JP4860258B2 - Rubber composition for sidewall and tire having sidewall comprising the same - Google Patents
Rubber composition for sidewall and tire having sidewall comprising the same Download PDFInfo
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- JP4860258B2 JP4860258B2 JP2005368287A JP2005368287A JP4860258B2 JP 4860258 B2 JP4860258 B2 JP 4860258B2 JP 2005368287 A JP2005368287 A JP 2005368287A JP 2005368287 A JP2005368287 A JP 2005368287A JP 4860258 B2 JP4860258 B2 JP 4860258B2
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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
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- 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
Description
本発明は、サイドウォール用ゴム組成物およびそれからなるサイドウォールを有するタイヤに関する。 The present invention relates to a rubber composition for a sidewall and a tire having a sidewall made of the rubber composition.
従来よりタイヤのトレッド用ゴム組成物を改良して、タイヤの転がり抵抗を低減させる（転がり抵抗性を向上させる）、あるいはウェットグリップ性能を向上させるなど数々の研究がなされている。しかし、トレッド用ゴム組成物の改良だけでは、転がり抵抗性の向上には限界があるため、他のコンポーネントにおいても転がり抵抗性の向上化を検討する必要があった。 Conventionally, many studies have been made such as improving the tire tread rubber composition to reduce tire rolling resistance (improve rolling resistance) or improve wet grip performance. However, since improvement in rolling resistance is limited only by improving the rubber composition for tread, it is necessary to consider improving rolling resistance in other components as well.
トレッドについで転がり抵抗に対する寄与が大きいタイヤ部材としては、サイドウォールがあげられる。 As a tire member having a large contribution to rolling resistance following the tread, a sidewall is exemplified.
一般的に転がり抵抗性を向上させるために、充填剤としてシリカを用いることが行われているが、サイドウォール用ゴム組成物にシリカを配合した場合、転がり抵抗は低減する一方で、耐久性（ゴム強度）が低下するという問題があった。 In general, silica is used as a filler in order to improve rolling resistance. However, when silica is compounded in a rubber composition for a sidewall, rolling resistance is reduced while durability ( There was a problem that the rubber strength was reduced.
また、従来から用いられている充填剤であるカーボンブラックの配合量を少なくすることが考えられるが、その場合でも、転がり抵抗は低減するが、耐久性（ゴム強度）が低下するという問題があった。 In addition, it is conceivable to reduce the blending amount of carbon black, which is a conventionally used filler, but even in that case, there is a problem that rolling resistance is reduced but durability (rubber strength) is lowered. It was.
特許文献１には、特定のサルファイドポリマーを配合するクローラ用ゴム組成物が開示されているが、サイドウォール用ゴム組成物を改良することによってタイヤの転がり抵抗性の向上させたものではなかった
以上のように、耐久性（ゴム強度）および転がり抵抗性の向上をバランスよく両立させたサイドウォール用ゴム組成物は今まで得られていなかった。
Patent Document 1 discloses a rubber composition for crawlers that contains a specific sulfide polymer, but the rolling resistance of the tire has not been improved by improving the rubber composition for sidewalls. As described above, a rubber composition for a side wall in which durability (rubber strength) and rolling resistance are improved in a well-balanced manner has not been obtained so far.
本発明は、耐久性および転がり抵抗性の向上をバランスよく両立させたサイドウォール用ゴム組成物およびそれからなるサイドウォールを有するタイヤ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 sidewall in which durability and rolling resistance are improved in a well-balanced manner, and a tire having a sidewall comprising the rubber composition.
本発明は、ゴム成分１００質量部に対して、補強剤を２５〜１００質量部、および一般式（１）
−（Ｒ−Ｓx）n− （１）
（式中、Ｒは
In the present invention, 25 to 100 parts by mass of the reinforcing agent and 100 parts by mass of the rubber component and the general formula (1)
− (R−S x ) n − (1)
(Where R is
ｘは３〜６の整数、ｎは１０〜４００の整数であり、ｍは２〜５の整数を表わす）
を満足する化合物を２〜３０質量部含有するサイドウォール用ゴム組成物に関する。
x is an integer of 3 to 6, n is an integer of 10 to 400, and m is an integer of 2 to 5)
It is related with the rubber composition for side walls containing 2-30 mass parts of compounds which satisfy | fill.
また、本発明は、前記サイドウォール用ゴム組成物からなるサイドウォールを有するタイヤに関する。 The present invention also relates to a tire having a sidewall made of the rubber composition for a sidewall.
本発明によれば、分子内に硫黄原子を含むポリマーを加硫剤として含有するサイドウォーｒ用ゴム組成物をサイドウォールとして用いることにより、サイドウォールの耐久性（ゴム強度）およびタイヤの転がり抵抗性の向上をバランスよく両立させることができる。 According to the present invention, durability of a sidewall (rubber strength) and tire rolling resistance can be obtained by using as a sidewall a rubber composition for a sidewall containing a polymer containing a sulfur atom in the molecule as a vulcanizing agent. It is possible to balance the improvement of the property in a balanced manner.
本発明のサイドウォール用ゴム組成物は、ゴム成分、補強剤、および一般式（１）
−（Ｒ−Ｓx）n− （１）
（式中、Ｒは
The rubber composition for a side wall of the present invention comprises a rubber component, a reinforcing agent, and a general formula (1)
− (R−S x ) n − (1)
(Where R is
ｘは３〜６の整数、ｎは１０〜４００の整数であり、ｍは２〜５の整数を表わす）
を満足する化合物（以下、化合物１）からなる。
x is an integer of 3 to 6, n is an integer of 10 to 400, and m is an integer of 2 to 5)
It consists of a compound satisfying the following (hereinafter referred to as Compound 1).
ゴム成分としては、天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合ゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、スチレン−イソプレン−ブタジエン共重合ゴム（ＳＩＢＲ）、スチレン−イソプレン共重合ゴム、イソプレン−ブタジエン共重合ゴムなどのジエン系ゴムがあげられる。これらは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が、ゴムの強度と低燃費性のバランスに優れる点で、ゴム成分としてＮＲおよび／またはＢＲが好ましい。 As rubber components, natural rubber (NR), various butadiene rubbers (BR), styrene-butadiene copolymer rubber (SBR), isoprene rubber (IR), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), Examples thereof include diene rubbers such as styrene-isoprene-butadiene copolymer rubber (SIBR), styrene-isoprene copolymer rubber, and isoprene-butadiene copolymer rubber. These may be used singly or in combination of two or more, but NR and / or BR is preferred as the rubber component in terms of excellent balance between rubber strength and fuel economy.
補強剤としては、シリカ、カーボンブラック、タルク、クレーなどが挙げられる。なかでも、ゴムの補強性および低燃費性の向上効果が得られることから、カーボンブラック、シリカが好ましく、カーボンブラックがより好ましい。 Examples of the reinforcing agent include silica, carbon black, talc, and clay. Among these, carbon black and silica are preferable, and carbon black is more preferable because an effect of improving rubber reinforcement and fuel efficiency can be obtained.
補強剤としてカーボンブラックを使用する場合、カーボンブラックのチッ素吸着比表面積（Ｎ2ＳＡ）は２０ｍ2／ｇ以上が好ましく、２５ｍ2／ｇ以上がより好ましい。Ｎ2ＳＡが２０ｍ2／ｇ未満では、サイドウォール用ゴム組成物としてのゴム強度が充分得られない傾向がある。また、カーボンブラックのＮ2ＳＡは２１０ｍ2／ｇ以下が好ましく、１９０ｍ2／ｇ以下がより好ましい。Ｎ2ＳＡが２１０ｍ2／ｇをこえると、未加硫時のゴム粘度が高くなって加工性の面で好ましくなく、また、燃費が悪化する傾向がある。 When carbon black is used as the reinforcing agent, the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 20 m 2 / g or more, and more preferably 25 m 2 / g or more. When N 2 SA is less than 20 m 2 / g, there is a tendency that sufficient rubber strength as a rubber composition for a sidewall cannot be obtained. Also, N 2 SA is preferably at most 210 m 2 / g of carbon black, 190 m 2 / g or less is more preferable. When N 2 SA exceeds 210 m 2 / g, the rubber viscosity at the time of unvulcanization becomes high, which is not preferable in terms of workability, and the fuel consumption tends to deteriorate.
補強剤の含有量は、ゴム成分１００質量部に対して２５質量部以上、好ましくは３０質量部以上である。含有量が２５質量部未満では、ゴム強度が低下する傾向があり好ましくない。また、補強剤の含有量は、ゴム成分１００質量部に対して１００質量部以下、好ましくは９５質量部以下である。含有量が１００質量部をこえると、未加硫時のゴム粘度が高くなり、加工性の面で好ましくなく、燃費が悪化する傾向があり好ましくない。 Content of a reinforcing agent is 25 mass parts or more with respect to 100 mass parts of rubber components, Preferably it is 30 mass parts or more. If the content is less than 25 parts by mass, the rubber strength tends to decrease, which is not preferable. Moreover, content of a reinforcing agent is 100 mass parts or less with respect to 100 mass parts of rubber components, Preferably it is 95 mass parts or less. When the content exceeds 100 parts by mass, the rubber viscosity at the time of unvulcanization increases, which is not preferable from the viewpoint of workability, and tends to deteriorate fuel consumption.
本発明で使用する化合物１は、一般式（１）
−（Ｒ−Ｓx）n− （１）
（式中、Ｒは
Compound 1 used in the present invention has the general formula (1)
− (R−S x ) n − (1)
(Where R is
ｘは３〜６の整数、ｎは１０〜４００の整数であり、ｍは２〜５の整数を表わす）
を満足する。本発明において、化合物１は加硫剤として用いられる。
x is an integer of 3 to 6, n is an integer of 10 to 400, and m is an integer of 2 to 5)
Satisfied. In the present invention, compound 1 is used as a vulcanizing agent.
一般式（１）中、ｘは３〜６の整数、好ましくは３〜５の整数である。ｘが３未満では、加硫が遅延され、ｎが６をこえると、ゴム組成物の製造が困難となる。 In general formula (1), x is an integer of 3-6, Preferably it is an integer of 3-5. When x is less than 3, vulcanization is delayed, and when n exceeds 6, it becomes difficult to produce a rubber composition.
一般式（１）中、ｎは１０〜４００の整数、好ましくは１０〜３００の整数である。ｎが１０未満では、化合物１が揮発しやすく取り扱いが困難になり、ｎが４００をこえると、ゴムとの相溶性が悪化する。 In general formula (1), n is an integer of 10 to 400, preferably an integer of 10 to 300. If n is less than 10, compound 1 is easily volatilized and difficult to handle, and if n exceeds 400, compatibility with rubber deteriorates.
一般式（１）中、ｍは２〜５の整数、好ましくは２〜４の整数、さらに好ましくは２〜３の整数である。ｍが２未満では、得られたゴム組成物の屈曲性能が低下する傾向があり、ｍが５をこえると、ゴム組成物の充分な硬度が獲られない傾向がある。 In general formula (1), m is an integer of 2-5, preferably an integer of 2-4, more preferably an integer of 2-3. If m is less than 2, the bending performance of the obtained rubber composition tends to be lowered, and if m exceeds 5, the rubber composition tends not to have sufficient hardness.
化合物１の含有量は、ゴム成分１００質量部に対して２質量部以上、好ましくは２．５質量部以上である。含有量が２質量部未満では、サイドウォール用ゴム組成物としてのゴム強度が充分に得られない傾向があり好ましくない。また、化合物１の含有量は、ゴム成分１００質量部に対して３０質量部以下、好ましくは２５質量部以下である。含有量が３０質量部をこえると、サイドウォールの耐久性が低下する。 The content of Compound 1 is 2 parts by mass or more, preferably 2.5 parts by mass or more with respect to 100 parts by mass of the rubber component. If the content is less than 2 parts by mass, the rubber strength as a rubber composition for a sidewall tends not to be sufficiently obtained, which is not preferable. Moreover, content of the compound 1 is 30 mass parts or less with respect to 100 mass parts of rubber components, Preferably it is 25 mass parts or less. When the content exceeds 30 parts by mass, the durability of the sidewall is lowered.
化合物１を本発明のサイドウォール用ゴム組成物に配合することで、以下のような架橋ユニットをゴムに導入することができ、加硫速度およびスコーチに影響を与えることなく、リバージョンを大幅に抑制することができる。また、一般の硫黄架橋では充分に得られないゴム組成物の耐熱性や、動的なストレスに対する耐性を得ることが可能である。さらに、ブルームしにくいため、外見上においても良好なサイドウォール用ゴム組成物を得ることができる。 By compounding compound 1 in the rubber composition for sidewalls of the present invention, the following crosslinking units can be introduced into the rubber, and the reversion can be greatly improved without affecting the vulcanization speed and scorch. Can be suppressed. Further, it is possible to obtain heat resistance of a rubber composition that cannot be sufficiently obtained by general sulfur crosslinking and resistance to dynamic stress. Furthermore, since it is hard to bloom, the rubber composition for sidewalls which is excellent in appearance can be obtained.
化合物１は、ゴム組成物の製造において、８０〜１３０℃の温度条件下で添加され、混練りされることが好ましい。８０℃未満では、充分な混練りがなされず、また、１３０℃をこえると、加硫が開始されてしまうため、充分な混練りがなされないという問題が生じる。 Compound 1 is preferably added and kneaded under the temperature condition of 80 to 130 ° C. in the production of the rubber composition. If the temperature is less than 80 ° C., sufficient kneading is not performed, and if the temperature exceeds 130 ° C., vulcanization is started, so that there is a problem that sufficient kneading is not performed.
化合物１は、硫黄などの加硫剤とともに使用することもできる。 Compound 1 can also be used with a vulcanizing agent such as sulfur.
本発明のサイドウォール用ゴム組成物には、前記加硫剤とともに、加硫促進剤を含有することが好ましい。加硫促進剤としては、スルフェンアミド系などの一般的なものが使用される。 The rubber composition for a side wall of the present invention preferably contains a vulcanization accelerator together with the vulcanizing agent. As the vulcanization accelerator, a general sulfenamide-based one is used.
加硫促進剤の含有量は、ゴム成分１００重量部に対して０．３〜１５重量部が好ましい。加硫促進剤の含有量が０．３重量部未満では、充分な加硫がなされず、ゴム強度が著しく低下する傾向がある。また、加硫促進剤の含有量が１５重量部をこえると、加硫速度が非常に速くなり、加工性の面で好ましくなく、ゴム強度も低下する傾向がある。 The content of the vulcanization accelerator is preferably 0.3 to 15 parts by weight with respect to 100 parts by weight of the rubber component. When the content of the vulcanization accelerator is less than 0.3 parts by weight, sufficient vulcanization is not performed and the rubber strength tends to be remarkably reduced. On the other hand, if the content of the vulcanization accelerator exceeds 15 parts by weight, the vulcanization speed becomes very fast, which is not preferable in terms of workability, and the rubber strength tends to decrease.
本発明のサイドウォール用ゴム組成物には、前記ゴム成分、補強剤、化合物１などの加硫剤および加硫促進剤のほかに、必要に応じて、硫黄などの加硫剤、軟化剤、ワックス、老化防止剤、ステアリン酸、酸化亜鉛などを配合することができる。 In addition to the rubber component, the reinforcing agent, the vulcanizing agent such as Compound 1, and the vulcanization accelerator, the rubber composition for a side wall of the present invention includes, if necessary, a vulcanizing agent such as sulfur, a softening agent, Wax, anti-aging agent, stearic acid, zinc oxide and the like can be blended.
本発明のタイヤは、前記ゴム組成物からなるサイドウォールを有することが好ましい。 本発明のタイヤは、加硫剤および加硫促進剤以外のものを混練りして混練物を得て、さらに該混練物に加硫剤および加硫促進剤を添加し混練して得られる未加硫ゴム組成物をサイドウォール形状に成形し、他のタイヤ部材と貼りあわせて未加硫タイヤを成形し、加硫することによって製造されることが好ましい。 The tire of the present invention preferably has a sidewall made of the rubber composition. The tire of the present invention is obtained by kneading a material other than a vulcanizing agent and a vulcanization accelerator to obtain a kneaded product, and further adding a vulcanizing agent and a vulcanization accelerator to the kneaded material and kneading. It is preferable that the vulcanized rubber composition is molded into a sidewall shape and bonded to another tire member to form an unvulcanized tire and vulcanized.
実施例にもとづいて本発明を詳細に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be described in detail based on examples, but the present invention is not limited to these examples.
実施例において使用した各種薬品について、以下に記載する。
ＮＲ：ＲＳＳ＃３
ＢＲ：宇部興産（株）製のＢＲ１５０Ｂ
カーボンブラック：昭和キャボット（株）製のＮ５５０（Ｎ2ＳＡ：４１ｍ2／ｇ）
プロセスオイル：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
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛２号
硫黄：軽井沢精錬所製の硫黄
化合物１：テトラサルファイドポリマー（ポリ−３，６−ジオキサオクタン−テトラスルフィド（ｍ＝２、ｘ＝４、ｎ＝２００））
Various chemicals used in the examples are described below.
NR: RSS # 3
BR: BR150B manufactured by Ube Industries, Ltd.
Carbon black: N550 manufactured by Showa Cabot Co., Ltd. (N 2 SA: 41 m 2 / g)
Process oil: Diana Process PS32 manufactured by Idemitsu Kosan Co., Ltd.
Wax: Sannoc Wax manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Anti-aging agent: Santoflex 13 manufactured by Flexis
Stearic acid: Tungsten zinc oxide manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide No. 2 manufactured by Mitsui Metal Mining Co., Ltd. -Tetrasulfide (m = 2, x = 4, n = 200))
加硫促進剤：大内新興化学工業（株）製のノクセラーＮＳ Vulcanization accelerator: Noxeller NS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例１〜３および比較例１〜２
（株）神戸製鋼所製１．７Ｌバンバリーを用いて、硫黄、化合物１および加硫促進剤を除く前記各種薬品を表１に示す配合内容にて１５０℃で５分間混練りした。得られた混練り物に硫黄、化合物１および加硫促進剤を加えて、二軸ローラーにて１０５℃で３分間練り込んだ混合物を１７５℃において１５分間加硫することでゴム組成物を作製した。得られたゴム組成物を用いて以下の試験を行なった。
Examples 1-3 and Comparative Examples 1-2
The various chemicals except sulfur, compound 1 and vulcanization accelerator were kneaded at 150 ° C. for 5 minutes using the contents shown in Table 1 using 1.7 L Banbury manufactured by Kobe Steel. Sulfur, compound 1 and a vulcanization accelerator were added to the obtained kneaded product, and a rubber composition was prepared by vulcanizing the mixture kneaded at 105 ° C. for 3 minutes with a biaxial roller at 175 ° C. for 15 minutes. . The following tests were performed using the obtained rubber composition.
（粘弾性試験）
（株）岩本製作所製のＶＥＳ−Ｆ−３により、周波数１０Ｈｚ、初期歪１０％、動歪２％で６０℃における調製したゴム組成物のｔａｎδ（損失正接）を測定した。ｔａｎδ値が小さいほど、転がり抵抗の低減に有利となる。
(Viscoelasticity test)
Using a VES-F-3 manufactured by Iwamoto Seisakusho, tan δ (loss tangent) of the rubber composition prepared at 60 ° C. was measured at a frequency of 10 Hz, an initial strain of 10%, and a dynamic strain of 2%. The smaller the tan δ value, the more advantageous the reduction of rolling resistance.
（引張試験）
ＪＩＳ Ｋ６２５１に基づき、調製したゴム組成物からなるダンベル３号型試験片にて引張試験を実施した。この試験により各加硫ゴム組成物について、破断時のモジュラスＴＢ（ＭＰａ）および破断時の伸びＥＢ（％）をそれぞれ測定し、それらの積（ＴＢ×ＥＢ）をゴム強度の指標として評価した。
(Tensile test)
Based on JIS K6251, the tensile test was implemented with the dumbbell No. 3 type | mold test piece which consists of a prepared rubber composition. With this test, the modulus TB (MPa) at break and the elongation EB (%) at break were measured for each vulcanized rubber composition, and the product (TB × EB) was evaluated as an index of rubber strength.
試験結果を表１に示す。 The test results are shown in Table 1.
化合物１を２〜３０質量部の範囲で配合した実施例１〜３のゴム組成物は、化合物１が配合されていない比較例１に比べて、ＴＢ×ＥＢの値が向上して優れたゴム強度を示し、さらに、ｔａｎδ値が低減するため、転がり抵抗の低減に有利であった。 The rubber compositions of Examples 1 to 3 in which Compound 1 was blended in the range of 2 to 30 parts by mass were superior in comparison with Comparative Example 1 in which Compound 1 was not blended and the TB × EB value was improved. The strength was further exhibited, and the tan δ value was reduced, which was advantageous in reducing rolling resistance.
一方、化合物１を３５質量部配合した比較例２のゴム組成物は、ｔａｎδ値は低減するものの、ＴＢ×ＥＢの値が低下するため好ましくない。 On the other hand, the rubber composition of Comparative Example 2 containing 35 parts by mass of Compound 1 is not preferable because the tan δ value decreases but the TB × EB value decreases.
Claims (2)
補強剤を２５〜１００質量部、および
一般式（１）
−（Ｒ−Ｓx）n− （１）
（式中、Ｒは
を満足する化合物を２〜３０質量部含有するサイドウォール用ゴム組成物。 For 100 parts by mass of a rubber component made of natural rubber and butadiene rubber,
25 to 100 parts by mass of reinforcing agent, and general formula (1)
− (R−S x ) n − (1)
(Where R is
A rubber composition for sidewalls containing 2 to 30 parts by mass of a compound satisfying the above.
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| JP4860258B2 true JP4860258B2 (en) | 2012-01-25 |
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| JP2007269872A (en) * | 2006-03-30 | 2007-10-18 | Sumitomo Rubber Ind Ltd | Rubber composition for sidewall, tire produced by using the same, rubber composition for clinch and tire produced by using the same |
| JP5101907B2 (en) * | 2006-04-06 | 2012-12-19 | 住友ゴム工業株式会社 | Rubber composition for covering steel cord and tire using the same |
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| JPS58167634A (en) * | 1982-03-30 | 1983-10-03 | Kawaguchi Kagaku Kogyo Kk | Vulcanizable rubber composition |
| JP4117987B2 (en) * | 1999-10-20 | 2008-07-16 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP4071950B2 (en) * | 2001-10-04 | 2008-04-02 | 住友ゴム工業株式会社 | Rubber composition for sidewall and pneumatic tire using the same |
| JP4344198B2 (en) * | 2003-08-26 | 2009-10-14 | 住友ゴム工業株式会社 | Rubber composition excellent in discoloration resistance and bending crack resistance, and pneumatic tire using the rubber composition for sidewall rubber |
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