JP2021195492A - Rubber composition, rubber composition for tire, rubber composition for tire tread, crosslinked rubber for tire, tire tread, and tire - Google Patents
Rubber composition, rubber composition for tire, rubber composition for tire tread, crosslinked rubber for tire, tire tread, and tire Download PDFInfo
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- JP2021195492A JP2021195492A JP2020104911A JP2020104911A JP2021195492A JP 2021195492 A JP2021195492 A JP 2021195492A JP 2020104911 A JP2020104911 A JP 2020104911A JP 2020104911 A JP2020104911 A JP 2020104911A JP 2021195492 A JP2021195492 A JP 2021195492A
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- rubber
- rubber composition
- tire
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- QKJGTZOWMVHEHS-UHFFFAOYSA-N triethoxy-[3-(phenyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSC1=CC=CC=C1 QKJGTZOWMVHEHS-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物、タイヤ用ゴム組成物、タイヤトレッド用ゴム組成物、タイヤ用架橋ゴム、タイヤトレッド及びタイヤに関する。 The present invention relates to a rubber composition, a rubber composition for a tire, a rubber composition for a tire tread, a crosslinked rubber for a tire, a tire tread and a tire.
近年、省エネルギーの社会的要請の下、自動車に対する低燃費化を進めるために、転がり抵抗の小さいタイヤが求められ、従来よりも低発熱性(低ロス性)に優れたゴム組成物が望まれている。
一方、自動車用タイヤの耐摩耗性の向上が望まれており、貯蔵弾性率、特に、動的貯蔵弾性率(G’)が大きなゴム組成物が望まれている。
In recent years, under the social demand for energy saving, tires with low rolling resistance have been required in order to promote fuel efficiency for automobiles, and a rubber composition having lower heat generation (lower loss) than before has been desired. There is.
On the other hand, it is desired to improve the wear resistance of automobile tires, and a rubber composition having a large storage elastic modulus, particularly a dynamic storage elastic modulus (G'), is desired.
特許文献1には、低発熱性であり、かつ、高弾性であるゴム組成物を提供することを目的として、天然ゴムや合成イソプレンゴムに対して特定の樹脂組成物及び熱可塑性樹脂を所定の割合で配合したゴム組成物が記載されている。 In Patent Document 1, a specific resin composition and a thermoplastic resin are specified with respect to natural rubber and synthetic isoprene rubber for the purpose of providing a rubber composition having low heat generation and high elasticity. The rubber compositions blended in proportion are described.
特許文献1では、特定のゴム成分に対しては低発熱性であり、かつ高弾性であるゴム組成物が得られたが、使用するゴム成分が限定されていた。また、添加する樹脂組成物及び熱可塑性樹脂の量が多く、ゴム組成物の処方の選択性が限定的であった。 In Patent Document 1, a rubber composition having low heat generation and high elasticity with respect to a specific rubber component was obtained, but the rubber component used was limited. In addition, the amount of the resin composition and the thermoplastic resin to be added was large, and the selectivity of the formulation of the rubber composition was limited.
本発明の課題は、高い動的貯蔵弾性率を有する架橋ゴムを製造可能なゴム組成物;高い動的貯蔵弾性率を有するタイヤ用架橋ゴム及びタイヤ、並びにこれらを製造可能なタイヤ用ゴム組成物;ならびに、高い動的貯蔵弾性率を有するタイヤトレッド及びこれを製造可能なタイヤトレッド用ゴム組成物を提供することであり、該課題を解決することを目的とする。 An object of the present invention is a rubber composition capable of producing a crosslinked rubber having a high dynamic storage elastic coefficient; a crosslinked rubber for a tire having a high dynamic storage elastic coefficient and a tire, and a rubber composition for a tire capable of producing the same. Moreover, it is an object of the present invention to provide a tire tread having a high dynamic storage elasticity and a rubber composition for a tire tread capable of producing the same, and to solve the problem.
本発明者は鋭意検討した結果、特定の構造を有する化合物を配合することにより、上記の課題を解決しうることを見出した。
すなわち、本発明は、以下の<1>〜<8>に関する。
<1> ジエン系ゴムを含むゴム成分と、架橋剤と、カルボキシ基に対して少なくともパラ位に、アミノ基又はアセトキシ基を有する安息香酸誘導体と、前記ゴム成分100質量部に対して20〜120質量部の充填材とを含むゴム組成物。
As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by blending a compound having a specific structure.
That is, the present invention relates to the following <1> to <8>.
<1> A rubber component containing a diene rubber, a cross-linking agent, a benzoic acid derivative having an amino group or an acetoxy group at least in the para position with respect to the carboxy group, and 20 to 120 to 100 parts by mass of the rubber component. A rubber composition containing a mass portion of a filler.
<2> 前記安息香酸誘導体の含有量が、前記ゴム成分100質量部に対して0.05〜10質量部である<1>に記載のゴム組成物。
<3> 前記架橋剤が加硫剤を含み、更に、加硫促進剤を含有し、前記安息香酸誘導体の含有量(b)に対する前記加硫促進剤の含有量(a)の質量比(a/b)が0.2〜5.0である<1>又は<2>に記載のゴム組成物。
<2> The rubber composition according to <1>, wherein the content of the benzoic acid derivative is 0.05 to 10 parts by mass with respect to 100 parts by mass of the rubber component.
<3> The cross-linking agent contains a vulcanizing agent, further contains a vulcanization accelerator, and the mass ratio (a) of the content (a) of the vulcanization accelerator to the content (b) of the benzoic acid derivative. The rubber composition according to <1> or <2>, wherein / b) is 0.2 to 5.0.
<4> <1>〜<3>のいずれか1つに記載のゴム組成物からなるタイヤ用ゴム組成物。
<5> <1>〜<3>のいずれか1つに記載のゴム組成物からなるタイヤトレッド用ゴム組成物。
<4> A rubber composition for a tire comprising the rubber composition according to any one of <1> to <3>.
<5> A rubber composition for a tire tread comprising the rubber composition according to any one of <1> to <3>.
<6> <4>に記載のタイヤ用ゴム組成物を架橋したタイヤ用架橋ゴム。 <6> A cross-linked rubber for a tire obtained by cross-linking the rubber composition for a tire according to <4>.
<7> <5>に記載のタイヤトレッド用ゴム組成物を架橋したタイヤトレッド。
<8> <6>に記載のタイヤ用架橋ゴムを含むタイヤ。
<7> A tire tread obtained by cross-linking the rubber composition for tire tread according to <5>.
<8> A tire containing the crosslinked rubber for the tire according to <6>.
本発明によれば、高い動的貯蔵弾性率を有する架橋ゴムを製造可能なゴム組成物;高い動的貯蔵弾性率を有するタイヤ用架橋ゴム及びタイヤ、並びにこれらを製造可能なタイヤ用ゴム組成物;ならびに、高い動的貯蔵弾性率を有するタイヤトレッド及びこれを製造可能なタイヤトレッド用ゴム組成物を提供することができる。 According to the present invention, a rubber composition capable of producing a crosslinked rubber having a high dynamic storage elastic coefficient; a crosslinked rubber for a tire having a high dynamic storage elastic coefficient and a tire, and a rubber composition for a tire capable of producing the same. Also, it is possible to provide a tire tread having a high dynamic storage elasticity and a rubber composition for a tire tread capable of producing the same.
以下に、本発明をその実施形態に基づき詳細に例示説明する。なお、以下の説明において、数値範囲を示す「A〜B」の記載は、端点であるA及びBを含む数値範囲を表し、「A以上B以下」(A<Bの場合)、又は、「A以下B以上」(A>Bの場合)を表す。 Hereinafter, the present invention will be illustrated in detail based on the embodiments thereof. In the following description, the description of "A to B" indicating the numerical range represents the numerical range including the end points A and B, and is "A or more and B or less" (in the case of A <B) or ". It represents "A or less and B or more" (when A> B).
<ゴム組成物>
本発明のゴム組成物は、ジエン系ゴムを含むゴム成分と、架橋剤と、カルボキシ基に対して少なくともパラ位に、アミノ基又はアセトキシ基を有する安息香酸誘導体と、ゴム成分100質量部に対して20〜120質量部の充填材とを含む。
以下、カルボキシ基に対して少なくともパラ位に、アミノ基又はアセトキシ基を有する安息香酸誘導体を、本発明における安息香酸誘導体と称する。
本発明者等は鋭意検討した結果、本発明における安息香酸誘導体を含むゴム組成物を架橋して得られる架橋ゴムは、高い動的貯蔵弾性率(G’)を有することを見出した。かかる効果が得られる詳細な機構は不明であるが、一部は以下のように推定される。
架橋の過程において、本発明における安息香酸誘導体と、ゴム成分とが擬似的に架橋を形成すると考えられ、高い動的貯蔵弾性率(G’)が達成されたものと推定される。
以下、本発明について詳述する。
<Rubber composition>
The rubber composition of the present invention comprises a rubber component containing a diene-based rubber, a cross-linking agent, a benzoic acid derivative having an amino group or an acetoxy group at least in the para position with respect to the carboxy group, and 100 parts by mass of the rubber component. 20 to 120 parts by mass of filler.
Hereinafter, a benzoic acid derivative having an amino group or an acetoxy group at least in the para position with respect to the carboxy group is referred to as a benzoic acid derivative in the present invention.
As a result of diligent studies, the present inventors have found that the crosslinked rubber obtained by crosslinking the rubber composition containing the benzoic acid derivative in the present invention has a high dynamic storage elastic modulus (G'). The detailed mechanism by which such an effect is obtained is unknown, but some are presumed as follows.
In the process of crosslinking, it is considered that the benzoic acid derivative in the present invention and the rubber component form a pseudo-crosslink, and it is presumed that a high dynamic storage elastic modulus (G') was achieved.
Hereinafter, the present invention will be described in detail.
〔ゴム成分〕
本発明のゴム組成物は、ジエン系ゴムを含むゴム成分を含有する。
ゴム成分は、ゴム工業界で使用されているジエン系ゴムを含むゴム成分から適宜選択ることができる。ジエン系ゴムは、天然ゴムあってもよいし、合成ゴムであってもよく、これらを単独で又は組み合わせて使用することができる。
ジエン系合成ゴムとしては、例えばスチレン−ブタジエン共重合体(SBR)、ポリブタジエン(BR)、ポリイソプレン(IR)、スチレン−イソプレン共重合体(SIR)、ブタジエン−イソプレン共重合体、ブタジエン−スチレン−イソプレン共重合体、アクリロニトリル−ブタジエン共重合体、クロロプレンゴム、ブチルゴム(IIR)、ハロゲン化ブチルゴムなどが挙げられる。また、その一部が多官能型変性剤、例えば四塩化スズのような変性剤を用いることにより分岐構造を有しているものでもよい。
ゴム成分は、ジエン系ゴムからなることが好ましく、また、スチレン−ブタジエン共重合体、又は天然ゴムを含有することが好ましい。ゴム成分は1種単独で使用してもよく、2種以上を併用してもよい。
[Rubber component]
The rubber composition of the present invention contains a rubber component containing a diene-based rubber.
The rubber component can be appropriately selected from rubber components including diene-based rubber used in the rubber industry. The diene-based rubber may be a natural rubber or a synthetic rubber, and these may be used alone or in combination.
Examples of the diene synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), styrene-isoprene copolymer (SIR), butadiene-isoprene copolymer, and butadiene-styrene-. Examples thereof include isoprene copolymer, acrylonitrile-butadiene copolymer, chloroprene rubber, butyl rubber (IIR), halogenated butyl rubber and the like. Further, a part thereof may have a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride.
The rubber component is preferably made of a diene-based rubber, and preferably contains a styrene-butadiene copolymer or a natural rubber. The rubber component may be used alone or in combination of two or more.
〔安息香酸誘導体〕
本発明のゴム組成物は、カルボキシ基に対して少なくともパラ位に、アミノ基又はアセトキシ基を有する安息香酸誘導体を含有する。本発明における安息香酸誘導体は、カルボキシ基に対してオルト位及びメタ位のいずれか一方又は両方に、更に、アミノ基又はアセトキシ基を有していてもよいし、ハロゲン原子、炭化水素基等の置換基を有していてもよい。
本発明のゴム組成物は、本発明における安息香酸誘導体を1種のみ含んでいてもよいし、2種以上を含んでいてもよい。
[Benzoic acid derivative]
The rubber composition of the present invention contains a benzoic acid derivative having an amino group or an acetoxy group at least in the para position with respect to the carboxy group. The benzoic acid derivative in the present invention may further have an amino group or an acetoxy group at one or both of the ortho-position and the meta-position with respect to the carboxy group, and may have a halogen atom, a hydrocarbon group and the like. It may have a substituent.
The rubber composition of the present invention may contain only one kind of the benzoic acid derivative of the present invention, or may contain two or more kinds.
以上の中でも、本発明における安息香酸誘導体は、パラ位のみにアミノ基又はアセトキシ基を有することが好ましく、具体的には、下記構造のp−アミノ安息香酸(pABA)及びp−アセトキシ安息香酸(pAcOBA)であることが好ましい。 Among the above, the benzoic acid derivative in the present invention preferably has an amino group or an acetoxy group only at the para position, and specifically, p-aminobenzoic acid (pABA) and p-acetoxybenzoic acid having the following structures (p-aminobenzoic acid (pABA)). It is preferably pAcOBA).
本発明における安息香酸誘導体は、市販品として入手してもよいし、合成してもよい。 The benzoic acid derivative in the present invention may be obtained as a commercial product or may be synthesized.
ゴム組成物中の本発明における安息香酸誘導体の含有量は、ゴム成分100質量部に対して、0.05〜10質量部であることが好ましい。かかる範囲であることで、架橋ゴムの貯蔵弾性率(G’)をより向上し、また50℃でのtanδを下げることができる。同様の観点から、ゴム組成物中の本発明における安息香酸誘導体の含有量は、0.1質量部以上であることがより好ましく、0.3質量部以上であることが更に好ましく、0.5質量部以上であることがより更に好ましく、また、5質量部以下であることがより好ましく、3質量部以下であることが更に好ましく、2.5質量部以下であるであることがより更に好ましい。 The content of the benzoic acid derivative in the present invention in the rubber composition is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the rubber component. Within such a range, the storage elastic modulus (G') of the crosslinked rubber can be further improved, and the tan δ at 50 ° C. can be lowered. From the same viewpoint, the content of the benzoic acid derivative in the present invention in the rubber composition is more preferably 0.1 part by mass or more, further preferably 0.3 part by mass or more, and 0.5 part by mass. It is more preferably more than parts by mass, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and even more preferably 2.5 parts by mass or less. ..
〔架橋剤〕
本発明のゴム組成物は、架橋剤を含有する。
架橋剤は、ゴム分子を架橋し得る成分であれば特に制限されない。例えば、硫黄架橋する加硫剤、過酸化物架橋する有機過酸化物、キノイド架橋するオキシむ化合物、アミン架橋するジアミン化合物等が挙げられる。通常は加硫剤が用いられる。
加硫剤は、通常、硫黄を用い、例えば、粉末硫黄、沈降硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄等を挙げることができる。
[Crosslinking agent]
The rubber composition of the present invention contains a cross-linking agent.
The cross-linking agent is not particularly limited as long as it is a component capable of cross-linking rubber molecules. Examples thereof include vulcanizing agents that crosslink sulfur, organic peroxides that crosslink peroxides, oxymu compounds that crosslink quinoids, and diamine compounds that crosslink amines. Usually, a vulcanizing agent is used.
Sulfur is usually used as the vulcanizing agent, and examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.
ゴム組成物において、架橋剤の含有量は、ゴム分子同士の架橋を充分に進行させる観点から、ゴム成分100質量部に対して、好ましくは0.1質量部以上、より好ましくは0.3質量部以上、更に好ましくは0.5質量部以上、より更に好ましくは1質量部以上であり、そして、耐老化防止性を向上させる観点から、好ましくは10質量部以下、より好ましくは5質量部以下、更に好ましくは3質量部以下である。 In the rubber composition, the content of the cross-linking agent is preferably 0.1 part by mass or more, more preferably 0.3 part by mass with respect to 100 parts by mass of the rubber component from the viewpoint of sufficiently advancing the cross-linking between the rubber molecules. More than parts, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the viewpoint of improving anti-aging resistance, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. More preferably, it is 3 parts by mass or less.
〔加硫促進剤〕
本発明のゴム組成物は、架橋剤が加硫剤を含む場合、更に、加硫促進剤を含有することが好ましい。
上記加硫促進剤としては、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。具体的には、CBS(N−シクロヘキシル−2−ベンゾチアゾールスルフェンアミド)、TBBS(N−t−ブチル−2−ベンゾチアゾールスルフェンアミド)、TBSI(N−t−ブチル−2−ベンゾチアゾールスルフェンイミド)等のスルフェンアミド系の加硫促進剤;DPG(ジフェニルグアニジン)等のグアニジン系の加硫促進剤;テトラオクチルチウラムジスルフィド、テトラベンジルチウラムジスルフィド等のチウラム系加硫促進剤;MBT(2−メルカプトベンゾチアゾール)、MBTS(ジ−2−ベンゾチアゾリルジスルフィド)等のチアゾール系加硫促進剤;ジアルキルジチオリン酸亜鉛等の加硫促進剤;などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
これらの中でも、本発明における安息香酸誘導体の存在下で、適度な加硫を進行させる観点から、加硫促進剤として、少なくともスルフェンアミド系の加硫促進剤を含有することが好ましく、少なくともCBS及びTBBSのいずれか一方又は両方を含有することがより好ましい。
[Vulcanization accelerator]
When the cross-linking agent contains a vulcanizing agent, the rubber composition of the present invention preferably further contains a vulcanization accelerator.
The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Specifically, CBS (N-cyclohexyl-2-benzothiazolesulfenamide), TBBS (N-t-butyl-2-benzothiazolesulfenamide), TBSI (N-t-butyl-2-benzothiazolesulfenamide) Sulfenamide-based vulcanization accelerator such as fenimide); guanidine-based vulcanization accelerator such as DPG (diphenylguanidine); thiuram-based vulcanization accelerator such as tetraoctylthiuram disulfide and tetrabenzylthiuram disulfide; MBT ( 2-mercaptobenzothiazole), a thiazole-based vulcanization accelerator such as MBTS (di-2-benzothiazolyl disulfide); a vulcanization accelerator such as zinc dialkyldithiophosphate; and the like. These may be used alone or in combination of two or more.
Among these, from the viewpoint of advancing appropriate vulcanization in the presence of the benzoic acid derivative in the present invention, it is preferable to contain at least a sulfenamide-based vulcanization accelerator as a vulcanization accelerator, and at least CBS. And, it is more preferable to contain either one or both of TBBS.
ゴム組成物中の加硫促進剤の含有量は、適切な加硫速度で、適度な加硫を進行させる観点から、ゴム成分100質量部に対して、好ましくは0.1質量部以上、より好ましくは0.3質量部以上、更に好ましくは0.5質量部以上、より更に好ましくは1質量部以上であり、そして、好ましくは10質量部以下、より好ましくは7.5質量部以下、更に好ましくは5質量部以下である。 The content of the vulcanization accelerator in the rubber composition is preferably 0.1 part by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of advancing appropriate vulcanization at an appropriate vulcanization rate. It is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 7.5 parts by mass or less, further. It is preferably 5 parts by mass or less.
また、ゴム組成物中、本発明における安息香酸誘導体の含有量(b)に対する加硫促進剤の含有量(a)の質量比(a/b)は、本発明における安息香酸誘導体の加硫阻害作用を抑制し、適度な加硫を進行させ、低発熱性である架橋ゴム組成物を得る観点から、好ましくは0.2以上、より好ましくは0.3以上、更に好ましくは1.0以上であり、そして、好ましくは5.0以下、より好ましくは3.0以下、更に好ましくは2.5以下である。 Further, the mass ratio (a / b) of the content (a) of the vulcanization accelerator to the content (b) of the benzoic acid derivative in the rubber composition in the rubber composition is the inhibition of vulcanization of the benzoic acid derivative in the present invention. From the viewpoint of suppressing the action, advancing appropriate vulcanization, and obtaining a crosslinked rubber composition having low heat generation, it is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 1.0 or more. Yes, and preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.
〔充填材〕
本発明のゴム組成物は、ゴム成分100質量部に対して20〜120質量部の充填材を含有する。
ゴム組成物が上記範囲の充填材を含むことで、架橋ゴムの補強性を向上し、50℃でのtanδをより低下することができる。
一般に、ゴム組成物が充填材を多く含むと、充填剤同士の擦れ合いにより架橋ゴムが発熱し易いが、ゴム組成物が本発明における安息香酸誘導体を含むことで、充填材の凝集を高め、発熱を抑制し得る。すなわち、50℃でのtanδを下げやすい。
架橋ゴムの補強性をより向上し、50℃でのtanδをより低下する観点から、ゴム組成物中の充填材の総含有量は、ゴム成分100質量部に対し、好ましくは30質量部以上、より好ましくは40質量部以上であり、そして、好ましくは90質量部以下、より好ましくは80質量部以下である。
[Filler]
The rubber composition of the present invention contains 20 to 120 parts by mass of a filler with respect to 100 parts by mass of the rubber component.
When the rubber composition contains the filler in the above range, the reinforcing property of the crosslinked rubber can be improved and the tan δ at 50 ° C. can be further lowered.
Generally, when the rubber composition contains a large amount of filler, the crosslinked rubber tends to generate heat due to rubbing between the fillers. However, when the rubber composition contains the benzoic acid derivative in the present invention, the aggregation of the filler is enhanced. Fever can be suppressed. That is, it is easy to lower the tan δ at 50 ° C.
From the viewpoint of further improving the reinforcing property of the crosslinked rubber and further lowering the tan δ at 50 ° C., the total content of the filler in the rubber composition is preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. It is more preferably 40 parts by mass or more, preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.
充填材としては、カーボンブラックのような有機充填材、シリカのような無機充填材、又はこれら2つのタイプの充填材をブレンドして使用してもよい。これらの中でも、カーボンブラック及びシリカから選ばれる1種以上の充填材が好ましく用いられる。
前記カーボンブラックとしては特に制限はなく、従来、ゴムの充填材として使用されているものの中から、任意のものを適宜選択して用いることができる。例えば、SRF、GPF、FEF、HAF、ISAF、SAFなどが用いられ、特に耐屈曲性及び耐破壊性に優れるFEF、HAF、ISAF、SAF等が好適に挙げられる。
カーボンブラックは、補強性の観点から、窒素吸着比表面積N2SA(JIS K 6217−2:2001に準拠する。)が、好ましくは30m2/g以上、より好ましくは35m2/g以上であり、そして、好ましくは150m2/g以下、より好ましくは130m2/g以下である。
カーボンブラックは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
As the filler, an organic filler such as carbon black, an inorganic filler such as silica, or a blend of these two types of filler may be used. Among these, one or more fillers selected from carbon black and silica are preferably used.
The carbon black is not particularly limited, and any carbon black that has been conventionally used as a filler for rubber can be appropriately selected and used. For example, SRF, GPF, FEF, HAF, ISAF, SAF and the like are used, and FEF, HAF, ISAF, SAF and the like, which are particularly excellent in bending resistance and fracture resistance, are preferably mentioned.
From the viewpoint of reinforcing property, carbon black has a nitrogen adsorption specific surface area N 2 SA (based on JIS K 6217-2: 2001), preferably 30 m 2 / g or more, and more preferably 35 m 2 / g or more. , And more preferably 150 m 2 / g or less, more preferably 130 m 2 / g or less.
One type of carbon black may be used alone, or two or more types may be used in combination.
一方、シリカとしては、例えば湿式シリカ(含水ケイ酸)、乾式シリカ(無水ケイ酸)、ケイ酸カルシウム、ケイ酸アルミニウムなどが挙げられるが、中でも湿式シリカが好ましい。
この湿式シリカのBET比表面積(ISO 5794/1に基づき測定する。)は、補強性の観点から、好ましくは40m2/g以上、より好ましくは80m2/g以上であり、そして、好ましくは350m2/g以下、より好ましくは300m2/g以下である。このようなシリカとしては東ソー・シリカ(株)製「Nipsil AQ」、「Nipsil KQ」、デグッサ社製「ウルトラジルVN3」等の市販品を用いることができる。
シリカは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
シリカ以外の無機充填材としては、水酸化アルミニウム、クレー、タルク、炭酸カルシウム、ゼオライト等が例示される。
On the other hand, examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like, with wet silica being preferred.
The BET specific surface area (measured based on ISO 5794/1) of this wet silica is preferably 40 m 2 / g or more, more preferably 80 m 2 / g or more, and preferably 350 m from the viewpoint of reinforcing property. It is 2 / g or less, more preferably 300 m 2 / g or less. As such silica, commercially available products such as "Nipsil AQ" and "Nipsil KQ" manufactured by Tosoh Silica Co., Ltd. and "Ultrazil VN3" manufactured by Degussa Co., Ltd. can be used.
One type of silica may be used alone, or two or more types may be used in combination.
Examples of the inorganic filler other than silica include aluminum hydroxide, clay, talc, calcium carbonate, zeolite and the like.
なお、本発明において、充填材としてカーボンブラック及びシリカを併用することが好ましく、この場合、本発明のゴム組成物中のカーボンブラックの含有量は、補強性及び低発熱性の観点から、ゴム成分100質量部に対して、好ましくは5質量部以上、より好ましくは10質量部以上、更に好ましくは15質量部以上であり、そして、好ましくは60質量部以下、より好ましくは55質量部以下、更に好ましくは50質量部以下である。
また、カーボンブラック及びシリカを併用する場合、本発明のゴム組成物中のシリカの含有量は、補強性及び低発熱性の観点から、ゴム成分100質量部に対して、好ましくは1質量部以上、より好ましくは3質量部以上、更に好ましくは5質量部以上、より更に好ましくは10質量部以上であり、そして、好ましくは50質量部以下、より好ましくは40質量部以下、更に好ましくは35質量部以下である。
In the present invention, it is preferable to use carbon black and silica together as a filler. In this case, the content of carbon black in the rubber composition of the present invention is a rubber component from the viewpoint of reinforcing property and low heat generation. With respect to 100 parts by mass, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and preferably 60 parts by mass or less, more preferably 55 parts by mass or less, further. It is preferably 50 parts by mass or less.
When carbon black and silica are used in combination, the content of silica in the rubber composition of the present invention is preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of reinforcing property and low heat generation. , More preferably 3 parts by mass or more, further preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass. It is less than a part.
(シランカップリング剤)
本発明のゴム組成物において、充填材としてシリカを使用する場合、その補強性を更に向上させる目的で、シランカップリング剤を配合することが好ましい。
シランカップリング剤としては、例えばビス(3−トリエトキシシリルプロピル)テトラスルフィド、ビス(3−トリエトキシシリルプロピル)トリスルフィド、ビス(3−トリエトキシシリルプロピル)ジスルフィド、ビス(2−トリエトキシシリルエチル)テトラスルフィド、ビス(3−トリメトキシシリルプロピル)テトラスルフィド、ビス(2−トリメトキシシリルエチル)テトラスルフィド、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、2−メルカプトエチルトリメトキシシラン、2−メルカプトエチルトリエトキシシラン、3−トリメトキシシリルプロピル−N,N−ジメチルチオカルバモイルテトラスルフィド、3−トリエトキシシリルプロピル−N,N−ジメチルチオカルバモイルテトラスルフィド、2−トリエトキシシリルエチル−N,N−ジメチルチオカルバモイルテトラスルフィド、3−トリメトキシシリルプロピルベンゾチアゾリルテトラスルフィド、3−トリエトキシシリルプロピルベンゾリルテトラスルフィド、3−トリエトキシシリルプロピルメタクリレートモノスルフィド、3−トリメトキシシリルプロピルメタクリレートモノスルフィド、ビス(3−ジエトキシメチルシリルプロピル)テトラスルフィド、3−メルカプトプロピルジメトキシメチルシラン、ジメトキシメチルシリルプロピル−N,N−ジメチルチオカルバモイルテトラスルフィド、ジメトキシメチルシリルプロピルベンゾチアゾリルテトラスルフィドなどが挙げられるが、これらの中で補強性改善効果などの点から、ビス(3−トリエトキシシリルプロピル)ポリスルフィド及び3−トリメトキシシリルプロピルベンゾチアジルテトラスルフィドが好適である。
これらのシランカップリング剤は、1種を単独で用いてもよく、2種以上組み合わせて用いてもよい。
(Silane coupling agent)
When silica is used as a filler in the rubber composition of the present invention, it is preferable to add a silane coupling agent for the purpose of further improving the reinforcing property thereof.
Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxysilyl). Ethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilyl Ethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxy Cyrilpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl Examples thereof include tetrasulfide, and among these, bis (3-triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiaziltetrasulfide are preferable from the viewpoint of improving the reinforcing property.
These silane coupling agents may be used alone or in combination of two or more.
本発明のゴム組成物においては、好ましいシランカップリング剤の配合量は、シランカップリング剤の種類などにより異なるが、シリカの分散性を向上させると共に、ゴム成分のゲル化を抑制する観点から、シリカ100質量部に対して、好ましくは0.5質量部以上、より好ましくは1質量部以上、更に好ましくは2質量部以上であり、そして、好ましくは20質量部以下、より好ましくは15質量部以下、更に好ましくは10質量部以下である。 In the rubber composition of the present invention, the preferable blending amount of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but from the viewpoint of improving the dispersibility of silica and suppressing the gelation of the rubber component, from the viewpoint of improving the dispersibility of silica. It is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass with respect to 100 parts by mass of silica. Hereinafter, it is more preferably 10 parts by mass or less.
〔その他の成分〕
本発明のゴム組成物は、上述の成分に加え、本発明の目的を損なわない範囲で、その他の添加剤を含有していてもよい。その他の添加剤としては、通常ゴム業界で使用される各種添加剤から適宜選択すればよく、具体的には、加硫促進助剤、老化防止剤、軟化剤、着色剤、難燃剤、滑剤、発泡剤、可塑剤、加工助剤、酸化防止剤、紫外線防止剤、帯電防止剤、着色防止剤、その他の配合剤等が挙げられる。
[Other ingredients]
The rubber composition of the present invention may contain other additives in addition to the above-mentioned components as long as the object of the present invention is not impaired. Other additives may be appropriately selected from various additives usually used in the rubber industry, and specifically, vulcanization accelerators, antistatic agents, softeners, colorants, flame retardants, lubricants, etc. Examples thereof include foaming agents, plasticizers, processing aids, antioxidants, ultraviolet inhibitors, antistatic agents, anticoloring agents, and other compounding agents.
(加硫促進助剤)
本発明のゴム組成物は、加硫を促進する観点から、亜鉛華、脂肪酸等の加硫促進助剤を含有してもよい。脂肪酸としては飽和、不飽和でもよく、また、直鎖状、分岐状のいずれであってもよい。また、炭素数も特に制限されるものではなく、例えば、炭素数1〜30、好ましくは15〜30のものを使用することができる。
脂肪酸の具体例としては、シクロヘキサン酸(シクロヘキサンカルボン酸)、側鎖を有するアルキルシクロペンタン等のナフテン酸、ヘキサン酸、オクタン酸、デカン酸(ネオデカン酸等の分岐状カルボン酸を含む)、ドデカン酸、テトラデカン酸、ヘキサデカン酸、オクタデカン酸(ステアリン酸)等の飽和脂肪酸、メタクリル酸、オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸、ロジン、トール油酸、アビエチン酸等の樹脂酸等が挙げられ、ステアリン酸が好ましい。これらは1種を単独で用いてもよく、2種以上を併用してもよい。本発明においては、ステアリン酸及び亜鉛華を好適に用いることができ、亜鉛華とステアリン酸とを併用することが特に好ましい。
これら加硫促進助剤のゴム組成物中の総含有量は、特に制限されるものではないが、混練作業性及び加硫促進の観点から、ゴム成分100質量部に対して、好ましくは0.5質量部以上、より好ましくは1質量部以上、更に好ましくは3質量部以上であり、そして、好ましくは15質量部以下、より好ましくは10質量部以下、更に好ましくは7質量部以下である。
(Vulcanization acceleration aid)
From the viewpoint of promoting vulcanization, the rubber composition of the present invention may contain a vulcanization promoting aid such as zinc oxide and fatty acid. The fatty acid may be saturated or unsaturated, and may be linear or branched. Further, the number of carbon atoms is not particularly limited, and for example, one having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms can be used.
Specific examples of the fatty acid include cyclohexaneic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain, hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acids such as neodecanoic acid), and dodecanoic acid. , Saturated fatty acids such as tetradecanoic acid, hexadecanoic acid and octadecanoic acid (stearic acid), unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid, resin acids such as rosin, tall oil acid and avietic acid. And stearic acid is preferred. These may be used alone or in combination of two or more. In the present invention, stearic acid and zinc oxide can be preferably used, and it is particularly preferable to use zinc oxide and stearic acid in combination.
The total content of these vulcanization accelerating aids in the rubber composition is not particularly limited, but from the viewpoint of kneading workability and vulcanization promotion, it is preferably 0. It is 5 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less.
(老化防止剤)
本発明のゴム組成物で使用できる老化防止剤としては、例えば3C(N−イソプロピル−N’−フェニル−p−フェニレンジアミン)、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]、TMDQ(2,2,4−トリメチル−1,2−ジヒドロキノリン重合体)、AW(6−エトキシ−2,2,4−トリメチル−1,2−ジヒドロキノリン)、ジフェニルアミンとアセトンの高温縮合物等を挙げることができる。
老化防止剤は、1種単独で使用してもよく、2種以上を併用してもよい。
ゴム組成物中の老化防止剤の配合量は、十分な耐候性及び耐オゾン性を付与すると共に、変色及び耐亀裂性の低下を抑制する観点から、ゴム成分100質量部に対して、好ましくは0.1質量部以上、より好ましくは0.3質量部以上、更に好ましくは1質量部以上であり、そして、好ましくは6質量部以下、より好ましくは5質量部以下、更に好ましくは3質量部以下である。
(Anti-aging agent)
Examples of the antioxidant that can be used in the rubber composition of the present invention include 3C (N-isopropyl-N'-phenyl-p-phenylenediamine) and 6C [N- (1,3-dimethylbutyl) -N'-phenyl. -P-Phenylenediamine], TMDQ (2,2,4-trimethyl-1,2-dihydroquinoline polymer), AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), diphenylamine And high temperature condensates of acetone and the like.
The anti-aging agent may be used alone or in combination of two or more.
The blending amount of the antiaging agent in the rubber composition is preferably with respect to 100 parts by mass of the rubber component from the viewpoint of imparting sufficient weather resistance and ozone resistance and suppressing discoloration and deterioration of crack resistance. 0.1 part by mass or more, more preferably 0.3 part by mass or more, further preferably 1 part by mass or more, and preferably 6 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass. It is as follows.
本発明のゴム組成物は、各種のゴム製品の製造に用いることができる。
ゴム製品としては、タイヤに加え、防振ゴム、免震ゴム、コンベアベルト等のベルト、ゴムクローラ、各種ホース等が挙げられる。
The rubber composition of the present invention can be used in the production of various rubber products.
Examples of rubber products include vibration-proof rubber, seismic isolation rubber, belts such as conveyor belts, rubber crawlers, and various hoses, in addition to tires.
<ゴム組成物の調製>
本発明のゴム組成物の製造方法は特に限定されない。
ゴム組成物は、ゴム成分、架橋剤、及び本発明における安息香酸誘導体の他、各種配合剤を配合して、バンバリーミキサー、ロール、インテンシブミキサー、二軸押出機等による混練り、熱入れ、押出等することにより製造することができる。
ゴム組成物の製造時に加硫が起こるのを抑制し、製造時のハンドリング性を向上させる観点から、ゴム組成物に含有させる成分のうち、架橋剤及び加硫促進剤を除く成分を予め配合して混合し(第1混練工程)、次いで、架橋剤及び加硫促進剤を配合して混合する(第2混練工程)ことにより、ゴム組成物を調製することが好ましい。
<Preparation of rubber composition>
The method for producing the rubber composition of the present invention is not particularly limited.
The rubber composition contains a rubber component, a cross-linking agent, a benzoic acid derivative in the present invention, and various compounding agents, and is kneaded, heated, and extruded by a Banbury mixer, a roll, an intensive mixer, a twin-screw extruder, or the like. It can be manufactured by the same.
From the viewpoint of suppressing the occurrence of vulcanization during the production of the rubber composition and improving the handleability during the production, the components contained in the rubber composition, excluding the cross-linking agent and the vulcanization accelerator, are pre-blended. It is preferable to prepare a rubber composition by mixing and mixing (first kneading step), and then blending and mixing a cross-linking agent and a vulcanization accelerator (second kneading step).
上記の方法によりゴム組成物を調製することにより、第一混練工程を高温条件下で行っても加硫が生じにくいので、ゴム組成物を生産性よく製造することができる。
第1混練工程における混練温度は、各成分の熱分解を抑制する観点から、最高温度が、好ましくは250℃以下、より好ましくは200℃以下、更に好ましくは180℃以下である。また、生産性の観点から、第1混練工程における混練温度は、好ましくは100℃以上、より好ましくは120℃以上、更に好ましくは140℃以上である。
第2混練工程における混練温度は、混練時の加硫の発生を抑制する観点から、最高温度が、好ましくは150℃以下、より好ましくは130℃以下である。また、生産性の観点から、第2混練工程における混練温度は、好ましくは80℃以上、より好ましくは100℃以上である。
By preparing the rubber composition by the above method, vulcanization is unlikely to occur even if the first kneading step is performed under high temperature conditions, so that the rubber composition can be produced with high productivity.
The maximum temperature of the kneading temperature in the first kneading step is preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower, from the viewpoint of suppressing thermal decomposition of each component. From the viewpoint of productivity, the kneading temperature in the first kneading step is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher.
The maximum temperature of the kneading temperature in the second kneading step is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of suppressing the occurrence of vulcanization during kneading. Further, from the viewpoint of productivity, the kneading temperature in the second kneading step is preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
<タイヤ用ゴム組成物、タイヤトレッド用ゴム組成物>
本発明のタイヤ用ゴム組成物は、本発明のゴム組成物からなる。
本発明のタイヤトレッド用ゴム組成物は、本発明のゴム組成物からなる。
本発明のゴム組成物は、高い弾性率と低いtanδのバランスに優れる架橋ゴムを製造することができるため、タイヤ、特にタイヤトレッドの製造に好適であり、タイヤ用ゴム組成物は、特に、タイヤトレッド用ゴム組成物として用いることが好ましい。
<Rubber composition for tires, rubber composition for tire tread>
The rubber composition for a tire of the present invention comprises the rubber composition of the present invention.
The rubber composition for a tire tread of the present invention comprises the rubber composition of the present invention.
Since the rubber composition of the present invention can produce a crosslinked rubber having an excellent balance between a high elastic modulus and a low tan δ, it is suitable for producing a tire, particularly a tire tread, and the rubber composition for a tire is particularly suitable for a tire. It is preferably used as a rubber composition for tread.
<タイヤ用架橋ゴム>
本発明のタイヤ用架橋ゴムは、本発明のタイヤ用ゴム組成物を架橋して得られる。
タイヤ用架橋ゴムは、ゴム分子同士に、架橋剤による架橋が形成されており、これに加え、本発明における安息香酸誘導体による擬似的な架橋が形成されていてもよい。
前記架橋の条件としては、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、架橋温度を120〜200℃とし、架橋時間を1分間〜900分間とすることが好ましい。
<Cross-linked rubber for tires>
The cross-linked rubber for a tire of the present invention is obtained by cross-linking the rubber composition for a tire of the present invention.
In the cross-linked rubber for tires, cross-linking is formed between the rubber molecules by a cross-linking agent, and in addition, pseudo-cross-linking by the benzoic acid derivative in the present invention may be formed.
The conditions for the cross-linking are not particularly limited and may be appropriately selected depending on the intended purpose, but the cross-linking temperature is preferably 120 to 200 ° C. and the cross-linking time is preferably 1 minute to 900 minutes.
<タイヤトレッド及びタイヤ>
本発明のタイヤトレッド及びタイヤは、本発明のタイヤ用架橋ゴムを含む。
本発明のタイヤ用架橋ゴムは、タイヤの製造に好適に使用される。
本発明のタイヤトレッド用ゴム組成物は、タイヤトレッドの製造に好適に使用される。すなわち、タイヤトレッドは、本発明のタイヤトレッド用ゴム組成物を架橋して得られる。本発明のタイヤ用架橋ゴムを、タイヤトレッドの製造に用いてもよい。
本発明のタイヤ用架橋ゴムの適用部位としては、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。例えば、既述のようにトレッド部に用いてもよいし、サイドウォール部、ビード部、インナーライナー、及びその他の補強ゴム部の少なくとも一つの部材に好適に用いることができる。
<Tire tread and tires>
The tire tread and the tire of the present invention include the crosslinked rubber for a tire of the present invention.
The crosslinked rubber for a tire of the present invention is suitably used for manufacturing a tire.
The rubber composition for a tire tread of the present invention is suitably used for producing a tire tread. That is, the tire tread is obtained by cross-linking the rubber composition for tire tread of the present invention. The crosslinked rubber for tires of the present invention may be used for manufacturing a tire tread.
The application site of the crosslinked rubber for a tire of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it may be used for the tread portion as described above, or may be suitably used for at least one member of the sidewall portion, the bead portion, the inner liner, and other reinforcing rubber portions.
また、本発明のタイヤは、本発明のタイヤ用ゴム組成物又はタイヤトレッド用ゴム組成物を用いる以外特に制限はなく、常法に従って製造することができる。すなわち、本発明のタイヤトレッド用ゴム組成物が未加硫の段階で、トレッド用部材に押出し加工され、タイヤ成形機上で通常の方法により貼付成形され、生タイヤが成形される。この生タイヤを加硫機中で加熱加圧してタイヤが製造される。また、該タイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。 Further, the tire of the present invention is not particularly limited except that the rubber composition for a tire or the rubber composition for a tire tread of the present invention is used, and can be produced according to a conventional method. That is, the rubber composition for tire tread of the present invention is extruded into a tread member at an unvulcanized stage, and is pasted and molded on a tire molding machine by a usual method to form a raw tire. The raw tire is manufactured by heating and pressurizing the raw tire in a vulcanizer. Further, as the gas to be filled in the tire, an inert gas such as nitrogen, argon or helium can be used in addition to normal air or air having an adjusted oxygen partial 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, but the present invention is not limited to the following examples.
<実施例1〜2及び比較例1〜3>
〔ゴム組成物の調整と架橋〕
表1に示す配合割合の成分をバンバリーミキサーを用いて混練してゴム組成物を調製し、更に加圧型加硫装置を用いて145℃で33分間加熱して架橋(加硫)し、架橋ゴム(加硫ゴム)を得た。表1に示す成分は以下の通りである。
・NR:天然ゴム、RSS #1
・カーボンブラック:東海カーボン社製、商品名「シースト3」、HAF、N2SA=79m2/g
・シリカ:東ソー・シリカ社製、商品名「Nipsil AQ」、BET比表面積=205m2/g
・シランカップリング剤:エボニック社製、商品名「Si69」、ビス[(3−トリエトキシシリル)プロピル]テトラスルフィド
・老防防止剤:大内新興化学工業社製、商品名「ノクラック6C」、N−フェニル−N’−(1,3−ジメチルブチル)−p−フェニレンジアミン
・加硫促進剤:三新化学工業社製、商品名「サンセラーNS−G」、N−(t−ブチル)−2−ベンゾチアゾールスルフェンアミド
・ステアリン酸:花王社製、商品名「ルナックS−70V」、
・亜鉛華:和光純薬工業社製
・硫黄:和光純薬工業社製
<Examples 1 and 2 and Comparative Examples 1 to 3>
[Adjustment and cross-linking of rubber composition]
The components of the blending ratio shown in Table 1 are kneaded using a Banbury mixer to prepare a rubber composition, and further heated at 145 ° C. for 33 minutes at 145 ° C. for cross-linking (vulcanization) using a pressure-type vulcanizer to cross-link (vulcanize) the cross-linked rubber. (Vulcanized rubber) was obtained. The components shown in Table 1 are as follows.
・ NR: Natural rubber, RSS # 1
-Carbon black: Made by Tokai Carbon Co., Ltd., trade name "Seast 3", HAF, N 2 SA = 79m 2 / g
-Silica: Made by Tosoh Silica, trade name "Nipsil AQ", BET specific surface area = 205 m 2 / g
・ Sulfen coupling agent: Ebonic, trade name “Si69”, bis [(3-triethoxysilyl) propyl] tetrasulfide ・ Anti-aging agent: Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name “Nocrack 6C”, N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine / vulcanization accelerator: manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sunceller NS-G", N- (t-butyl)- 2-Benzothiazole sulfenamide stearic acid: manufactured by Kao, trade name "Lunac S-70V",
・ Zinc oxide: manufactured by Wako Pure Chemical Industries, Ltd. ・ Sulfur: manufactured by Wako Pure Chemical Industries, Ltd.
化合物
・pABA:p−アミノ安息香酸(東京化成工業社製)
・pAcOBA:p−アセトキシ安息香酸(東京化成工業社製)
・BA:安息香酸(東京化成工業社製、下記構造)
・pCBA:p−カルボキシ安息香酸(東京化成工業社製、下記構造)
Compound ・ pABA: p-aminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
-PAcOBA: p-acetoxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ BA: Benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., structure below)
-PCBA: p-carboxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., structure below)
〔評価〕
得られた架橋ゴムに対して、貯蔵弾性率(G’(50℃、5%))及び損失正接(tanδ(50℃、5%))の測定を行った。
具体的には、得られた架橋ゴムに対して、粘弾性測定装置「ARES−G2」(TAインスツルメント社製)を用いて、周波数10Hzの条件下で、50℃における歪み5%時の動的貯蔵弾性率(引張動的貯蔵弾性率、G’(50℃、5%))及び損失正接(tanδ(50℃、5%))を測定した。
動的貯蔵弾性率(G’)に関しては、比較例1の動的貯蔵弾性率(G’)を100として、指数表示した。なお、G’の値が大きい程、車両の操縦安定性及び耐摩耗性に優れていることを示す。
また、損失正接(tanδ)に関しては、比較例1の損失正接(tanδ)を100として、指数表示した。なお、tanδの値が小さいほど、低発熱性であり、タイヤに用いた際に低転がり抵抗性であることを示す。
〔evaluation〕
The storage elastic modulus (G'(50 ° C., 5%)) and loss tangent (tan δ (50 ° C., 5%)) were measured for the obtained crosslinked rubber.
Specifically, the obtained crosslinked rubber was subjected to a viscoelasticity measuring device "ARES-G2" (manufactured by TA Instruments) under the condition of a frequency of 10 Hz and a strain of 5% at 50 ° C. Dynamic storage elastic modulus (tensile dynamic storage elastic modulus, G'(50 ° C., 5%)) and loss tangent (tan δ (50 ° C., 5%)) were measured.
The dynamic storage elastic modulus (G') was expressed exponentially with the dynamic storage elastic modulus (G') of Comparative Example 1 as 100. The larger the value of G', the better the steering stability and wear resistance of the vehicle.
Further, regarding the loss tangent (tan δ), the loss tangent (tan δ) of Comparative Example 1 was set as 100 and displayed as an exponential notation. The smaller the value of tan δ, the lower the heat generation and the lower the rolling resistance when used in a tire.
表1の結果から、特定の構造を有する化合物を添加することによって、高い動的貯蔵弾性率(G’)を有する架橋ゴムが得られることが示された。 From the results in Table 1, it was shown that a crosslinked rubber having a high dynamic storage elastic modulus (G') can be obtained by adding a compound having a specific structure.
本発明によれば、高い動的貯蔵弾性率を有する架橋ゴムが得られるゴム組成物が提供され、該ゴム組成物及び架橋ゴムは、タイヤの製造に適用可能であり、特に、タイヤトレッドの製造に有用である。該ゴム組成物又は架橋ゴムをタイヤトレッドに用いたタイヤは、耐摩耗性に優れると共に、低発熱性であり、省エネルギー性に優れると期待される。 INDUSTRIAL APPLICABILITY According to the present invention, a rubber composition for obtaining a crosslinked rubber having a high dynamic storage elastic modulus is provided, and the rubber composition and the crosslinked rubber can be applied to the production of a tire, and in particular, the production of a tire tread. It is useful for. A tire using the rubber composition or crosslinked rubber for a tire tread is expected to have excellent wear resistance, low heat generation, and excellent energy saving.
Claims (8)
架橋剤と、
カルボキシ基に対して少なくともパラ位に、アミノ基又はアセトキシ基を有する安息香酸誘導体と、
前記ゴム成分100質量部に対して20〜120質量部の充填材と
を含むゴム組成物。 Rubber components including diene rubber and
With a cross-linking agent,
A benzoic acid derivative having an amino group or an acetoxy group at least in the para position with respect to the carboxy group.
A rubber composition containing 20 to 120 parts by mass of a filler with respect to 100 parts by mass of the rubber component.
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JP2012229357A (en) * | 2011-04-27 | 2012-11-22 | Yokohama Rubber Co Ltd:The | Rubber composition for tire, and pneumatic tire using the same |
JP2019077072A (en) * | 2017-10-23 | 2019-05-23 | 横浜ゴム株式会社 | Laminate for pneumatic tire, inner liner material and method for producing pneumatic tire |
JP2021195493A (en) * | 2020-06-17 | 2021-12-27 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire, crosslinked rubber for tire, tire and additive for rubber |
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JP2012229357A (en) * | 2011-04-27 | 2012-11-22 | Yokohama Rubber Co Ltd:The | Rubber composition for tire, and pneumatic tire using the same |
JP2019077072A (en) * | 2017-10-23 | 2019-05-23 | 横浜ゴム株式会社 | Laminate for pneumatic tire, inner liner material and method for producing pneumatic tire |
JP2021195493A (en) * | 2020-06-17 | 2021-12-27 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire, crosslinked rubber for tire, tire and additive for rubber |
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JP2021195493A (en) * | 2020-06-17 | 2021-12-27 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire, crosslinked rubber for tire, tire and additive for rubber |
JP7511392B2 (en) | 2020-06-17 | 2024-07-05 | 株式会社ブリヂストン | Rubber composition, rubber composition for tires, crosslinked rubber for tires, additives for tires and rubber |
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