JP4857694B2 - Rubber composition for tire tread - Google Patents
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- JP4857694B2 JP4857694B2 JP2005291199A JP2005291199A JP4857694B2 JP 4857694 B2 JP4857694 B2 JP 4857694B2 JP 2005291199 A JP2005291199 A JP 2005291199A JP 2005291199 A JP2005291199 A JP 2005291199A JP 4857694 B2 JP4857694 B2 JP 4857694B2
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Description
本発明は、タイヤトレッド用ゴム組成物に関し、更に詳細には、環境上安全で、未加硫ゴムの粘度を下げ加工性を改善させる特定の軟化剤を配合したタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for tire treads, and more particularly, to a rubber composition for tire treads that is environmentally safe and contains a specific softening agent that lowers the viscosity of unvulcanized rubber and improves processability.
近年、環境あるいは人体への悪影響を考慮して、エキストラクトに代えてＰＣＡ成分を３％未満に抑えたＭＥＳ，ＴＤＡＥと呼ばれる石油系軟化剤の開発が進んでいるが、これらはゴムに添加したときの可塑化効果が不十分であるという欠点を有しており、より可塑化効果の優れた軟化剤の開発が望まれていた。特に、最近の低燃費指向によりゴム用充填剤としてシリカ配合が用いられる場合には、未加硫ゴムの粘度が高くなり、シリカの分散性、加工性などの点で可塑化効果の高い軟化剤が益々要求されるようになってきた。この点、植物油は天然産品であり、安全性・環境面で優れた軟化剤であるが、ゴムへ配合した場合ブリードなどの問題があった。 In recent years, considering the adverse effects on the environment or the human body, development of petroleum-based softeners called MES and TDAE, in which the PCA component is suppressed to less than 3% in place of the extract, has been developed. The development of a softener with a more excellent plasticizing effect has been desired because of the drawback that the plasticizing effect is insufficient. In particular, when silica compounding is used as a rubber filler due to the recent trend toward low fuel consumption, the viscosity of unvulcanized rubber increases, and the softening agent has a high plasticizing effect in terms of silica dispersibility and processability. Is increasingly required. In this respect, vegetable oil is a natural product and is an excellent softening agent in terms of safety and environment, but has problems such as bleeding when blended into rubber.
前記したシリカ配合系ゴム組成物に対して、側鎖の不飽和結合をエポキシ化したエポキシ化変性スチレン−ブタジエンゴムを所定量ゴム成分中に配合することにより、弾性率の実質的低下を招くことなく耐熱老化性を改善する技術が、以下の特許文献１により提案されている。また、熱安定性、着色性に優れた安定性を有する塩化ビニル系樹脂組成物を得る目的で、当該塩化ビニル系樹脂組成物中にヨウ素価６０以上のパーム油をエポキシ化して得られるエポキシ化パーム油を所定量配合する技術が、以下の特許文献２により提案されている。しかしながら、かかる特定のエポキシ化パーム油をゴム用の軟化剤として、タイヤトレッド用ゴム組成物、特にシリカ配合系のタイヤトレッド用ゴム組成物に配合する技術は、未だ提案されていない。 By blending a predetermined amount of epoxidized modified styrene-butadiene rubber with epoxidized unsaturated bonds in the side chain into the above-described silica compounded rubber composition, the elastic modulus is substantially lowered. The following patent document 1 proposes a technique for improving heat aging resistance. In addition, for the purpose of obtaining a vinyl chloride resin composition having excellent thermal stability and colorability, epoxidation obtained by epoxidizing palm oil having an iodine value of 60 or more in the vinyl chloride resin composition A technique for blending a predetermined amount of palm oil is proposed in Patent Document 2 below. However, a technique for blending such a specific epoxidized palm oil into a rubber composition for tire treads, particularly a rubber composition for tire treads based on silica has not been proposed yet as a softener for rubber.
よって、本発明では、特定のエポキシ化パーム油軟化剤の配合により、タイヤトレッド用ゴム組成物、特にシリカ配合系のタイヤトレッド用ゴム組成物における未加硫ゴムの粘度を低減させ、また、環境・安全面でも好適なタイヤトレッド用ゴム組成物を提供することを目的とする。 Therefore, in the present invention, by blending a specific epoxidized palm oil softener, the viscosity of the unvulcanized rubber in the rubber composition for tire treads, particularly the rubber composition for tire treads based on silica, is reduced. -It aims at providing the rubber composition for tire treads suitable also in terms of safety.
本発明によれば、ジエン系ゴム１００重量部に、ヨウ素価６０以上のパーム油をエポキシ化して得られるエポキシ化パーム油０．１〜１００重量部を配合してなるタイヤトレッド用ゴム組成物が提供される。 According to the present invention, there is provided a rubber composition for a tire tread comprising 100 parts by weight of a diene rubber and 0.1-100 parts by weight of epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 60 or more. Provided.
更に、本発明によれば、ジエン系ゴム１００重量部に、シリカ５〜８０重量部、ヨウ素価６０以上のパーム油をエポキシ化して得られるエポキシ化パーム油０．１〜１００重量部を配合してなるタイヤトレッド用ゴム組成物が提供される。 Further, according to the present invention, 100 parts by weight of diene rubber is blended with 0.1 to 100 parts by weight of epoxidized palm oil obtained by epoxidizing 5 to 80 parts by weight of silica and palm oil having an iodine value of 60 or more. A tire tread rubber composition is provided.
本発明でゴム組成物に配合されるエポキシ化パーム油は、ヨウ素価６０以上のパーム油をエポキシ化することによって得られるエポキシ化パーム油である。本来、当該パーム油自体は、オイルパームの果実部分より抽出される油で、抽出物は常温で固体と液体とが混ざった状態のものであり、これをウィンタリング法、乳化分別法などの方法によって液体部分を分別したものがいわゆる「パームオレイン」と呼ばれるものである。本発明で使用されるエポキシ化パーム油は、原料となるこのパーム油を２０℃以下の低温にて数時間から数日間放置して固形分を沈殿させ、その上澄み油を、過酸化水素あるいは過酢酸等の有機過酸を用いてエポキシ化することによって得られる。ヨウ素価６０以上のパーム油は、前記エポキシ化の程度を調節することによって得られる。 Epoxidized palm oil blended in the rubber composition in the present invention is epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 60 or more. Originally, the palm oil itself is an oil extracted from the fruit portion of oil palm, and the extract is a mixture of a solid and a liquid at room temperature, and this is a method such as a wintering method or an emulsification fractionation method. The liquid part is separated by the so-called “palm olein”. In the epoxidized palm oil used in the present invention, the palm oil used as a raw material is allowed to stand for several hours to several days at a low temperature of 20 ° C. or less to precipitate a solid content. It can be obtained by epoxidation using an organic peracid such as acetic acid. Palm oil having an iodine value of 60 or more can be obtained by adjusting the degree of epoxidation.
本発明で使用されるエポキシ化パーム油は、そのヨウ素価が６０以上、より好ましくは６５以上のものとすることが重要であり、このヨウ素価が６０未満ではブリードを発生するので好ましくない。また、当該ヨウ素価が６０以上のエポキシ化パーム油の配合量は、ゴム組成物におけるゴム成分１００重量部に対して０．１〜１００重量部、より好ましくは２〜８０重量部とすることが必要である。この配合量が０．１重量部未満では、十分な粘度低減効果が得られず、逆に１００重量部を超えると、ブリードが発生するので実用的ではない。 It is important that the epoxidized palm oil used in the present invention has an iodine value of 60 or more, more preferably 65 or more. If the iodine value is less than 60, bleeding occurs, which is not preferable. Moreover, the compounding quantity of the said epoxidized palm oil whose iodine value is 60 or more shall be 0.1-100 weight part with respect to 100 weight part of rubber components in a rubber composition, More preferably, it shall be 2-80 weight part. is necessary. If the blending amount is less than 0.1 parts by weight, a sufficient viscosity reducing effect cannot be obtained. Conversely, if it exceeds 100 parts by weight, bleeding occurs, which is not practical.
本発明のゴム組成物に配合されるシリカについては、当該タイヤトレッド用ゴム組成物に一般に使用されている各種シリカ、あるいはその表面処理シリカなどを使用することができる。これらシリカの配合量としては、５〜８０重量部とすることが好ましい。この配合量が５重量部未満では、当該シリカによる所期の効果を達成することができず、また、８０重量部を超えると、所望の混合・加工性等が悪化するので好ましくない。 As for silica compounded in the rubber composition of the present invention, various silicas generally used in the tire tread rubber composition or surface-treated silica thereof can be used. The blending amount of these silicas is preferably 5 to 80 parts by weight. If the blending amount is less than 5 parts by weight, the desired effect of the silica cannot be achieved, and if it exceeds 80 parts by weight, the desired mixing / workability is deteriorated.
本発明のゴム組成物に使用されるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、アクリルニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、クロロプレンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、イソプレン−ブタジエン共重合体ゴムなどが挙げられる。これらのジエン系ゴムは、単独又は二種以上のブレンドゴムとして使用されてよい。 Examples of the diene rubber used in the rubber composition of the present invention include natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), Acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber Etc. These diene rubbers may be used alone or as a blend rubber of two or more.
本発明のタイヤトレッド用ゴム組成物には、他の配合剤として、加硫又は架橋剤、加硫又は架橋促進剤、カーボンブラック等の補強剤、シランカップリング剤、老化防止剤、可塑剤、充填剤など、かかる一般タイヤ用に配合されている各種配合剤及び添加剤が配合され、かかる配合剤及び添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In the rubber composition for tire treads of the present invention, as other compounding agents, vulcanization or crosslinking agent, vulcanization or crosslinking accelerator, reinforcing agent such as carbon black, silane coupling agent, anti-aging agent, plasticizer, Various compounding agents and additives blended for such general tires such as fillers are blended, and the blending amounts of these blending agents and additives are the conventional general blending amounts as long as they do not contradict the purpose of the present invention. It can be.
以下、実施例及び比較例によって本発明を更に説明するが、本発明の技術的範囲をこれらの実施例によって限定するものでないことは言うまでもない。 EXAMPLES Hereinafter, although this invention is further demonstrated by an Example and a comparative example, it cannot be overemphasized that the technical scope of this invention is not limited by these Examples.
試験サンプルの作製
以下の表１及び表２に示す加硫促進剤と硫黄を除く各成分を１．８Ｌの密閉型ミキサーで５分間混練し、１６０℃に達した時に放出したマスターバッチに加硫促進剤と硫黄を８インチのオープンロールで混練して、それぞれのゴム組成物を得た。これらのゴム組成物を以下の粘度試験（ムーニー粘度）に供した。
Preparation of test sample Each component except sulfur accelerator and sulfur shown in Table 1 and Table 2 below was kneaded for 5 minutes in a 1.8 L closed mixer and vulcanized into a master batch released when it reached 160 ° C. Accelerator and sulfur were kneaded with an 8-inch open roll to obtain respective rubber compositions. These rubber compositions were subjected to the following viscosity test (Mooney viscosity).
試験方法
ムーニー粘度（ＭＬ1+4)： ＪＩＳ Ｋ ６３００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の条件下で測定した。比較例１及び３の結果を１００として、非シリカ配合系ゴム組成物及びシリカ配合系ゴム組成物についての結果を指数で示す。数値が小さい程、良好であることを示す。
Test method Mooney viscosity (ML 1 + 4 ): In accordance with JIS K 6300, a Mooney viscometer was used with an L-shaped rotor (38.1 mm diameter, 5.5 mm thickness), preheating time 1 minute, rotation of rotor The time was measured for 4 minutes at 100 ° C. under 2 rpm. The results of Comparative Examples 1 and 3 are taken as 100, and the results for the non-silica blended rubber composition and the silica blended rubber composition are shown as an index. It shows that it is so favorable that a numerical value is small.
実施例１〜５及び比較例１〜５
結果を、以下の表１及び表２に示す。
The results are shown in Table 1 and Table 2 below.
これらの結果によれば、非シリカ配合系ゴム組成物及びシリカ配合系ゴム組成物のいずれの場合にも、所定量のエポキシ化パーム油を軟化剤として配合した本発明の実施例では、従来の軟化剤を配合したものに比して、格別な粘度の低減効果が得られていることが示されている。 According to these results, in both the non-silica compounded rubber composition and the silica compounded rubber composition, in the examples of the present invention in which a predetermined amount of epoxidized palm oil was compounded as a softener, It has been shown that an exceptional effect of reducing the viscosity is obtained as compared with a blended softener.
よって、本発明の軟化剤をタイヤトレッド用ゴム組成物、特にシリカ配合系タイヤトレッド用ゴム組成物に使用すれば、極めて有用である。 Therefore, if the softening agent of the present invention is used for a rubber composition for tire treads, particularly a rubber composition for silica compounded tire treads, it is extremely useful.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005291199A JP4857694B2 (en) | 2005-10-04 | 2005-10-04 | Rubber composition for tire tread |
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| JP2005291199A JP4857694B2 (en) | 2005-10-04 | 2005-10-04 | Rubber composition for tire tread |
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| JP2007099892A JP2007099892A (en) | 2007-04-19 |
| JP4857694B2 true JP4857694B2 (en) | 2012-01-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101023759B1 (en) * | 2008-03-28 | 2011-03-21 | 금호타이어 주식회사 | Tire Tread Rubber Composition |
| US8261796B2 (en) * | 2008-11-06 | 2012-09-11 | The Goodyear Tire & Rubber Company | Tire with component containing polybenzobisoxazole short fiber and epoxidized palm oil |
| US20110146873A1 (en) * | 2009-12-22 | 2011-06-23 | Marc Weydert | Pneumatic tire with rubber component containing epoxidized palm oil |
| MY176032A (en) * | 2012-05-16 | 2020-07-22 | Lembaga Getah Malaysia | A rubber compound for the production of motorcycle tyre treads, process for producing the rubber compound and the motorcycle tyre tread produced |
| EP3237526B1 (en) | 2014-12-23 | 2022-05-18 | Bridgestone Americas Tire Operations, LLC | Tire comprising an oil-containing rubber composition |
| JP7259641B2 (en) * | 2019-08-23 | 2023-04-18 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3773330B2 (en) * | 1997-08-01 | 2006-05-10 | 旭電化工業株式会社 | Vinyl chloride resin composition |
| JP4517470B2 (en) * | 1999-07-30 | 2010-08-04 | Ｊｓｒ株式会社 | Rubber composition and tire |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
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