JP2003041064A - Rubber composition for hose - Google Patents
Rubber composition for hoseInfo
- Publication number
- JP2003041064A JP2003041064A JP2001229095A JP2001229095A JP2003041064A JP 2003041064 A JP2003041064 A JP 2003041064A JP 2001229095 A JP2001229095 A JP 2001229095A JP 2001229095 A JP2001229095 A JP 2001229095A JP 2003041064 A JP2003041064 A JP 2003041064A
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- rubber
- rubber composition
- spb
- hose
- weight
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- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、押出し加工性や耐久性
に優れるゴムホースの内管に好適なゴム組成物に関する
ものであり、ホースのカバーゴムや伝導ベルト、運搬用
ベルト、ゴムロール、ゴムクローラ、ゴムブシュ、パッ
キン、防振ゴム等の工業用品及び紳士靴、婦人靴、スポ
ーツシューズ等の履物にも用いる事ができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition suitable for an inner tube of a rubber hose which is excellent in extrusion processability and durability. It can also be used for industrial products such as rubber bushes, packing, anti-vibration rubber, and footwear such as men's shoes, women's shoes, and sports shoes.
【０００２】[0002]
【従来の技術】一般にゴムホースは、補強層を鋏んでカ
バーゴムと内管とに分けられ、通常のホースは内管を押
出し、その上に繊維またはスチールワイヤーを巻いて補
し、さらにその上にカバーゴムを付けてから加硫して製
造される。従って、内管は未加硫物では押出し加工性
（粘度・スウェル）、加硫物に於いては移動する物体・
媒体に対する抵抗性（硬度・高強度・耐溶媒性）や耐屈
曲性・耐振動性等が要求される。そこで、カーボンブラ
ックなどの無機補強剤や短繊維による改良（特開平９−
１１８７８９）等が試みられている。配合物のスウェル
を小さくし硬度や強度を高くするため、カーボンブラッ
ク等の無機補強剤を増量すると、配合物の粘度が上昇し
たり、耐屈曲性や反撥弾性（耐振動性）を低下させてし
まう欠点があり、短繊維による方法は分散性や異方性が
あるため作業が煩雑になる等の問題がある。2. Description of the Related Art Generally, a rubber hose is divided into a cover rubber and an inner tube by scissoring a reinforcing layer, and a normal hose is formed by extruding an inner tube and winding a fiber or steel wire on it to supplement it. It is manufactured by attaching a cover rubber and then vulcanizing. Therefore, the inner pipe is extrudable (viscosity, swell) in the unvulcanized product and the moving object in the vulcanized product.
Resistance to media (hardness, high strength, solvent resistance), bending resistance, vibration resistance, etc. are required. Therefore, improvement using an inorganic reinforcing agent such as carbon black or short fibers (Japanese Patent Laid-Open No. 9-
118789) has been tried. Increasing the amount of an inorganic reinforcing agent such as carbon black in order to reduce the swell of the composition and increase the hardness and strength may increase the viscosity of the composition and decrease the flex resistance and impact resilience (vibration resistance). However, the method using short fibers has dispersibility and anisotropy, which causes a problem that the work becomes complicated.
【０００３】[0003]
【発明が解決しようとする課題】上記の従来技術の問題
点を解決し、押出し加工性や耐久性に優れるゴムホース
の内管に好適なゴム組成物を提供する。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The above-mentioned problems of the prior art are solved, and a rubber composition suitable for an inner tube of a rubber hose which is excellent in extrusion processability and durability is provided.
【０００４】[0004]
【課題を解決するための手段】本発明は、加硫可能なゴ
ム１００重量部に対して、（ａ）還元粘度が０．１〜４
のシンジオタクチック−１，２−ポリブタジエン（ＳＰ
Ｂ）が１〜３０重量部と、（ｂ） 無機補強剤が３０〜
７０重量部とが配合されたゴム組成物であって、ＪＩＳ
Ｋ６２５３ のタイプＡで測定した硬度が５５〜８０で
あることを特徴とするホース用ゴム組成物に関する。According to the present invention, (a) the reduced viscosity is 0.1 to 4 relative to 100 parts by weight of vulcanizable rubber.
Syndiotactic-1,2-polybutadiene (SP
B) is 1 to 30 parts by weight, and (b) the inorganic reinforcing agent is 30 to 30 parts by weight.
A rubber composition containing 70 parts by weight of JIS
A rubber composition for a hose having a hardness of 55 to 80 measured by type A of K6253.
【０００５】また、本発明は、（ａ）のＳＰＢの１３Ｃ
−ＮＭＲによる１，２結合含量が７０％以上で且つ１．
２結合中のシンジオタクシティーが９０％以上あること
を特徴とする上記のホース用ゴム組成物に関する。Further, the present invention relates to 13C of SPB in (a).
-1,2 bond content by NMR is 70% or more and 1.
The rubber composition for a hose as described above, wherein the syndiotacticity in the two bonds is 90% or more.
【０００６】また、本発明は、（ａ）のＳＰＢの融点が
１１０℃以上であることを特徴とする上記のホース用ゴ
ム組成物に関する。The present invention also relates to the above rubber composition for a hose, wherein the SPB of (a) has a melting point of 110 ° C. or higher.
【０００７】また、本発明は、（ｂ）の無機補強剤がカ
ーボンブラックであることを特徴とする上記のホース用
ゴム組成物に関する。The present invention also relates to the above rubber composition for hoses, wherein the inorganic reinforcing agent (b) is carbon black.
【０００８】[0008]
【発明の実施の形態】本発明の加硫可能なゴムとして
は、エチレンプロピレンジエンゴム（ＥＰＤＭ）、ニト
リルゴム（ＮＢＲ）、ブチルゴム（ＩＩＲ）、クロロプ
レンゴム（ＣＲ）、天然ゴム（ＮＲ）、ポリイソプレ
ン、ハイシスポリブタジエンゴム、ローシスポリブタジ
エンゴム（ＢＲ）、スチレン−ブタジエンゴム、ブチル
ゴム、塩素化ブチルゴム、臭素化ブチルゴム、アクリロ
ニトリル−ブタジエンゴム等を挙げることができる。こ
れらの中でも天然ゴムが好ましい。又、これらゴムの誘
導体、例えば錫化合物で変性されたポリブタジエンゴム
やこれらのゴムをエポキシ変性したものや、シラン変
性、或いはマレイン化したものも用いられる。これらの
ゴムは単独でも、二種以上組合せて用いても良い。BEST MODE FOR CARRYING OUT THE INVENTION As the vulcanizable rubber of the present invention, ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), natural rubber (NR), poly Examples thereof include isoprene, high cis polybutadiene rubber, low cis polybutadiene rubber (BR), styrene-butadiene rubber, butyl rubber, chlorinated butyl rubber, brominated butyl rubber and acrylonitrile-butadiene rubber. Of these, natural rubber is preferable. Derivatives of these rubbers, for example, polybutadiene rubber modified with a tin compound, epoxy-modified rubbers, silane-modified rubbers, or maleated rubbers may also be used. These rubbers may be used alone or in combination of two or more.
【０００９】本発明の（ａ）還元粘度が０．１〜４のシ
ンジオタクチック−１，２−ポリブタジエン（ＳＰＢ）
は、融点が１１０℃以上のものが好ましい。より好まし
くは１１０〜２００℃、特に好ましくは１３０〜１６０
℃のものを用いることができる。また本発明のＳＰＢ
は、１３Ｃ−ＮＭＲによる１，２結合含量が７０％以上
で且つ１．２結合中のシンジオタクシティーが９０％以
上であることが好ましい。(A) Syndiotactic-1,2-polybutadiene (SPB) having a reduced viscosity of 0.1 to 4 of the present invention
Preferably has a melting point of 110 ° C. or higher. More preferably 110 to 200 ° C., particularly preferably 130 to 160.
The thing of ℃ can be used. The SPB of the present invention
Preferably has a 1,2-bond content of 70% or more by 13 C-NMR and a syndiotacticity of 1.2 bonds of 90% or more.
【００１０】本発明のＳＰＢは、例えば、特開平９〜２
０８１１号公報に記載されている懸濁重合法によって製
造できる。すなわち、ブタジエンの存在下、コバルト化
合物、第Ｉ〜ＩＩＩ族の有機金属化合物または水素化金
属化合物、並びにケトン、カルボン酸エステル、ニトリ
ル、スルホキシド、アミド及び燐酸エステルからなる群
から選ばれた化合物を接触させて得られた熟成液（Ａ成
分）、並びに、二硫化炭素、イソチオシアン酸フェニル
及びキサントゲン酸化合物からなる群から選ばれた化合
物（Ｂ成分）からなる触媒を用いて製造できる。融点
は、ケトン、カルボン酸エステル、ニトリル、スルホキ
シド、アミド及び燐酸エステルからなる群から選ばれた
化合物によって調節することができる。また、可溶性コ
バルト−有機アルミニウム化合物−二硫化炭素−融点調
節剤からなる触媒系からなる溶液重合法を用いてもよ
い。The SPB of the present invention is disclosed, for example, in JP-A-9-2.
It can be produced by the suspension polymerization method described in Japanese Patent Publication No. 0811. That is, in the presence of butadiene, a cobalt compound, an organometallic compound of Group I to III or a metal hydride compound, and a compound selected from the group consisting of a ketone, a carboxylic acid ester, a nitrile, a sulfoxide, an amide and a phosphoric acid ester are contacted. It can be produced by using the aged liquid (component A) thus obtained and a catalyst comprising a compound (component B) selected from the group consisting of carbon disulfide, phenyl isothiocyanate and a xanthogenic acid compound. The melting point can be adjusted by a compound selected from the group consisting of a ketone, a carboxylic acid ester, a nitrile, a sulfoxide, an amide and a phosphoric acid ester. Alternatively, a solution polymerization method comprising a catalyst system composed of soluble cobalt-organoaluminum compound-carbon disulfide-melting point modifier may be used.
【００１１】本発明の（ｂ） 無機補強剤としては、各
種のカーボンブラック、ホワイトカーボン、活性化炭酸
カルシウム、超微粒子珪酸マグネシウム等などが挙げら
れる。特に好ましくは、粒子径が９０ｎｍ以下、ジブチ
ルフタレート（ＤＢＰ）吸油量が７０ｍｌ／１００ｇ以
上のカーボンブラックで、例えば、ＦＥＦ，ＦＦ，ＧＰ
Ｆ，ＳＡＦ，ＩＳＡＦ，ＳＲＦ，ＨＡＦ等が挙げられ
る。Examples of the inorganic reinforcing agent (b) of the present invention include various kinds of carbon black, white carbon, activated calcium carbonate, ultrafine magnesium silicate and the like. Particularly preferred is carbon black having a particle diameter of 90 nm or less and a dibutyl phthalate (DBP) oil absorption of 70 ml / 100 g or more, such as FEF, FF, GP.
F, SAF, ISAF, SRF, HAF and the like can be mentioned.
【００１２】本発明のゴム組成物の配合割合は、加硫可
能なゴム１００重量部に対して、（ａ）還元粘度が０．
１〜４のシンジオタクチック−１，２−ポリブタジエン
（ＳＰＢ）が１〜３０重量部、好ましくは、３〜２５重
量部と、（ｂ） 無機補強剤が３０〜７０重量部、好ま
しくは、３５〜６５重量部である。The compounding ratio of the rubber composition of the present invention is such that (a) the reduced viscosity is 0.
1 to 4 parts by weight of syndiotactic-1,2-polybutadiene (SPB), preferably 3 to 25 parts by weight, and (b) 30 to 70 parts by weight of an inorganic reinforcing agent, preferably 35 ~ 65 parts by weight.
【００１３】本発明のゴム組成物は、前記各成分を通常
行われているバンバリー、オープンロール、ニーダー、
二軸混練り機などを用いて混練りすることで得られる。The rubber composition of the present invention comprises a Banbury, an open roll, a kneader, and
It can be obtained by kneading using a biaxial kneader or the like.
【００１４】本発明のゴム組成物には、必要に応じて、
加硫剤、加硫助剤、老化防止剤、充填剤、プロセスオイ
ル、亜鉛華、ステアリン酸など、通常ゴム業界で用いら
れる配合剤を混練してもよい。The rubber composition of the present invention contains, if necessary,
Vulcanizing agents, vulcanization aids, antioxidants, fillers, process oils, zinc white, stearic acid, and other compounding agents usually used in the rubber industry may be kneaded.
【００１５】加硫剤としては、公知の加硫剤、例えば硫
黄、有機過酸化物、樹脂加硫剤、酸化マグネシウムなど
の金属酸化物などが用いられる。As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide are used.
【００１６】加硫助剤としては、公知の加硫助剤、例え
ばアルデヒド類、アンモニア類、アミン類、グアニジン
類、チオウレア類、チアゾール類、チウラム類、ジチオ
カーバメイト類、キサンテート類などが用いられる。As the vulcanization aid, known vulcanization aids such as aldehydes, ammonias, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates and xanthates can be used.
【００１７】老化防止剤としては、アミン・ケトン系、
イミダゾール系、アミン系、フェノール系、硫黄系及び
燐系などが挙げられる。As the anti-aging agent, amine / ketone type,
Examples thereof include imidazole type, amine type, phenol type, sulfur type and phosphorus type.
【００１８】充填剤としては、炭酸カルシウム、塩基性
炭酸マグネシウム、クレー、リサージュ、珪藻土等の無
機充填剤、再生ゴム、粉末ゴム等の有機充填剤が挙げら
れる。Examples of the filler include inorganic fillers such as calcium carbonate, basic magnesium carbonate, clay, Lissajous and diatomaceous earth, and organic fillers such as recycled rubber and powder rubber.
【００１９】プロセスオイルは、アロマティック系、ナ
フテン系、パラフィン系のいずれを用いてもよい。The process oil may be any of aromatic type, naphthene type and paraffin type.
【００２０】また、本発明のゴム組成物は、ＪＩＳ Ｋ
６２５３ のタイプＡで測定した硬度が５５〜８０であ
り、５５〜７０であることが特に好ましい。The rubber composition of the present invention has a JIS K
The hardness of 6253 measured by type A is 55 to 80, and particularly preferably 55 to 70.
【００２１】[0021]
【実施例】ＳＰＢの１，２結合含量及びシンジオタクシ
ティーは、１３Ｃ−ＮＭＲによって測定した。EXAMPLES The 1,2-bond content and syndiotacticity of SPB were measured by 13 C-NMR.
【００２２】還元粘度は、ＳＰＢ０．２ｇをｏ−ジクロ
ロベンゼン１００ｃｃに溶解し、１３５℃の温度でウベ
ローデ粘度計にて測定した。The reduced viscosity was measured by dissolving 0.2 g of SPB in 100 cc of o-dichlorobenzene and measuring it with a Ubbelohde viscometer at a temperature of 135 ° C.
【００２３】ホース用ゴム組成物の特性は次のように評
価した。The characteristics of the rubber composition for hoses were evaluated as follows.
【００２４】配合物粘度指数及びダイスウェル指数は、
ＭＰＴ（モンサント社製加工性試験機）により温度１０
０℃、ダイ（Ｄ＝２ｍｍ，Ｌ／Ｄ＝１６）、１５０／Ｓ
ｅｃの条件で押出した時の粘度と押出し物のダイスウェ
ルを測定し、比較例１を１００として指数表示した指数
が小さいほど良好である。The formulation viscosity index and die swell index are
Temperature 10 by MPT (Monsanto workability tester)
0 ℃, Die (D = 2mm, L / D = 16), 150 / S
The viscosity when extruded under the condition of ec and the die swell of the extruded product were measured, and the smaller the index shown as an index with Comparative Example 1 as 100, the better.
【００２５】硬度は、ＪＩＳ−Ｋ−６２５３に規定され
ている測定法に従ってデュロメーター式で測定した。The hardness was measured by the durometer method according to the measuring method specified in JIS-K-6253.
【００２６】反撥弾性指数は、ＪＩＳ−Ｋ−６２５５に
規定されている測定法に従って測定し、比較例１を１０
０として指数表示した。指数が大きいほど良好である。The impact resilience index was measured according to the measuring method specified in JIS-K-6255, and Comparative Example 1 was 10
It was displayed as an index of 0. The larger the index, the better.
【００２７】耐屈曲性指数：ＪＩＳ−Ｋ−６２６０に従
い、２ｍｍの傷が１５ｍｍの長さに達した回数を測定
し、比較例１を１００として指数表示した。指数が大き
いほど良好である。Flexing resistance index: According to JIS-K-6260, the number of times a flaw of 2 mm reached a length of 15 mm was measured, and Comparative Example 1 was set as 100 and indicated as an index. The larger the index, the better.
【００２８】（参考例１）ＳＰＢ−１の製造
（熟成液の調製） 窒素置換した400mL オートクレーブ
熟成槽にブタジエン 150g( 2.8モル）を注入する。コバ
ルトオクトエートを 0.6ミリモルおよびトリエチルアル
ミニウム 1.8ミリモルを添加して 室温で 5時間攪拌し
た。（重合）窒素置換した 1.5L のオートクレーブにイ
オン交換水 600mL、ポリビニルアルコール 2g 、塩化メ
チレン 120mL及びアセトン0.４７７モルを添加して、攪
拌しながら10℃に温度設定した。前記で調製した熟成液
をオートクレーブ中に添加して10℃で10分間分散させた
後、二硫化炭素 0.8ミリモルを添加して重合を開始し
た。30℃で60分間重合した。重合後、未反応モノマーを
開放し、老化防止剤を添加し、ポリビニルアルコールを
水洗浄し、ペーパーフィルターで濾過後、乾燥してＳＰ
Ｂを得た。ＳＰＢの収量は１３０ｇであり、ＳＰＢの融
点は1５０℃であった。還元粘度は、１．２であった。
１３Ｃ−ＮＭＲによる１，２結合含量は、８５％、１．
２結合中のシンジオタクシティーは１００％であった。Reference Example 1 Production of SPB-1 (Preparation of Aging Solution) 150 g (2.8 mol) of butadiene was injected into a 400 mL autoclave aging tank whose atmosphere was replaced with nitrogen. 0.6 mmol of cobalt octoate and 1.8 mmol of triethylaluminum were added, and the mixture was stirred at room temperature for 5 hours. (Polymerization) 600 mL of ion-exchanged water, 2 g of polyvinyl alcohol, 120 mL of methylene chloride and 0.477 mol of acetone were added to a 1.5 L autoclave purged with nitrogen, and the temperature was set to 10 ° C. with stirring. The aged liquid prepared above was added to an autoclave and dispersed at 10 ° C. for 10 minutes, and then 0.8 mmol of carbon disulfide was added to initiate polymerization. Polymerization was carried out at 30 ° C for 60 minutes. After the polymerization, unreacted monomers are released, an antioxidant is added, polyvinyl alcohol is washed with water, filtered with a paper filter, and dried to make SP.
B was obtained. The yield of SPB was 130 g and the melting point of SPB was 150 ° C. The reduced viscosity was 1.2.
The content of 1,2 bonds by 13 C-NMR is 85%.
The syndiotacticity in the two bonds was 100%.
【００２９】（参考例２）アセトンを０．６モル添加し
た以外は、参考例２と同様にした。ＳＰＢの収量は１２
０ｇ であり、ＳＰＢの融点は1３０℃であった。還元粘
度は、１．３であった。１３Ｃ−ＮＭＲによる１，２結
合含量は、８２％、１．２結合中のシンジオタクシティ
ーは１００％であった。Reference Example 2 The procedure of Reference Example 2 was repeated except that 0.6 mol of acetone was added. SPB yield is 12
It was 0 g, and the melting point of SPB was 130 ° C. The reduced viscosity was 1.3. The content of 1,2 bonds by 13 C-NMR was 82%, and syndiotacticity in 1.2 bonds was 100%.
【００３０】（実施例１〜５）（比較例１〜２）
参考例１及び２のＳＰＢを用い、表１に示す配合処方に
従って、１．７Ｌの試験用バンバリーミキサーを使用し
天然ゴムとカーボンブラック等を混練してから加硫剤を
オープンロールで混合した。(Examples 1 to 5) (Comparative Examples 1 to 2) Using the SPBs of Reference Examples 1 and 2, according to the formulation shown in Table 1, using a 1.7 L test Banbury mixer, natural rubber and carbon After kneading black and the like, the vulcanizing agent was mixed with an open roll.
【００３１】次いで、温度１５０℃で３０分間プレス加
硫し、得られた加硫試験片により物性を評価した。Next, press vulcanization was carried out at a temperature of 150 ° C. for 30 minutes, and the vulcanized test pieces obtained were used to evaluate the physical properties.
【００３２】[0032]
【表１】 [Table 1]
【００３３】ホース用組成物は、ダイスウェルや耐屈曲
性等が改善され、押出し加工性と耐久性が高度にバラン
スしている。The composition for hoses has improved die swell and bending resistance, and has a highly balanced extrudability and durability.
【００３４】比較例のＳＰＢを含まない組成物において
は、ダイスウェルや反撥弾性等が劣っていた。The SPB-free composition of Comparative Example was inferior in die swell and impact resilience.
【００３５】[0035]
【発明の効果】本発明において、押出し加工性や耐久性
に優れるゴムホースの内管に好適なゴム組成物を提供さ
れる。INDUSTRIAL APPLICABILITY The present invention provides a rubber composition suitable for an inner tube of a rubber hose which is excellent in extrusion processability and durability.
Claims (4)
（ａ）還元粘度が０．１〜４のシンジオタクチック−
１，２−ポリブタジエン（ＳＰＢ）が１〜３０重量部
と、（ｂ） 無機補強剤が３０〜７０重量部とが配合さ
れたゴム組成物であって、ＪＩＳ Ｋ６２５３ のタイプ
Ａで測定した硬度が５５〜８０であることを特徴とする
ホース用ゴム組成物。1. To 100 parts by weight of vulcanizable rubber,
(A) Syndiotactic with a reduced viscosity of 0.1 to 4
A rubber composition containing 1 to 30 parts by weight of 1,2-polybutadiene (SPB) and 30 to 70 parts by weight of (b) an inorganic reinforcing agent, and having a hardness measured by JIS K6253 type A. 55-80, The rubber composition for hoses characterized by the above-mentioned.
１，２結合含量が７０％以上で且つ１．２結合中のシン
ジオタクシティーが９０％以上であることを特徴とする
請求項１に記載のホース用ゴム組成物。2. The 1,2-bond content of (a) SPB by 13 C-NMR is 70% or more, and the syndiotacticity in 1.2 bond is 90% or more. The rubber composition for a hose according to.
ることを特徴とする請求項１〜２に記載のホース用ゴム
組成物。3. The rubber composition for a hose according to claim 1, wherein the melting point of SPB (a) is 110 ° C. or higher.
あることを特徴とする請求項１〜３に記載のホース用ゴ
ム組成物。4. The rubber composition for a hose according to claim 1, wherein the inorganic reinforcing agent (b) is carbon black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001229095A JP4496683B2 (en) | 2001-07-30 | 2001-07-30 | Rubber composition for hose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001229095A JP4496683B2 (en) | 2001-07-30 | 2001-07-30 | Rubber composition for hose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003041064A true JP2003041064A (en) | 2003-02-13 |
| JP4496683B2 JP4496683B2 (en) | 2010-07-07 |
Family
ID=19061493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001229095A Expired - Fee Related JP4496683B2 (en) | 2001-07-30 | 2001-07-30 | Rubber composition for hose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4496683B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006054808A1 (en) | 2004-12-20 | 2006-05-26 | Ube Industries, Ltd. | Process for production of polybutadiene rubber and rubber compositions |
| US7700691B2 (en) | 2003-12-12 | 2010-04-20 | Ube Industries, Ltd. | Vinyl-cis-polybutadiene rubber and butadiene rubber composition using the same |
| US7884154B2 (en) | 2004-12-21 | 2011-02-08 | Ube Industries, Ltd. | Rubber composition |
| JP2012182999A (en) * | 2011-03-03 | 2012-09-27 | Nissin Kogyo Co Ltd | Rubber composition for teat cup liner and teat cup liner |
| JP2017122171A (en) * | 2016-01-06 | 2017-07-13 | 住友ゴム工業株式会社 | Rubber composition for crawler and rubber crawler |
| CN109206680A (en) * | 2018-09-10 | 2019-01-15 | 河北卫星化工股份有限公司 | A kind of method of reinforcement natural rubber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105139A (en) * | 2001-07-24 | 2003-04-09 | Ube Ind Ltd | Rubber composition for belt |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5529535A (en) * | 1978-08-23 | 1980-03-01 | Ube Ind Ltd | Preparation of reinforced rubber composition |
| JPS5878754A (en) * | 1981-11-06 | 1983-05-12 | 株式会社ブリヂストン | Hose |
| JPH0463847A (en) * | 1990-10-29 | 1992-02-28 | Ube Ind Ltd | Polybutadiene rubber composition for tire side wall |
| JP3415217B2 (en) * | 1992-09-29 | 2003-06-09 | 株式会社ブリヂストン | Pneumatic tires for heavy vehicles |
| JP3369278B2 (en) * | 1993-12-27 | 2003-01-20 | 株式会社ブリヂストン | Rubber composition |
| JPH0987425A (en) * | 1995-09-27 | 1997-03-31 | Sumitomo Chem Co Ltd | Rubber composition |
| JPH11349732A (en) * | 1998-06-04 | 1999-12-21 | Ube Ind Ltd | Rubber composition for tire |
-
2001
- 2001-07-30 JP JP2001229095A patent/JP4496683B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105139A (en) * | 2001-07-24 | 2003-04-09 | Ube Ind Ltd | Rubber composition for belt |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700691B2 (en) | 2003-12-12 | 2010-04-20 | Ube Industries, Ltd. | Vinyl-cis-polybutadiene rubber and butadiene rubber composition using the same |
| US7863385B2 (en) | 2003-12-12 | 2011-01-04 | Ube Industries, Ltd. | Vinyl-cis-polybutadiene rubber and butadiene rubber composition using the same |
| WO2006054808A1 (en) | 2004-12-20 | 2006-05-26 | Ube Industries, Ltd. | Process for production of polybutadiene rubber and rubber compositions |
| EP1842875A4 (en) * | 2004-12-20 | 2009-09-16 | Ube Industries | Process for production of polybutadiene rubber and rubber compositions |
| KR100963998B1 (en) | 2004-12-20 | 2010-06-15 | 우베 고산 가부시키가이샤 | Process for production of polybutadiene rubber and rubber compositions |
| US7884155B2 (en) | 2004-12-20 | 2011-02-08 | Ube Industries, Ltd. | Process for producing polybutadiene rubber and rubber composition |
| US7884154B2 (en) | 2004-12-21 | 2011-02-08 | Ube Industries, Ltd. | Rubber composition |
| JP2012182999A (en) * | 2011-03-03 | 2012-09-27 | Nissin Kogyo Co Ltd | Rubber composition for teat cup liner and teat cup liner |
| JP2017122171A (en) * | 2016-01-06 | 2017-07-13 | 住友ゴム工業株式会社 | Rubber composition for crawler and rubber crawler |
| CN109206680A (en) * | 2018-09-10 | 2019-01-15 | 河北卫星化工股份有限公司 | A kind of method of reinforcement natural rubber |
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| Publication number | Publication date |
|---|---|
| JP4496683B2 (en) | 2010-07-07 |
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