JP2003213040A - Softener for rubber, rubber composition using the same, and oil-extended rubber - Google Patents
Softener for rubber, rubber composition using the same, and oil-extended rubberInfo
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- JP2003213040A JP2003213040A JP2002015457A JP2002015457A JP2003213040A JP 2003213040 A JP2003213040 A JP 2003213040A JP 2002015457 A JP2002015457 A JP 2002015457A JP 2002015457 A JP2002015457 A JP 2002015457A JP 2003213040 A JP2003213040 A JP 2003213040A
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- rubber
- oil
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- asphalt
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ゴム用軟化剤に関
し、詳しくは、特定のアスファルトを含有した軟化剤、
それを用いたゴム組成物及び油展ゴムに関する。TECHNICAL FIELD The present invention relates to a softening agent for rubber, and more specifically, a softening agent containing a specific asphalt,
A rubber composition and an oil-extended rubber using the same.
【０００２】[0002]
【従来の技術】従来から、ゴム組成物の軟化剤及び合成
ゴムの伸展油としては、高ロス特性付与性やゴムとの親
和性の観点から、高芳香族系油（アロマティックオイ
ル）がタイヤ用ゴム組成物やその他の領域で好んで用い
られてきた。近年は、石油を原料として製造される高芳
香族系油を処理して得られる、いわゆるTreated Distil
led Aromatic Extracts （Ｔ−ＤＡＥ），Mild Extract
edSolvates （ＭＥＳ）などと称されるＰＣＡが３重量
％未満の高芳香族系油が使用され始めている。2. Description of the Related Art Conventionally, as a softening agent for a rubber composition and an extender oil for synthetic rubber, a highly aromatic oil (aromatic oil) is used as a tire from the viewpoints of imparting high loss characteristics and affinity with rubber. It has been favored for use in rubber compositions and other areas. In recent years, the so-called Treated Distil obtained by processing highly aromatic oils produced from petroleum
led Aromatic Extracts (T-DAE), Mild Extract
Highly aromatic oils containing less than 3% by weight of PCA, such as edSolvates (MES), have begun to be used.
【０００３】しかし、このような代替オイルは、従来の
高芳香族系油に比べて軟化点が低く、単純に置き換えた
場合、そのゴム組成物の粘弾性（Ｇ' ，ｔａｎδ）の温
度依存性が低温側にシフトする傾向がある。そのため、
耐ウェットスキッド性の指標となる０℃のｔａｎδ値が
低下し、タイヤの耐ウェットスキッド性が低下するとい
う不具合が生じるおそれがあった。また、パラフィン系
ストレートアスファルトを様々なプロセスオイルと混合
し使用するという試みもある（特開平１１−３０２４５
９号公報など）。しかし、パラフィン系ストレートアス
ファルトはゴム組成物のムーニー粘度を大きく上昇させ
るうえに、天然ゴムおよびジエン系合成ゴムとの相溶性
が低く、耐破壊特性の低下や低転がり抵抗の指標となる
６０℃のｔａｎδ値を増加させ得ることがわかった。However, such an alternative oil has a lower softening point than conventional highly aromatic oils, and when simply replaced, the temperature dependence of the viscoelasticity (G ', tan δ) of the rubber composition. Tend to shift to lower temperatures. for that reason,
The tan δ value at 0 ° C., which is an index of wet skid resistance, may decrease, which may cause a problem that the wet skid resistance of the tire decreases. There is also an attempt to mix and use paraffin-based straight asphalt with various process oils (JP-A-11-30245).
No. 9, etc.). However, the paraffinic straight asphalt greatly increases the Mooney viscosity of the rubber composition, and has low compatibility with natural rubber and diene synthetic rubber, and it has a low fracture resistance and an index of low rolling resistance of 60 ° C. It has been found that the tan δ value can be increased.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
状況下で、ＰＣＡ成分が問題となる高芳香族系油に代え
て、しかも、従来の高芳香族系油配合の場合に比べて
も、作業性を低下することなく、同等若しくはそれ以上
の優れた耐破壊特性と良好なロス特性（動的損失特性）
付与性を与えるゴム用軟化剤、それを用いたゴム組成物
及び油展ゴムを提供することを目的とするものである。Under the circumstances, the present invention replaces the highly aromatic oil in which the PCA component becomes a problem, and moreover, compared with the case of the conventional highly aromatic oil blending. Also has the same or better fracture resistance and good loss characteristics (dynamic loss characteristics) without reducing workability.
An object of the present invention is to provide a rubber softening agent that imparts impartability, a rubber composition using the same, and an oil-extended rubber.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記課題を
克服するため、アスファルテン分が５重量％以下である
アスファルトと特定のプロセスオイルとを適正比で混合
することが有効であることを見出し、本発明を完成する
に至った。すなわち、本発明は、天然ゴム及び合成ゴム
から選ばれた少なくとも一種のゴム成分と、アスファ
ルテン分が５重量％以下であるアスファルトとＡＳＴ
ＭＤ２１４０に準拠して測定されたナフテン環炭素含有
量（％ＣN）が３０以下のプロセスオイル又は水素化処
理していないナフテン系のプロセスオイルとからなり、
かつ多環芳香族化合物（ＰＣＡ）が３重量％以下の軟化
剤とを含有することを特徴とするゴム組成物を提供する
ものである。In order to overcome the above-mentioned problems, the present inventor has found that it is effective to mix asphalt having an asphaltene content of 5% by weight or less and a specific process oil in an appropriate ratio. Heading out, the present invention has been completed. That is, the present invention relates to at least one rubber component selected from natural rubber and synthetic rubber, asphalt having an asphaltene content of 5% by weight or less, and AST.
A process oil having a naphthene ring carbon content (% C N ) of 30 or less measured according to MD2140 or a naphthene-based process oil that has not been hydrotreated,
The present invention also provides a rubber composition containing a polycyclic aromatic compound (PCA) in an amount of 3% by weight or less and a softening agent.
【０００６】また本発明は、アスファルテン分が５重
量％以下であるアスファルトとＡＳＴＭ Ｄ２１４０
に準拠して測定されたナフテン環炭素含有量（％ＣN）
が３０以下のプロセスオイル又は水素化処理していない
ナフテン系のプロセスオイルとからなり、かつ多環芳香
族化合物（ＰＣＡ）が３重量％以下であることを特徴と
するゴム用軟化剤を提供するものである。さらに、本発
明は、伸展油として、アスファルテン分が５重量％以
下であるアスファルトとＡＳＴＭ Ｄ２１４０に準拠
して測定されたナフテン環炭素含有量（％ＣN）が３０
以下のプロセスオイル又は水素化処理していないナフテ
ン系のプロセスオイルとからなり、かつ多環芳香族化合
物（ＰＣＡ）が３重量％以下である軟化剤を含有するこ
とを特徴とする油展ゴムをも提供するものである。The present invention also relates to asphalt having an asphaltene content of 5% by weight or less and ASTM D2140.
Naphthene ring carbon content (% C N ) measured according to
A process oil of 30 or less or a naphthene-based process oil that has not been hydrotreated, and a polycyclic aromatic compound (PCA) content of 3% by weight or less. It is a thing. Further, the present invention provides an asphalt oil having an asphaltene content of 5% by weight or less as an extender oil and a naphthene ring carbon content (% C N ) of 30 as measured according to ASTM D2140.
An oil-extended rubber comprising the following process oil or a naphthene-based process oil that has not been hydrotreated, and containing a softening agent having a polycyclic aromatic compound (PCA) content of 3% by weight or less. Is also provided.
【０００７】[0007]
【発明の実施の形態】本発明における軟化剤は、アス
ファルテン分が５重量％以下であるアスファルトと、
ＡＳＴＭ Ｄ２１４０に準拠して測定された（通称環分
析による）ナフテン環炭素含有量（％ＣN）が３０以下
のプロセスオイル又は水素化処理していないナフテン系
のプロセスオイルとを混合することにより調製される。
ここで、アスファルテン分（日本石油学会法により測
定）が５重量％以下であるアスファルトは、ナフテン系
原油より採取されたアスファルトが好ましい。また、１
２０℃における動粘度は３００ｍｍ2／秒以下であるこ
とが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The softening agent in the present invention is asphalt having an asphaltene content of 5% by weight or less,
Prepared by mixing with a process oil having a naphthene ring carbon content (% C N ) of 30 or less (commonly called ring analysis) measured according to ASTM D2140 or a non-hydrotreated naphthene-based process oil To be done.
Here, the asphalt having an asphaltene content (measured by the Japan Petroleum Institute method) of 5% by weight or less is preferably asphalt collected from naphthenic crude oil. Also, 1
The kinematic viscosity at 20 ° C. is preferably 300 mm 2 / sec or less.
【０００８】一方、前記としてのプロセスオイルは、
ＡＳＴＭ Ｄ２１４０に準拠して測定されたナフテン環
炭素含有量（％ＣN）が３０以下のプロセスオイル、又
は水素化処理していないナフテン系のプロセスオイルが
用いられる。ここで、ナフテン環炭素含有量(％ＣN)が
３０以下のプロセスオイルの種類は、特に制限されず、
例えば、高芳香族系油、ナフテン系油、パラフィン系油
等、通常、ゴム業界で用いられるものを、単独又は混合
して用いることができる。これらの中では、芳香族炭素
含有量(％ＣA)及び高ロス性付与性の観点より高芳香族
系油の使用が好ましい。また、前記プロセスオイルは、
ＰＣＡ成分３重量％以下のものが好ましく用いられる。
このため、プロセスオイルからＰＣＡ成分を除去する必
要がある場合は、選択的に溶剤抽出する方法，水素化処
理により仕上げる方法などの二次的処理が行われる。但
し、水素化処理により仕上げたプロセスオイルを用いて
調製した軟化剤は、ゴム組成物の配合によっては、ロス
特性の最適化における組成比で芳香族炭素の含有量（％
ＣA）が小さくなりすぎて、耐破壊性や耐摩耗性が低下
することがある。On the other hand, the above process oil is
A process oil having a naphthene ring carbon content (% C N ) of 30 or less measured according to ASTM D2140 or a non-hydrogenated naphthene-based process oil is used. Here, the kind of process oil having a naphthene ring carbon content (% C N ) of 30 or less is not particularly limited,
For example, highly aromatic oils, naphthene oils, paraffin oils and the like which are usually used in the rubber industry can be used alone or in combination. Among these, use of an aromatic carbon content (% C A) and a high loss factor imparting high aromatic oil in view of preferred. Further, the process oil is
A PCA component of 3% by weight or less is preferably used.
Therefore, when it is necessary to remove the PCA component from the process oil, a secondary treatment such as a method of selectively extracting with a solvent or a method of finishing with a hydrogenation treatment is performed. However, the softening agent prepared by using the process oil finished by hydrotreating may have a content ratio of aromatic carbon (%) at the composition ratio in the optimization of loss characteristics depending on the composition of the rubber composition.
C A ) may become too small and the fracture resistance and wear resistance may decrease.
【０００９】また本発明の軟化剤は、ＰＣＡの含有量を
３重量％以下とする。ＰＣＡの含有量が３重量％以下に
おいて本発明における顕著な効果が得られる。本発明で
用いる軟化剤において、前記アスファルトの含有量は、
特に制限されないが、好ましくは軟化剤総量に対して５
〜９５重量％、更に好ましくは３０〜８０重量％であ
る。アスファルトが５重量％未満ではロス特性付与性が
十分でなく、９５重量％を超えると転がり抵抗が大きく
なることがある。The softener of the present invention has a PCA content of 3% by weight or less. When the content of PCA is 3% by weight or less, the remarkable effect of the present invention can be obtained. In the softener used in the present invention, the content of the asphalt is
Although not particularly limited, it is preferably 5 with respect to the total amount of the softening agent.
˜95% by weight, more preferably 30 to 80% by weight. If the asphalt is less than 5% by weight, the loss property imparting property is not sufficient, and if it exceeds 95% by weight, rolling resistance may increase.
【００１０】上記軟化剤は、配合油或いはゴム伸展油と
してのいずれの軟化剤にも適用される。本発明における
軟化剤の１００℃における動粘度は、天然ゴム又は合成
ゴムへの油展、或いはゴム組成物への配合時の作業性
（混練機への導入のし易さ）の観点から３５０ｍｍ2／
秒以下であることが好ましく、更に２００ｍｍ2／秒以
下、特に１５０ｍｍ2／秒以下が好ましい。本発明の軟
化剤の調製方法は、特に制限されず、アスファルトを予
め他の軟化剤成分に混合するか、或いは従来の軟化剤の
精製過程において、アスファルトの主要成分を軟化剤中
に適正比率に存在させることにより調製した軟化剤を用
いてもよいが、軟化剤の調製の容易さや経済性の観点よ
り、アスフアルトをプロセスオイル（伸展油、配合油を
含む）に溶解することにより調製する方法が好ましい。The above softener can be applied to any softener as a compounding oil or a rubber extending oil. The kinematic viscosity of the softening agent of the present invention at 100 ° C. is 350 mm 2 from the viewpoint of workability at the time of oil extension to natural rubber or synthetic rubber, or compounding into a rubber composition (ease of introduction into a kneader). /
It is preferably not more than seconds, more preferably not more than 200 mm 2 / second, particularly preferably not more than 150 mm 2 / second. The preparation method of the softening agent of the present invention is not particularly limited, and asphalt is mixed with other softening agent components in advance, or in the conventional softening agent refining process, the main components of the asphalt are mixed in the softening agent at an appropriate ratio. A softening agent prepared by allowing it to exist may be used, but from the viewpoint of ease of preparation of the softening agent and economical efficiency, a method of preparing asphalt by dissolving it in process oil (including extending oil and compounding oil) is used. preferable.
【００１１】また、本発明におけるゴム組成物又は油展
ゴムの製造において、前記アスファルトを含む軟化剤
は、ゴム配合時に添加してもよく、合成ゴム製造時に伸
展油として添加してもよい。ここで用いられるゴム成分
としては、天然ゴム，合成ゴムのいずれをも用いること
ができる。合成ゴムとしては特に制限されず、例えばブ
タジエンゴム（ＢＲ），イソプレンゴム（ＩＲ），スチ
レン−ブタジエン共重合体ゴム（ＳＢＲ），ブチルゴム
（ＩＩＲ），ハロゲン化ＩＩＲ，エチレン−プロピレン
−ジエン三元共重合体（ＥＰＤＭ）等が挙げられ、用途
に応じて適宜選択することができる。In the production of the rubber composition or the oil-extended rubber of the present invention, the softening agent containing asphalt may be added at the time of compounding the rubber, or may be added as an extender oil at the time of producing the synthetic rubber. As the rubber component used here, either natural rubber or synthetic rubber can be used. The synthetic rubber is not particularly limited, and examples thereof include butadiene rubber (BR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butyl rubber (IIR), halogenated IIR, ethylene-propylene-diene ternary copolymer. A polymer (EPDM) and the like can be mentioned, and it can be appropriately selected depending on the application.
【００１２】本発明における前記軟化剤のゴム組成物へ
の配合量は、ロス特性付与性，耐摩耗性，耐破壊性のバ
ランスの観点より、ゴム成分１００重量部に対して軟化
剤を１重量部から２００重量部が好ましく、さらに好ま
しくは３重量部から１５０重量部、特に好ましくは５重
量部から１００重量部である。ここで軟化剤の配合量と
は、いわゆる伸展油及び配合油の両者の総量をいう。ま
た、合成ゴムの伸展油として用いる場合は、合成ゴムの
ゴム成分１００重量部に対して５重量部から１５０重量
部が好ましく、さらに好ましくは７重量部から１００重
量部、特に好ましくは１０重量部から５０重量部であ
り、配合油として用いる場合は、ゴム成分１００重量部
に対して１重量部から７０重量部が好ましく、さらに好
ましく５重量部から５０重量部である。The amount of the softening agent to be added to the rubber composition in the present invention is 1 part by weight of the softening agent per 100 parts by weight of the rubber component from the viewpoint of the balance of loss property imparting property, abrasion resistance and fracture resistance. It is preferably from 200 parts by weight to 200 parts by weight, more preferably from 3 parts by weight to 150 parts by weight, particularly preferably from 5 parts by weight to 100 parts by weight. Here, the compounding amount of the softening agent means the total amount of both the so-called extending oil and the compounding oil. When used as an extender oil for synthetic rubber, it is preferably 5 to 150 parts by weight, more preferably 7 to 100 parts by weight, particularly preferably 10 parts by weight, relative to 100 parts by weight of the rubber component of the synthetic rubber. To 50 parts by weight, and when used as a compounded oil, it is preferably 1 to 70 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the rubber component.
【００１３】本発明のゴム組成物に用いられるアスファ
ルト含有軟化剤は、その一部を他の軟化剤に置き換える
ことができる。ただしその場合も、軟化剤の総配合量が
上記の範囲内であることが好ましく、本発明の効果を十
分に得るためには、本発明の軟化剤を軟化剤総量の５０
重量％以上含有することが好ましい。本発明のゴム組成
物は、補強性充填剤として、ゴム成分１００重量部に対
して２０重量部〜１５０重量部、好ましくは２５重量部
〜１２０重量部、更に好ましくは３０重量部〜１０５重
量部のカーボンブラック、シリカ等を用いることができ
る。The asphalt-containing softening agent used in the rubber composition of the present invention can be partially replaced with another softening agent. However, even in that case, it is preferable that the total amount of the softening agent is within the above range, and in order to sufficiently obtain the effect of the present invention, the softening agent of the present invention is added to the softening agent in an amount of 50
It is preferable that the content is at least wt%. The rubber composition of the present invention, as a reinforcing filler, is 20 parts by weight to 150 parts by weight, preferably 25 parts by weight to 120 parts by weight, and more preferably 30 parts by weight to 105 parts by weight, relative to 100 parts by weight of the rubber component. Carbon black, silica, etc. can be used.
【００１４】本発明のゴム組成物は、架橋剤を加えてこ
れを加熱する。この場合、架橋剤としては、有機過酸化
物、硫黄、有機硫黄化合物などの通常ゴム組成物の架橋
に使用できるものであればいずれも使用できる。硫黄、
有機硫黄化合物を架橋剤として用いる場合、通常ゴム業
界で用いられる加硫促進剤を適宜用いることができる。
本発明のゴム組成物は、上記各成分の他にも、ゴム成分
１００重量部に対して５重量部〜２００重量部、好まし
くは２５重量部〜１２０重量部、更に好ましくは３０重
量部〜１０５重量部の通常ゴム業界で用いられる無機充
填剤を含むことができる。上記の他にも、本発明のゴム
組成物は、老化防止剤や加硫助剤など、通常ゴム業界で
用いられる各種成分を適宜配合することができる。The rubber composition of the present invention is added with a crosslinking agent and heated. In this case, as the cross-linking agent, any one can be used as long as it can be used for cross-linking a usual rubber composition, such as organic peroxide, sulfur and organic sulfur compounds. sulfur,
When the organic sulfur compound is used as the crosslinking agent, a vulcanization accelerator usually used in the rubber industry can be appropriately used.
In addition to the above components, the rubber composition of the present invention is 5 to 200 parts by weight, preferably 25 to 120 parts by weight, and more preferably 30 to 105 parts by weight per 100 parts by weight of the rubber component. Parts by weight of inorganic fillers commonly used in the rubber industry may be included. In addition to the above, the rubber composition of the present invention may appropriately contain various components commonly used in the rubber industry, such as an antioxidant and a vulcanization aid.
【００１５】[0015]
【実施例】以下に実施例及び比較例を挙げて本発明を更
に具体的に説明するが、本発明はこれらの例によって何
ら限定されるものではない。なお、アスファルト、軟化
剤及びゴム組成物についての諸物性は、以下の方法に従
って測定した。EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Various physical properties of the asphalt, the softening agent and the rubber composition were measured according to the following methods.
【００１６】（１）アスファルトの物性
（ａ）針入度
針入度は、ＪＩＳ Ｋ２２０７に準拠し、２５℃にて測
定した。
（ｂ）動粘度
ＪＩＳ Ｋ２２８３−１９９３に準拠し、１２０℃にて
測定した。
（２）軟化剤の物性
（ａ）環分析による各種炭素の含有量の測定
ＡＳＴＭ Ｄ２１４０に準拠し、軟化剤中の芳香族炭素
含有量（％ＣA）、ナフテン環炭素含有量（％ＣN）、パ
ラフィン鎖炭素含有量（％ＣP）を測定した。
（ｂ）動粘度
ＪＩＳ Ｋ２２８３−１９９３に準拠し、１００℃にて
測定した。
（ｃ）アニリン点
ＪＩＳ Ｋ２２５６−１９８５に準拠し、測定した。
（ｄ）ＰＣＡ
ＩＰ３４６法に準拠し、ＤＭＳＯ抽出量（重量％）を測
定した。(1) Physical Properties of Asphalt (a) Penetration Penetration was measured at 25 ° C. according to JIS K2207. (B) Kinematic viscosity Measured at 120 ° C according to JIS K2283-1993. (2) Physical Properties of Softening Agent (a) Measurement of Content of Various Carbons by Ring Analysis Based on ASTM D2140, aromatic carbon content (% C A ) and naphthene ring carbon content (% C N in softening agent ), And the paraffin chain carbon content (% C P ) was measured. (B) Kinematic viscosity Based on JIS K2283-1993, it was measured at 100 ° C. (C) Aniline point It was measured according to JIS K2256-1985. (D) The DMSO extraction amount (% by weight) was measured according to the PCA IP346 method.
【００１７】（３）ゴム組成物の試験方法
（ａ）作業性
ＪＩＳ Ｋ６３００−１９９４に準拠し、未加硫ゴム組
成物サンプルの１３０℃におけるＭＬ1+4を、ムーニー
粘度測定機〔東洋精機（株）製〕を用いて測定した。評
価は、○：作業性優れる、△：作業性やや良好、×：作
業性劣るの基準で判定した。
（ｂ）耐破壊特性
ＪＩＳ Ｋ６３０１−１９９５に準拠し、加硫ゴムシー
ト（１５０ｍｍ×１５０ｍｍ×２ｍｍ）をＪＩＳ−３号
の刃型で打抜いて試験片を準備した。この試験片を 引
張試験機〔東洋精機（株）製ストログラフ ＡＲ−１〕
を用いて２５℃における破断強度を測定しコントロール
を１００として指数表示した。指数は値が大きいほど耐
破壊特性が良好であることを示す。(3) Testing method of rubber composition (a) Workability In accordance with JIS K6300-1994, ML 1 + 4 of an unvulcanized rubber composition sample at 130 ° C. was measured with a Mooney viscosity measuring machine [Toyo Seiki ( Co., Ltd.]. The evaluation was made according to the criteria of ◯: excellent workability, Δ: somewhat good workability, and x: poor workability. (B) Destruction resistance property According to JIS K6301-1995, a vulcanized rubber sheet (150 mm × 150 mm × 2 mm) was punched with a JIS-3 blade to prepare a test piece. Tensile tester [Toyo Seiki Co., Ltd. Strograph AR-1]
Was used to measure the breaking strength at 25 ° C., and the index was displayed with the control as 100. The larger the index, the better the fracture resistance.
【００１８】（ｃ）ロス特性（動的損失特性）
粘弾性試験機〔東洋精機（株）製レオログラフソリッド
Ｌ−１Ｒ型〕により、試験片として５ｍｍ×４５ｍｍ×
２ｍｍの加硫ゴムシートを用いて、歪５％，周波数１５
Ｈｚで、０℃及び６０℃におけるtan δを測定した。こ
こで、
０℃tan δについては、測定値をコントロールを１０
０として指数表示した。この値が大きいほど耐ウェット
スキッド性は良好である。
６０℃tan δについては、測定値の逆数を、コントロ
ールを１００とした指数で表示した。この値が大きいほ
ど低燃費性は良好である。
（ｄ）耐摩耗性
ランボーン型摩耗性試験機により、スリップ率６０％で
加硫ゴムの摩耗量を測定し指数表示した。指数は値が大
きいほど良好であることを示す。(C) Loss characteristics (dynamic loss characteristics) 5 mm × 45 mm × as a test piece by a viscoelasticity tester [Rheograph Solid L-1R type manufactured by Toyo Seiki Co., Ltd.]
Using a 2 mm vulcanized rubber sheet, strain 5%, frequency 15
The tan δ was measured at 0 ° C. and 60 ° C. in Hz. Here, for 0 ° C. tan δ, the measured value is 10
It was displayed as an index of 0. The larger this value, the better the wet skid resistance. Regarding 60 ° C. tan δ, the reciprocal of the measured value is shown as an index with the control being 100. The larger this value, the better the fuel economy. (D) Abrasion resistance A Lambourn abrasion tester was used to measure the amount of abrasion of the vulcanized rubber at a slip ratio of 60% and display it as an index. The larger the index, the better the index.
【００１９】実施例１〜６、比較例１〜５及び参考例１
以下の実施例及び比較例において用いた軟化剤、油展合
成ゴム及びゴム試験片の作成は次の方法で行った。
（１）軟化剤の調製方法
予め７０℃の加熱した、第１表に示すプロセスオイルを
所定量精秤した。このオイルに、予め８５℃に加熱して
粘度を下げ、所定量を精秤した第２表に示すアスファル
トを７０℃に保温しながら混入したのち５分間攪拌を継
続し、第４表に示す組成の各種軟化剤を調製した。な
お、得られた軟化剤中のＰＣＡ成分量は、同第４表に示
した。Examples 1 to 6, Comparative Examples 1 to 5 and Reference Example 1 Softeners, oil-extended synthetic rubbers and rubber test pieces used in the following Examples and Comparative Examples were prepared by the following method. (1) Method for preparing softening agent A predetermined amount of process oil shown in Table 1, which had been heated to 70 ° C. in advance, was precisely weighed. This oil was heated to 85 ° C. in advance to reduce the viscosity, and a predetermined amount of asphalt shown in Table 2 was mixed while keeping the temperature at 70 ° C., and then stirring was continued for 5 minutes to prepare the composition shown in Table 4. Various softeners were prepared. The amount of PCA component in the obtained softening agent is shown in Table 4 above.
【００２０】[0020]
【表１】 [Table 1]
【００２１】（注）
プロセスオイルＡ：ＭＥＳ相当品
プロセスオイルＢ：ＴＤＡＥ相当品
プロセスオイルＣ：ＤＡＥ（アロマティックオイル）相
当品(Note) Process oil A: Equivalent to MES Process oil B: Equivalent to TDAE Process oil C: Equivalent to DAE (aromatic oil)
【００２２】[0022]
【表２】 [Table 2]
【００２３】（注）
＊１：柔らか過ぎて測定不可能
（２）油展合成ゴムの調製
５リットルのビーカーにシクロヘキサン４リットルを入
れ、乳化重合ＳＢＲ０１２０〔商標；ジェイエスアール
（株）製〕５００ｇを攪拌して溶解した。次に、このポ
リマー溶液を、５リットルのビーカーを用いて２リット
ルの２−プロパノール中に攪拌しながら滴下しながら再
沈殿を行い、続いて加熱真空乾燥して油展オイルが除去
されたポリマーを得た。このようにして得られた精製ポ
リマーを、５リットルのビーカーを用いて３リットルの
シクロヘキサンに充分に再溶解させ、この溶液に２，６
−ジ−ｔ−ブチル−ｐ−クレゾール０.5ｇをイソプロパ
ノール５ｍｌに溶解した溶液を加え、さらに前記調製し
た軟化剤を添加した後、通常の方法にて乾燥させ油展合
成ゴムを得た。(Note) * 1: It is too soft to measure. (2) Preparation of oil-extended synthetic rubber 4 liters of cyclohexane was placed in a 5 liter beaker, and 500 g of emulsion-polymerized SBR0120 (trademark; manufactured by JSR Co., Ltd.) was added. Stir to dissolve. Next, the polymer solution was reprecipitated while being dropped into 2 liters of 2-propanol using a 5 liter beaker while stirring, and subsequently heated and vacuum dried to obtain a polymer from which oil-extended oil was removed. Obtained. The purified polymer thus obtained was sufficiently redissolved in 3 liters of cyclohexane using a 5 liter beaker.
A solution prepared by dissolving 0.5 g of -di-t-butyl-p-cresol in 5 ml of isopropanol was added, and the softening agent prepared above was further added, followed by drying by an ordinary method to obtain an oil-extended synthetic rubber.
【００２４】（３）ゴム試験片の作成
上記により得られたＳＢＲ油展ゴムを用い、第３表に示
す配合処方により、表面温度７０℃のロールを用いて、
マスターバッチ混練りをした後、続いてファイナル混練
りしてシート状にした。その後、これを所定の金型を用
いて温度１６０℃、圧力３０ｋｇ／ｃｍ2、加熱時間１
５分の条件で加硫した後脱型し、所定の試験片を作成し
た。(3) Preparation of rubber test piece Using the SBR oil-extended rubber obtained as described above, according to the formulation shown in Table 3, using a roll having a surface temperature of 70 ° C.,
After kneading the master batch, the final kneading was carried out to form a sheet. Then, using a predetermined mold, this was heated at a temperature of 160 ° C., a pressure of 30 kg / cm 2 , and a heating time of 1
After vulcanization under the condition of 5 minutes, it was demolded to prepare a predetermined test piece.
【００２５】[0025]
【表３】 [Table 3]
【００２６】＊２：スチレン−ブタジエン共重合体ゴム
（ジェイエスアール（株）製、ＳＢＲ０１２０のゴム成
分）
＊３：東海カーボン（株）製，商標「東海シースト６」
＊４：第４表に示す組成の軟化剤
＊５：日本油脂（株）製，商標「ＢＲ−ステアリン酸」
＊６：白水化学（株）製，商標「１号亜鉛華」
＊７：ノクセラーＤＭ，〔商標、大内新興化学工業
（株）製、ジベンゾチアジルジスルフィド〕
＊８：ノクセラーＤＰＧ，〔商標、大内新興化学工業
（株）製、ジフェニルグアニジン〕
＊９：硫黄（軽井沢精錬所製）
上記により得られたゴム組成物について、未加硫ゴム組
成物の作業性を評価するとともに、加硫ゴムの耐破壊特
性、耐摩耗性を測定した。また、０℃及び６０℃におけ
るｔａｎδを測定しロス特性を評価した。なお、各ゴム
組成物の物性評価においては、実施例１〜３及び比較例
１，３については比較例２をコントロールとし、実施例
４〜６、比較例５及び参考例１については比較例４をコ
ントロールとした。結果を第４表に示す。* 2: Styrene-butadiene copolymer rubber (made by JSR Co., Ltd., rubber component of SBR0120) * 3: Tokai Carbon Co., Ltd., trademark "Tokai Seast 6" * 4: shown in Table 4 Composition softening agent * 5: Nippon Oil & Fats Co., Ltd., trademark "BR-stearic acid" * 6: Shiramizu Chemical Co., Ltd., trademark "No. 1 Zinc Flower" * 7: Nocceller DM, [Trademark, Ouchi Shinko Chemical Industry Co., Ltd., dibenzothiazyl disulfide] * 8: Nocceller DPG, [trademark, Ouchi Shinko Chemical Industry Co., Ltd., diphenylguanidine] * 9: Sulfur (Karuizawa Smelting Co., Ltd.) Rubber obtained by the above For the composition, the workability of the unvulcanized rubber composition was evaluated, and the fracture resistance and abrasion resistance of the vulcanized rubber were measured. Also, tan δ at 0 ° C. and 60 ° C. was measured to evaluate loss characteristics. In the evaluation of physical properties of each rubber composition, Comparative Example 2 was used as a control for Examples 1 to 3 and Comparative Examples 1 and 3, and Comparative Example 4 was used for Examples 4 to 6, Comparative Example 5 and Reference Example 1. Was used as a control. The results are shown in Table 4.
【００２７】[0027]
【表４】 [Table 4]
【００２８】上記の結果より、本発明の実施例は、それ
ぞれコントロールに比べて同等に近いか或いはそれ以上
の優れた性能が得られることがわかる。但し、軟化剤中
のアスファルト混合量が９５重量％を超える実施例１及
び４では、６０℃でのロス特性の評価指数は小さくな
り、転がり抵抗には不利となる傾向を示している。From the above results, it can be seen that each of the examples of the present invention has excellent performance that is close to or higher than that of the control. However, in Examples 1 and 4 in which the amount of asphalt mixed in the softening agent exceeds 95% by weight, the evaluation index of the loss characteristic at 60 ° C. becomes small and the rolling resistance tends to be disadvantageous.
【００２９】[0029]
【発明の効果】以上のように、本発明によれば、アスフ
ァルテン分を含み、かつＰＣＡ成分が３重量％以下の特
定軟化剤を用いることにより、従来の芳香族系油使用の
場合に比べても、同等若しくはそれ以上の優れたロス特
性と耐破壊特性とを有するゴム組成物が得られるため、
タイヤ、防振ゴム、防舷材等の様々なゴム物品に好まし
く用いることができる。As described above, according to the present invention, by using the specific softening agent containing the asphaltene component and having the PCA component of 3% by weight or less, compared with the case of using the conventional aromatic oil, Also, because it is possible to obtain a rubber composition having equal or higher excellent loss characteristics and fracture resistance,
It can be preferably used for various rubber articles such as tires, anti-vibration rubber and fenders.
Claims (6)
くとも一種のゴム成分と、アスファルテン分が５重量
％以下であるアスファルトとＡＳＴＭ Ｄ２１４０に
準拠して測定されたナフテン環炭素含有量（％ＣN）が
３０以下のプロセスオイル又は水素化処理していないナ
フテン系のプロセスオイルからなり、かつ多環芳香族化
合物（ＰＣＡ）が３重量％以下の軟化剤とを含有するこ
とを特徴とするゴム組成物。1. At least one rubber component selected from natural rubber and synthetic rubber, asphalt having an asphaltene content of 5% by weight or less, and a naphthene ring carbon content (% C N measured according to ASTM D2140). ) Is 30 or less process oil or naphthenic process oil which is not hydrotreated, and a polycyclic aromatic compound (PCA) contains 3% by weight or less of a softening agent. object.
るアスファルトとＡＳＴＭ Ｄ２１４０に準拠して測
定されたナフテン環炭素含有量（％ＣN）が３０以下の
プロセスオイル又は水素化処理していないナフテン系の
プロセスオイルとからなり、かつ多環芳香族化合物（Ｐ
ＣＡ）が３重量％以下であることを特徴とするゴム用軟
化剤。2. An asphalt having an asphaltene content of 5% by weight or less and a process oil having a naphthene ring carbon content (% C N ) of 30 or less measured according to ASTM D2140 or an unhydrogenated naphthenic oil. Process oil and polycyclic aromatic compound (P
CA) is 3% by weight or less, a softening agent for rubber.
重量％以下であるアスファルトとＡＳＴＭ Ｄ２１４
０に準拠して測定されたナフテン環炭素含有量（％
ＣN）が３０以下のプロセスオイル又は水素化処理して
いないナフテン系のプロセスオイルとからなり、かつ多
環芳香族化合物（ＰＣＡ）が３重量％以下である軟化剤
を含有することを特徴とする油展ゴム。3. Asphaltene content of 5 as extender oil
Asphalt and ASTM D214 below wt%
Naphthene ring carbon content measured according to 0 (%
C N ) is 30 or less, or a naphthenic process oil which is not hydrotreated, and contains a polycyclic aromatic compound (PCA) in an amount of 3% by weight or less. Oil-extended rubber.
アスファルトである請求項１記載のゴム組成物。4. The rubber composition according to claim 1, wherein the asphalt is a naphthenic straight asphalt.
が３００ｍｍ2／秒以下である請求項１記載のゴム組成
物。5. The rubber composition according to claim 1, wherein the asphalt has a kinematic viscosity at 120 ° C. of 300 mm 2 / sec or less.
部に対して１重量部から２００重量部である請求項１記
載のゴム組成物。6. The rubber composition according to claim 1, wherein the compounding amount of the softening agent is 1 part by weight to 200 parts by weight with respect to 100 parts by weight of the rubber component.
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| JP2002015457A JP4102075B2 (en) | 2002-01-24 | 2002-01-24 | Rubber softener, rubber composition using the same, and oil-extended rubber |
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|---|---|
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| JP4102075B2 JP4102075B2 (en) | 2008-06-18 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008501822A (en) * | 2004-06-03 | 2008-01-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing rubber extender oil composition |
| US7678855B2 (en) | 2005-08-10 | 2010-03-16 | Bridgestone Corporation | Rubber composition |
| JP2010126664A (en) * | 2008-11-28 | 2010-06-10 | Showa Shell Sekiyu Kk | Process oil and rubber extender oil |
| WO2011030431A1 (en) | 2009-09-10 | 2011-03-17 | 株式会社ブリヂストン | Run-flat tire |
| US7972496B2 (en) | 2005-05-31 | 2011-07-05 | Idemitsu Kosan Co., Ltd. | Process oil, process for production of deasphalted oil, process for production of extract, and process for production of process oil |
| CN103087331A (en) * | 2013-01-25 | 2013-05-08 | 灵宝金地杜仲产业有限公司 | Process for extracting gutta-percha by natural fermentation method |
| CN103589453A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Preparation method of aromatic rubber oil |
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2002
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008501822A (en) * | 2004-06-03 | 2008-01-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing rubber extender oil composition |
| US7972496B2 (en) | 2005-05-31 | 2011-07-05 | Idemitsu Kosan Co., Ltd. | Process oil, process for production of deasphalted oil, process for production of extract, and process for production of process oil |
| US8758595B2 (en) | 2005-05-31 | 2014-06-24 | Idemitsu Kosan Co., Ltd. | Process oil, process for production of deasphalted oil, process for production of extract, and process for production of process oil |
| US7678855B2 (en) | 2005-08-10 | 2010-03-16 | Bridgestone Corporation | Rubber composition |
| JP2010126664A (en) * | 2008-11-28 | 2010-06-10 | Showa Shell Sekiyu Kk | Process oil and rubber extender oil |
| WO2011030431A1 (en) | 2009-09-10 | 2011-03-17 | 株式会社ブリヂストン | Run-flat tire |
| US9493041B2 (en) | 2009-09-10 | 2016-11-15 | Bridgestone Corporation | Run-flat tire |
| CN103589453A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Preparation method of aromatic rubber oil |
| CN103589453B (en) * | 2012-08-14 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of preparation method of aromatic rubber oil |
| CN103087331A (en) * | 2013-01-25 | 2013-05-08 | 灵宝金地杜仲产业有限公司 | Process for extracting gutta-percha by natural fermentation method |
| CN105254971A (en) * | 2015-12-03 | 2016-01-20 | 傅家兴 | Rubber softener |
| US11104105B2 (en) | 2017-04-12 | 2021-08-31 | Bridgestone Corporation | Tire, and method for manufacturing tire |
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