JP2005146115A - Tire tread rubber composition - Google Patents
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- JP2005146115A JP2005146115A JP2003385499A JP2003385499A JP2005146115A JP 2005146115 A JP2005146115 A JP 2005146115A JP 2003385499 A JP2003385499 A JP 2003385499A JP 2003385499 A JP2003385499 A JP 2003385499A JP 2005146115 A JP2005146115 A JP 2005146115A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
Description
本発明は、タイヤトレッド用ゴム組成物に関し、とくにグリップ性能の向上および転がり抵抗の低減を両立させる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 a tire tread, and particularly relates to a rubber composition for a tire tread that achieves both improvement in grip performance and reduction in rolling resistance.
タイヤのグリップ性能を向上させる方法として、液状スチレン−ブタジエンゴムを使用する方法が知られている。しかしながら、液状スチレン−ブタジエンゴムを使用すると、グリップ性能は向上するが、転がり抵抗が増大するという問題があった。 As a method for improving the grip performance of a tire, a method using liquid styrene-butadiene rubber is known. However, when liquid styrene-butadiene rubber is used, grip performance is improved, but there is a problem that rolling resistance increases.
また、転がり抵抗を低減させる方法として、シリカを配合させたゴム組成物のゴム成分に、一般のスチレン−ブタジエンゴムにアルコキシシリル基やグリシジルアミノ基などで変性したスチレン−ブタジエンゴムを使用する方法が知られている。しかしながら、このような変性スチレン−ブタジエンゴムを使用すると、転がり抵抗は低減するが、グリップ性能が低下するという問題があった。 In addition, as a method for reducing rolling resistance, a method of using a styrene-butadiene rubber modified with an alkoxysilyl group, a glycidylamino group or the like on a general styrene-butadiene rubber as a rubber component of a rubber composition in which silica is compounded. Are known. However, when such a modified styrene-butadiene rubber is used, although rolling resistance is reduced, there is a problem that grip performance is lowered.
さらに、両末端にアミノ基を有する重量平均分子量が1000〜180000であるスチレン−ブタジエンゴムをシリカ配合ゴム成分に配合する方法が知られている(特許文献1参照)。しかしながら、ゴムの混練時の加工性が不充分であり、また、グリップ性能の向上および転がり抵抗の低減の両立が不充分であるという問題があった。 Furthermore, a method is known in which a styrene-butadiene rubber having amino groups at both ends and having a weight average molecular weight of 1000 to 18000 is blended with a silica-blended rubber component (see Patent Document 1). However, there is a problem that workability at the time of rubber kneading is insufficient, and that both improvement in grip performance and reduction in rolling resistance are insufficient.
本発明は、グリップ性能の向上および転がり抵抗の低減を両立することができる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。 An object of the present invention is to provide a rubber composition for a tire tread that can achieve both improvement in grip performance and reduction in rolling resistance.
本発明は、ジエン系ゴム100重量部に対して、シリカ10重量部以上、および数平均分子量が2000〜50000の液状スチレン−ブタジエンゴム1〜25重量部を含むゴム組成物であって、液状スチレン−ブタジエンゴムがアルコキシシリル基および/またはグリシジルアミノ基で変性されていることを特徴とするタイヤトレッド用ゴム組成物に関する。 The present invention is a rubber composition comprising 10 parts by weight or more of silica and 1 to 25 parts by weight of a liquid styrene-butadiene rubber having a number average molecular weight of 2000 to 50000 with respect to 100 parts by weight of a diene rubber. The present invention relates to a rubber composition for a tire tread, wherein the butadiene rubber is modified with an alkoxysilyl group and / or a glycidylamino group.
本発明によれば、シリカを配合させたゴム成分に、低分子量の変性液状SBRを配合することによって、シリカを配合させたゴム成分の転がり抵抗が低減されているという利点を維持したまま、さらにグリップ性能を向上させることができる。 According to the present invention, by blending the low molecular weight modified liquid SBR with the rubber component blended with silica, the rolling resistance of the rubber component blended with silica is reduced, while maintaining the advantage. Grip performance can be improved.
さらなる効果として、低分子量の変性液状SBRはゴムの軟化効果を有するので、従来多量に使用されていたオイルを減らすことができる。 As a further effect, the low molecular weight modified liquid SBR has a rubber softening effect, so that it is possible to reduce oil that has been used in large amounts in the past.
本発明のゴム組成物は、ジエン系ゴム、液状スチレン−ブタジエンゴム(液状SBR)およびシリカを含有する。 The rubber composition of the present invention contains diene rubber, liquid styrene-butadiene rubber (liquid SBR) and silica.
ジエン系ゴムとしては、天然ゴム(NR)、スチレン−ブタジエンゴム(SBR)、ブタジエンゴム(BR)などが用いられる。 As the diene rubber, natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), or the like is used.
液状SBRの数平均分子量の下限については2000、好ましくは2500である。上限については50000、好ましくは25000、より好ましくは15000である。数平均分子量が2000未満では、ゴムが発熱しやすくなり、転がり抵抗が増大し、また、耐摩耗性も低い。50000をこえると、充分にグリップ性能を向上することができない。 The lower limit of the number average molecular weight of the liquid SBR is 2000, preferably 2500. About an upper limit, it is 50000, Preferably it is 25000, More preferably, it is 15000. When the number average molecular weight is less than 2000, the rubber is likely to generate heat, rolling resistance increases, and wear resistance is low. If it exceeds 50,000, the grip performance cannot be improved sufficiently.
液状SBRのスチレン単位量は、15〜50重量%であることが好ましい。スチレン単位量が15重量%未満では、グリップ性能を充分に向上できない傾向がある。また、スチレン単位量が50重量%をこえると、ゴム成分との相溶性が悪化する傾向がある。 The styrene unit amount of the liquid SBR is preferably 15 to 50% by weight. If the styrene unit amount is less than 15% by weight, the grip performance tends not to be sufficiently improved. Moreover, when the styrene unit amount exceeds 50% by weight, the compatibility with the rubber component tends to deteriorate.
液状SBRは、シリカとの接着性を向上させるために、官能基としてアルコキシシリル基および/またはグリシジルアミノ基を導入することによって変性される。 Liquid SBR is modified by introducing an alkoxysilyl group and / or a glycidylamino group as a functional group in order to improve the adhesion to silica.
液状SBRの官能基での変性率の下限については5%であることが好ましく、10%であることがより好ましい。上限については80%であることが好ましく、60%であることがより好ましい。変性率が5%未満では、シリカとの接着性が小さいため、転がり抵抗を充分に低減できない傾向がある。また、90%をこえると、シリカとの相互作用が強くなりすぎるため、ゴム混練時の加工性が低下する傾向がある。 The lower limit of the modification rate at the functional group of the liquid SBR is preferably 5%, more preferably 10%. The upper limit is preferably 80%, and more preferably 60%. If the modification rate is less than 5%, the adhesiveness with silica is small, so there is a tendency that the rolling resistance cannot be sufficiently reduced. On the other hand, if it exceeds 90%, the interaction with silica becomes too strong, and the processability during rubber kneading tends to be lowered.
液状SBRの配合量は、ジエン系ゴム100重量部に対して、下限については1重量部、好ましくは3重量部、より好ましくは5重量部である。上限については25重量部、好ましくは20重量部、より好ましくは15重量部である。液状SBRの配合量が1重量部未満では、グリップ性能を充分に向上できない。また、25重量部をこえると、ゴム混練時の加工性が低下し、また転がり抵抗が低減されない。 The blending amount of the liquid SBR is 1 part by weight, preferably 3 parts by weight, more preferably 5 parts by weight with respect to 100 parts by weight of the diene rubber. The upper limit is 25 parts by weight, preferably 20 parts by weight, more preferably 15 parts by weight. If the amount of liquid SBR is less than 1 part by weight, the grip performance cannot be sufficiently improved. On the other hand, if the amount exceeds 25 parts by weight, the workability during rubber kneading is lowered, and the rolling resistance is not reduced.
本発明で使用されるシリカの配合量は、ジエン系ゴム100重量部に対して、10重量部以上である。下限については25重量部であることが好ましく、40重量部であることがより好ましい。上限については100重量部であることが好ましく、80重量部であることがより好ましい。シリカの配合量が10重量部未満では、グリップ性能の向上および転がり抵抗の低減を両立できない。また、100重量部をこえると、転がり抵抗が増大する傾向がある。 The compounding quantity of the silica used by this invention is 10 weight part or more with respect to 100 weight part of diene rubbers. The lower limit is preferably 25 parts by weight, and more preferably 40 parts by weight. The upper limit is preferably 100 parts by weight, and more preferably 80 parts by weight. When the amount of silica is less than 10 parts by weight, it is impossible to achieve both improvement in grip performance and reduction in rolling resistance. Moreover, when it exceeds 100 weight part, there exists a tendency for rolling resistance to increase.
シリカのチッ素吸着比表面積(N2SA)の下限については50m2/gであることが好ましく、100m2/gであることがより好ましい。上限については、300m2/gであることが好ましく、250m2/gであることがより好ましい。N2SAが50m2/g未満では、耐摩耗性が低い傾向がある。また、300m2/gをこえると、ゴム混練時の加工性に低下する傾向がある。 The lower limit of the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 50 m 2 / g, and more preferably 100 m 2 / g. The upper limit, preferably from 300 meters 2 / g, and more preferably 250m 2 / g. When N 2 SA is less than 50 m 2 / g, wear resistance tends to be low. Moreover, when it exceeds 300 m < 2 > / g, there exists a tendency for the workability at the time of rubber kneading to fall.
本発明のゴム組成物には、前記成分のほかにも、通常ゴム工業で使用される添加剤、たとえば、カーボンブラック、シランカップリング剤、オイル、ワックス、老化防止剤、ステアリン酸、亜鉛華、加硫剤、加硫促進剤などを、適宜配合することができる。 In addition to the above components, the rubber composition of the present invention includes additives usually used in the rubber industry, such as carbon black, silane coupling agents, oils, waxes, anti-aging agents, stearic acid, zinc white, Vulcanizing agents, vulcanization accelerators, and the like can be appropriately blended.
本発明のゴム組成物は、タイヤトレッドに好適に用いられる。 The rubber composition of the present invention is suitably used for tire treads.
以下、実施例に基づいて本発明を具体的に説明するが、本発明はこれらのみに制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not restrict | limited only to these.
製造例(低分子量変性液状SBRの製造)
過去特許を参考にし、常法によりリチウムジメチルアミドを開始剤とし、スチレンと1,3ブタジエンよりアニオン重合で合成された溶液重合スチレンブタジエンゴムの重合活性末端に、メチルトリエトキシシランを変性剤として反応させることで、末端変性した変性液状SBRを得た。
Production example (production of low molecular weight modified liquid SBR)
Referring to past patents, reaction with lithium trimethylamide as the initiator and methyltriethoxysilane as the modifier at the polymerization active terminal of solution-polymerized styrene-butadiene rubber synthesized by anionic polymerization from styrene and 1,3-butadiene. By doing so, a modified liquid SBR having a terminal modified was obtained.
以下に実施例および比較例で用いた材料および試験方法をまとめて示す。 The materials and test methods used in the examples and comparative examples are summarized below.
(材料の説明)
SBR:日本ゼオン(株)製のNS116
低分子量変性液状SBR:製造例で製造した変性液状SBR(スチレン単位量:18重量%、ビニル含量:50重量%、数平均分子量:10000)
非変性液状SBR:Sartomer社製のライコン100(スチレン単位量:20重量%、ビニル含量:70重量%、数平均分子量:4500)
シリカ:デグッサ社製のVN3(N2SA:175m2/g)
カーボンブラック:昭和キャボット(株)製のN220(N2SA:125m2/g)
シランカップリング剤:デグッサ社製のSi69
オイル:出光興産(株)製のダイアナプロセスPS32
ワックス:大内新興化学工業(株)製のサンノックワックス
老化防止剤:フレキシス社製のサントフレックス13
ステアリン酸:日本油脂(株)製の桐
亜鉛華:三井金属鉱業(株)製の酸化亜鉛2号
硫黄:(株)軽井沢精錬所製のイオウ
加硫促進剤NS:大内新興化学工業(株)製のノクセラーNS
加硫促進剤DPG:大内新興化学工業(株)製のノクセラーD
(Description of materials)
SBR: NS116 manufactured by Nippon Zeon Co., Ltd.
Low molecular weight modified liquid SBR: Modified liquid SBR produced in the production example (styrene unit amount: 18% by weight, vinyl content: 50% by weight, number average molecular weight: 10,000)
Non-modified liquid SBR: Rycon 100 manufactured by Sartomer (styrene unit amount: 20% by weight, vinyl content: 70% by weight, number average molecular weight: 4500)
Silica: VN3 manufactured by Degussa (N 2 SA: 175 m 2 / g)
Carbon black: N220 made by Showa Cabot Co., Ltd. (N 2 SA: 125 m 2 / g)
Silane coupling agent: Si69 manufactured by Degussa
Oil: Diana Process PS32 manufactured by Idemitsu Kosan Co., Ltd.
Wax: Sannoc Wax manufactured by Ouchi Shinsei Chemical Co., Ltd. Anti-aging agent: Santoflex 13 manufactured by Flexis
Stearic acid: Tung Zinc Hana manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide No. 2 manufactured by Mitsui Metal Mining Co., Ltd. Sulfur: Sulfur vulcanization accelerator manufactured by Karuizawa Seisakusho Co., Ltd. NS: Ouchi Shinsei Chemical Industry Co., Ltd. ) Noxeller NS made
Vulcanization accelerator DPG: NOCELLER D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例1〜3および比較例1〜3
(ゴム組成物の作製)
表1記載の配合内容にしたがって、硫黄、加硫促進剤以外の材料を、バンバリーミキサーを用いて5〜10分間混練りした。得られた混練り物に、硫黄および加硫促進剤を加えて2軸オーブンロールにて80℃で5分間練り込み、170℃で12分間加硫することによって、ゴム組成物を得た。
Examples 1-3 and Comparative Examples 1-3
(Production of rubber composition)
According to the blending contents shown in Table 1, materials other than sulfur and a vulcanization accelerator were kneaded for 5 to 10 minutes using a Banbury mixer. To the obtained kneaded product, sulfur and a vulcanization accelerator were added, kneaded at 80 ° C. for 5 minutes with a biaxial oven roll, and vulcanized at 170 ° C. for 12 minutes to obtain a rubber composition.
得られたゴム組成物について、前記の試験を行なった結果を表1に示す。 Table 1 shows the results of the above tests performed on the obtained rubber composition.
(試験方法)
硬度(Hs)
得られたゴム組成物の硬度を、25℃でJIS−A硬度計で測定した。
(Test method)
Hardness (Hs)
The hardness of the obtained rubber composition was measured with a JIS-A hardness meter at 25 ° C.
粘弾性測定(グリップ指数、転がり抵抗指数)
(株)岩本製作所製の粘弾性スペクトロメーター(VES−F−3)を用いて、周波数10Hz、初期歪み10%、動歪み2%の条件で温度分散測定を行なった。30℃におけるtanδを、比較例1の場合を100として指数化し、グリップ指数とした。グリップ指数が大きいほどグリップ性能が良好であることを示す。また、60℃におけるtanδを、比較例1の場合を100として指数化し、転がり抵抗指数とした。転がり抵抗指数が小さいほど、転がり抵抗が低減されていることを示す。
Viscoelasticity measurement (grip index, rolling resistance index)
Using a viscoelastic spectrometer (VES-F-3) manufactured by Iwamoto Seisakusho Co., Ltd., temperature dispersion measurement was performed under conditions of a frequency of 10 Hz, an initial strain of 10%, and a dynamic strain of 2%. The tan δ at 30 ° C. was indexed by setting the case of Comparative Example 1 to 100, and was used as the grip index. The larger the grip index, the better the grip performance. Further, tan δ at 60 ° C. was indexed with the case of Comparative Example 1 being 100, and was defined as a rolling resistance index. It shows that rolling resistance is reduced, so that a rolling resistance index | exponent is small.
ランボーン摩耗指数
ランボーン試験機で、室温25℃、スリップ率20%、試験時間5分の条件でランボーン摩耗量を測定し、比較例1を100とした時の指数表示とした。ランボーン摩耗指数が大きいほど、耐摩耗性が向上していることを示す。
Lambourn wear index The Lambourn wear amount was measured with a Lambourn tester under the conditions of room temperature 25 ° C., slip rate 20%, test time 5 minutes, and the index display when Comparative Example 1 was taken as 100 was used. It shows that abrasion resistance is improving, so that a Lambourn wear index is large.
シリカ配合ゴムに低分子量変性液状SBRを適量配合した実施例1〜3では、グリップ性能の向上および転がり抵抗の低減を両立することができた。 In Examples 1 to 3, in which an appropriate amount of low molecular weight modified liquid SBR was blended with silica blended rubber, it was possible to achieve both improved grip performance and reduced rolling resistance.
通常の液状SBRを配合した比較例2では、グリップ性能は向上するが、転がり抵抗が増大した。 In Comparative Example 2 containing normal liquid SBR, the grip performance was improved, but the rolling resistance was increased.
また、低分子量変性液状SBRを配合したが、シリカを用いなかった比較例3でも、グリップ性能は向上するが、転がり抵抗が増大した。 Moreover, although the low molecular weight modified | denatured liquid SBR was mix | blended, also in the comparative example 3 which did not use a silica, although grip performance improved, rolling resistance increased.
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WO2019155798A1 (en) * | 2018-02-07 | 2019-08-15 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
JP2019523331A (en) * | 2016-08-17 | 2019-08-22 | コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Sulfur crosslinkable rubber mixture and vehicle tire |
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US10570275B2 (en) | 2017-08-30 | 2020-02-25 | The Goodyear Tire & Rubber Company | Pneumatic tire having tread with alkoxysilane-terminated polybutadiene |
CN111032771A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for heavy duty tire and tire |
KR102224148B1 (en) * | 2019-10-16 | 2021-03-09 | 금호석유화학 주식회사 | A rubber composition for tire tread and a method for manufacturing the same |
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