JPH11302459A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPH11302459A JPH11302459A JP4476499A JP4476499A JPH11302459A JP H11302459 A JPH11302459 A JP H11302459A JP 4476499 A JP4476499 A JP 4476499A JP 4476499 A JP4476499 A JP 4476499A JP H11302459 A JPH11302459 A JP H11302459A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- softener
- rubber
- asphalt
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、ゴム組成物に関
し、詳しくは、ゴム成分にアスファルテン分を0.1重量
%〜4重量%の範囲で含有する軟化剤を混合することに
より、高ヒステリシスロス特性と破壊特性が改良された
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, and more particularly, to a high hysteresis loss by mixing a rubber component with a softener containing asphaltenes in a range of 0.1% by weight to 4% by weight. The present invention relates to a rubber composition having improved properties and fracture properties.
【0002】[0002]
【従来の技術】従来、アスファルトは、種々の目的のた
めにゴム組成物に添加されてきた。例えば、欧州特許公
開公報708137号においては、アスファルトを配合
したゴム組成物をタイヤトレッドに使うことにより、長
時間置いた後も、表面に黒い染みを残さないタイヤを提
供できることが開示されている。2. Description of the Related Art Hitherto, asphalt has been added to rubber compositions for various purposes. For example, European Patent Publication 708137 discloses that by using a rubber composition containing asphalt for a tire tread, a tire can be provided which does not leave black stains on the surface even after being left for a long time.
【0003】[0003]
【発明が解決しようとする課題】アスファルトをゴム組
成物に混合させ、高ロス性能、及び破壊特性を向上させ
ることは公知である。しかし、アスファルトは粘凋でか
つベタついている為、混合時に混合機等に付着/粘着し
てしまい、ゴム組成物中には規定量混合できなかった
り、あるいは、ゴム組成物中に混合できても、ゴム中で
の分散が十分で無い為に、破壊特性が十分でなかったり
する場合があった。It is known that asphalt is mixed with a rubber composition to improve high loss performance and breakage characteristics. However, since asphalt is viscous and sticky, it adheres / adheres to a mixer or the like at the time of mixing, so that a prescribed amount cannot be mixed in the rubber composition, or even if it can be mixed in the rubber composition. In some cases, the dispersion properties in rubber were not sufficient, so that the breaking characteristics were not sufficient.
【0004】[0004]
【課題を解決するための手段】本発明者は、アスファル
トを混合することにより、ゴム組成物の高ロス性能、及
び破壊特性が改良される点につき鋭意検討した結果、特
定量のアスファルテン分を含む軟化剤、特に芳香族系炭
化水素含有量の多い軟化剤を用いることにより、より効
率的にゴム組成物の物性が改良できることを見出し、本
発明を完成するに至った。Means for Solving the Problems The present inventor has made intensive studies on the fact that the high loss performance and the breaking characteristics of a rubber composition are improved by mixing asphalt, and as a result, a specific amount of asphaltene is contained. The present inventors have found that the physical properties of a rubber composition can be more efficiently improved by using a softener, particularly a softener having a high aromatic hydrocarbon content, and have completed the present invention.
【0005】本発明は、上記課題を克服するため、アス
ファルトを直接ゴムの混合時に配合するのではなく、ア
スファルトを予め軟化剤に混合するか、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るも
のである。[0005] In order to overcome the above-mentioned problems, the present invention does not mix asphalt directly when mixing rubber, but instead mixes asphalt with a softening agent in advance or softens the main components of asphalt during the purification process of the softening agent. It uses a softener prepared by allowing it to be present in an appropriate ratio in the agent.
【0006】即ち、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100重量部及び
アスファルテン分を0.1重量%〜4重量%の範囲で含有
する軟化剤1重量部〜120重量部からなるゴム組成物
である。ここで使用する軟化剤のASTM D2140
に準拠して測定される(つまり、通称環分析による)芳
香族炭素の含有量(%CA )は、18以上であることが
好ましい。又、軟化剤の精製の容易さを考えると、本発
明の軟化剤は、従来の軟化剤であるプロセスオイルにア
スファルトを混合して調製することが好ましく、使用す
るアスファルトはストレートアスファルトが好ましい。That is, according to the present invention, 100 parts by weight of at least one kind of rubber component selected from natural rubber and synthetic rubber and 1 part by weight of a softener containing 0.1 to 4% by weight of asphaltene are contained. It is a rubber composition consisting of 120 parts by weight. ASTM D2140 of the softener used here
The aromatic carbon content (% C A ) measured according to (that is, by a so-called ring analysis) is preferably 18 or more. Considering the ease of purification of the softener, the softener of the present invention is preferably prepared by mixing asphalt with a process oil which is a conventional softener, and the asphalt used is preferably straight asphalt.
【0007】[0007]
【発明の実施の形態】本発明では、ゴム成分として天然
ゴム又は合成ゴムを用いることが出来る。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(B
R)、イソプレンゴム(IR)、スチレン−ブタジエン
共重合体(SBR)、ブチルゴム(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。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, natural rubber or synthetic rubber can be used as a rubber component. The synthetic rubber is not particularly limited. For example, a butadiene rubber (B
R), isoprene rubber (IR), styrene-butadiene copolymer (SBR), butyl rubber (IIR), ethylene-propylene-diene terpolymer (EPDM), and the like, which can be appropriately selected according to the application. Can be.
【0008】本発明で用いる軟化剤は、アスファルテン
分が軟化剤の総量の0.1重量%〜4重量%の範囲で含ま
れることが必要であり、好ましくは0.3重量%〜3.0重
量%含まれる。アスファルテン分が0.1重量%未満では
高ヒステリシスロス性付与性能が十分でなく、4重量%
を超えると粘着性が大きくなり作業性が極端に悪くな
る。The softener used in the present invention must contain asphaltenes in the range of 0.1% by weight to 4% by weight of the total amount of the softener, preferably 0.3% by weight to 3.0% by weight. % By weight. If the asphaltene content is less than 0.1% by weight, the effect of imparting high hysteresis loss is not sufficient, and 4% by weight.
If it exceeds 300, the tackiness will increase and the workability will be extremely poor.
【0009】本発明で用いる軟化剤のASTM D21
40に準拠して測定される%CA は、18以上であるこ
とが好ましく、より好ましくは23以上、更に好ましく
は25以上である。%CA が18未満では、アスファル
テン分が適正量含有されていても高ロス性付与性能が十
分でない場合がある。The softener used in the present invention, ASTM D21
The% C A measured according to 40, is preferably 18 or more, more preferably 23 or more, more preferably 25 or more. % The C A is less than 18, it may be asphaltene component it has been contained the proper amount of high loss-imparting performance not sufficient.
【0010】本発明の軟化剤の100℃における動粘度
は、ゴム組成物への配合時の作業性(混練機への導入の
しやすさ)の観点から100mm2 /sec以下である
ことが好ましく、さらに好ましくは90mm2 /sec
以下、特に好ましくは80mm2 /sec以下である。The kinematic viscosity of the softener of the present invention at 100 ° C. is preferably 100 mm 2 / sec or less from the viewpoint of workability (easiness of introduction into a kneader) at the time of compounding into a rubber composition. And more preferably 90 mm 2 / sec.
Or less, particularly preferably 80 mm 2 / sec or less.
【0011】本発明の軟化剤は、環境上の理由からIP
346法によるジメチルスルホキシド(DMSO)抽出
物量、即ち、Polycyclic Aromatics( 以下PCAと略
す)の含有量が3重量%未満であることが好ましい。[0011] The softener of the present invention may be used for environmental reasons due to IP.
It is preferable that the amount of dimethyl sulfoxide (DMSO) extract by the 346 method, that is, the content of Polycyclic Aromatics (hereinafter abbreviated as PCA) is less than 3% by weight.
【0012】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、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良いが、軟化剤の調製の容易
さや経済性の観点より、アスファルトをプロセスオイル
(伸展油、配合油を含む)に溶解させて調製する方法が
好ましい。The method for preparing the softener of the present invention is not particularly limited, and the asphalt may be mixed with other softener components in advance, or the main components of asphalt may be appropriately added to the softener in the conventional purification process of the softener. A softening agent prepared by being present in the ratio may be used, but from the viewpoint of ease of preparation of the softening agent and economy, a method of preparing asphalt by dissolving it in process oil (including extender oil and blended oil). Is preferred.
【0013】プロセスオイルにアスファルトを予め溶解
させる場合に用いられるプロセスオイルやアスファルト
の種類は、特に制限されない。プロセスオイルとして
は、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
用いることが出来るが、%CA 及び高ロス性付与性能の
観点より高芳香族系油の使用が好ましい。また、アスフ
ァルトとしては、高ロス性付与性能の強いストレートア
スファルトを用いることが好ましい。The type of process oil or asphalt used when asphalt is previously dissolved in process oil is not particularly limited. Process oils include high aromatic oils, naphthenic oils, paraffin oils, etc.
Usually, those used in the rubber industry, alone or as a mixture but can be used,% C A and the use of highly aromatic oils in view of the high loss factor supply ability is preferred. In addition, as the asphalt, it is preferable to use straight asphalt having a high loss-imparting property.
【0014】用いるアスファルトの針入度は20〜10
0の範囲であることが好ましく、さらに好ましくは40
〜90、特に好ましくは60〜80である。混入させる
アスファルトの針入度が20未満では、アスファルトを
オイルに混入した時の分散性が悪くなり、ゴム物性のバ
ラツキの原因になったり、混入後の軟化剤の粘度が高く
なり作業性が低下する傾向にあり、100を超えると高
ロス性付与性能が十分でないことがある。The penetration of the asphalt used is 20 to 10
0, more preferably 40.
To 90, particularly preferably 60 to 80. If the penetration of the asphalt to be mixed is less than 20, the dispersibility when asphalt is mixed into the oil will be poor, causing the dispersion of rubber physical properties, and the viscosity of the softening agent after mixing will increase, and the workability will decrease. When it exceeds 100, the high loss imparting performance may not be sufficient.
【0015】プロセスオイルへのアスファルトの添加量
は特に制限されないが、高ヒステリシスロス性付与性能
及び作業性(粘度)の適正化、及びアスファルテン成分
の分散低下等の理由から、プロセスオイルの重量に対
し、8重量%〜40重量%であることが好ましい。The amount of asphalt to be added to the process oil is not particularly limited. However, the amount of the asphalt added to the process oil may be reduced due to reasons such as high hysteresis loss imparting performance, optimizing workability (viscosity), and reduction in asphaltene component dispersion. , 8% to 40% by weight.
【0016】本発明のアスファルト分を含む軟化剤は、
ゴム配合時に添加しても、合成ゴムの製造時に伸展油と
して添加しても良い。[0016] The softener containing asphalt component of the present invention comprises:
It may be added at the time of rubber compounding, or may be added as an extender oil during the production of synthetic rubber.
【0017】本発明のアスファルト分を含む軟化剤のゴ
ム組成物への配合量は、高ヒステリシスロス性付与性能
と作業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〜120重量部、特に1重量
部〜100重量部であることが好ましい。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。The amount of the softener containing the asphalt component of the present invention to be added to the rubber composition is from 1 part by weight of the softener to 100 parts by weight of the rubber component from the viewpoint of the balance between high hysteresis loss imparting performance and workability. Parts by weight to 120 parts by weight, particularly preferably 1 part by weight to 100 parts by weight. Here, the blending amount of the softener refers to the total amount of both the extending oil and the blended oil.
【0018】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の総重量を基にして5重量%〜
45重量%、さらには10重量%〜40重量%、特には
12重量%〜38重量%添加されることが好ましく、ゴ
ム組成物への配合油として用いる場合は、ゴム組成物総
重量を基にして0.2重量%〜45重量%、さらには0.5
重量%〜40重量%、 特に好ましくは、1 重量%〜35
重量%であることが好ましい。When used as an extender oil for synthetic rubber, 5% by weight to 5% by weight based on the total weight of the rubber component of the synthetic rubber.
It is preferably added in an amount of 45% by weight, more preferably 10% by weight to 40% by weight, and particularly preferably 12% by weight to 38% by weight. When used as a compounding oil in a rubber composition, it is based on the total weight of the rubber composition. 0.2% to 45% by weight, and even 0.5%
% To 40% by weight, particularly preferably 1% to 35% by weight.
% By weight.
【0019】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、アスファルト含有軟化剤を軟化剤総
量の50重量%以上加えることが好ましい。The asphalt-containing softener used in the rubber composition of the present invention can be partially replaced with another softener. However, also in that case, the total amount of the softener is preferably within the above range, and in order to sufficiently obtain the effects of the present invention, it is necessary to add the asphalt-containing softener to 50% by weight or more of the total softener. preferable.
【0020】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 rubber composition of the present invention is used as a reinforcing filler in an amount of from 20 parts by weight to 150 parts by weight based on 100 parts by weight of the rubber component.
Parts by weight, preferably 25 to 120 parts by weight, more preferably 30 to 105 parts by weight, of carbon black, silica and the like can be used.
【0021】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。[0021] The rubber composition of the present invention is heated by adding a crosslinking agent. In this case, any crosslinking agent can be used as long as it can be used for crosslinking ordinary rubber compositions, such as organic peroxides, sulfur, and organic sulfur compounds. sulfur,
When an organic sulfur compound is used as a crosslinking agent, a vulcanization accelerator usually used in the rubber industry can be appropriately used.
【0022】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32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。The rubber composition of the present invention may contain, in addition to the above components, 5 to 200 parts by weight, preferably 25 to 120 parts by weight, and more preferably 32 parts by weight based on 100 parts by weight of the rubber component. Parts to 105 parts by weight of inorganic fillers commonly used in the rubber industry.
【0023】上記の他にも、本発明のゴム組成物は、老
化防止剤など、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。In addition to the above, the rubber composition of the present invention can appropriately contain various components usually used in the rubber industry, such as an antioxidant.
【0024】[0024]
【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、本発明はその要旨を越えない限
り、以下の実施例に限定されるものではない。EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.
【0025】アスファルト、軟化剤及びゴム組成物の物
性は、以下の方法にしたがって測定した。The physical properties of the asphalt, softener and rubber composition were measured according to the following methods.
【0026】(1)アスファルトの物性 (a)針入度 針入度は、JIS K2207に準拠して25℃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 :重量%)、ナフテン環炭素含有量(%
CN :重量%)、パラフィン鎖炭素含有量(%CP :重
量%)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. in accordance with JIS K2207. (2) Physical Properties of Softener (a) Measurement of Various Carbon Contents by Ring Analysis According to ASTM D2140, aromatic carbon content (% C A : wt%), naphthene ring carbon content ( %
C N : weight%) and the paraffin chain carbon content (% C P : weight%) were measured. (B) Kinematic viscosity Measured at 100 ° C in accordance with JIS K2283-1993. (C) Aniline point Measured in accordance with JIS K2256-1985. (D) The amount of DMSO extracted (% by weight) was measured according to the PCA IP346 method.
【0027】(3)ゴム組成物の試験方法 (a)軟化性能の試験方法 JIS K6300−1994に準拠し、未加硫ゴムサ
ンプルの130℃におけるML1+4 をムーニー粘度測定
機(東洋精機社製)を用いて測定した。評価は、○:軟
化性能優れる、△:軟化過多、×:軟化性能劣るとし
た。 (b)破壊特性の試験方法 JIS K6301−1995に準拠し、加硫ゴムシー
ト(150mm×150mm×2mm)にJIS−3号
の刃型を用い試験片を準備した。この試験片を引張試験
機(東洋精機製ストログラフ AR−1)を用いて25
℃における破断時の伸び及び強度を測定し、○:伸びが
出て、破壊性能優れる、△:伸びは出るが、破壊強度が
悪くなる、−:伸びは出ないが、破壊強度は良好、×:
伸びも出ず、破壊性能も劣ると評価した。 (c)ヒステリシスロス特性の試験方法 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)を用いて、加硫ゴムシート(5mm×45
mm×2mm)の0℃及び25℃におけるtanδを測定
し、それぞれにより低温ヒステリシスロス特性、室温ヒ
ステリシスロス特性を評価した。評価は、◎:高ヒステ
リシスロス特性優れる、×:高ヒステリシスロス特性悪
い、○:高ヒステリシスロス特性問題無しとした。 (d)ゴム混合作業性 ゴム混練り時の作業性を、ロールへの密着性として評価
した。ロールへ密着せず、混合が容易なものを◎(作業
性優良) 、ロールへの付着は見られるが混合は容易なも
のを○(作業性良好)、ロールへの付着が激しいものを
×(作業性悪)として評価した。 (e)取り扱い作業性 ゴム成分に軟化剤を伸展する時の作業性を容器への軟化
剤の密着性として評価した。作業性が良好なものは○、
悪いものは×として表してある。(3) Test method for rubber composition (a) Test method for softening performance According to JIS K6300-1994, ML 1 + 4 of an unvulcanized rubber sample at 130 ° C. was measured using a Mooney viscosity meter (Toyo Seiki Co., Ltd.) Was used for the measurement. The evaluation was ○: excellent softening performance, Δ: excessive softening, ×: poor softening performance. (B) Test method for fracture characteristics In accordance with JIS K6301-1995, test pieces were prepared using vulcanized rubber sheets (150 mm x 150 mm x 2 mm) using JIS-3 blades. This test piece was subjected to a tensile tester (Strograph AR-1 manufactured by Toyo Seiki) for 25 minutes.
The elongation and strength at the time of rupture at 0 ° C. were measured. ○: elongation was obtained and the breaking performance was excellent. Δ: elongation was obtained but the breaking strength was poor. −: No elongation was obtained, but the breaking strength was good. :
No elongation was observed and the breaking performance was evaluated as poor. (C) Test method for hysteresis loss characteristics Using a viscoelasticity tester (Rheorograph Solid L-1R type manufactured by Toyo Seiki Co., Ltd.), a vulcanized rubber sheet (5 mm × 45)
mm × 2 mm) at 0 ° C. and 25 ° C., and the low-temperature hysteresis loss characteristics and the room-temperature hysteresis loss characteristics were evaluated respectively. The evaluation was ◎: excellent in hysteresis loss characteristics, ×: poor in hysteresis loss characteristics, ○: no problem with high hysteresis loss characteristics. (D) Rubber Mixing Workability The workability during rubber kneading was evaluated as adhesion to a roll. ◎ (Excellent workability) for those that do not adhere to the roll and are easy to mix; ○ (good for workability) where adhesion to the roll is observed but easy to mix; x (for good adhesion to the roll) It was evaluated as poor workability. (E) Workability The workability when the softener was extended to the rubber component was evaluated as the adhesion of the softener to the container. Good workability is ○,
Bad ones are represented by x.
【0028】(1)軟化剤の調製方法 予め70℃の加熱した、市販の高芳香族系油(富士興産
(株) 製,アロマックス3)の所定量を精秤した後、予
め85℃に加熱して粘度を下げ、所定量を精秤したスト
レートアスファルトを70℃に保温しながら混入したの
ち5分間攪拌を継続し、本発明の軟化剤を調製した。使
用した高芳香族系油の物性を第1表に示す。(1) Preparation method of softener A predetermined amount of a commercially available highly aromatic oil (Aromax 3 manufactured by Fujikosan Co., Ltd.) heated to 70 ° C. was precisely weighed, and then preliminarily heated to 85 ° C. The viscosity was lowered by heating, and a predetermined amount of straight asphalt was mixed while keeping the temperature at 70 ° C., and then stirring was continued for 5 minutes to prepare the softener of the present invention. Table 1 shows the physical properties of the high aromatic oil used.
【0029】[0029]
【表1】 [Table 1]
【0030】(2)油展合成ゴムの調製 5リットル(L)の耐圧反応容器に乾燥済のシクロヘキ
サン1200g、スチレン80g及びブタジエン120
gを投入し、内容物を50℃に調整した。更に、ランダ
マイザーとしてテトラヒドロフラン60mmolを投入
した後、開始剤として1.6mmolのn−ブチルリチウ
ム(n−BuLi)を溶解した1.6N濃度のn−ヘキサ
ン溶液を加えた。その後、50℃で2時間重合した。重
合完了後、重合系に2,6−ジ−t−ブチル−p−クレ
ゾール(BHT)0.5gをイソプロパノール5mlに溶
解した溶液を加え、重合を停止させた。重合停止後、第
2表の処方で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。(2) Preparation of oil-extended synthetic rubber 1200 g of dried cyclohexane, 80 g of styrene and 120 g of butadiene were placed in a 5-liter (L) pressure-resistant reaction vessel.
g was added, and the content was adjusted to 50 ° C. Further, after adding 60 mmol of tetrahydrofuran as a randomizer, a 1.6N n-hexane solution in which 1.6 mmol of n-butyllithium (n-BuLi) was dissolved was added as an initiator. Thereafter, polymerization was carried out at 50 ° C. for 2 hours. After completion of the polymerization, a solution prepared by dissolving 0.5 g of 2,6-di-t-butyl-p-cresol (BHT) in 5 ml of isopropanol was added to the polymerization system to terminate the polymerization. After terminating the polymerization, a softener was added according to the formulation shown in Table 2, and then dried by a usual method to obtain an oil-extended synthetic rubber.
【0031】(3)試験片の調製方法 第2表に示す配合処方のマスターバッチ用原材料を混練
機を用い混合した後、表面温度70℃のロールを用いて
シート状にした。その後、このマスターバッチと最終原
材料を混練機を用いて混合した後、表面温度70℃のロ
ールを用いてシート状にした。その後、これを適当な金
型に充填し、温度160℃、圧力30kg/cm2 、加
熱時間15分の条件で加硫した後脱型し、所定の試験片
を調製した。(3) Preparation of Test Specimens The raw materials for the master batch having the composition shown in Table 2 were mixed using a kneader, and then formed into a sheet using a roll having a surface temperature of 70 ° C. Thereafter, the master batch and the final raw material were mixed using a kneader, and then formed into a sheet using a roll having a surface temperature of 70 ° C. Thereafter, this was filled in an appropriate mold, vulcanized under the conditions of a temperature of 160 ° C., a pressure of 30 kg / cm 2 , and a heating time of 15 minutes, and then demolded to prepare a predetermined test piece.
【0032】[0032]
【表2】 [Table 2]
【0033】*1:乳化重合SBR,JSR(株) 製,
商標#1500 *2:N220ISAF,東海カーボン(株)製,商標
シースト6 *3:第1表の高芳香族系油を用いて調製して使用(配
合1では配合油として、配合2では伸展油としてそれぞ
れ使用) *4:ノクセラーD(商標),大内新興化学工業(株)
製 *5:ノクセラーDM(商標),大内新興化学工業
(株)製 *6:ノクセラーNS(商標),大内新興化学工業
(株)製 *7:ノクラック6C(商標),大内新興化学工業
(株)製* 1: Emulsion polymerization SBR, manufactured by JSR Corporation,
Trademark # 1500 * 2: N220ISAF, manufactured by Tokai Carbon Co., Ltd., Trademark Seast 6 * 3: Prepared and used using the highly aromatic oil shown in Table 1 (Formulation 1 as a compounded oil, Formulation 2 as an extender oil) * 4: Noxeller D (trademark), Ouchi Shinko Chemical Industry Co., Ltd.
* 5: Noxeller DM (trademark), manufactured by Ouchi Shinko Chemical Industry Co., Ltd. * 6: Noxeller NS (trademark), manufactured by Ouchi Shinko Chemical Industry Co., Ltd. * 7: Nocrack 6C (trademark), Ouchi Shinko Chemical Industrial Co., Ltd.
【0034】[0034]
【表3】 [Table 3]
【0035】[0035]
【表4】 [Table 4]
【0036】*1: ゴム成分100重量部あたりの配
合部数(重量部) *2: A−予め高芳香族系油にアスファルトを混合し
た軟化剤を使用 B−高芳香族系油とアスファルトを別々に混合 *3: STAはストレートアスファルトを示す* 1: Number of parts (parts by weight) per 100 parts by weight of rubber component * 2: A: A softener in which asphalt was previously mixed with highly aromatic oil B: Separation of highly aromatic oil and asphalt * 3: STA indicates straight asphalt
【0037】第3表は、第2表の配合1に従って調製し
たゴム組成物に関する。比較例1は、軟化剤にアスファ
ルテン分を全く含まない例で、コントロールである。比
較例2は、アスファルトと高芳香族系油を別々にゴム成
分に混合した場合でゴム混練時の作業性が非常に悪い。
比較例3,4及び実施例1〜3より、アスファルテン分
が0.1重量%未満のときはゴム組成物の高ロス性が十分
に得られず、4重量%を超えると作業性が劣ることが判
る。さらに、本発明の範囲であれば高ロス性のゴム組成
物を容易に得ることができ、アスファルテン分が0.3重
量%〜3.0重量%のときにさらに効果が顕著であること
が判る。また、実施例2,4〜6より、%CA が18以
上の方が、ゴム組成物への高ロス性付与性能が顕著であ
り、%CA が23以上、さらには25以上のとき、一段
と効果が大きいことが判る。さらに、実施例3,7よ
り、軟化剤の動粘度は100mm2 /sec以下の方が
作業性が向上することが判る。比較例5,6より、軟化
剤の配合量はゴム成分100重量部に対して1重量部未
満では添加効果がなく、120重量部を超えて配合する
と混合作業性が低下することが判る。Table 3 relates to the rubber compositions prepared according to Formulation 1 of Table 2. Comparative Example 1 is a control which is an example in which the asphaltene component is not included in the softener at all. In Comparative Example 2, the asphalt and the highly aromatic oil were separately mixed into the rubber component, and the workability during rubber kneading was very poor.
According to Comparative Examples 3 and 4 and Examples 1 to 3, when the asphaltenes content is less than 0.1% by weight, the high loss property of the rubber composition cannot be sufficiently obtained, and when the asphaltene content exceeds 4% by weight, the workability is inferior. I understand. Further, within the range of the present invention, a high-loss rubber composition can be easily obtained, and it is understood that the effect is more remarkable when the asphaltenes content is 0.3% by weight to 3.0% by weight. . Also, from Examples 2,4~6,% C A is the direction of 18 or more, a high loss imparting performance to the rubber composition is the remarkable,% C A is 23 or more, more at 25 or higher, It turns out that the effect is even greater. Further, from Examples 3 and 7, it can be seen that the workability is improved when the kinematic viscosity of the softener is 100 mm 2 / sec or less. From Comparative Examples 5 and 6, it can be seen that if the compounding amount of the softening agent is less than 1 part by weight with respect to 100 parts by weight of the rubber component, there is no effect, and if the compounding amount exceeds 120 parts by weight, the mixing workability decreases.
【0038】[0038]
【表5】 [Table 5]
【0039】*1:C−予めアスファルトをプロセスオ
イルに混合した軟化剤を伸展 D−プロセスオイルとアスファルトを別々に伸展 STA:ストレートアスファルト* 1: C-extending softener in which asphalt was previously mixed with process oil D-extending process oil and asphalt separately STA: straight asphalt
【0040】第4表は、第2表の配合2に従って調製し
たゴム組成物に関する。比較例7は、合成ゴムの伸展油
としてアスファルテン分を全く含まない軟化剤を用いた
例で、コントロールである。比較例8は、アスファルト
を軟化剤と別々にポリマーに油展した場合で油展作業時
の作業性が非常に悪い。比較例7,実施例8,実施例9
よりアスファルテン分含有軟化剤を伸展油として用いた
場合にも、配合油として用いた場合と同様の効果がある
ことが判る。Table 4 relates to the rubber compositions prepared according to Formulation 2 of Table 2. Comparative Example 7 is an example in which a softener containing no asphaltene component was used as a synthetic rubber extender oil, which is a control. Comparative Example 8 was a case where asphalt was oil-extended into a polymer separately from a softener, and the workability during oil-extending operation was very poor. Comparative Example 7, Example 8, Example 9
It can be seen that the use of asphaltene-containing softener as the extender oil has the same effect as the use of the blended oil.
【0041】[0041]
【発明の効果】以上のように、本発明のゴム組成物は、
特定量のアスファルテン分を含む軟化剤を用いることに
より、作業性を悪化させることなく、高ロス性能や破壊
特性が改良されるため、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, the rubber composition of the present invention
By using a softener containing a specific amount of asphaltenes, high loss performance and breakage characteristics are improved without deteriorating workability, so that it can be used for various rubber articles such as tires, anti-vibration rubber, fenders, etc. It can be preferably used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C08L 95:00) ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 95:00)
Claims (4)
くとも一種のゴム成分100重量部及びアスファルテン
分を0.1重量%〜4重量%の範囲で含有する軟化剤1重
量部〜120重量部からなるゴム組成物。1. A rubber composition comprising 100 parts by weight of at least one rubber component selected from natural rubber and synthetic rubber and 1 part by weight to 120 parts by weight of a softening agent containing asphaltenes in a range of 0.1% by weight to 4% by weight. Rubber composition.
て測定された芳香族炭素含有量(%CA )が、18以上
である請求項1記載のゴム組成物。2. The rubber composition according to claim 1, wherein the aromatic carbon content (% C A ) measured according to ASDM D2140 of the softener is 18 or more.
トとを混合して得られたものである請求項1記載のゴム
組成物。3. The rubber composition according to claim 1, wherein the softening agent is obtained by mixing a process oil and asphalt.
トである請求項3記載のゴム組成物。4. The rubber composition according to claim 3, wherein the asphalt is straight asphalt.
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JP4476499A JP4364963B2 (en) | 1998-02-23 | 1999-02-23 | Rubber composition |
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JP10-40184 | 1998-02-23 | ||
JP4018498 | 1998-02-23 | ||
JP4476499A JP4364963B2 (en) | 1998-02-23 | 1999-02-23 | Rubber composition |
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JPH11302459A true JPH11302459A (en) | 1999-11-02 |
JP4364963B2 JP4364963B2 (en) | 2009-11-18 |
Family
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JP4476499A Expired - Lifetime JP4364963B2 (en) | 1998-02-23 | 1999-02-23 | Rubber composition |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004046239A1 (en) * | 2002-11-15 | 2004-06-03 | Bridgestone Corporation | Rubber composition for tread and tire |
JP2005002295A (en) * | 2003-06-16 | 2005-01-06 | Bridgestone Corp | Rubber composition for tire and tire |
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 |
JP2008168898A (en) * | 2008-03-21 | 2008-07-24 | Bridgestone Corp | Pneumatic tire |
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 |
CN109810521A (en) * | 2018-05-11 | 2019-05-28 | 江苏宝利国际投资股份有限公司 | A kind of high glue master batch of bitumen and its low-temperature environment-friendly metaplasia production. art |
US11104105B2 (en) | 2017-04-12 | 2021-08-31 | Bridgestone Corporation | Tire, and method for manufacturing tire |
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1999
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004046239A1 (en) * | 2002-11-15 | 2004-06-03 | Bridgestone Corporation | Rubber composition for tread and tire |
US7709561B2 (en) | 2002-11-15 | 2010-05-04 | Bridgestone Corporation | Rubber composition for tread and tire |
JP2005002295A (en) * | 2003-06-16 | 2005-01-06 | Bridgestone Corp | Rubber composition for tire and tire |
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 |
JP2008168898A (en) * | 2008-03-21 | 2008-07-24 | Bridgestone Corp | Pneumatic tire |
JP4629748B2 (en) * | 2008-03-21 | 2011-02-09 | 株式会社ブリヂストン | Pneumatic tire |
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 |
US11104105B2 (en) | 2017-04-12 | 2021-08-31 | Bridgestone Corporation | Tire, and method for manufacturing tire |
CN109810521A (en) * | 2018-05-11 | 2019-05-28 | 江苏宝利国际投资股份有限公司 | A kind of high glue master batch of bitumen and its low-temperature environment-friendly metaplasia production. art |
CN109810521B (en) * | 2018-05-11 | 2021-04-16 | 江苏宝利国际投资股份有限公司 | High-rubber asphalt master batch and low-temperature environment-friendly production process thereof |
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