JPH07118449A - Rubber composition and production thereof - Google Patents
Rubber composition and production thereofInfo
- Publication number
- JPH07118449A JPH07118449A JP5269196A JP26919693A JPH07118449A JP H07118449 A JPH07118449 A JP H07118449A JP 5269196 A JP5269196 A JP 5269196A JP 26919693 A JP26919693 A JP 26919693A JP H07118449 A JPH07118449 A JP H07118449A
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- JP
- Japan
- Prior art keywords
- weight
- silica
- rubber composition
- rubber
- parts
- 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.)
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Classifications
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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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐摩耗性に優れ、転が
り抵抗の改良されたタイヤのトレッド用として適するゴ
ム組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition which has excellent wear resistance and is suitable for a tread of a tire having improved rolling resistance.
【０００２】[0002]
【従来の技術】省資源及び環境対策の観点から自動車の
燃費を改善する要求はますます強くなり、タイヤに対し
ては転がり抵抗の改善されたトレッドを有するタイヤが
求められてきた。従来からトレッド用ゴム材料に補強剤
としてカーボンブラックが用いられているが、近年補強
剤としてシリカを用い、さらなる転がり抵抗を改善しよ
うと盛んに試みられている。確かに転がり抵抗の改善に
は効果があるが、耐摩耗性はカーボンブラックを用いた
場合と比較して劣っており、改善が必要である。2. Description of the Related Art From the viewpoint of resource saving and environmental measures, the demand for improving the fuel efficiency of automobiles has become stronger and stronger, and tires having treads with improved rolling resistance have been demanded. Carbon black has conventionally been used as a reinforcing agent in rubber materials for treads, but in recent years, silica has been used as a reinforcing agent, and attempts have been actively made to further improve rolling resistance. Certainly, it is effective in improving rolling resistance, but wear resistance is inferior to that in the case of using carbon black, and improvement is required.
【０００３】この原因の一つは、シリカは、カーボンブ
ラックと異なりゴム材料との親和性が小さいために、補
強効果の発現にとって重要であるフィラーゲルが生成し
難いことにある。シリカとゴム材料の親和性を高めるた
めにシランカップリング剤を使用する方法が種々提案さ
れてはいるが効果は充分とはいえず改善が求められてい
る。One of the causes of this is that, unlike carbon black, silica has a small affinity with rubber materials, so that it is difficult to form a filler gel, which is important for manifesting the reinforcing effect. Various methods have been proposed for using a silane coupling agent in order to increase the affinity between silica and a rubber material, but the effect is not sufficient and improvement is required.
【０００４】[0004]
【発明が解決しようとする課題】本発明者等は、このよ
うな問題点を解決し、耐摩耗性と転がり抵抗が改善され
たシリカを補強剤とするゴム組成物を開発すべく鋭意検
討した結果、特定な単量耐組成のゴムを用い、シリカと
混合することによって目的が達成されることを見いだし
本発明を完成するに到った。DISCLOSURE OF THE INVENTION The present inventors have diligently studied to solve such problems and develop a rubber composition containing silica as a reinforcing agent, which has improved abrasion resistance and rolling resistance. As a result, they have found that the object can be achieved by using a rubber having a specific monomer-resistant composition and mixing it with silica, and completed the present invention.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、一般式
ＣＨ2 ＝ＣＲ1 −ＣＲ2 ＝ＣＨ2 （式中Ｒ1 は水素又
は低級アルキル基、Ｒ2 は低級アルキル基を表す）で示
されるモノマー０．５〜３０重量％、芳香族ビニルモノ
マー５〜６０重量％及びブタジエン２０〜９４．５重量
％を共重合させて得られる共重合ゴム１００重量部にシ
リカ２０〜１５０重量部を配合してなり、トルエン不溶
分が２５〜８０重量％であることを特徴とするゴム組成
物及び前記共重合ゴム１００重量部とシリカ２０〜１５
０重量部とを混合した後にシリカ以外の配合剤を添加し
て混合することを特徴とするゴム組成物の製造方法が提
供される。According to the present invention, the general formula CH 2 ═CR 1 —CR 2 ═CH 2 (wherein R 1 represents hydrogen or a lower alkyl group, and R 2 represents a lower alkyl group). 20 to 150 parts by weight of silica is added to 100 parts by weight of a copolymer rubber obtained by copolymerizing 0.5 to 30% by weight of the monomer shown, 5 to 60% by weight of an aromatic vinyl monomer and 20 to 94.5% by weight of butadiene. A rubber composition comprising 100 to 100 parts by weight of the above-mentioned copolymer rubber and 20 to 15 silica, which is compounded and has a toluene insoluble content of 25 to 80% by weight.
Provided is a method for producing a rubber composition, which comprises mixing 0 part by weight and then adding and mixing a compounding agent other than silica.
【０００６】上記一般式で示されるモノマーの使用量
は、全モノマー中０．５〜３０重量％である。５重量％
未満ではフィラーゲルの生成が少なく、強度特性が不充
分となり、３０重量％を超えると耐摩耗性が低下する。
好ましくは３〜２０重量％である。芳香族ビニルモルマ
ーの使用量は、全モノマー中５〜６０重量％である。５
重量％未満では強度特性が低下し、６０重量％を超える
と反発弾性が低下する。好ましくは１０〜４０重量％で
ある。The amount of the monomer represented by the above general formula used is 0.5 to 30% by weight based on all the monomers. 5% by weight
If the amount is less than the above, the amount of filler gel is less generated and the strength characteristics are insufficient, and if it exceeds 30% by weight, the abrasion resistance is deteriorated.
It is preferably 3 to 20% by weight. The amount of the aromatic vinyl molmer used is 5 to 60% by weight based on the total amount of the monomers. 5
If it is less than 60% by weight, the strength properties will deteriorate, and if it exceeds 60% by weight, the impact resilience will decrease. It is preferably 10 to 40% by weight.
【０００７】ブタジエンの使用量は、全モノマー中２０
〜９４．５重量％を超えると加工性が劣り、組成物の調
製が困難となる。好ましくは４０〜８０重量％である。
本発明で使用する共重合ゴムは以上のモノマーを共重合
することによって得られる。重合方法としては乳化重合
（ラジカル重合）や溶液重合（例えば、アニオン重合
等）が用いられる。重合の様式としては、バッチ式ある
いは連続式重合が用いられる。特に好ましい重合方法は
溶液重合であり、ｎ−ブチルリチウム等の有機アルカリ
金属触媒やアルカリ土類金属触媒によるアニオン重合で
ある。アニオン重合においては、触媒と共に通常使用さ
れる第３級アミン、エーテル類等を適宜用いることがで
きる。得られた共重合ゴムは、重合耐溶液に老化防止剤
等を添加した後、スチームストリッピング等によって凝
固分離され、乾燥される。The amount of butadiene used is 20 in all monomers.
If it exceeds 94.5% by weight, the processability is poor and it becomes difficult to prepare the composition. It is preferably 40 to 80% by weight.
The copolymer rubber used in the present invention can be obtained by copolymerizing the above monomers. As the polymerization method, emulsion polymerization (radical polymerization) or solution polymerization (for example, anionic polymerization) is used. As the mode of polymerization, batch type or continuous type is used. A particularly preferred polymerization method is solution polymerization, and anionic polymerization using an organic alkali metal catalyst such as n-butyllithium or an alkaline earth metal catalyst. In the anionic polymerization, tertiary amines, ethers and the like which are usually used with a catalyst can be appropriately used. The obtained copolymer rubber is coagulated and separated by steam stripping or the like after adding an antioxidant and the like to the polymerization resistant solution and dried.
【０００８】本発明のゴム組成物は、本発明の共重合ゴ
ムとシリカを先ずバンバリー等の混合機で混合し、次い
で他の原料ゴム及びその他の必要な配合剤を添加し、混
合することによって製造される。本発明の共重合ゴムと
シリカの混合時にはプロセスオイルは添加してもよい
が、ゴム組成物を用いたタイヤ等のゴム製品の酸化劣化
やオゾン劣化を防止するための老化防止剤やオゾン劣化
防止剤等の極性配合剤の添加はフィラーゲル量の生成を
低下させるので好ましくない。The rubber composition of the present invention is obtained by first mixing the copolymer rubber of the present invention and silica in a mixer such as Banbury, and then adding and mixing other raw material rubbers and other necessary compounding agents. Manufactured. Process oil may be added at the time of mixing the copolymer rubber of the present invention and silica, but an antioxidant and ozone deterioration preventive agent for preventing oxidative deterioration and ozone deterioration of rubber products such as tires using the rubber composition. The addition of a polar compounding agent such as an agent lowers the production of the amount of filler gel and is not preferred.
【０００９】混合時の温度は通常８０〜２００℃である
が、好ましくは１００〜１７０℃、さらに好ましくは１
２０〜１５０℃である。この温度で２分以上混合するの
が好ましい。８０°よりも低い温度ではシリカと共重合
ゴムとがゲルを形成しにくく、２００℃を超えると共重
合ゴム自身の劣化や焼けが生じるので好ましくないから
である。シリカの投入は一括でもよいが、好ましくは２
回以上の分割投入をするくと分散が容易になり、シリカ
と共重合ゴムとが反応し易くなる。The temperature during mixing is usually 80 to 200 ° C, preferably 100 to 170 ° C, more preferably 1
20 to 150 ° C. It is preferable to mix at this temperature for 2 minutes or more. This is because at a temperature lower than 80 °, it is difficult for silica and the copolymer rubber to form a gel, and when the temperature exceeds 200 ° C., the copolymer rubber itself is deteriorated or burnt, which is not preferable. Silica may be added all at once, but preferably 2
Dispersion becomes easier if the divided addition is repeated more than once, and the silica and the copolymer rubber easily react.
【００１０】本発明のゴム組成物は、耐摩耗性が改善さ
れるためには、トルエン不溶分が２５〜８０重量％であ
ることが必要である。２５重量％未満では、補強性が不
十分で強度、耐摩耗性が低下し、８０重量％を超えると
加工性が劣り、耐摩耗性や転がり抵抗も悪くなる。好ま
しくは、３０〜６５重量％である。シリカは、乾式法に
よる超微粒子のシリカ又は湿式法によるシリカのいずれ
でもよい。好ましくは湿式法によるシリカである。さら
に好ましくは、湿式法によって得られたシリカを造粒し
たものがよい。The rubber composition of the present invention must have a toluene insoluble content of 25 to 80% by weight in order to improve wear resistance. If it is less than 25% by weight, the reinforcing property is insufficient and the strength and wear resistance are reduced, and if it exceeds 80% by weight, the workability is poor and the wear resistance and rolling resistance are poor. Preferably, it is 30 to 65% by weight. The silica may be either ultrafine silica particles by a dry method or silica particles by a wet method. Preferred is silica by a wet method. More preferably, the silica obtained by the wet method is granulated.
【００１１】シリカは、上記共重合ゴム１００重量部に
対し２０〜１５０重量部配合する。２０重量部未満では
補強性に劣り、１５０重量部を超えると混練加工性が著
しく悪くなり、強度特性にも悪影響を及ぼす。配合に際
しては、共重合ゴムと造粒されたシリカを密閉型混練機
に入れ、約８０〜２００℃で混練するのがよく、好まし
くは１００〜１７０℃、さらに好ましくは１２０〜１５
０℃で２分以上混練するのがよい。８０℃よりも低い温
度ではシリカと共重合ゴムとがゲルを形成しにくく、２
００℃を超えると共重合ゴム自身の劣化や焼けが生じる
ので好ましくないからである。シリカの投入は一括でも
よいが、好ましくは２回以上の分割投入をすると分散が
容易になり、シリカと共重合ゴムとが反応し易くなる。Silica is compounded in an amount of 20 to 150 parts by weight with respect to 100 parts by weight of the copolymer rubber. If it is less than 20 parts by weight, the reinforcing property is poor, and if it exceeds 150 parts by weight, the kneading workability is remarkably deteriorated and the strength characteristics are also adversely affected. At the time of compounding, the copolymer rubber and the granulated silica may be put into a closed type kneader and kneaded at about 80 to 200 ° C, preferably 100 to 170 ° C, more preferably 120 to 15 ° C.
It is preferable to knead at 0 ° C for 2 minutes or more. At temperatures lower than 80 ° C, it is difficult for silica and copolymer rubber to form a gel.
This is because if the temperature exceeds 00 ° C, the copolymer rubber itself may deteriorate or burn, which is not preferable. The silica may be added all at once, but preferably, the addition is performed twice or more to facilitate dispersion and facilitate reaction between silica and the copolymer rubber.
【００１２】このように混合して得られるゴム組成物に
は、通常使用される硫黄加硫系（硫黄／亜鉛華／ステア
リン酸／各種加硫促進剤／他）、ジエチレングリコール
等の加硫活性剤、シランカップリング剤、加工助剤、プ
ロセスオイル、カーボンブラック、炭酸カルシウム、タ
ルク等の補強剤や充填剤等が必要に応じて添加される。
また、必要に応じ、原料ゴムとして本発明の共重合ゴム
と他のゴム、例えばポリブタジエンゴム（高シス含量〜
低シス含量）、スチレン−ブタジエン共重合ゴム（溶液
重合、乳化重合）ＥＰＤＭ等をブレンドすることもでき
る。The rubber composition obtained by mixing as described above includes a sulfur vulcanization system (sulfur / zinc white / stearic acid / various vulcanization accelerators / others) usually used, and a vulcanization activator such as diethylene glycol. A silane coupling agent, a processing aid, a process oil, carbon black, calcium carbonate, a reinforcing agent such as talc, a filler, and the like are added as necessary.
In addition, if necessary, as a raw material rubber, the copolymer rubber of the present invention and other rubbers such as polybutadiene rubber (high cis content to
A low cis content), styrene-butadiene copolymer rubber (solution polymerization, emulsion polymerization) EPDM, etc. can also be blended.
【００１３】[0013]
(a) 実施例１〜４、比較例１〜４ 15リットル攪拌機付きオートクレーブにスチレン300g、
ブタジエン525g、イソプレン75g 、シクロヘキサン8500
g を入れ、TMEDA 3.0 ミリモル、n-BuLiを10.0ミリモル
加え、65℃で重合を行った。重合開始後10分からブタジ
エン600gを60分に亘って連続的に添加した。モノマー添
加終了後約30分で重合転化率は100%となり、メタノール
約２cc入れて反応を停止させた。この溶液に、2,6-ジタ
ーシャリーブチルフェノール(BHT) を10g 入れて、スチ
ームストリッピング法によって凝固回収し、真空乾燥し
て共重合ゴムを得た。同様にして実施例２〜比較例４で
使用する共重合ゴムを製造した。(a) Examples 1 to 4 and Comparative Examples 1 to 4 300 g of styrene in an autoclave equipped with a 15 liter stirrer,
Butadiene 525g, Isoprene 75g, Cyclohexane 8500
g was added, TMEDA (3.0 mmol) and n-BuLi (10.0 mmol) were added, and polymerization was carried out at 65 ° C. After 10 minutes from the start of polymerization, 600 g of butadiene was continuously added over 60 minutes. About 30 minutes after the addition of the monomer was completed, the polymerization conversion rate reached 100%, and about 2 cc of methanol was added to stop the reaction. To this solution, 10 g of 2,6-ditertiary butylphenol (BHT) was added, solidified and recovered by a steam stripping method, and vacuum dried to obtain a copolymer rubber. Similarly, the copolymer rubbers used in Examples 2 to 4 were manufactured.
【００１４】この共重合ゴム120gを密閉型混練機に入
れ、素練りを140 ℃で１分間行い、日本シリカ製ニプシ
ルAQを30g 投入して1.5 分間混練した。ついで、シリカ
（日本シリカ製ニプシルAQ) と亜鉛華、ステアリン酸等
を表１に示す量で入れ、３分間混練した。密閉型混練機
から配合物を取り出し、70℃のオープンミルでシート状
にして一部を取り出してトルエンに浸漬した。このゴム
組成物をさらにオープンミルで混練して加硫促進剤と硫
黄を添加してシートを作製し、160 ℃で40分間加硫して
測定試料を作製した。120 g of this copolymer rubber was placed in a closed type kneader, and mastication was carried out at 140 ° C. for 1 minute, and 30 g of NIPSIL AQ manufactured by Nippon Silica was added and kneaded for 1.5 minutes. Then, silica (Nipsil AQ manufactured by Nippon Silica), zinc white, stearic acid and the like were added in the amounts shown in Table 1 and kneaded for 3 minutes. The mixture was taken out from the closed type kneader, formed into a sheet by an open mill at 70 ° C., a part of the sheet was taken out and immersed in toluene. This rubber composition was further kneaded with an open mill to add a vulcanization accelerator and sulfur to prepare a sheet, which was then vulcanized at 160 ° C. for 40 minutes to prepare a measurement sample.
【００１５】比較例４として、実施例３と同じ共重合ゴ
ムと、表１の配合処方中の硫黄以外の全配合剤とを上記
と同じ条件で混合してゴム組成物を得た。この組成物に
硫黄をオープンミルを用いて添加した。上記同様にして
評価用の加硫物を作成した。表 １ 共重合ゴム 100重量部 ニプシルAQ 50重量部 亜鉛華 3重量部 ステアリン酸 1.5重量部 ジエチレングリコール 2重量部 ノクセラーCZ 2重量部 硫黄 325 2重量部 アロマオイル 5重量部 得られた測定試料（実施例１〜３、比較例１〜４）につ
き、下記により耐摩耗性および転がり抵抗を測定して評
価した。この結果を表２に示す。As Comparative Example 4, a rubber composition was obtained by mixing the same copolymer rubber as in Example 3 and all the compounding ingredients other than sulfur in the compounding recipe of Table 1 under the same conditions as above. Sulfur was added to this composition using an open mill. A vulcanizate for evaluation was prepared in the same manner as above. Table 1 Copolymer rubber 100 parts by weight Nipsyl AQ 50 parts by weight Zinc white 3 parts by weight Stearic acid 1.5 parts by weight Diethylene glycol 2 parts by weight Nocceller CZ 2 parts by weight Sulfur 325 2 parts by weight Aroma oil 5 parts by weight Obtained measurement samples (Examples 1 to 3 and Comparative Examples 1 to 4), the wear resistance and rolling resistance were measured and evaluated as follows. The results are shown in Table 2.
【００１６】耐摩耗性の測定方法：ピコ摩耗試験機を用
いて常法により測定。比較例３を100 とする指数評価。
数値の大きい方が耐摩耗性に優れている。転がり抵抗の測定方法 ：リュプケ式反発弾性試験機を用
い、60℃で測定。比較例３を100 とする指数評価。数値
の大きい方が転がり抵抗が小さく、優れている。 Abrasion resistance measuring method : Measured by a conventional method using a pico abrasion tester. Index evaluation with Comparative Example 3 as 100.
The larger the number, the better the abrasion resistance. Rolling resistance measurement method : Measured at 60 ° C using a Lupke type impact resilience tester. Index evaluation with Comparative Example 3 as 100. The higher the value, the lower the rolling resistance and the better.
【００１７】 表２から明らかなように、イソプレン含有量が少ない場
合には耐摩耗性および転がり抵抗において優れているが
（実施例１〜４）、イソプレン含有量が多くなると耐摩
耗性が著しく低下してしまう（比較例１、２、４）。ま
た、イソプレンのない比較例３ではゲル量が少ないが、
イソプレンが僅かに入った実施例１ではゲル量が増加し
ており、耐摩耗性も向上している。従来の混合方法で調
製した比較例４のゴム組成物ではトルエン不溶分が本発
明範囲外となり、耐摩耗性は改善される。[0017] As is clear from Table 2, when the isoprene content is low, the wear resistance and rolling resistance are excellent (Examples 1 to 4), but when the isoprene content is high, the wear resistance is significantly reduced. (Comparative Examples 1, 2, 4). In Comparative Example 3 without isoprene, the amount of gel was small,
In Example 1 containing a small amount of isoprene, the amount of gel increased and the wear resistance also improved. In the rubber composition of Comparative Example 4 prepared by the conventional mixing method, the toluene insoluble content is out of the range of the present invention, and the wear resistance is improved.
【００１８】[0018]
【発明の効果】以上説明したように本発明のゴム組成物
は、前記の一般式で表わされる共役ジエンモノマーを
０．５〜３０重量％、芳香族モノビニル化合物を５〜６
０重量％、およびブタジエンを２０〜９４．９重量％を
共重合させて得られる共重合ゴム１００重量部に対し、
シリカ２０〜１５０重量部を配合してなり、トルエン不
溶分が２５〜８０重量％であるために、耐摩耗性および
転がり抵抗の両方を向上させることが可能となる。As described above, the rubber composition of the present invention contains 0.5 to 30% by weight of the conjugated diene monomer represented by the above general formula and 5 to 6 of the aromatic monovinyl compound.
0% by weight and 100 to 100 parts by weight of a copolymer rubber obtained by copolymerizing 20 to 94.9% by weight of butadiene,
Since 20 to 150 parts by weight of silica is blended and the toluene insoluble content is 25 to 80% by weight, both abrasion resistance and rolling resistance can be improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 日座 操 神奈川県平塚市追分２番１号 横浜ゴム株 式会社平塚製造所内 (72)発明者 中村 昌生 神奈川県川崎市川崎区夜光１−２−１ 日 本ゼオン株式会社内 (72)発明者 高岸 幸雄 神奈川県川崎市川崎区夜光１−２−１ 日 本ゼオン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Misao Misato 2-1, Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Plant (72) Inventor Masao Nakamura 1-2-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa 1 Nihon Zeon Co., Ltd. (72) Inventor Yukio Takagishi 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd.
Claims (2)
2 （式中Ｒ1 は水素又は低級アルキル基、Ｒ2 は低級ア
ルキル基を表す）で示されるモノマー０．５〜３０重量
％、芳香族ビニルモノマー５〜６０重量％及びブタジエ
ン２０〜９４．５重量％を共重合させて得られる共重合
ゴム１００重量部にシリカ２０〜１５０重量部を配合し
てなり、トルエン不溶分が２５〜８０重量％であること
を特徴とするゴム組成物。1. The general formula CH 2 = CR 1 -CR 2 = CH.
0.5 to 30% by weight of a monomer represented by 2 (wherein R 1 represents hydrogen or a lower alkyl group, R 2 represents a lower alkyl group), 5 to 60% by weight of an aromatic vinyl monomer, and 20 to 94.5 of butadiene. A rubber composition comprising 100 parts by weight of a copolymer rubber obtained by copolymerizing 20% by weight of silica and 20 to 150 parts by weight of silica, and having a toluene insoluble content of 25 to 80% by weight.
０〜１５０重量部とを混合した後にシリカ以外の配合剤
を添加して混合することを特徴とするゴム組成物の製造
方法。2. 100 parts by weight of the copolymer rubber and silica 2
A method for producing a rubber composition, which comprises mixing 0 to 150 parts by weight and then adding and mixing a compounding agent other than silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26919693A JP3341788B2 (en) | 1993-10-27 | 1993-10-27 | Rubber composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26919693A JP3341788B2 (en) | 1993-10-27 | 1993-10-27 | Rubber composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07118449A true JPH07118449A (en) | 1995-05-09 |
| JP3341788B2 JP3341788B2 (en) | 2002-11-05 |
Family
ID=17469019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26919693A Expired - Lifetime JP3341788B2 (en) | 1993-10-27 | 1993-10-27 | Rubber composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3341788B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004067625A1 (en) * | 2003-01-31 | 2004-08-12 | Tokuyama Corporation | Diene rubber composition and process for producing the same |
| EP1679342A1 (en) * | 2003-10-31 | 2006-07-12 | Zeon Corporation | Silica-containing conjugated diene based rubber composition and formed article |
| JP2007204550A (en) * | 2006-01-31 | 2007-08-16 | Bridgestone Corp | Modified natural rubber, and rubber composition and tire obtained using the same |
| WO2015083746A1 (en) * | 2013-12-03 | 2015-06-11 | バンドー化学株式会社 | Conveyor belt |
-
1993
- 1993-10-27 JP JP26919693A patent/JP3341788B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004067625A1 (en) * | 2003-01-31 | 2004-08-12 | Tokuyama Corporation | Diene rubber composition and process for producing the same |
| JPWO2004067625A1 (en) * | 2003-01-31 | 2006-05-18 | 株式会社トクヤマ | Diene rubber composition and method for producing the same |
| US7619028B2 (en) | 2003-01-31 | 2009-11-17 | Tokuyama Corporation | Diene rubber composition and process for producing the same |
| JP4583308B2 (en) * | 2003-01-31 | 2010-11-17 | 株式会社トクヤマ | Diene rubber composition and method for producing the same |
| EP1679342A1 (en) * | 2003-10-31 | 2006-07-12 | Zeon Corporation | Silica-containing conjugated diene based rubber composition and formed article |
| EP1679342A4 (en) * | 2003-10-31 | 2009-08-26 | Zeon Corp | Silica-containing conjugated diene based rubber composition and formed article |
| JP2007204550A (en) * | 2006-01-31 | 2007-08-16 | Bridgestone Corp | Modified natural rubber, and rubber composition and tire obtained using the same |
| WO2015083746A1 (en) * | 2013-12-03 | 2015-06-11 | バンドー化学株式会社 | Conveyor belt |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3341788B2 (en) | 2002-11-05 |
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