JP5194546B2 - Rubber composition - Google Patents
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- JP5194546B2 JP5194546B2 JP2007115890A JP2007115890A JP5194546B2 JP 5194546 B2 JP5194546 B2 JP 5194546B2 JP 2007115890 A JP2007115890 A JP 2007115890A JP 2007115890 A JP2007115890 A JP 2007115890A JP 5194546 B2 JP5194546 B2 JP 5194546B2
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- 0 CC*C1C(C)CC*1 Chemical compound CC*C1C(C)CC*1 0.000 description 1
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Description
本発明は、ゴム組成物に関し、更に詳しくはジエン系ゴムにリン酸エステル化合物を配合したシリカ分散性に優れたゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly to a rubber composition excellent in silica dispersibility in which a phosphate compound is blended with a diene rubber.
ジエン系ゴムにカーボンブラック又はカーボンブラック及びシリカ等の充填剤を配合してジエン系ゴムを補強したゴム組成物は知られているが、ゴム組成物の物性、特にヒステリシスロスの低減を一層高めるために、ゴム中のフィラーの分散性を高める研究が種々すすめられている。 A rubber composition is known in which a filler such as carbon black or carbon black and silica is added to a diene rubber to reinforce the diene rubber, but in order to further improve the physical properties of the rubber composition, in particular, reduction of hysteresis loss In addition, various studies for increasing the dispersibility of fillers in rubber have been promoted.
一方、特許文献１には、リン酸エステルをゴムに配合することが記載されているが、これはゴム組成物の導電性を確保せんとするものである。 On the other hand, Patent Document 1 describes that a phosphoric ester is blended with rubber, which is intended to ensure the conductivity of the rubber composition.
本発明の目的は、ジエン系ゴム並びにシリカ又はシリカ及びカーボンブラック等の充填剤を含有するジエン系ゴム組成物において、フィラー分散性に優れ、スコーチが起こりにくく、またウェット制動性に優れたタイヤトレッド用などとして使用するのに好適なゴム組成物を提供することにある。 An object of the present invention is a tire tread having excellent filler dispersibility, less scorch, and excellent wet braking performance in a diene rubber composition containing a diene rubber and a filler such as silica or silica and carbon black. An object of the present invention is to provide a rubber composition suitable for use in applications.
本発明に従えば、ジエン系ゴム１００重量部、シリカ５０重量％以上を含む補強性充填剤５０〜１４０重量部、シリカ重量に対して５〜１４重量％のシランカップリング剤、式（Ｉ）： According to the present invention, 100 parts by weight of a diene rubber, 50 to 140 parts by weight of a reinforcing filler containing 50% by weight or more of silica, 5 to 14% by weight of silane coupling agent relative to the weight of silica, formula (I) :
（式中、Ｒ1はＣ4〜Ｃ15のアルキル鎖を表し、Ｒ2はＣ4〜Ｃ15のアルキル鎖を表し、そしてＲ3はＨ又はＣ1〜Ｃ8のアルキル基を表す）
のリン酸化合物０．１〜３重量部を含んでなるゴム組成物並びにそれをキャップトレッドに用いた空気入りタイヤが提供される。
(Wherein R 1 represents a C 4 to C 15 alkyl chain, R 2 represents a C 4 to C 15 alkyl chain, and R 3 represents H or a C 1 to C 8 alkyl group)
A rubber composition comprising 0.1 to 3 parts by weight of the phosphoric acid compound and a pneumatic tire using the rubber composition for a cap tread are provided.
本発明によれば、前記式（Ｉ）で表される特定のリン酸エステル化合物をジエン系ゴムに配合することにより、従来のジエン系ゴム組成物よりシリカ分散性に優れたゴム組成物を得ることができ、ゴムを長時間練っても加工性の良いゴムを得ることができ、またウェット制動性にも優れたゴム組成物を得ることができる。 According to the present invention, a rubber composition having a silica dispersibility superior to that of a conventional diene rubber composition is obtained by blending the specific phosphate ester compound represented by the formula (I) with a diene rubber. It is possible to obtain a rubber having good processability even if the rubber is kneaded for a long time, and to obtain a rubber composition having excellent wet braking properties.
本発明者らは前記課題を解決すべく研究を進めた結果、前記式（Ｉ）の特定のリン酸エステル化合物をジエン系ゴム、特にＳＢＲ，ＢＲ，ＩＲ及び／又はＩＩＲに配合することにより、従来のジエン系ゴム組成物よりシリカ分散に優れたゴム組成物を得ることに成功した。 As a result of researches to solve the above problems, the present inventors have formulated the specific phosphate ester compound of the formula (I) into a diene rubber, particularly SBR, BR, IR and / or IIR, The present inventors have succeeded in obtaining a rubber composition having a silica dispersion superior to that of a conventional diene rubber composition.
即ち、本発明は、ジエン系ゴム１００重量部、シリカを５０重量％以上、好ましくは４０〜１１０重量部含む補強性充填剤５０〜１４０重量部、好ましくは５０〜８０重量部、シリカ重量に対して５〜１４重量％の、好ましくは５〜１１重量％シランカップリング剤、前記式（Ｉ）（式中、Ｒ1はＣnＨ2n+1で表わされる（４≦ｎ≦１５、好ましくは４≦ｎ≦８）のアルキル鎖を表し、Ｒ2はＣ4〜Ｃ15、好ましくはＣ4〜Ｃ8、例えばＣmＨ2m+1（４≦ｍ≦１５、好ましくは４≦ｍ≦８）のアルキル鎖を表し、
Ｒ3はＨ又は、Ｃ1〜Ｃ8のアルキル鎖、ＣLＨ2L+1（１≦Ｌ≦８）を表し、好ましくはＨである。）
のリン酸化合物を０．１〜３重量部、好ましくは０．５〜２重量部含むゴム組成物である。
That is, the present invention relates to a reinforcing filler containing 100 parts by weight of diene rubber and 50% by weight or more, preferably 40 to 110 parts by weight of silica, preferably 50 to 80 parts by weight, preferably 50 to 80 parts by weight, based on silica weight. 5 to 14% by weight, preferably 5 to 11% by weight of a silane coupling agent, the above formula (I) (wherein R 1 is represented by C n H 2n + 1 (4 ≦ n ≦ 15, preferably 4 ≦ n ≦ 8) and R 2 is C 4 to C 15 , preferably C 4 to C 8 , for example C m H 2m + 1 (4 ≦ m ≦ 15, preferably 4 ≦ m ≦ 8). ) Represents an alkyl chain,
R 3 represents H or a C 1 to C 8 alkyl chain, C L H 2L + 1 (1 ≦ L ≦ 8), preferably H. )
A rubber composition containing 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight of the phosphoric acid compound.
かかるリン酸化合物は公知の化合物であり、例えばリン酸とアルコールの脱水縮合やリン酸塩化物とアルコールとを塩基性の条件下に反応させることにより容易に得ることができ、和光純薬工業（株）や東京化成工業（株）などから試薬などとして市販もされている。 Such a phosphoric acid compound is a known compound and can be easily obtained, for example, by dehydration condensation of phosphoric acid and alcohol or by reacting a phosphate compound and alcohol under basic conditions. Co., Ltd.) and Tokyo Chemical Industry Co., Ltd. are also commercially available as reagents.
本発明において、シリカ以外の補強性充填剤としてはカーボンブラックをあげることができ、この補強性充填剤の量が５０重量部未満では、本発明の効果が小さく、逆に１４０重量部を超えると混合性が悪化するので好ましくない。なお、シリカ及びカーボンブラックとしてはゴム組成物に配合できる任意のものを使用することができる。本発明においては補強性充填剤のうちのシリカが４０〜１１０重量部、好ましくは５０〜１００重量部、更に好ましくは、６０〜９０重量部であるのが好ましい。シリカの量は多ければ多いほど本発明の効果の面では良いが、多すぎるとゴムの破断強度を逆に低くしてしまい、耐摩耗性が悪化するので好ましくない。 In the present invention, carbon black can be used as the reinforcing filler other than silica. If the amount of the reinforcing filler is less than 50 parts by weight, the effect of the present invention is small, and conversely if it exceeds 140 parts by weight. Since mixing property deteriorates, it is not preferable. Note that any silica and carbon black that can be blended in the rubber composition can be used. In the present invention, silica in the reinforcing filler is 40 to 110 parts by weight, preferably 50 to 100 parts by weight, and more preferably 60 to 90 parts by weight. The larger the amount of silica, the better the effect of the present invention is. However, if the amount is too large, the breaking strength of the rubber is lowered, and the wear resistance is deteriorated.
本発明においては、シリカ重量に対して使用するシランカップリング剤の量が５重量％未満では、シリカの凝集を抑えることが難しくなって、破断強度などの物性が低下するので好ましくなく、逆に１４重量％を超えるとコストが高くなりすぎて好ましくない。本発明で用いるシランカップリング剤としてはメルカプトシリル基を有するシランカップリング剤を用いるのが、好ましく、具体的にはγ−トリエトキシシリルプロピルメルカプトシラン、γ−トリメトキシシリルプロピルメルカプトシランなどがあげられる。 In the present invention, if the amount of the silane coupling agent used relative to the silica weight is less than 5% by weight, it is difficult to suppress the aggregation of the silica and the physical properties such as the breaking strength are lowered. If it exceeds 14% by weight, the cost becomes too high, which is not preferable. As the silane coupling agent used in the present invention, a silane coupling agent having a mercaptosilyl group is preferably used. Specific examples include γ-triethoxysilylpropyl mercaptosilane and γ-trimethoxysilylpropyl mercaptosilane. It is done.
本発明では式（Ｉ）のリン酸化合物を配合するが、その量がジエン系ゴム１００重量部に対し、０．１重量部未満では本発明の効果がほとんど得られず、逆に３重量部超では配合効果が大きくならないので経済的に意味がない。 In the present invention, the phosphoric acid compound of the formula (I) is blended, but if the amount is less than 0.1 parts by weight with respect to 100 parts by weight of the diene rubber, the effect of the present invention is hardly obtained, and conversely 3 parts by weight. If it is super, the blending effect will not increase, so it is economically meaningless.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックやシリカ以外のフィラー、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は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 addition to the components described above, the rubber composition according to the present invention includes tires such as fillers other than carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, and plasticizers. Various additives that are generally blended for use in other rubber compositions can be blended, and such additives are kneaded by a general method to form a composition that is used for vulcanization or crosslinking. can do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜５及び比較例１〜４
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで５分間混練し、１６０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。
Examples 1-5 and Comparative Examples 1-4
Sample preparation In the formulation shown in Table I, components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.8 liter closed mixer, and released when the temperature reached 160 ° C. to obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で２０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
スコーチタイム：ＪＩＳ Ｋ６３００に準じて、温度１２５℃に粘度が５ポイント上昇する時間を測定した。なお結果は比較例１の値を１００として指数表示した。この値が大きい程よい。
シリカ分散性：αテクノロジー社製ＲＰＡ２０００を用い、歪せん断力Ｇ’を測定した。未加硫ゴムを用いて１６０℃×２０分の加硫を行い、歪０．２８％〜３０％までのＧ’を測定し、その差異（Ｇ’（０．２８％）−Ｇ’（３０％））を示す。なお結果は比較例１の値を１００として指数表示した。この値が小さいほどシリカ分散性に優れる。
Rubber property evaluation test method Scorch time: According to JIS K6300, the time for the viscosity to rise by 5 points at a temperature of 125 ° C. was measured. The results are shown as an index with the value of Comparative Example 1 being 100. A larger value is better.
Silica dispersibility: Strain shearing force G ′ was measured using RPA2000 manufactured by α Technology. Vulcanization was performed at 160 ° C. for 20 minutes using unvulcanized rubber, and G ′ of strains from 0.28% to 30% was measured. The difference (G ′ (0.28%) − G ′ (30 %)). The results are shown as an index with the value of Comparative Example 1 being 100. The smaller this value, the better the silica dispersibility.
ウェット制動距離：：東洋精機社製粘弾性スペクトロメータを用い−１０℃において；２０Ｈｚ、動歪０．５％ 静歪２％を写え測定した値を用いた。なお結果は比較例１の値を１００として指数表示した。この値が小さいほど湿潤時の制動距離が短い。 Wet braking distance :: Using a viscoelastic spectrometer manufactured by Toyo Seiki Co., Ltd. at −10 ° C .; 20 Hz, dynamic strain 0.5%, static strain 2%, and measured values were used. The results are shown as an index with the value of Comparative Example 1 being 100. The smaller this value, the shorter the braking distance when wet.
表Ｉ脚注
＊１：ランクセス社製ＶＳＬ５０２５（３７．５ｐｈｒ油展溶液重合ＳＢＲ）
＊２：日本ゼオン（株）製Ｎｉｐｏｌ ＢＲ１２２０
＊３：Ｄｅｇｕｓｓａ社製Ｕｌｔｒａｓｉｌ ７０００ＧＲ
＊４：東海カーボン（株）製Ｎ２３４
＊５：大内新興化学工業（株）製サンノック
＊６：日本油脂工業（株）製ビーズステアリン酸
＊７：正同化学（株）製酸化亜鉛３種
＊８：フレキシス社製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ
＊９：（株）ジャパンエナジー製プロセスＸ−１４０
＊１０：Ｄｅｇｕｓｓａ社製ＳＩ６９
＊１１：信越化学工業（株）製トリメトキシシリルプロピルメルカプトシラン
Table I footnote * 1: VSL5025 (37.5 phr oil-extended solution polymerization SBR) manufactured by LANXESS
* 2: Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
* 3: Ultrasil 7000GR manufactured by Degussa
* 4: Tokai Carbon Co., Ltd. N234
* 5: Sunnock manufactured by Ouchi Shinsei Chemical Co., Ltd. * 6: Beads stearic acid manufactured by Nippon Oil & Fats Industries Co., Ltd. * 7: Three types of zinc oxide manufactured by Shodo Chemical Co., Ltd. * 8: SANTOFLEX 6PPD manufactured by Flexis Co., Ltd.
* 9: Process X-140 manufactured by Japan Energy Co., Ltd.
* 10: SI69 manufactured by Degussa
* 11: Shin-Etsu Chemical Co., Ltd. trimethoxysilylpropylmercaptosilane
＊１２：和光純薬工業（株）製試薬ジブチルフォスフェート（リン酸エステル） * 12: Reagent dibutyl phosphate (phosphate ester) manufactured by Wako Pure Chemical Industries, Ltd.
＊１３：和光純薬工業（株）製試薬ジオクチルフォスフェート（リン酸エステル） * 13: Reagent dioctyl phosphate (phosphate ester) manufactured by Wako Pure Chemical Industries, Ltd.
＊１４：細井化学工業（株）製油処理硫黄
＊１５：大内新興化学工業（株）製ＣＺ−Ｇ
* 14: Hosei Chemical Industries Co., Ltd. oil-treated sulfur * 15: Ouchi Shinsei Chemical Co., Ltd. CZ-G
本発明によれば、上記実施例においても示されるように、ゴムの加工性の指標となるスコーチタイムを延長させることができ、かつシリカ分散性にも優れ、ウェット制動距離を短縮化することができるので、空気入りタイヤ、その他各種ゴム製品、特に空気入りタイヤのキャップトレッド用として使用するのに好適である。 According to the present invention, as shown in the above embodiment, it is possible to extend the scorch time, which is an index of rubber processability, and is excellent in silica dispersibility, and shorten the wet braking distance. Therefore, it is suitable for use as a pneumatic tire and other rubber products, particularly as a cap tread for a pneumatic tire.
Claims (5)
Ｒ2はＣ4〜Ｃ15のアルキル鎖を表し、そして
Ｒ 3 はＨを表す）
のリン酸化合物０．１〜３重量部を含んでなるゴム組成物。 100 parts by weight of a diene rubber, 50 to 140 parts by weight of a reinforcing filler containing 50% by weight or more of silica, 5 to 14% by weight of a silane coupling agent based on the weight of silica, formula (I):
R 2 represents a C 4 to C 15 alkyl chain, and
R 3 represents H )
A rubber composition comprising 0.1 to 3 parts by weight of a phosphoric acid compound.
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| JP2007115890A JP5194546B2 (en) | 2007-04-25 | 2007-04-25 | Rubber composition |
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| JP2007115890A JP5194546B2 (en) | 2007-04-25 | 2007-04-25 | Rubber composition |
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| JP5194546B2 true JP5194546B2 (en) | 2013-05-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2968006B1 (en) | 2010-11-26 | 2012-12-21 | Michelin Soc Tech | TIRE TREAD TIRE |
| JP6079182B2 (en) * | 2012-12-05 | 2017-02-15 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| FR3008414B1 (en) * | 2013-07-15 | 2016-06-10 | Michelin & Cie | TIRE TREAD TIRE |
| JP6698261B2 (en) * | 2014-12-15 | 2020-05-27 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Snow tire having a tread containing a rubber composition |
| JP6235097B2 (en) * | 2015-10-27 | 2017-11-22 | 住友ゴム工業株式会社 | Pneumatic tire and crosslinked rubber composition |
| JP6235096B2 (en) * | 2015-10-27 | 2017-11-22 | 住友ゴム工業株式会社 | Pneumatic tire and crosslinked rubber composition |
| US10639932B2 (en) | 2015-10-27 | 2020-05-05 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire and crosslinked rubber composition |
| JP6915242B2 (en) | 2016-08-17 | 2021-08-04 | 住友ゴム工業株式会社 | Rubber composition and its manufacturing method |
| WO2022071558A1 (en) * | 2020-10-01 | 2022-04-07 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire, vulcanized rubber, rubber-metal composite material, tire, industrial belt, crawler and hose |
| WO2022071560A1 (en) * | 2020-10-01 | 2022-04-07 | 株式会社ブリヂストン | Rubber composition, rubber composition for tires, vulcanized rubber, rubber-metal composite, tire, industrial belt, crawler, and hose |
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| ES2141958T3 (en) * | 1994-10-11 | 2000-04-01 | Bridgestone Corp | RUBBER MIXTURE AND VARIOUS INGREDIENTS IMPROVED AS TO ACCUMULATION OF ELECTRO-STATIC LOAD AND PNEUMATIC COVER MANUFACTURED FROM THE SAME. |
| JP3608378B2 (en) * | 1998-04-03 | 2005-01-12 | Ｎｏｋ株式会社 | NBR composition |
| JP4278765B2 (en) * | 1999-02-01 | 2009-06-17 | 住友ゴム工業株式会社 | Method for producing rubber composition |
| JP2002275311A (en) * | 2001-01-10 | 2002-09-25 | Bridgestone Corp | Rubber composition and tire |
| JP4663207B2 (en) * | 2002-12-04 | 2011-04-06 | 住友ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire using the same |
| JP2005154586A (en) * | 2003-11-26 | 2005-06-16 | Sumitomo Rubber Ind Ltd | Rubber composition |
| JP4785388B2 (en) * | 2004-03-26 | 2011-10-05 | 株式会社ブリヂストン | Rubber composition for tread and pneumatic tire using the same |
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