JP5093970B2 - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
- Publication number
- JP5093970B2 JP5093970B2 JP2003390951A JP2003390951A JP5093970B2 JP 5093970 B2 JP5093970 B2 JP 5093970B2 JP 2003390951 A JP2003390951 A JP 2003390951A JP 2003390951 A JP2003390951 A JP 2003390951A JP 5093970 B2 JP5093970 B2 JP 5093970B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- parts
- silica
- rubber composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 55
- 239000005060 rubber Substances 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 title claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 57
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 19
- 239000002174 Styrene-butadiene Substances 0.000 claims description 13
- 229920003244 diene elastomer Polymers 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- 238000010551 living anionic polymerization reaction Methods 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はタイヤトレッド用ゴム組成物に関し、更に詳しくは加工性及びシリカ分散性の良好なシリカ配合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 silica-containing tire treads having good processability and silica dispersibility.
非特許文献１に記載されているように、トレッドゴムにシリカを配合したタイヤは年々増加傾向にある。その性能は、シリカの反応や分散に影響され、ゴムの混合時にシリカをいかに分散させるかが重要である。一方、非特許文献２に記載されているように、摩擦力にはゴムの強度も関与している。ゴムの強度を向上させるためには特許文献１や２にあるように高分子量の乳化重合ＳＢＲを用いることが効果的であるが、乳化重合ＳＢＲは長い分岐鎖を持つために、シリカが上手く分散できないことが問題であった。 As described in Non-Patent Document 1, tires in which silica is mixed with tread rubber tend to increase year by year. The performance is affected by the reaction and dispersion of the silica, and how to disperse the silica during rubber mixing is important. On the other hand, as described in Non-Patent Document 2, the frictional force also involves the strength of rubber. In order to improve the strength of rubber, it is effective to use high molecular weight emulsion polymerization SBR as described in Patent Documents 1 and 2, but since emulsion polymerization SBR has a long branched chain, silica is well dispersed. The problem was not being able to.
従って、本発明は、前記した従来技術の問題点を排除して、シリカ配合タイヤトレッド用ゴム組成物の加工性を改良すると共に、シリカの分散性を向上させてゴム組成物の強度を確保することにある。 Therefore, the present invention eliminates the problems of the prior art described above, improves the processability of the rubber composition for silica-containing tire treads, and improves the dispersibility of silica to ensure the strength of the rubber composition. There is.
本発明に従えば、（ｉ）ガラス転移温度（Ｔｇ）が−４５℃〜−１５℃である乳化重合スチレン−ブタジエン共重合体ゴム（ＳＢＲ）９５〜６０重量％及びガラス転移温度（Ｔｇ）が−７５℃〜−１５℃であり重量平均分子量Ｍｗが１５万〜５０万であるリビングアニオン重合により重合されたジエン系ゴム５〜４０重量％からなるブレンドゴムを少なくとも６０重量部含むゴム成分１００重量部に対し、（ii）シリカ５〜１００重量部を含んで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, (i) 95-60 wt% of an emulsion-polymerized styrene-butadiene copolymer rubber (SBR) having a glass transition temperature (Tg) of −45 ° C. to −15 ° C. and a glass transition temperature (Tg) of 100 parts by weight of a rubber component containing at least 60 parts by weight of a blend rubber composed of 5 to 40% by weight of a diene rubber polymerized by living anionic polymerization having a weight average molecular weight Mw of 150,000 to 500,000 and a temperature of -75 ° C to -15 ° C to section, (ii) a rubber composition for a tire tread comprising silica 5-100 parts by weight are provided.
通常シリカは、ゴム中で凝集しやすいために、分散が悪い状態ではムーニー粘度が著しく上昇する。特に、乳化重合のＳＢＲを用いた場合には、分散が不十分であるため、粘度の上昇が大きくなり加工性に問題が生じていたが、本発明によれば、Ｍｗ＜５０万の溶液重合ＳＢＲ（ＳＳＢＲ）を配合することにより、シリカの分散が改善され、ムーニー粘度が下り、加工性が改善される。但し、ＳＳＢＲだけで構成したゴムは、強度が不足するので実用上好ましくない。 Usually, silica easily aggregates in rubber, so that the Mooney viscosity increases remarkably in a poor dispersion state. In particular, when SBR of emulsion polymerization is used, since the dispersion is insufficient, the increase in viscosity is large, resulting in a problem in processability. According to the present invention, solution polymerization with Mw <500,000 By blending SBR (SSBR), silica dispersion is improved, Mooney viscosity is lowered, and processability is improved. However, a rubber composed only of SSBR is not practically preferable because its strength is insufficient.
シリカは、カーボンブラックに比べると自己凝集しやすいためゴム中に分散させにくいという問題があり、また、ゴム分子との親和性も低いために、機械的なせん断力が十分に加わりにくい。従って、シリカをゴム中に機械的に分散させることは困難である。特に、乳化重合ＳＢＲは、長い分岐鎖があるために粘度が高く、シリカの分散には不利である。この問題を解決するために、本発明では重量平均分子量Ｍｗが１５万〜５０万、好ましくは２０万〜４８万のリビングアニオン重合で重合したジエン系ゴム（例えば、ＳＢＲ、ＩＲ、ＢＲ、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）を５〜４０重量部％、好ましくは７〜３８重量％と乳化重合ＳＢＲ９５〜６０重量％、好ましくは９３〜６３重量％、そしてその他の任意的なジエン系ゴム（例えば天然ゴム、ブチルゴム、ハロゲン化ブチルゴム、アクリロニトリル−ブタジエン共重合体ゴム、乳化重合ＢＲ）０〜４０重量％（ゴムの合計１００重量％）からなるゴム組成物に、シリカを５〜１００重量部、好ましくは１０〜９５重量部配合したタイヤトレッドゴム組成物を提供することによって前記課題が解決される。 Silica is more likely to be self-aggregated than carbon black, and thus has a problem that it is difficult to disperse in rubber, and since it has a low affinity with rubber molecules, it is difficult to sufficiently apply mechanical shearing force. Therefore, it is difficult to mechanically disperse silica in rubber. In particular, emulsion polymerization SBR has a high viscosity due to the presence of long branched chains, which is disadvantageous for silica dispersion. In order to solve this problem, in the present invention, a diene rubber polymerized by living anionic polymerization having a weight average molecular weight Mw of 150,000 to 500,000, preferably 200,000 to 480,000 (for example, SBR, IR, BR, styrene- Isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber) 5 to 40 parts by weight, preferably 7 to 38% by weight, emulsion polymerization SBR 95 to 60% by weight, preferably 93 to 63% by weight, and others A rubber composition comprising 0 to 40% by weight (total 100% by weight of rubber) of any diene rubber (for example, natural rubber, butyl rubber, halogenated butyl rubber, acrylonitrile-butadiene copolymer rubber, emulsion polymerization BR), By providing a tire tread rubber composition containing 5 to 100 parts by weight of silica, preferably 10 to 95 parts by weight Serial problem can be solved.
リビングアニオン重合ＳＢＲ（溶液重合ＳＢＲ）は、ほとんど分岐鎖がなく、重量平均分子量Ｍｗが５０万未満、好ましくは４８万以下であれば粘度が低いためにシリカの分散性が向上する。但し、Ｍｗが１５万未満によるとゴムの強度が低下するので好ましくない。乳化重合ＳＢＲを配合することにより、十分な強度のゴムが得られる。また、前述のごとく、その他のジエン系ゴムを配合してもよいが、その配合量はゴム合計量１００重量部中４０重量部以下である。この配合量が多過ぎると、本発明の目的である、十分なシリカの分散と十分なゴムの強度が得られないので好ましくない。
また前記リビングアニオン重合によるジエン系ゴムがアルキル−リチウムを開始剤とした芳香族ビニルと共役ジエンとの共重合体であって芳香族ビニルを１０〜３５重量％及び共役ジエン中のビニル結合量を１０〜８０重量％含んだ共重合体ゴムである前記ゴム組成物であるのが十分なシリカの分散とゴムの強度を満足し、かつより高い摩擦力を得られるので好ましい。
Living anion polymerization SBR (solution polymerization SBR) has almost no branched chain, and if the weight average molecular weight Mw is less than 500,000, preferably 480,000 or less, the viscosity is low and the dispersibility of silica is improved. However, if Mw is less than 150,000, the strength of the rubber is lowered, which is not preferable. By blending the emulsion polymerization SBR, a rubber having sufficient strength can be obtained. Moreover, as mentioned above, other diene rubbers may be blended, but the blending amount is 40 parts by weight or less in 100 parts by weight of the total amount of rubber. If the amount is too large, it is not preferable because sufficient silica dispersion and sufficient rubber strength, which are the objects of the present invention, cannot be obtained.
The diene rubber produced by the living anion polymerization is a copolymer of an aromatic vinyl and a conjugated diene using an alkyl-lithium as an initiator, the aromatic vinyl being 10 to 35% by weight, and the amount of vinyl bonds in the conjugated diene. The rubber composition, which is a copolymer rubber containing 10 to 80% by weight, is preferable because sufficient silica dispersion and rubber strength are satisfied, and higher frictional force can be obtained.
本発明においては、前記リビングアニオン重合（例えばＮａ−ナフタレン、Ｋ−ナフタレン、Ｎａ−α−メチルスチレン四量体ジアニオン、アルキル−Ｌｉなどの触媒（特にアルキル−Ｌｉ触媒が分岐が少ないゴムが得られ、特に好ましい）を用いてジエンモノマーを含むモノマーをヘキサン、ＴＨＦ、ベンゼンなどの溶媒中で溶液重合）して得られるジエン系ゴムを５〜４０重量％及び乳化重合ＳＢＲを含むブレンドゴムを、合計ゴム量１００重量部中、６０重量部以上、好ましくは６２重量部以上含むことが必要であり、前記リビングアニオン重合されたジエン系ゴムの量が少な過ぎるとシリカの分散が不十分となるので好ましくなく、逆に多過ぎると十分な強度のゴム組成物が得られないので好ましくない。 In the present invention, a catalyst such as the above-mentioned living anionic polymerization (for example, Na-naphthalene, K-naphthalene, Na-α-methylstyrene tetramer dianion, alkyl-Li, etc.) The blended rubber containing 5 to 40% by weight of a diene rubber obtained by solution polymerization of a monomer containing a diene monomer in a solvent such as hexane, THF or benzene) and an emulsion polymerization SBR It is necessary to contain 60 parts by weight or more, preferably 62 parts by weight or more in 100 parts by weight of rubber, and if the amount of the living anion polymerized diene rubber is too small, silica dispersion becomes insufficient, which is preferable. On the other hand, if the amount is too large, a rubber composition having sufficient strength cannot be obtained.
本発明において使用するシリカは従来からタイヤ用などに使用されている任意のシリカ、例えば天然シリカ、合成シリカ、より具体的には乾式シリカ、湿式シリカとすることができる。本発明の組成物においてシリカの配合量が少な過ぎると摩擦力の向上が不十分であるので好ましくなく、逆に多過ぎるとシリカを十分に分散させることが困難となるので好ましくない。 The silica used in the present invention may be any silica conventionally used for tires, for example, natural silica, synthetic silica, more specifically dry silica or wet silica. In the composition of the present invention, if the amount of silica is too small, the frictional force is not sufficiently improved, and on the contrary, if it is too large, it is difficult to sufficiently disperse the silica.
本発明の好ましい態様に従えば、前記必須成分に加えて、カーボンブラックをゴム成分１００重量部に対し５〜１００重量部、好ましくは７〜９５重量部配合する。この配合量が少な過ぎるとカーボンブラックの配合の効果がなく、逆に多過ぎるとシリカの配合効果が損われるおそれがあるので好ましくない。本発明において使用するカーボンブラックは従来からタイヤ用その他に一般的に使用されている任意のカーボンブラックとすることができるが、本発明の目的からすれば、窒素吸着比表面積（Ｎ2ＳＡ）が７５〜３００ｍ2／ｇのものが特に好ましい。 According to a preferred embodiment of the present invention, in addition to the essential components, carbon black is blended in an amount of 5 to 100 parts by weight, preferably 7 to 95 parts by weight, based on 100 parts by weight of the rubber component. If the blending amount is too small, the effect of blending carbon black is not obtained. On the other hand, if the blending amount is too large, the blending effect of silica may be impaired. The carbon black used in the present invention can be any carbon black conventionally used for tires and others, but for the purposes of the present invention, the nitrogen adsorption specific surface area (N 2 SA) is The thing of 75-300 m < 2 > / g is especially preferable.
本発明に係るゴム組成物には、前記した成分に加えて、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、その他一般ゴム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、加硫して組成物とし、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 is generally used for tires such as vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plasticizers, and other general rubbers. It is possible to add various additives that are blended in a general manner, and such additives can be used for vulcanization or cross-linking by kneading and vulcanizing by a general method to obtain a composition. 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１〜２及び比較例１〜３
表Ｉに示す配合において、加硫系を除くマスターバッチの各成分（重量部）を１．７リットルの実験室バンバリーミキサーで６０rpm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系をオープンロールで混練し、シート状未加硫ゴム組成物を得た。このゴムシートを用いて以下に示す試験法で未加硫物性を評価した。結果は表Ｉに示す。
Examples 1-2 and Comparative Examples 1-3
In the formulation shown in Table I, each component (parts by weight) of the master batch excluding the vulcanization system was kneaded with a 1.7 liter laboratory Banbury mixer at 60 rpm for 5 minutes, and released when reaching 160 ° C. Got a batch. The master batch was kneaded with a vulcanization system with an open roll to obtain a sheet-like unvulcanized rubber composition. Using this rubber sheet, unvulcanized physical properties were evaluated by the following test methods. The results are shown in Table I.
次に得られたゴムシートを１５×１５×０．２cmの金型中で１６０℃で３０分間加硫して２mm厚の加硫ゴムシートを作製し、以下に示す試験法で加硫ゴムの引張強さを測定した。結果は表Ｉに示す。 Next, the obtained rubber sheet was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 30 minutes to prepare a vulcanized rubber sheet having a thickness of 2 mm. Tensile strength was measured. The results are shown in Table I.
ゴム物性評価試験法
ムーニー粘度ＭＬ1+4（１００℃）：ＪＩＳ Ｋ−６３００に準拠して、ムーニー粘度計にてＬ型ローター（３８．１mm径、厚さ５．５mm）で測定。（予熱１分、測定４分、１００℃、２rpm）
引張試験：ＪＩＳ Ｋ−６２５１に準拠してＪＩＳ ３号ダンベルを打ち抜き、５００mm／分の引張速度で測定した破断強度を示す。
Rubber physical property evaluation test method Mooney viscosity ML 1 + 4 (100 ° C): According to JIS K-6300, Mooney viscometer with L-shaped rotor (38.1 mm diameter, thickness 5.5 mm) Measurement. (Preheating 1 minute, measurement 4 minutes, 100 ° C., 2 rpm)
Tensile test: JIS No. 3 dumbbell was punched in accordance with JIS K-6251, and the breaking strength measured at a tensile speed of 500 mm / min is shown.
表Ｉ脚注
＊１ ＮＩＰＯＬ９５２８Ｒ：日本ゼオン（株）製 乳化重合スチレン−ブタジエン共重合体ゴム、３７．５phr油展、Ｔｇ＝−３５℃、Ｍｗ＝８３万
＊２ ＮＳ １１６：日本ゼオン（株）製 リビングアニオン重合スチレン−ブタジエン共重合体ゴム、３７．５phr油展、Ｔｇ＝−２５℃、Ｍｗ＝４０万
＊３ ＶＳＬ５０２５：ＢＡＹＥＲ製 リビングアニオン重合スチレン−ブタジエン共重合体ゴム、３７．５phr油展、Ｔｇ＝−２０℃、Ｍｗ＝７８万
＊４ ＮＩＰＯＬ１７１２：日本ゼオン（株）製 乳化重合スチレン−ブタジエン共重合体ゴム、３７．５phr油展、Ｔｇ＝−５１℃、Ｍｗ＝５２万
＊５ ＤＩＡＡ：三菱化学（株）製 カーボンブラック、Ｎ2 ＳＡ＝１４２ｍ2／ｇ
＊６ Ｎｉｐｓｉｌ ＡＱ：日本シリカ工業製、湿式シリカ
＊７ Ｓｉ−６９デグッサ製、シランカップリング剤
＊８ ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ：ＦＬＥＸＳＹＳ製 老化防止剤
＊９ 酸化亜鉛３種：正同化学工業（株）製
＊１０ ステアリン酸：日本油脂（株）製
＊１１ ＳＡＮＴＯＣＵＲＥ ＮＳ：ＦＬＥＸＳＩＳ製 加硫促進剤
＊１２ 硫黄：（株）軽井沢精練所製
Table I Footnote * 1 NIPOL9528R: manufactured by Nippon Zeon Co., Ltd. Emulsion polymerization styrene-butadiene copolymer rubber, 37.5 phr oil exhibition, Tg = -35 ° C., Mw = 830,000 * 2 NS 116: manufactured by Nippon Zeon Co., Ltd. Living anion polymerization styrene-butadiene copolymer rubber, 37.5 phr oil exhibition, Tg = −25 ° C., Mw = 400,000 * 3 VSL5025: BAYER Living anion polymerization styrene-butadiene copolymer rubber, 37.5 phr oil exhibition, Tg = −20 ° C., Mw = 780,000 * 4 NIPOL 1712: manufactured by Nippon Zeon Co., Ltd. Emulsion polymerized styrene-butadiene copolymer rubber, 37.5 phr oil exhibition, Tg = −51 ° C., Mw = 520,000 * 5 DIAA: Carbon black manufactured by Mitsubishi Chemical Corporation, N 2 SA = 142 m 2 / g
* 6 Nipsil AQ: Nippon Silica Kogyo Co., Ltd., wet silica * 7 Si-69 Degussa, Silane coupling agent * 8 SANTOFLEX 6PPD: Anti-aging agent manufactured by FLEXSYS 10 Stearic acid: manufactured by Nippon Oil & Fats Co., Ltd. * 11 SANTOCURE NS: manufactured by FLEXSIS Vulcanization accelerator * 12 Sulfur: manufactured by Karuizawa Seiren Co., Ltd.
本発明に従ったゴム組成物は引張特性などのゴム強度及び加工性を改良することができるので、例えば空気入りタイヤのタイヤトレッド用などとして好適に使用することができる。 Since the rubber composition according to the present invention can improve rubber strength such as tensile properties and processability, it can be suitably used, for example, for a tire tread of a pneumatic tire.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003390951A JP5093970B2 (en) | 2003-11-20 | 2003-11-20 | Rubber composition for tire tread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003390951A JP5093970B2 (en) | 2003-11-20 | 2003-11-20 | Rubber composition for tire tread |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005154473A JP2005154473A (en) | 2005-06-16 |
| JP5093970B2 true JP5093970B2 (en) | 2012-12-12 |
Family
ID=34718174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003390951A Expired - Fee Related JP5093970B2 (en) | 2003-11-20 | 2003-11-20 | Rubber composition for tire tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5093970B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607005A (en) * | 2019-09-23 | 2019-12-24 | 四川大学 | Emulsion polystyrene butadiene rubber composite material with high wet skid resistance and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102019121267B4 (en) | 2018-08-10 | 2025-01-02 | Asahi Kasei Kabushiki Kaisha | Modified conjugated diene polymer compositions, manufacturing process of modified conjugated diene polymer compositions and vulcanized product |
| CN114174405B (en) * | 2019-12-05 | 2023-11-24 | 住友橡胶工业株式会社 | Tire with a tire body |
| CN117813346A (en) * | 2021-08-26 | 2024-04-02 | 日本瑞翁株式会社 | Latex composition and impregnated molded body |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1277581B1 (en) * | 1995-09-14 | 1997-11-11 | Enichem Elastomers | ELASTOMERIC COMPOSITION USEFUL AS A TREAD FOR TIRES |
| JP2000119446A (en) * | 1998-10-19 | 2000-04-25 | Jsr Corp | Rubber composition |
| JP2000239444A (en) * | 1999-02-19 | 2000-09-05 | Bridgestone Corp | Rubber composition and pneumatic tire for heavy load |
| WO2002059193A1 (en) * | 2001-01-25 | 2002-08-01 | The Yokohama Rubber Co., Ltd. | Rubber composition |
| JP3933966B2 (en) * | 2002-03-15 | 2007-06-20 | 日本ゼオン株式会社 | Diene rubber, method for producing the same, rubber composition, method for producing the same, and cross-linked product |
-
2003
- 2003-11-20 JP JP2003390951A patent/JP5093970B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607005A (en) * | 2019-09-23 | 2019-12-24 | 四川大学 | Emulsion polystyrene butadiene rubber composite material with high wet skid resistance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005154473A (en) | 2005-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107849160B (en) | Modified conjugated diene polymer, preparation method thereof and modifier | |
| JP4294070B2 (en) | Rubber composition for tire | |
| JP6340095B2 (en) | Rubber composition for tire tread | |
| JP7091716B2 (en) | Rubber composition for tires | |
| JP2016003274A (en) | Rubber composition and pneumatic tire using the same | |
| WO2020189328A1 (en) | Studless tire rubber composition and studless tire using same | |
| JP2008019334A (en) | Rubber composition for tire tread | |
| JP5569226B2 (en) | Rubber composition for tire tread | |
| JP5093970B2 (en) | Rubber composition for tire tread | |
| JP2008138086A (en) | Rubber composition for tire tread | |
| JP2002363346A (en) | Rubber composition for tire tread and pneumatic tire made by using it | |
| JP2004277506A (en) | Rubber composition for tire and pneumatic tire | |
| JP2006131718A (en) | Rubber composition | |
| JP2009051975A (en) | Rubber composition for tire | |
| JP5038040B2 (en) | Rubber composition for tire tread and tire | |
| JP2006137897A (en) | Rubber composition | |
| JP2009007422A (en) | Rubber composition and tire | |
| JP2005350595A (en) | Pneumatic tire | |
| JP2009114367A (en) | Rubber composition for tire tread and pneumatic tire having tread using it | |
| JP4111765B2 (en) | Rubber composition for tire tread | |
| JP4215774B2 (en) | Heavy duty pneumatic tire | |
| JP2005194418A (en) | Rubber composition for pneumatic tire | |
| JP5003011B2 (en) | Rubber composition | |
| JP4616550B2 (en) | Rubber composition for tire tread | |
| JPH09118783A (en) | Rubber composition for tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060926 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090402 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091006 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091207 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100506 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100514 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100611 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120918 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5093970 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150928 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150928 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |