styrene butadiene rubber can be determined by a measuring method of JIS K6239 “How to Determine the Microstructure of Raw Rubber-Solution Polymerized SBR”.
本発明のタイヤ用ゴム組成物は、イソプレン系ゴムおよびスチレンブタジエンゴム以外の他のジエン系ゴムを含有してもよい。他のジエン系ゴムとしては、例えば、ブタジエンゴム、アクリロニトリル‐ブタジエンゴム等が挙げられる。これらジエン系ゴムは、単独又は任意のブレンドとして使用することができる。 The rubber composition for tires of the present invention may contain other diene rubbers other than isoprene rubber and styrene butadiene rubber. Examples of other diene rubbers include butadiene rubber and acrylonitrile-butadiene rubber. These diene rubbers can be used alone or as any blend.
本発明のタイヤ用ゴム組成物は、シリカが必ず配合される。シリカを配合することでゴム組成物の強度を高めることができる。シリカの配合量は、ジエン系ゴム１００質量部に対して、３０質量部〜１５０質量部、好ましくは５０質量部〜９０質量部である。シリカの配合量が３０質量部未満であると、ゴム組成物の機械的特性を改良する効果が充分に得られない。シリカの配合量が１５０質量部を超えると、ゴム組成物の発熱性が大きくなりタイヤにしたとき転がり抵抗が大きくなる。 The rubber composition for tires of the present invention always contains silica. The intensity | strength of a rubber composition can be raised by mix | blending a silica. The compounding quantity of a silica is 30 mass parts-150 mass parts with respect to 100 mass parts of diene rubbers, Preferably it is 50 mass parts-90 mass parts. When the amount of silica is less than 30 parts by mass, the effect of improving the mechanical properties of the rubber composition cannot be sufficiently obtained. If the blending amount of silica exceeds 150 parts by mass, the rubber composition will have high heat build-up and rolling resistance will increase when a tire is formed.
本発明で使用するシリカは、ＣＴＡＢ吸着比表面積が１００ｍ2 ／ｇ〜２５０ｍ2 ／ｇ、好ましくは１２０ｍ2 ／ｇ〜１８０ｍ2 ／ｇである。シリカのＣＴＡＢ吸着比表面積が１００ｍ2 ／ｇ未満であると、ゴム組成物のゴム強度、ゴム硬度などの機械的特性が低下する。シリカのＣＴＡＢ吸着比表面積が２５０ｍ2 ／ｇを超えると、シリカの分散性が低下し、ゴム組成物の６０℃におけるｔａｎδ（以下、ｔａｎδ（６０℃）という）が大きくなる。尚、本発明において、シリカのＣＴＡＢ吸着比表面積は、ＩＳＯ ５７９４に準拠して測定するものとする。 Silica used in the present invention, CTAB adsorption specific surface area of 100m 2 / g~250m 2 / g, preferably from 120m 2 / g~180m 2 / g. When the CTAB adsorption specific surface area of silica is less than 100 m 2 / g, mechanical properties such as rubber strength and rubber hardness of the rubber composition are lowered. When the CTAB adsorption specific surface area of the silica exceeds 250 m 2 / g, the dispersibility of the silica decreases, and the tan δ at 60 ° C. (hereinafter referred to as tan δ (60 ° C.)) of the rubber composition increases. In the present invention, the CTAB adsorption specific surface area of silica is measured according to ISO 5794.
本発明のタイヤ用ゴム組成物は、粉末再生ゴムおよび変性再生ゴムが必ず配合される。本発明において「粉末再生ゴム」とは、タイヤ等の使用済みのゴム製品（廃ゴム製品）の一部を粉砕処理して得られたゴム材料であり、脱硫処理や官能化等の変性処理は施されていないものである。この粉末再生ゴムは、脱硫処理が施された再生ゴムや後述の変性再生ゴムのように反応性は高くないが、これら処理が施された再生ゴムのみを用いた場合に低下し易い加硫物性（例えば破断エネルギー等の特性）を改善するのに有利な材料である。本発明において「変性再生ゴム」とは、タイヤ等の使用済みのゴム製品（廃ゴム製品）の一部を粉砕処理した後、脱硫処理を行い、更に、チウラムスルフィド系化合物で官能化することで得られたゴム材料である。この変性再生ゴムは、脱硫および官能化によりゴム中の架橋構造の一部が切断されて反応性が高まっているため、再生材料を用いた場合に懸念される硬度の低下、発熱性の悪化、未加硫ゴムの粘度の上昇等の問題を改善するのに有利な材料である。尚、変性再生ゴムの官能化処理に用いるチウラムスルフィド系化合物としては、アルキルチウラムスルフィド、アリールチウラムスルフィド、ヘテロ環式チウラムスルフィド、チウラムジスルフィド、チウラムポリスルフィド、テトラベンジルチウラムジスルフィド、テトラアルキルチウラムジスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、ジペンタメチルチウラムモノスルフィド等を例示することができる。上述の粉末再生ゴムと変性再生ゴムとを併用することで、再生ゴムを配合したゴム組成物であっても、加工性および加硫物性を向上することができる。 The rubber composition for tires of the present invention always contains powder recycled rubber and modified recycled rubber. In the present invention, “powder recycled rubber” is a rubber material obtained by pulverizing a part of a used rubber product (waste rubber product) such as a tire, and a modification treatment such as desulfurization treatment or functionalization is performed. It has not been applied. This powder recycled rubber is not highly reactive like desulfurized recycled rubber and modified modified rubber, which will be described later. It is an advantageous material for improving (for example, characteristics such as breaking energy). In the present invention, “modified reclaimed rubber” refers to a part of used rubber products (waste rubber products) such as tires that is pulverized, desulfurized, and then functionalized with a thiuram sulfide compound. This is a rubber material obtained. This modified reclaimed rubber has increased reactivity due to the desulfurization and functionalization of a part of the cross-linked structure in the rubber, resulting in a decrease in hardness, exothermic deterioration, which is a concern when using reclaimed materials, It is an advantageous material for improving problems such as an increase in viscosity of unvulcanized rubber. The thiuram sulfide compounds used for functionalization of the modified recycled rubber include alkyl thiuram sulfide, aryl thiuram sulfide, heterocyclic thiuram sulfide, thiuram disulfide, thiuram polysulfide, tetrabenzyl thiuram disulfide, tetraalkyl thiuram disulfide, tetramethyl. Examples include thiuram disulfide, tetraethylthiuram disulfide, dipentamethylthiuram monosulfide and the like. By using the above-mentioned powder recycled rubber and modified recycled rubber in combination, processability and vulcanized physical properties can be improved even with a rubber composition blended with recycled rubber.
粉末再生ゴムの配合量は、ジエン系ゴム１００質量部に対して、５質量部〜１５０質量部、好ましくは１０質量部〜１２０質量部である。粉末再生ゴムの配合量が５質量部未満であると、ゴム組成物の破断物性が悪化する。粉末再生ゴムの配合量が１５０質量部を超えると、ゴム組成物の物性（粘度、硬度、破断物性、発熱性）が悪化する。また、変性再生ゴムの配合量は、ジエン系ゴム１００質量部に対して、５質量部〜１５０質量部、好ましくは１０質量部〜８０質量部である。変性再生ゴムの配合量が５質量部未満であると、ゴム組成物の物性（粘度）が悪化する。変性再生ゴムの配合量が１５０質量部を超えると、ゴム組成物の物性（粘度、硬度、破断物性、発熱性）が悪化する。 The compounding amount of the powder recycled rubber is 5 to 150 parts by mass, preferably 10 to 120 parts by mass with respect to 100 parts by mass of the diene rubber. When the blended amount of the powder recycled rubber is less than 5 parts by mass, the fracture property of the rubber composition is deteriorated. If the blended amount of the powdered recycled rubber exceeds 150 parts by mass, the physical properties (viscosity, hardness, rupture physical properties, exothermic properties) of the rubber composition are deteriorated. The amount of the modified recycled rubber is 5 parts by mass to 150 parts by mass, preferably 10 parts by mass to 80 parts by mass with respect to 100 parts by mass of the diene rubber. If the amount of the modified recycled rubber is less than 5 parts by mass, the physical properties (viscosity) of the rubber composition will deteriorate. When the amount of the modified recycled rubber exceeds 150 parts by mass, the physical properties (viscosity, hardness, rupture physical properties, exothermic property) of the rubber composition are deteriorated.
粉末再生ゴムおよび変性再生ゴムを多く配合することで、原料中の再生材料比率を高めることができ、環境負荷を低減するには有利である。そのため、粉末再生ゴムおよび変性再生ゴムの総量（配合量の和）を、ジエン系ゴム１００質量部に対して好ましくは２０質量部以上、より好ましくは４０質量部〜１５０質量部にするとよい。従来の再生ゴムを配合したゴム組成物では、再生ゴムの配合量がゴム組成物の主体となるジエン系ゴム１００質量部に対して１０質量部程度であったので、原料中の再生材料比率を大幅に高めることができる。粉末再生ゴムおよび変性再生ゴムの両者の配合量が多く、総量が１６０質量部を超えると、ゴム物性を改善する効果が限定的になり、粘度、硬度、破断伸び、発熱性が低下する。 By blending a large amount of powdered recycled rubber and modified recycled rubber, the ratio of recycled material in the raw material can be increased, which is advantageous for reducing the environmental burden. Therefore, the total amount of powdered recycled rubber and modified recycled rubber (sum of the blended amounts) is preferably 20 parts by mass or more, more preferably 40 parts by mass to 150 parts by mass with respect to 100 parts by mass of the diene rubber. In the conventional rubber composition containing the recycled rubber, the amount of the recycled rubber is about 10 parts by mass with respect to 100 parts by mass of the diene rubber as the main component of the rubber composition. Can greatly increase. When the blended amount of both the powdered recycled rubber and the modified recycled rubber is large and the total amount exceeds 160 parts by mass, the effect of improving the rubber physical properties is limited, and the viscosity, hardness, elongation at break and exothermicity are lowered.
更に、粉末再生ゴムと変性再生ゴムとの配合量の比（粉末再生ゴム：変性再生ゴム）は、好ましくは１：１〜１：３、より好ましくは１：１〜１：２にするとよい。これにより、粉末再生ゴムと変性再生ゴムとのバランスが良好になり、原料中の再生材料比率（再生ゴム比率）を高めながら、加工性および加硫物性を向上するには有利になる。粉末再生ゴムと変性再生ゴムとの配合量の比が上記範囲から外れて、変性再生ゴムに対して粉末再生ゴムの配合量が多過ぎると、ゴム物性を改善する効果が限定的になり、粘度、硬度、破断物性、発熱性が低下し、粉末再生ゴムに対して変性再生ゴムの配合量が多過ぎると、ゴム物性を改善する効果が限定的になり、破断物性が低下する。 Furthermore, the ratio of the blended amount of the powder recycled rubber and the modified recycled rubber (powder recycled rubber: modified recycled rubber) is preferably 1: 1 to 1: 3, more preferably 1: 1 to 1: 2. Thereby, the balance between the powdered recycled rubber and the modified recycled rubber becomes good, which is advantageous for improving processability and vulcanized physical properties while increasing the ratio of recycled material in the raw material (recycled rubber ratio). If the ratio of the blended amount of the powdered recycled rubber and the modified recycled rubber is out of the above range and the blended amount of the powdered recycled rubber is too large relative to the modified recycled rubber, the effect of improving the rubber properties will be limited and the viscosity will be reduced. When the blended amount of the modified recycled rubber is too large relative to the powder recycled rubber, the effect of improving the rubber physical properties is limited and the fracture physical properties are lowered.
本発明で使用する粉末再生ゴムは粒径が小さいことが好ましい。特に、粉末再生ゴムの粒径が、好ましくは８０メッシュ以上、より好ましくは１００メッシュ〜１４０メッシュであるとよい。これにより、原料中の再生材料比率（再生ゴム比率）を高めながら、加工性および加硫物性を向上するには有利になる。粉末再生ゴムの粒径が８０メッシュ未満であると、粒径が大き過ぎて破断伸びを改善する効果が限定的になる。尚、変性再生ゴムは、上述の変性処理の後、シート状または板状に加工されて供される材料であるので、上記粉末再生ゴムのように粒径は考慮されない。 The powder recycled rubber used in the present invention preferably has a small particle size. In particular, the particle diameter of the powder recycled rubber is preferably 80 mesh or more, more preferably 100 mesh to 140 mesh. This is advantageous for improving processability and vulcanization properties while increasing the ratio of recycled material in the raw material (recycled rubber ratio). If the particle size of the powder recycled rubber is less than 80 mesh, the particle size is too large and the effect of improving the breaking elongation is limited. The modified recycled rubber is a material that is processed into a sheet shape or a plate shape after the above-described modification treatment, so that the particle size is not considered as in the case of the powder recycled rubber.
本発明のタイヤ用ゴム組成物は、上記配合剤に加えて、更に、石油系樹脂を配合することができる。石油系樹脂とは、原油を蒸留、分解、改質などの処理をして得られた成分を重合して製造される芳香族系炭化水素樹脂、或いは、飽和または不飽和脂肪族系炭化水素樹脂である。石油系樹脂として、例えばＣ5 系石油樹脂（イソプレン、１，３‐ペンタジエン、シクロペンタジエン、メチルブテン、ペンテンなどの留分を重合した脂肪族系石油樹脂）、Ｃ9 系石油樹脂（α‐メチルスチレン、ｏ‐ビニルトルエン、ｍ‐ビニルトルエン、ｐ‐ビニルトルエンなどの留分を重合した芳香族系石油樹脂）、Ｃ5 Ｃ9 共重合石油樹脂などが挙げられる。これらの樹脂は、単独又は複数のブレンドとして使用することができる。これら石油系樹脂を配合することで、粘着性を高めることができる。石油系樹脂の配合量は、ジエン系ゴム１００質量部に対して、好ましくは２質量部〜２０質量部、より好ましくは５質量部〜１５質量部である。石油系樹脂の配合量が２質量部未満であると、石油系樹脂によって付加される効果（粘着性）が充分に得られない。石油系樹脂の配合量が２０質量部を超えると、耐摩耗性や加工性が低下する。 In addition to the said compounding agent, the rubber composition for tires of this invention can further mix | blend petroleum-type resin. Petroleum resins are aromatic hydrocarbon resins produced by polymerizing components obtained by subjecting crude oil to distillation, decomposition, reforming, etc., or saturated or unsaturated aliphatic hydrocarbon resins. It is. As petroleum resins, for example, C 5 petroleum resins (isoprene, 1,3-pentadiene, cyclopentadiene, methylbutene, aliphatic petroleum resins obtained by polymerizing fractions such pentene), C 9 petroleum resins (alpha-methyl styrene , o- vinyltoluene, m- vinyltoluene, p- aromatic petroleum resin fractions was polymerized, such as vinyl toluene), such as C 5 C 9 copolymer petroleum resin. These resins can be used alone or as a blend. By blending these petroleum resins, the tackiness can be increased. The blending amount of the petroleum resin is preferably 2 parts by mass to 20 parts by mass, and more preferably 5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the diene rubber. When the blending amount of the petroleum resin is less than 2 parts by mass, the effect (adhesiveness) added by the petroleum resin cannot be sufficiently obtained. When the blending amount of the petroleum-based resin exceeds 20 parts by mass, the wear resistance and workability deteriorate.
本発明で使用する石油系樹脂は、軟化点が好ましくは６０℃〜１５０℃、より好ましくは１１０℃〜１３０℃である。石油系樹脂の軟化点をこのような範囲内に設定することで、石油系樹脂によって付加される粘着性を効果的に高めることができる。石油系樹脂の軟化点が６０℃未満であると、硬度が低下する。石油系樹脂の軟化点が１５０℃を超えると、粘度が増加する。尚、本発明において、石油系樹脂の軟化点は、ＪＩＳ Ｋ６２２０−１（環球法）に準拠して測定するものとする。 The petroleum-based resin used in the present invention has a softening point of preferably 60 ° C to 150 ° C, more preferably 110 ° C to 130 ° C. By setting the softening point of the petroleum resin within such a range, the adhesiveness added by the petroleum resin can be effectively increased. Hardness falls that the softening point of petroleum resin is less than 60 degreeC. When the softening point of the petroleum resin exceeds 150 ° C., the viscosity increases. In the present invention, the softening point of the petroleum-based resin is measured according to JIS K6220-1 (ring and ball method).
本発明のタイヤ用ゴム組成物には、上記以外の他の配合剤を添加することができる。他の配合剤としては、シリカ以外の他の補強性充填剤、加硫又は架橋剤、加硫促進剤、老化防止剤、液状ポリマー、熱硬化性樹脂、熱可塑性樹脂など、一般的に空気入りタイヤに使用される各種配合剤を例示することができる。これら配合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にすることができる。また混練機としは、通常のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用することができる。 Other compounding agents other than those described above can be added to the rubber composition for tires of the present invention. Other compounding agents are generally pneumatic, such as reinforcing fillers other than silica, vulcanization or crosslinking agents, vulcanization accelerators, anti-aging agents, liquid polymers, thermosetting resins, thermoplastic resins, etc. Various compounding agents used for a tire can be illustrated. The compounding amounts of these compounding agents can be conventional conventional compounding amounts as long as they do not contradict the purpose of the present invention. Moreover, as a kneading machine, a normal rubber kneading machine, for example, a Banbury mixer, a kneader, a roll or the like can be used.
本発明のタイヤ用ゴム組成物は、空気入りタイヤのトレッド部に好適に用いることができる。本発明のタイヤ用ゴム組成物は、上述のように加工性や加硫物性が良好であるため、このタイヤ用ゴム組成物をトレッド部に用いた空気入りタイヤは、ゴム組成物中に再生ゴムが含まれていても、従来の新ゴムのみを用いた空気入りタイヤと同等の優れた走行性能を発揮することができる。 The rubber composition for tires of the present invention can be suitably used for a tread portion of a pneumatic tire. Since the rubber composition for tires of the present invention has good processability and vulcanized physical properties as described above, a pneumatic tire using the tire rubber composition for a tread portion is regenerated rubber in the rubber composition. Even if it is included, excellent running performance equivalent to a conventional pneumatic tire using only a new rubber can be exhibited.
以下、実施例によって本発明を更に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, the scope of the present invention is not limited to these Examples.
表１〜２に示す配合からなる２１種類のゴム組成物（標準例１、比較例１〜８、実施例１〜１２）を、それぞれ加硫促進剤および硫黄を除く配合成分を秤量し、１．８Ｌの密閉式バンバリーミキサーで５分間混練し、温度１５０℃でマスターバッチを放出し室温冷却した。その後、このマスターバッチを１．８Ｌの密閉式バンバリーミキサーに供し、加硫促進剤及び硫黄を加え２分間混合してゴム組成物を調製した。次に、得られたゴム組成物を所定の金型中で１６０℃、２０分間プレス加硫して加硫ゴム試験片を作製した。尚、スチレンブタジエンゴムはオイル分を含むため、表１〜２においては、括弧内に正味のゴム量を記載した。 21 types of rubber compositions (standard example 1, comparative examples 1-8, and examples 1-12) having the formulations shown in Tables 1 and 2 were weighed for the respective components except for the vulcanization accelerator and sulfur. The mixture was kneaded with an 8 L closed Banbury mixer for 5 minutes, and the master batch was discharged at a temperature of 150 ° C. and cooled at room temperature. Thereafter, this master batch was subjected to a 1.8 L closed Banbury mixer, a vulcanization accelerator and sulfur were added and mixed for 2 minutes to prepare a rubber composition. Next, the obtained rubber composition was press vulcanized in a predetermined mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber test piece. In addition, since styrene butadiene rubber contains an oil component, in Tables 1-2, the amount of net rubber was described in the parenthesis.
得られた２１種類のゴム組成物について、下記に示す方法により、粘度、硬度、破断エネルギー、０℃におけるｔａｎδの評価を行った。 The obtained 21 types of rubber compositions were evaluated for viscosity, hardness, breaking energy, and tan δ at 0 ° C. by the following methods.
粘度
得られたゴム組成物のムーニー粘度をＪＩＳ Ｋ６３００に準拠して、ムーニー粘度計にてＬ型ロータ（３８．１ｍｍ径、５．５ｍｍ厚）を使用し、予熱時間１分、ロータの回転時間４分、１００℃、２ｒｐｍの条件で測定した。得られた結果は、標準例１の値を１００とする指数として、表１〜２の「粘度」の欄に示した。この指数値が小さいほど粘度が小さく加工性が優れることを意味する。
Viscosity The Mooney viscosity of the obtained rubber composition is based on JIS K6300, using a Mooney viscometer with an L-shaped rotor (38.1 mm diameter, 5.5 mm thickness), preheating time 1 minute, rotor rotation time The measurement was performed for 4 minutes at 100 ° C. and 2 rpm. The obtained results are shown in the column of “Viscosity” in Tables 1 and 2 as an index with the value of Standard Example 1 being 100. A smaller index value means smaller viscosity and better processability.
硬度
得られた試験片を用いて、ＪＩＳ Ｋ６２５３に準拠し、デュロメータのタイプＡにより温度２０℃におけるゴム硬さを測定した。得られた結果は、標準例１の値を１００とする指数として、表１〜２の「硬度」の欄に示した。この指数値が大きいほど硬度が大きいことを意味する。
Hardness Using the obtained test piece, the rubber hardness at a temperature of 20 ° C. was measured with a durometer type A according to JIS K6253. The obtained results are shown in the column of “Hardness” in Tables 1 and 2 as an index with the value of Standard Example 1 being 100. It means that hardness is so large that this index value is large.
破断エネルギー
得られた試験片からＪＩＳ Ｋ６２５１に準拠してＪＩＳ３号ダンベル型試験片（厚さ２ｍｍ）を切り出し、この試験片の引張り破断強度および破断伸びを、ＪＩＳ Ｋ６２５１に準拠し、温度２３℃、引張り速度５００ｍｍ／分の条件で測定し、これらの積を破断エネルギーとして算出した。得られた結果は、標準例１の値を１００とする指数として、表１〜２の「破断エネルギー」の欄に示した。この指数値が大きいほど、引張り破断時のエネルギーが大きく、破断物性が優れることを意味する。
Breaking energy A JIS No. 3 dumbbell-shaped test piece (thickness 2 mm) was cut out from the obtained test piece in accordance with JIS K6251, and the tensile breaking strength and elongation at break of this test piece were measured in accordance with JIS K6251 at a temperature of 23 ° C. Measurement was performed under the condition of a pulling speed of 500 mm / min, and these products were calculated as breaking energy. The obtained results are shown in the column of “Breaking energy” in Tables 1 and 2 as an index with the value of standard example 1 being 100. The larger the index value, the larger the energy at the time of tensile fracture, which means that the fracture property is excellent.
０℃におけるｔａｎδ
得られた試験片をＪＩＳ Ｋ６３９４に準拠して、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み１０％、振幅±２％、周波数２０Ｈｚの条件で、温度０℃における損失正接ｔａｎδを測定した。得られたｔａｎδの結果は、標準例１の値を１００とする指数として表１〜２の「ｔａｎδ（０℃）」の欄に示した。この指数値が大きいほど０℃におけるｔａｎδが大きく、タイヤ（トレッド部）に利用したときのウェットグリップ性が優れることを意味する。
Tan δ at 0 ° C
Based on JIS K6394, the obtained test piece was subjected to a loss tangent tan δ at a temperature of 0 ° C. using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of an initial strain of 10%, an amplitude of ± 2%, and a frequency of 20 Hz. It was measured. The obtained tan δ results are shown in the column of “tan δ (0 ° C.)” in Tables 1 and 2 as an index with the value of Standard Example 1 being 100. The larger the index value, the larger the tan δ at 0 ° C., which means that the wet grip property when used for a tire (tread portion) is excellent.
表１〜２において使用した原材料の種類を下記に示す。
・ＮＲ：天然ゴム、ＳＴＲ２０
・ＳＢＲ１：スチレンブタジエンゴム、日本ゼオン社製 Ｎｉｐｏｌ １７２３（スチレン含有量：２３．５質量％、ゴム成分１００質量部に対しオイル分３７．５質量部を含む油展品）
・ＳＢＲ２：スチレンブタジエンゴム、日本ゼオン社製 Ｎｉｐｏｌ １７３９（スチレン含有量：４０質量％、ゴム成分１００質量部に対しオイル分３７．５質量部を含む油展品）
・シリカ１：Ｓｏｌｖａｙ社製 ＺＥＯＳＩＬ １１６５ＭＰ（ＣＴＡＢ吸着比表面積：１５５ｍ2 ／ｇ）
・シリカ２：Ｓｏｌｖａｙ社製 ＺＥＯＳＩＬ １０８５ＧＲ（ＣＴＡＢ吸着比表面積：８０ｍ2 ／ｇ）
・変性再生ゴム：Ｌｅｈｉｇｈ社製 ＥｋｏＤｙｎｅ、テトラベンジルチウラムスルフィドで官能化された変性再生ゴム
・粉末再生ゴム１：Ｌｅｈｉｇｈ社製 ＧＦ‐８０ ＲＥＰＲＯＣＥＳＳＥＤ ＧＲＯＵＮＤ ＲＵＢＢＥＲ（粒径：８０メッシュ）
・粉末再生ゴム２：Ｌｅｈｉｇｈ社製 １４０ ＭＥＳＨ ＧＲＯＵＮＤ ＲＵＢＢＥＲ（粒径：１４０メッシュ）
・シランカップリング剤：Ｅｖｏｎｉｋ社製 Ｓｉ６９
・オイル：昭和シェル石油社製 エキストラクト４号Ｓ
・石油系樹脂１：ＪＸＴＧエネルギー社製 日石ネオポリマー１２０（軟化点：１２０℃）
・石油系樹脂２：ヤスハラケミカル社製 ＹＳレジンＴＯ‐１２５（芳香族変性テルペン樹脂、軟化点：１２５℃）
・ステアリン酸：日新理化社製 ステアリン酸５０Ｓ
・酸化亜鉛：正同化学工業社製 酸化亜鉛３種
・老化防止剤：ＬＡＮＸＥＳＳ社製 ＶＵＬＫＡＮＯＸ ４０２０
・ワックス：日本精蝋社製 ＯＺＯＡＣＥ‐００１５Ａ
・加硫促進剤１：大内新興化学工業社製 ノクセラーＣＺ‐Ｇ
・加硫促進剤２：住友化学社製 ソクシノール Ｄ‐Ｇ
・硫黄：細井化学工業社製 油処理イオウ（硫黄含量：９５％）
The types of raw materials used in Tables 1 and 2 are shown below.
・ NR: Natural rubber, STR20
SBR1: styrene butadiene rubber, Nipol 1723 manufactured by Nippon Zeon Co., Ltd. (Styrene content: 23.5% by mass, oil extended product containing 37.5 parts by mass of oil with respect to 100 parts by mass of rubber component)
SBR2: styrene-butadiene rubber, Nipol 1739 manufactured by Nippon Zeon Co., Ltd. (Styrene content: 40% by mass, oil-extended product containing 37.5 parts by mass of oil with respect to 100 parts by mass of rubber component)
Silica 1: ZEOSIL 1165MP (CTAB adsorption specific surface area: 155 m 2 / g) manufactured by Solvay
Silica 2: ZEOSIL 1085GR manufactured by Solvay (CTAB adsorption specific surface area: 80 m 2 / g)
-Modified recycled rubber: EkoDyne manufactured by Lehigh, modified recycled rubber functionalized with tetrabenzylthiuram sulfide-Powdered recycled rubber 1: GF-80 REPROCESSED GROUND RUBBER manufactured by Lehigh (particle size: 80 mesh)
・ Powder reclaimed rubber 2: manufactured by Lehigh 140 MESH GROUND RUBBER (particle size: 140 mesh)
Silane coupling agent: Si69 made by Evonik
・ Oil: Showa Shell Sekiyu Extract 4 S
Petroleum-based resin 1: Nisseki Neopolymer 120 (softening point: 120 ° C.) manufactured by JXTG Energy
Petroleum-based resin 2: YS resin TO-125 (aromatic modified terpene resin, softening point: 125 ° C.) manufactured by Yasuhara Chemical Co., Ltd.
・ Stearic acid: Stearic acid 50S manufactured by Nisshin Rika Co., Ltd.
・ Zinc oxide: 3 types of zinc oxide manufactured by Shodo Chemical Industries, Ltd. ・ Anti-aging agent: VULKANOX 4020 manufactured by LANXESS
・ Wax: Nippon Seiwa Co., Ltd. OZOACE-0015A
・ Vulcanization accelerator 1: Nouchira CZ-G manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
・ Vulcanization accelerator 2: Sumocinol DG manufactured by Sumitomo Chemical Co., Ltd.
・ Sulfur: Oil treatment sulfur manufactured by Hosoi Chemical Co., Ltd. (sulfur content: 95%)
表１〜２から明らかなように、実施例１〜１２のゴム組成物は、標準例１に対して粘度、硬度、破断エネルギー、０℃におけるｔａｎδをバランスよく向上した。 As is clear from Tables 1 and 2, the rubber compositions of Examples 1 to 12 improved the viscosity, hardness, breaking energy, and tan δ at 0 ° C in a well-balanced manner with respect to Standard Example 1.
一方、比較例１のゴム組成物は、再生ゴムとして変性再生ゴムを単独で配合しているので、破断物性（破断エネルギー）が低下した。比較例２のゴム組成物は、粉末再生ゴムの粒径が１４０メッシュであるものの、再生ゴムとして粉末再生ゴムを単独で配合しているので、粘度が悪化した。比較例３のゴム組成物は、粉末再生ゴムおよび変性再生ゴムの配合量が共に多過ぎるため、破断物性が悪化した。比較例４のゴム組成物は、ゴム成分が天然ゴムのみで構成されるので、０℃におけるｔａｎδが低下した。比較例５のゴム組成物は、天然ゴムの配合量が多過ぎる（スチレンブタジエンゴムの配合量が少な過ぎる）ため、tanδが悪化した。比較例６のゴム組成物は、スチレンブタジエンゴムの配合量が多過ぎる（天然ゴムの配合量が少な過ぎる）ため、粘度が悪化した。比較例７のゴム組成物は、ゴム成分がスチレンブタジエンゴムのみで構成されるので、粘度および破断物性（破断エネルギー）が悪化した。比較例８のゴム組成物は、シリカのＣＴＡＢ吸着比表面積が小さ過ぎるため、破断物性（破断エネルギー）が低下した。 On the other hand, since the rubber composition of Comparative Example 1 contains a modified recycled rubber alone as a recycled rubber, its fracture property (rupture energy) was lowered. In the rubber composition of Comparative Example 2, although the particle diameter of the powder recycled rubber was 140 mesh, the viscosity was deteriorated because the powder recycled rubber was blended alone as the recycled rubber. The rubber composition of Comparative Example 3 was deteriorated in fracture properties because both the powdered recycled rubber and the modified recycled rubber were mixed in too much amount. In the rubber composition of Comparative Example 4, since the rubber component is composed only of natural rubber, tan δ at 0 ° C. decreased. In the rubber composition of Comparative Example 5, tan δ was deteriorated because the blending amount of natural rubber was too large (the blending amount of styrene butadiene rubber was too small). Since the rubber composition of Comparative Example 6 contained too much styrene butadiene rubber (too little natural rubber), the viscosity deteriorated. The rubber composition of Comparative Example 7 was deteriorated in viscosity and breaking physical properties (breaking energy) because the rubber component was composed only of styrene butadiene rubber. Since the rubber composition of Comparative Example 8 had a CTAB adsorption specific surface area of silica that was too small, the fracture property (break energy) was lowered.
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