JP2003268157A - Rubber composition and pneumatic tire made by using it - Google Patents
Rubber composition and pneumatic tire made by using itInfo
- Publication number
- JP2003268157A JP2003268157A JP2002072231A JP2002072231A JP2003268157A JP 2003268157 A JP2003268157 A JP 2003268157A JP 2002072231 A JP2002072231 A JP 2002072231A JP 2002072231 A JP2002072231 A JP 2002072231A JP 2003268157 A JP2003268157 A JP 2003268157A
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- rubber
- rubber composition
- polysulphurized
- polysulfide
- 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
- Tires In General (AREA)
- 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、更に詳しくは、潤滑油添加剤の一種である硫黄系極
圧添加剤を加工助剤としてゴムに配合したゴム組成物、
およびそれを使用した空気入りタイヤに関する。TECHNICAL FIELD The present invention relates to a rubber composition, and more specifically, a rubber composition in which a sulfur-based extreme pressure additive, which is one of lubricating oil additives, is blended with a rubber as a processing aid.
And a pneumatic tire using the same.
【０００２】[0002]
【従来の技術】従来、ゴム用加工助剤として、脂肪酸エ
ステルや油脂を硫黄や塩化硫黄により架橋し、ゲル化さ
せた油脂重合体、いわゆる“ファクチス”が使用されて
いる。しかし、これには、硬度、モジュラスが低下する
という問題がある。当該硫黄系極圧添加剤を、ゴム用加
工助剤としてゴムに配合した先行技術は見当たらない。2. Description of the Related Art Hitherto, as a rubber processing aid, an oil-and-fat polymer obtained by cross-linking a fatty acid ester or an oil or fat with sulfur or sulfur chloride to form a gel, so-called "factis" has been used. However, this has a problem that hardness and modulus are lowered. No prior art is found in which the sulfur-based extreme pressure additive is compounded with rubber as a processing aid for rubber.
【０００３】[0003]
【発明が解決しようとする課題】したがって、本発明で
は、硫黄系極圧添加剤をゴムに加工助剤として配合する
ことにより、ゴム硬度の低下を抑制しつつ、ムーニー粘
度を低下させるという加工性を向上させたゴム組成物を
提供することを目的とする。Therefore, in the present invention, by adding a sulfur-based extreme pressure additive to a rubber as a processing aid, it is possible to suppress the decrease in rubber hardness while reducing the Mooney viscosity. An object of the present invention is to provide a rubber composition having improved rubber composition.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、硫黄加
硫可能なジエン系ゴム１００重量部に対して、多硫化炭
化水素、多硫化脂肪酸、多硫化脂肪酸エステルおよび多
硫化油脂の群から選ばれる硫黄系極圧添加剤の少なくと
も一種を１〜５０重量部配合してなるゴム組成物が提供
される。According to the present invention, 100 parts by weight of a sulfur-vulcanizable diene rubber is selected from the group of polysulfide hydrocarbons, polysulfide fatty acids, polysulfide fatty acid esters and polysulfide oils and fats. Provided is a rubber composition containing 1 to 50 parts by weight of at least one selected sulfur-based extreme pressure additive.
【０００５】また、本発明によれば、当該ゴム組成物を
タイヤ部材に使用した空気入りタイヤが提供される。Further, according to the present invention, there is provided a pneumatic tire using the rubber composition for a tire member.
【０００６】[0006]
【発明の実施の形態】本発明では、従来から潤滑油添加
剤の一種としてとして使用されてきた多硫化炭化水素、
多硫化脂肪酸、多硫化脂肪酸エステルおよび多硫化油脂
等の硫黄系極圧添加剤を、硫黄加硫可能なジエン系ゴム
に配合すると、ゴム硬度の低下が抑制され、かつムーニ
ー粘度が低下するという加工性の向上が見られることを
始めて見出したものである。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a polysulfide hydrocarbon, which has been used as a kind of lubricating oil additive,
When sulfur extreme pressure additives such as polysulphurized fatty acids, polysulphurized fatty acid esters and polysulphurized fats and oils are blended with a sulfur vulcanizable diene rubber, the decrease in rubber hardness is suppressed and the Mooney viscosity is reduced. This is the first finding that the improvement in sex is seen.
【０００７】本発明のゴム組成物に使用される硫黄加硫
可能なジエン系ゴム成分には、天然ゴム（ＮＲ）、およ
びジエン系合成ゴムとしての、例えば、ポリイソプレン
ゴム（ＩＰ）、各種スチレン−ブタジエン共重合体ゴム
（ＳＢＲ）、各種ポリブタジエンゴム（ＢＲ）、アクリ
ロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、ブチ
ルゴム（ＩＩＲ）等が使用される。これらは、単独で、
あるいは２種以上のゴム混合物として使用することがで
きる。天然ゴムとジエン系合成ゴムの２種以上のゴム混
合物として使用する場合には、天然ゴムの配合比率が２
０〜１００重量部であるゴム組成物とすることが所望の
目的を達成する上で好ましい。The sulfur-vulcanizable diene rubber component used in the rubber composition of the present invention includes natural rubber (NR) and diene synthetic rubber such as polyisoprene rubber (IP) and various styrenes. -Butadiene copolymer rubber (SBR), various polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), etc. are used. These are
Alternatively, it can be used as a mixture of two or more rubbers. When used as a rubber mixture of two or more kinds of natural rubber and diene synthetic rubber, the compounding ratio of natural rubber is 2
The rubber composition is preferably 0 to 100 parts by weight in order to achieve the desired purpose.
【０００８】本発明のゴム加工剤として使用される硫黄
系極圧添加剤としては、多硫化炭化水素、多硫化脂肪
酸、多硫化脂肪酸エステルおよび多硫化油脂から選ばれ
る少なくとも一種の多硫化化合物が用いられる。これら
は市販の公知の化合物であり、これが単独で、または任
意の混合物として使用されてよい。この多硫化化合物に
含まれる硫黄含有量は重量比で５〜５０重量％であり、
また、該多硫化化合物中に含まれる平均硫黄分子数は２
〜６であることが、製品が高硬度で、かつ加工時におけ
るムーニー粘度が低いという本発明の作用効果を達成す
る上で好ましい。そして、この配合量は、総量で１〜５
０重量部、より好ましくは３〜３０重量部が好適であ
り、この配合量が少ないと所望の作用効果を発揮でき
ず、また、逆に多過ぎると、所望の硬度およびモジュラ
スが得られないので好ましくない。As the sulfur-based extreme pressure additive used as the rubber processing agent of the present invention, at least one polysulfide compound selected from polysulfide hydrocarbons, polysulfide fatty acids, polysulfide fatty acid esters and polysulfide oils and fats is used. To be These are known compounds which are commercially available and may be used alone or as an arbitrary mixture. The sulfur content of this polysulfide compound is 5 to 50% by weight,
The average number of sulfur molecules contained in the polysulfide compound is 2
It is preferably from 6 to 6 in order to achieve the effect of the present invention that the product has high hardness and the Mooney viscosity during processing is low. And this compounding quantity is 1-5 in total.
0 part by weight, more preferably 3 to 30 parts by weight is suitable. If the amount is too small, the desired action and effect cannot be exhibited. On the contrary, if the amount is too large, the desired hardness and modulus cannot be obtained. Not preferable.
【０００９】前記硫黄系極圧添加剤の具体例としては、
以下の多硫化化合物を有効に使用することができる。多硫化炭化水素
式：ＣnＨ2n+1−（Ｓ）x−ＣnＨ2n+1 （式中、ｎは３
〜２５であり、ｘは２〜６である）で表わされる多硫化
炭化水素化合物を挙げることができ、具体的には、以下
の式（Ｉ）で示される多硫化Ｃ5オレフィンが挙げられ
る。Specific examples of the sulfur-based extreme pressure additive include:
The following polysulfide compounds can be effectively used. Polysulfide hydrocarbons formula: C n H 2n + 1 - (S) x -C n H 2n + 1 ( wherein, n 3
To 25 and x is 2 to 6), and specific examples thereof include polysulfide C 5 olefins represented by the following formula (I).
【化１】 [Chemical 1]
【００１０】多硫化脂肪酸
パルミトオレイン酸、オレイン酸、バクセン酸、リノー
ル酸、リノレン酸、エレオステアリン酸、アラキジン
酸、アラキドン酸、ネルボン酸等の不飽和脂肪酸の多硫
化物が挙げられる。 Polysulfated fatty acids : Polysulfates of unsaturated fatty acids such as palmitooleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid and nervonic acid can be mentioned.
【００１１】多硫化脂肪酸エステル
オレイン酸、エライジン酸、リノール酸、リノレン酸、
ステアロール酸、リシノール酸、リシノエライジン酸、
ブラシジン酸、エルカ酸等のメチルおよびエチルエステ
ル化合物の多硫化物が挙げられる。具体的には、例え
ば、以下の式（ＩＩ）で示される脂肪酸の２量体や、そ
れぞれ式（ＩＩＩ）、（ＩＶ）および（Ｖ）で示される
１量体（例えば３６重量％）、２量体（例えば４７重量
％）および３量体（例えば９重量％）の混合物等が挙げ
られる。 Polysulfide fatty acid ester Oleic acid, elaidic acid, linoleic acid, linolenic acid,
Stearolic acid, ricinoleic acid, ricinoelaidic acid,
Mention may be made of polysulfides of methyl and ethyl ester compounds such as brassic acid and erucic acid. Specifically, for example, a dimer of a fatty acid represented by the following formula (II) and a dimer represented by the formulas (III), (IV) and (V) (for example, 36% by weight), 2 Examples include a mixture of a trimer (for example, 47% by weight) and a trimer (for example, 9% by weight).
【００１２】[0012]
【化２】 [Chemical 2]
【００１３】[0013]
【化３】 [Chemical 3]
【００１４】多硫化油脂
具体的には、例えば、以下の式（ＶＩ）および（ＶＩ
Ｉ）で示される分子内硫黄架橋構造および分子間硫黄架
橋構造のものが挙げられる。Specifically, for example, polysulfide oils and fats are represented by the following formulas (VI) and (VI)
Examples thereof include those having an intramolecular sulfur crosslinked structure and an intermolecular sulfur crosslinked structure represented by I).
【００１５】[0015]
【化４】 [Chemical 4]
【００１６】本発明のゴム組成物には、前記した成分に
加えて、通常のカーボンブラックやシリカなどの補強
剤、加硫または架橋剤、加硫または架橋促進剤、各種オ
イル、老化防止剤、可塑剤などのタイヤ用、その他一般
ゴム用に一般的に配合されている各種添加剤が配合され
て用いられる。かかる配合物は、一般的な方法で混練、
加硫してゴム組成物とし、加硫または架橋製品とするこ
とができる。これら添加剤の配合量も、本発明の目的に
反しない限り、従来の一般的な配合量とすることができ
る。In the rubber composition of the present invention, in addition to the above-mentioned components, usual reinforcing agents such as carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, antiaging agents, Various additives generally used for tires such as plasticizers and other general rubbers are blended and used. Such a compound is kneaded by a general method,
It can be vulcanized into a rubber composition to give a vulcanized or crosslinked product. The amounts of these additives to be added can also be the conventional amounts generally used unless the object of the present invention is violated.
【００１７】本発明のゴム組成物は、これを空気入りタ
イヤにおけるトレッド、ビードフィラー、サイドウォー
ル、カーカス、リムクッション、ベルトクッション、エ
ッジカバーシート、ベルトエッジクッション等の各部材
に使用する時は、その特性を有効に発揮するので、極め
て有用である。When the rubber composition of the present invention is used for each member such as a tread, a bead filler, a sidewall, a carcass, a rim cushion, a belt cushion, an edge cover sheet and a belt edge cushion in a pneumatic tire, It is extremely useful because it exhibits its characteristics effectively.
【００１８】[0018]
【実施例】以下、標準例、実施例および比較例によって
本発明を更に説明するが、本発明の技術的範囲をこれら
の実施例によって限定するものでないことは言うまでも
ない。EXAMPLES The present invention will be further described below with reference to standard examples, examples and comparative examples, but it goes without saying that the technical scope of the present invention is not limited by these examples.
【００１９】試験サンプルの作製
以下の表１に示す配合における加硫促進剤と硫黄を除く
成分を、１.７リットルの密閉式バンバリーミキサーで
５分間混練し、１６５±５℃に達した時に放出したマス
ターバッチに加硫促進剤と硫黄を８インチのオープンロ
ールで混練してゴム組成物を得た。得られたゴム組成物
のムーニー粘度を測定した。次いで、このゴム組成物を
１５×１５×０.２ｃｍの金型中で、１６０℃で２０分
間プレス加硫して目的とする試験片を作製し、これによ
り硬さ（Ｈｓ）および引張強さを測定、評価した。Preparation of test sample The vulcanization accelerator and the components other than sulfur in the formulations shown in Table 1 below were kneaded for 5 minutes in a 1.7 liter closed Banbury mixer, and were released when the temperature reached 165 ± 5 ° C. A rubber composition was obtained by kneading the vulcanization accelerator and sulfur with the prepared masterbatch using an 8-inch open roll. The Mooney viscosity of the obtained rubber composition was measured. Then, this rubber composition was press-vulcanized in a mold of 15 × 15 × 0.2 cm at 160 ° C. for 20 minutes to prepare a desired test piece, which had a hardness (Hs) and a tensile strength. Was measured and evaluated.
【００２０】試験方法
１）ムーニー粘度：ＪＩＳ Ｋ６３００に準拠して、１
００℃にて測定した。標準例を１００として、指数で評
価した。指数の低い方が粘度が低く、加工性が優れてい
ることを示す。
２）硬さ（Ｈｓ）：ＪＩＳ Ｋ６３００に準拠して、室
温にて測定した。標準例を１００として、指数で評価し
た。指数の高い方が硬さが大きく、優れていることを示
す。
３）引張強さ（Ｍ１００）：ＪＩＳ Ｋ６２５１に準拠
して、１００％モジュラス（Ｍ１００）ＭＰaを測定し
た。標準例を１００として、指数で評価した。指数の高
い方が引張強さが大きく、優れていることを示す。 Test method 1) Mooney viscosity: 1 according to JIS K6300
It was measured at 00 ° C. The standard example was set to 100 and evaluated by an index. The lower the index, the lower the viscosity and the better the processability. 2) Hardness (Hs): Measured at room temperature according to JIS K6300. The standard example was set to 100 and evaluated by an index. The higher the index, the greater the hardness and the better. 3) Tensile strength (M100): 100% modulus (M100) MPa was measured according to JIS K6251. The standard example was set to 100 and evaluated by an index. The higher the index, the greater the tensile strength and the better.
【００２１】標準例１〜２、実施例１〜９および比較例
１〜６
結果を表１に示す。 Standard Examples 1-2, Examples 1-9 and Comparative Examples
The results of 1 to 6 are shown in Table 1.
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】上記表１の結果よりみて、本発明の硫黄
系極圧添加剤を加工助剤に使用した実施例のゴム組成物
では、ムーニー粘度が標準例の何も添加しないものより
も低くてゴム加工性が改良されていながら、硬さおよび
引張強さの点では低下しておらず、むしろ向上している
ことがわかる。これに比して、従来での加工助剤のアロ
マ系オイルを用いた比較例では、ムーニー粘度が下がっ
て加工性は向上するも、硬さおよび引張り強さの点で、
大きく低下していることがわかる。よって、本発明のゴ
ム組成物は、その硬度および機械的特性の低下を抑制し
つつ、その加工性を向上させていることから、特に、空
気入りタイヤの各部材にこれを使用すれば、極めて有用
である。From the results shown in Table 1 above, in the rubber compositions of the examples in which the sulfur-based extreme pressure additive of the present invention was used as a processing aid, the Mooney viscosity was higher than that of the standard example in which nothing was added. It can be seen that although the rubber processability is low and the rubber processability is improved, the hardness and the tensile strength are not decreased, but rather improved. In contrast, in the comparative example using the conventional processing aid aroma oil, although the Mooney viscosity is lowered and the workability is improved, in terms of hardness and tensile strength,
It can be seen that it has dropped significantly. Therefore, the rubber composition of the present invention, while suppressing the deterioration of its hardness and mechanical properties, has improved its workability, particularly when this is used for each member of the pneumatic tire, It is useful.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石川 泰弘 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 Ｆターム(参考） 4J002 AC011 AC031 AC061 AC071 AC081 AE012 BB181 EV046 GN01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yasuhiro Ishikawa 2-1, Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Ceremony Company Hiratsuka Factory F-term (reference) 4J002 AC011 AC031 AC061 AC071 AC081 AE012 BB181 EV046 GN01
Claims (5)
部に対して、多硫化炭化水素、多硫化脂肪酸、多硫化脂
肪酸エステルおよび多硫化油脂の群から選ばれる硫黄系
極圧添加剤の少なくとも一種を１〜５０重量部配合して
なるゴム組成物。1. At least a sulfur-based extreme pressure additive selected from the group consisting of polysulphurized hydrocarbons, polysulphurized fatty acids, polysulphurized fatty acid esters, and polysulphurized fats and oils based on 100 parts by weight of a sulfur-vulcanizable diene rubber. A rubber composition containing 1 to 50 parts by weight of one type.
合比率が２０〜１００重量部である、請求項１に記載の
ゴム組成物。2. The rubber composition according to claim 1, wherein the compounding ratio of the natural rubber in the diene rubber is 20 to 100 parts by weight.
硫化脂肪酸エステルおよび多硫化油脂の群から選ばれる
硫黄系極圧添加剤のそれぞれに含まれる硫黄含有量が重
量比で５〜５０重量％である、請求項１または２に記載
のゴム組成物。3. The sulfur content contained in each of the sulfur-based extreme pressure additives selected from the group consisting of polysulphurized hydrocarbons, polysulphurized fatty acids, polysulphurized fatty acid esters and polysulphurized fats and oils is 5 to 50 wt% by weight. %, The rubber composition according to claim 1 or 2.
硫化脂肪酸エステルおよび多硫化油脂の群から選ばれる
硫黄系極圧添加剤のそれぞれの硫黄系極圧添加剤中に含
まれる平均硫黄分子数が２〜６である、請求項１〜３の
いずれか１項に記載のゴム組成物。4. An average sulfur molecule contained in each of the sulfur-based extreme pressure additives of the sulfur-based extreme pressure additives selected from the group of the polysulfide hydrocarbons, polysulfide fatty acids, polysulfide fatty acid esters and polysulfide fats and oils. The rubber composition according to any one of claims 1 to 3, wherein the number is 2 to 6.
ム組成物を用いた空気入りタイヤ。5. A pneumatic tire using the rubber composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002072231A JP4059691B2 (en) | 2002-03-15 | 2002-03-15 | Rubber composition and pneumatic tire using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002072231A JP4059691B2 (en) | 2002-03-15 | 2002-03-15 | Rubber composition and pneumatic tire using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003268157A true JP2003268157A (en) | 2003-09-25 |
| JP4059691B2 JP4059691B2 (en) | 2008-03-12 |
Family
ID=29202282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002072231A Expired - Lifetime JP4059691B2 (en) | 2002-03-15 | 2002-03-15 | Rubber composition and pneumatic tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4059691B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201217525D0 (en) | 2012-10-01 | 2012-11-14 | Isis Innovation | Composition for hydrogen generation |
| US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
-
2002
- 2002-03-15 JP JP2002072231A patent/JP4059691B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP4059691B2 (en) | 2008-03-12 |
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