JP4088290B2 - Rubber composition for tire tread and tire comprising the same - Google Patents
Rubber composition for tire tread and tire comprising the same Download PDFInfo
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Description
本発明は、タイヤトレッド用ゴム組成物およびそれからなるタイヤに関する。 The present invention relates to a rubber composition for a tire tread and a tire comprising the same.
近年、自動車の高速化が要求されるにつれ、タイヤについて、優れた制動性、とくに湿潤路面における制動性(ウェット制動性)が要求されている。 In recent years, as the speed of automobiles has been increased, excellent braking performance, particularly braking performance on wet road surfaces (wet braking performance) has been demanded for tires.
従来、タイヤトレッドの制動性を高めるために、タイヤトレッド用ゴム組成物には、ガラス転移温度の高いスチレンブタジエンゴムを配合する、あるいは、粒子径の小さいカーボンブラックを多量に配合することがなされてきた。しかし、制動性が向上するにつれて、タイヤトレッドの耐摩耗性が悪化し、さらに−10℃〜−30℃の温度条件下においてタイヤトレッドが脆化する、つまり、低温における耐脆化性が低下するという問題があった。 Conventionally, in order to improve the braking performance of a tire tread, a rubber composition for a tire tread has been blended with a styrene butadiene rubber having a high glass transition temperature or a large amount of carbon black having a small particle diameter. It was. However, as the braking performance improves, the wear resistance of the tire tread deteriorates, and further the tire tread becomes brittle under the temperature condition of −10 ° C. to −30 ° C., that is, the brittleness resistance at low temperature is lowered. There was a problem.
また、特許文献1には、液状ブタジエンゴムを配合したタイヤ用ゴム組成物が開示されている。しかし、スチレンブタジエンゴムの配合を想定したものではない。 Patent Document 1 discloses a tire rubber composition containing liquid butadiene rubber. However, it does not assume the blending of styrene butadiene rubber.
本発明は、耐摩耗性、ウェット制動性および低温における耐脆化性を高次にバランスよく向上させるタイヤトレッド用ゴム組成物、ならびにそれからな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 tire tread that improves the wear resistance, wet braking performance and brittleness resistance at low temperatures in a well-balanced manner, and a tire comprising the same.
本発明は、(a)スチレン量が10〜30重量%およびビニル量が25〜75重量%であるスチレン−ブタジエンゴム50〜80重量%、(b)天然ゴム5〜30重量%、ならびに(c)分子末端に水酸基を有し、数平均分子量が1500以上である液状ブタジエンゴム5〜20重量%からなるゴム成分100重量部に対して、シリカを50〜120重量部を含有するタイヤトレッド用ゴム組成物に関する。 The present invention comprises (a) 50-80% by weight styrene-butadiene rubber having a styrene content of 10-30% by weight and a vinyl content of 25-75% by weight, (b) 5-30% by weight of natural rubber, and (c ) Tire tread rubber containing 50 to 120 parts by weight of silica with respect to 100 parts by weight of a rubber component comprising 5 to 20% by weight of a liquid butadiene rubber having a hydroxyl group at the molecular end and a number average molecular weight of 1500 or more. Relates to the composition.
また、本発明は、前記タイヤトレッド用ゴム組成物からなるタイヤトレッドを有するタイヤに関する。 The present invention also relates to a tire having a tire tread made of the tire tread rubber composition.
本発明によれば、ゴム成分として特定のスチレンブタジエンゴム、ブタジエンゴムおよび天然ゴムを特定比率含有し、さらにシリカを多量に配合することにより、耐摩耗性、ウェット制動性および低温における耐脆化性を高次にバランスよく向上させた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, the rubber component contains a specific ratio of specific styrene butadiene rubber, butadiene rubber and natural rubber, and further contains a large amount of silica to thereby provide wear resistance, wet braking performance and resistance to embrittlement at low temperatures. It is possible to provide a rubber composition for a tire tread that is improved in a well-balanced manner.
本発明のタイヤトレッド用ゴム組成物は、ゴム成分およびシリカからなる。 The rubber composition for tire treads of the present invention comprises a rubber component and silica.
ゴム成分は、(a)スチレン量が10〜30重量%およびビニル量が25〜75重量%であるスチレン−ブタジエンゴム(以下、SBR(a)とする)、(b)天然ゴム(以下、NR(b)とする)、ならびに(c)分子末端に水酸基を有し、数平均分子量が1500以上である液状ブタジエンゴム(以下、液状BR(c)とする)からなる。 The rubber component includes (a) a styrene-butadiene rubber (hereinafter referred to as SBR (a)) having a styrene content of 10 to 30% by weight and a vinyl content of 25 to 75% by weight, and (b) a natural rubber (hereinafter referred to as NR). (B)) and (c) a liquid butadiene rubber having a hydroxyl group at the molecular end and a number average molecular weight of 1500 or more (hereinafter referred to as liquid BR (c)).
SBR(a)におけるスチレン量は10重量%以上、好ましくは15重量%以上である。スチレン量が10重量%未満では、ゴム成分全体として、充分な制動性が得られない。また、SBR(a)におけるスチレン量は30重量%以下、好ましくは25重量%以下である。スチレン量が30重量%をこえると、充分なウェット制動性は得られるが、低温における耐脆化性能、および耐摩耗性が悪化する。ここでスチレン量とは、NMR装置を用いて1H−NMRを測定し、SBR(a)のスペクトルより求めた6.7〜7.2ppmのスチレン単位に基づくフェニルプロトンから計算される。 The amount of styrene in SBR (a) is 10% by weight or more, preferably 15% by weight or more. When the amount of styrene is less than 10% by weight, sufficient braking performance cannot be obtained as a whole rubber component. The amount of styrene in SBR (a) is 30% by weight or less, preferably 25% by weight or less. If the amount of styrene exceeds 30% by weight, sufficient wet braking performance can be obtained, but the resistance to embrittlement and wear resistance at low temperatures deteriorate. Here, the amount of styrene is calculated from phenyl protons based on 6.7 to 7.2 ppm styrene units obtained from the spectrum of SBR (a) by measuring 1 H-NMR using an NMR apparatus.
SBR(a)におけるビニル量は25重量%以上、好ましくは30重量%以上である。ビニル量が25重量%未満では、ゴム成分全体として、充分な制動性が得られない。また、SBR(a)におけるビニル量は75重量%以下、好ましくは65重量%以下である。ビニル量が75重量%をこえると、充分なウェット制動性は得られるが、低温における耐脆化性能、および耐摩耗性、転がり抵抗が悪化する。ここでビニル量とは、NMR装置を用いて1H−NMRを測定し、SBR(a)のスペクトルより求めた4.7〜5.2ppmのブタジエン単位に基づくビニル結合のメチレンプロトンから計算される。 The amount of vinyl in SBR (a) is 25% by weight or more, preferably 30% by weight or more. When the vinyl content is less than 25% by weight, sufficient braking performance cannot be obtained as a whole rubber component. Further, the vinyl content in SBR (a) is 75% by weight or less, preferably 65% by weight or less. If the vinyl content exceeds 75% by weight, sufficient wet braking performance can be obtained, but the resistance to embrittlement at low temperatures, wear resistance, and rolling resistance deteriorate. Here, the vinyl content is calculated from a methylene proton of a vinyl bond based on 4.7 to 5.2 ppm butadiene units obtained from a spectrum of SBR (a) by measuring 1 H-NMR using an NMR apparatus. .
ゴム成分中におけるSBR(a)の含有率は50重量%以上、好ましくは60重量%以上である。含有率が50重量%未満では、充分な制動性が得られない。また、ゴム成分中におけるSBR(a)の含有率は80重量%以下、好ましくは75重量%以下である。含有率が80重量%をこえると、低温における耐脆化性能および耐摩耗性が悪化する。 The content of SBR (a) in the rubber component is 50% by weight or more, preferably 60% by weight or more. If the content is less than 50% by weight, sufficient braking performance cannot be obtained. Further, the content of SBR (a) in the rubber component is 80% by weight or less, preferably 75% by weight or less. When the content exceeds 80% by weight, the embrittlement resistance and wear resistance at low temperatures deteriorate.
NR(b)としては、一般のゴム工業において使用されるもの、例えば、RSS♯3、TSR20などがあげられる。 Examples of NR (b) include those used in the general rubber industry, such as RSS # 3 and TSR20.
ゴム成分中におけるNR(b)の含有率は5重量%以上、好ましくは15重量%以上である。含有率が5重量%未満では、耐摩耗性が悪化する。また、ゴム成分中におけるNR(b)の含有率は30重量%以下である。 The content of NR (b) in the rubber component is 5% by weight or more, preferably 15% by weight or more. When the content is less than 5% by weight, the wear resistance is deteriorated. Further, the content of NR (b) in the rubber component is 30% by weight or less.
液状BR(c)は、分子末端に水酸基を有する。水酸基を分子末端に有することで、親水性の水酸基部分と疎水性のポリブタジエン部分の両方を持つため、親水性のシリカと疎水性のポリマーやオイルなどをうまく混合させるという効果が得られる。 Liquid BR (c) has a hydroxyl group at the molecular end. By having a hydroxyl group at the molecular end, it has both a hydrophilic hydroxyl portion and a hydrophobic polybutadiene portion, so that the effect of successfully mixing hydrophilic silica with a hydrophobic polymer or oil can be obtained.
液状BR(c)の水酸基含有量は0.2〜3mol/kgであることが好ましい。水酸基含有量が0.2mol/kg未満では、前記したような水酸基を含有させることで得られる効果が得られない。また、水酸基含有量が3mol/kgをこえると、ブルーミングが生じる傾向がある。なお、水酸基含有量は、JIS K 1557にもとづいて測定される。 The hydroxyl group content of the liquid BR (c) is preferably 0.2 to 3 mol / kg. When the hydroxyl group content is less than 0.2 mol / kg, the effect obtained by containing the hydroxyl group as described above cannot be obtained. Further, when the hydroxyl group content exceeds 3 mol / kg, blooming tends to occur. The hydroxyl group content is measured based on JIS K 1557.
液状BR(c)の数平均分子量は1500以上、好ましくは2000以上である。数平均分子量が1500未満では、他のゴム成分との相容性が悪化する。また、液状BR(c)の数平均分子量は5000以下であることが好ましく、4000以下であることがより好ましい。 The number average molecular weight of liquid BR (c) is 1500 or more, preferably 2000 or more. If the number average molecular weight is less than 1500, the compatibility with other rubber components deteriorates. In addition, the number average molecular weight of the liquid BR (c) is preferably 5000 or less, and more preferably 4000 or less.
ゴム成分中における液状BR(c)の含有率は5重量%以上である。含有率が5重量%未満では、良好な低温脆化温度が得られない。また、ゴム成分中におけるBR(c)の含有率は20重量%以下、好ましくは15重量%以下である。含有率が20重量%をこえると、ウェット制動性が低下する。 The content of liquid BR (c) in the rubber component is 5% by weight or more. When the content is less than 5% by weight, a good low temperature embrittlement temperature cannot be obtained. The content of BR (c) in the rubber component is 20% by weight or less, preferably 15% by weight or less. When the content exceeds 20% by weight, the wet braking performance is lowered.
シリカとしては、とくに制限はなく、湿式法または乾式法により調製されたものを用いることができる。 Silica is not particularly limited, and silica prepared by a wet method or a dry method can be used.
シリカの含有量は、ゴム成分100重量部に対して50重量部以上、好ましくは70重量部以上である。含有量が50重量部未満では、ゴムの強度が下がる、あるいは、耐摩耗性も悪化する。また、シリカの含有量は120重量部以下、好ましくは100重量部以下である。含有量が120重量部をこえると、ゴムが硬くなる。 The content of silica is 50 parts by weight or more, preferably 70 parts by weight or more with respect to 100 parts by weight of the rubber component. When the content is less than 50 parts by weight, the strength of the rubber decreases or the wear resistance deteriorates. The silica content is 120 parts by weight or less, preferably 100 parts by weight or less. When the content exceeds 120 parts by weight, the rubber becomes hard.
本発明のタイヤトレッド用ゴム組成物は、前記成分をバンバリー、ロールで混合することにより製造することができる。また、必要であれば、その性能を損なわない範囲で、さらに他の酸化亜鉛、ステアリン酸、老化防止剤、軟化剤、ワックス、加硫促進剤、硫黄などの添加剤を配合してもよい。 The rubber composition for a tire tread of the present invention can be produced by mixing the above components with a banbury and a roll. Further, if necessary, other additives such as zinc oxide, stearic acid, anti-aging agent, softening agent, wax, vulcanization accelerator, and sulfur may be blended as long as the performance is not impaired.
本発明のタイヤは、本発明のタイヤトレッド用ゴム組成物からなるタイヤトレッドを用いて通常の方法により製造される。すなわち、前記ゴム成分およびシリカ、ならびに必要に応じて前記各種添加剤を配合した本発明のサイドウォール用ゴム組成物を未加硫の段階でタイヤのタイヤトレッドの形状に合わせて押し出し加工し、タイヤ成型機上にて通常の方法にて成形し、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧してタイヤを製造することができる。 The tire of the present invention is produced by a usual method using the tire tread comprising the rubber composition for a tire tread of the present invention. That is, the rubber composition for a sidewall of the present invention containing the rubber component, silica, and, if necessary, the various additives is extruded in accordance with the shape of the tire tread of the tire at an unvulcanized stage. An unvulcanized tire is formed by a conventional method on a molding machine. This unvulcanized tire can be heated and pressed in a vulcanizer to produce a tire.
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.
以下に、本発明において使用した各種薬品について説明する。
SBR1:JSR(株)製のSL574(スチレン量:15重量%、ビニル量:57重量%)
SBR2:旭化成(株)製のT2330(スチレン量:25重量%、ビニル量:30重量%)
SBR3:住友化学工業(株)製のSE9599(スチレン量:40重量%、ビニル量:50重量%)
SBR4:住友化学工業(株)製のN9520(スチレン量:35重量%、ビニル量:18重量%)
NR:TSR20
BR:出光興産(株)製のR45HT(水酸基末端液状ポリブタジエン、数平均分子量:2800、水酸基含有量:0.83mol/kg)
シリカ:デグッサ社製のウルトラシルVN3
カップリング剤:デグッサ社製のSi69
ステアリン酸:日本油脂(株)製のステアリン酸
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛
老化防止剤:大内新興化学工業(株)製のノクラック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)
オイル:出光興産(株)製のダイナプロセスオイルPW32
Wax:大内新興化学工業(株)製のサンノックワックス
硫黄:鶴見化学工業(株)製の粉末硫黄
加硫促進剤:大内新興化学工業(株)製のノクセラーCZ(N−cyclohexyl−2−benzothiazyl−sulfenamide)
Below, the various chemical | medical agents used in this invention are demonstrated.
SBR1: SL574 manufactured by JSR Corporation (styrene content: 15% by weight, vinyl content: 57% by weight)
SBR2: T2330 manufactured by Asahi Kasei Corporation (styrene content: 25% by weight, vinyl content: 30% by weight)
SBR3: SE9599 manufactured by Sumitomo Chemical Co., Ltd. (styrene content: 40% by weight, vinyl content: 50% by weight)
SBR4: N9520 manufactured by Sumitomo Chemical Co., Ltd. (styrene content: 35% by weight, vinyl content: 18% by weight)
NR: TSR20
BR: R45HT manufactured by Idemitsu Kosan Co., Ltd. (hydroxyl-terminated liquid polybutadiene, number average molecular weight: 2800, hydroxyl group content: 0.83 mol / kg)
Silica: Ultrasil VN3 manufactured by Degussa
Coupling agent: Si69 manufactured by Degussa
Stearic acid: Zinc stearate manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide anti-aging agent manufactured by Mitsui Mining & Smelting Co., Ltd .: NOCRACK 6C (N-1,3-dimethylbutyl) manufactured by Ouchi Shinsei Chemical -N'-phenyl-p-phenylenediamine)
Oil: Dyna Process Oil PW32 manufactured by Idemitsu Kosan Co., Ltd.
Wax: Sunnock wax sulfur manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd .: Noxeller CZ (N-cyclohexyl-2 manufactured by Ouchi New Chemical Co., Ltd.) -Benzothiazyl-sulfenamide)
実施例1〜3および比較例1〜3
(ゴム組成物の調製)
硫黄および加硫促進剤を除く表1の配合内容を(株)神戸製鋼製の1.7Lバンバリーを用いて165℃で混練りした後、得られた混練り物に硫黄、加硫促進剤を加えて、二軸ローラーにて110℃で練り込み、未加硫混合物を得た。未加硫混合物を175℃において10分間加硫することでゴム組成物を調製した。調製したゴム組成物を用いて、以下の試験に使用した。
Examples 1-3 and Comparative Examples 1-3
(Preparation of rubber composition)
After kneading the blended contents in Table 1 excluding sulfur and vulcanization accelerator at 165 ° C. using 1.7 L Banbury manufactured by Kobe Steel Co., Ltd., sulfur and vulcanization accelerator were added to the obtained kneaded product. Then, the mixture was kneaded at 110 ° C. with a biaxial roller to obtain an unvulcanized mixture. A rubber composition was prepared by vulcanizing the unvulcanized mixture at 175 ° C. for 10 minutes. The prepared rubber composition was used for the following tests.
(低温脆化試験)
JIS K3601の低温脆化破壊試験法にしたがって、低温脆化試験をおこなった。脆化温度が−35度以上では、低温において充分な耐脆化性が得られない。
(Low temperature embrittlement test)
A low temperature embrittlement test was conducted according to the low temperature embrittlement fracture test method of JIS K3601. If the embrittlement temperature is −35 ° C. or more, sufficient embrittlement resistance cannot be obtained at low temperatures.
(耐摩耗性)
ランボーン型摩耗試験機を用いて、室温、負荷荷重2.5kgf、スリップ率40%、2分間の条件で、調製したゴム組成物の摩耗量を測定した。比較例1の摩耗量の逆数を100として、それぞれ指数で表わした。数値が大きいほど耐摩耗性が良好であり、数値が95以下では充分な耐摩耗性が得られていないことを示す。
(Abrasion resistance)
The amount of wear of the prepared rubber composition was measured under the conditions of room temperature, applied load of 2.5 kgf, slip rate of 40%, and 2 minutes using a Lambourn type wear tester. The reciprocal of the amount of wear in Comparative Example 1 was taken as 100, and each was represented by an index. The larger the value is, the better the wear resistance is. When the value is 95 or less, sufficient wear resistance is not obtained.
(タイヤの調製)
前記ゴム組成物からなるトレッドを有するサイズ185/65R14のタイヤを作製し、車に装着してウェット制動性試験をおこなった。
(Tire preparation)
A tire having a size of 185 / 65R14 having a tread made of the rubber composition was prepared, and mounted on a vehicle for a wet braking test.
(ウェット制動性)
前記タイヤを排気量1800ccの乗用車に装着して、散水した路面上で初速度100km/hからの制動距離を測定し、比較例1を100として、それぞれ指数表示した。数値が大きいほど、ウェット制動性が良好であり、数値が95以下では充分なウェット制動性が得られていないことを示す。
(Wet braking)
The tire was mounted on a 1800 cc passenger car and the braking distance from the initial speed of 100 km / h was measured on the watered road surface. It shows that wet braking performance is so favorable that a numerical value is large, and sufficient wet braking performance is not acquired with a numerical value of 95 or less.
試験結果を表1に示す。 The test results are shown in Table 1.
Claims (2)
(b)天然ゴム5〜30重量%、ならびに
(c)分子末端に水酸基を有し、数平均分子量が1500以上である液状ブタジエンゴム5〜20重量%
からなるゴム成分100重量部に対して、
シリカを50〜120重量部を含有するタイヤトレッド用ゴム組成物。 (A) 50-80% by weight of styrene-butadiene rubber having a styrene content of 10-30% by weight and a vinyl content of 25-75% by weight;
(B) 5-30% by weight of natural rubber, and (c) 5-20% by weight of liquid butadiene rubber having a hydroxyl group at the molecular end and a number average molecular weight of 1500 or more.
For 100 parts by weight of the rubber component consisting of
A rubber composition for a tire tread containing 50 to 120 parts by weight of silica.
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Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101125559B1 (en) | 2010-11-26 | 2012-03-22 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
KR101716058B1 (en) * | 2015-12-15 | 2017-03-14 | 금호타이어 주식회사 | Tire tread composition with improved dry performance and tire using the same |
US10457798B2 (en) | 2017-08-30 | 2019-10-29 | The Goodyear Tire & Rubber Company | Pneumatic tire having tread with hydroxy-terminated polybutadiene |
US20190061425A1 (en) * | 2017-08-30 | 2019-02-28 | The Goodyear Tire & Rubber Company | Pneumatic tire |
JP7434703B2 (en) * | 2018-08-06 | 2024-02-21 | 住友ゴム工業株式会社 | Rubber composition for tread and pneumatic tire |
CN110183744A (en) * | 2019-04-26 | 2019-08-30 | 中策橡胶集团有限公司 | A kind of mixing method of snowfield tire and snowfield tire tread rubber composition and rubber composition |
KR102267701B1 (en) | 2019-12-11 | 2021-06-22 | 한국타이어앤테크놀로지 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
WO2021235400A1 (en) * | 2020-05-21 | 2021-11-25 | 住友ゴム工業株式会社 | Pneumatic tire |
CN114957820B (en) * | 2022-04-27 | 2023-08-29 | 中策橡胶集团股份有限公司 | Tread rubber composition, mixing method and application thereof, and tire |
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