JP3295456B2 - Rubber composition containing new crosslinking agent - Google Patents
Rubber composition containing new crosslinking agentInfo
- Publication number
- JP3295456B2 JP3295456B2 JP22807492A JP22807492A JP3295456B2 JP 3295456 B2 JP3295456 B2 JP 3295456B2 JP 22807492 A JP22807492 A JP 22807492A JP 22807492 A JP22807492 A JP 22807492A JP 3295456 B2 JP3295456 B2 JP 3295456B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- rubber composition
- vulcanization
- present
- crosslinking agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は屈曲疲労性と耐熱性とに
優れたゴム組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition having excellent flex fatigue and heat resistance.
【０００２】[0002]
【従来の技術】従来、タイヤ等の各種ゴム製品用の加硫
ゴムの耐熱性向上を図るため、電子線（ＥＶ）加硫や、
テトラメチルチウラムジサルファイド（ＴＭＴＤ）等の
サルファ−ドナ加硫剤を配合し、モノスルフィドの多い
架橋構造をつくることが知られている。しかし、このよ
うなモノスルフィド架橋構造は、ポリマ−分子の運動性
を拘束し、耐屈曲疲労性が大きく低下してしまう事実が
ある。一方、コンベンショナルキュアと呼ばれるポリス
ルフィド架橋形態では、耐屈曲疲労性には優れるが、Ｓ
−Ｓ結合が熱的に弱いため、一般に耐熱性に劣ることが
分かっている。従って、屈曲疲労性と耐熱性とを同時に
満足する理想的な架橋構造としては、（ポリマ−）−Ｓ
−Ｒ−Ｓ−（ポリマ−）といった構造が考えられる。2. Description of the Related Art Conventionally, in order to improve the heat resistance of vulcanized rubber for various rubber products such as tires, electron beam (EV) vulcanization,
It is known that a sulfa-dona vulcanizing agent such as tetramethylthiuram disulfide (TMTD) is blended to form a crosslinked structure containing a large amount of monosulfide. However, there is a fact that such a monosulfide cross-linked structure restricts the mobility of the polymer molecule and greatly reduces the bending fatigue resistance. On the other hand, the polysulfide cross-linked form called conventional cure has excellent flex fatigue resistance,
It has been found that heat resistance is generally inferior because the -S bond is thermally weak. Therefore, an ideal crosslinked structure that simultaneously satisfies both bending fatigue resistance and heat resistance is (polymer) -S
A structure such as —RS— (polymer) is conceivable.
【０００３】[0003]
【発明が解決しようとする課題】しかるに、かかる架橋
構造に類似する構造を生成する架橋剤が、特公昭５５−
４１３６号公報によって開示されている。しかし、この
公報に示されている加硫剤は、耐熱性を重視していない
ため、（ポリマ−）−Ｓｘ−Ｒ−Ｓｘ−（ポリマ−）、
ｘ≧１となり、熱的に比較的弱いＳ−Ｓ結合がポリマ−
中に導入される確率が高い。又、分子中にアミン構造を
有しない化合物は、加硫速度が極めて遅く工業的利用に
適さず、アミン構造を有する化合物は適度な加硫速度が
得られるが、この開示された加硫剤は、１９８２年西ド
イツにおいて規制された発ガン性Ｎ−ニトロソアミンを
発生させるジアミンを含み、安全性に問題がある。However, a cross-linking agent that forms a structure similar to such a cross-linked structure is disclosed in
No. 4136 discloses this. However, the vulcanizing agents described in this publication do not place importance on heat resistance, and therefore, (polymer) -Sx-R-Sx- (polymer),
x ≧ 1 and the thermally weak SS bond is polymer
The probability of being introduced during is high. Further, compounds having no amine structure in the molecule have a very low vulcanization rate and are not suitable for industrial use, and compounds having an amine structure can obtain an appropriate vulcanization rate. , Containing diamines that generate carcinogenic N-nitrosamines regulated in West Germany in 1982, with safety concerns.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記問題を
解決するために鋭意検討した結果、原料ゴム組成物に特
定の化合物を配合することにより、耐屈曲疲労性及び耐
熱性が大巾に向上することを見出し、本発明を完成する
に至った。Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventor has found that by blending a specific compound into a raw rubber composition, the bending fatigue resistance and heat resistance can be greatly improved. And completed the present invention.
【０００５】即ち、加硫可能な原料ゴム１００重量部に
対し、式１〜式２にて示す化合物（式中、Ｒ1 、Ｒ2 は
アルキル基、シクロアルキル基、フェニル基、ベンゾチ
アゾール基を表し、Ｒ1 、Ｒ2 は同一でも良く、異って
も良い。Ｒ3 、Ｒ4 、Ｒ5 はアルキル基、シクロアルキ
ル基、フェニル基を表し、Ｒ3 、Ｒ4 、Ｒ5 は同一でも
良く、異っても良い）より選ばれた少なくとも１種を、
０．１重量部以上配合したことを特徴とするゴム組成物
である。That is, with respect to 100 parts by weight of a vulcanizable raw rubber, compounds represented by the formulas 1 and 2 (wherein R 1 and R 2 represent an alkyl group, a cycloalkyl group, a phenyl group or a benzothiazole group) R 1 and R 2 may be the same or different, and R 3 , R 4 and R 5 represent an alkyl group, a cycloalkyl group or a phenyl group, and R 3 , R 4 and R 5 may be the same. At least one selected from
A rubber composition characterized by being added in an amount of 0.1 part by weight or more.
【０００６】[0006]
【式１】(Equation 1)
【０００７】[0007]
【式２】(Equation 2)
【０００８】[0008]
【０００９】本発明に係る化合物をゴム組成物に配合
し、実際にゴム材料を製造する場合には、かかる架橋剤
の他に通常のゴム配合剤として使用されている加硫促進
剤（加硫促進助剤）を使用すると、加硫速度が早くなり
生産性が向上される。又、加硫促進剤に加え、硫黄も併
用すると、架橋密度に対する相乗効果が得られ、より少
ない配合量で目的の架橋密度が得られる。特に硫黄を併
用した場合、隣接する通常の硫黄−促進剤系の加硫ゴム
との共架橋性が良く、タイヤトレッド等の数種のゴムと
隣接するゴム組成物に適しているものが得られる。硫黄
を併用した場合の加硫密度に対する相乗効果は、硫黄／
本発明の化合物の比が５／１〜１／５の範囲にあること
が好ましい。そして、この比が５／１を越すと架橋鎖中
の（ポリマ−）−Ｓ−Ｒ−Ｓ−（ポリマ−）という構造
の架橋鎖が少なくなり、所期の耐熱性と耐屈曲疲労性の
両立が難しくなる。又、この比が１／５を下回ると、隣
接する通常の硫黄−促進剤加硫との共加硫性が悪くな
り、ゴムとゴムとの界面の剥離の原因となってしまう。When the compound according to the present invention is compounded in a rubber composition to actually produce a rubber material, a vulcanization accelerator (vulcanization accelerator) used as a general rubber compounding agent in addition to the crosslinking agent is used. (Acceleration aid) increases the vulcanization rate and improves productivity. When sulfur is used in addition to the vulcanization accelerator, a synergistic effect on the crosslink density is obtained, and the desired crosslink density can be obtained with a smaller amount. Particularly when sulfur is used in combination, it has good co-crosslinking properties with the adjacent normal sulfur-accelerated vulcanized rubber, and is suitable for several types of rubber such as tire treads and the like and the rubber composition adjacent thereto. . The synergistic effect on vulcanization density when sulfur is used in combination is sulfur /
Preferably, the ratio of the compounds of the invention is in the range from 5/1 to 1/5. When the ratio exceeds 5/1, the number of cross-linked chains having a structure of (polymer) -S-R-S- (polymer) in the cross-linked chains decreases, and the desired heat resistance and bending fatigue resistance are reduced. Compatibility is difficult. On the other hand, if this ratio is less than 1/5, the co-vulcanizability with the adjacent normal sulfur-promoter vulcanizates will be poor, causing peeling of the rubber-rubber interface.
【００１０】又、ゴムに通常配合される充填材、軟化
剤、可塑剤、老化防止剤等のその他の加工助剤を一緒に
混合しても本発明の効果になんら影響を与えない。The effects of the present invention are not affected at all even if other processing aids such as fillers, softeners, plasticizers and anti-aging agents, which are usually added to rubber, are mixed together.
【００１１】本発明に係る加硫可能な原料ゴムには天然
ゴム、スチレン−ブタジエン共重合体ゴム、ポリイソプ
レンゴム、ニトリルゴム、ポリブタジエンゴム、エチレ
ン−プロピレン−タ−ポリマ−、ブチルゴム等のゴム、
或いはこれらの混合物等が含まれる。The vulcanizable raw rubber according to the present invention includes rubbers such as natural rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, nitrile rubber, polybutadiene rubber, ethylene-propylene-terpolymer, butyl rubber, and the like.
Alternatively, a mixture thereof or the like is included.
【００１２】一方、本発明で未加硫原料ゴムに配合され
る化合物としては、ビス（ｐ−トルエンスルホニルチ
オ）メタン、１、２−ビス（ｐ−トルエンスルホニルチ
オ）エタン、１、２−ビス（２−ベンゾチアジルスルホ
ニルチオ）エタン、１、６−ビス（ｐ−トルエンスルホ
ニルチオ）ヘキサン、１、５−ビス（ｐ−トルエンスル
ホニルチオ）ジエチルエ−テル、１、２−ビス（Ｎ−シ
クロヘキシル−ｐ−トルエンスルホンアミドチオ）エタ
ン、１、２−ビス（Ｎ−メチル・ｐ−トルエンスルホン
アミドチオ）エタン、１、６−ビス（Ｎシクロヘキシル
−ｐ−トルエンスホンアミドチオ）ヘキサン、１、２−
ビス（フェニルスルホンチオ）エタン、１、３−ビス
（ｐ−トルエンスルホニルチオ）ベンゼン等が挙げられ
る。On the other hand, as the compound to be compounded in the unvulcanized raw rubber in the present invention, bis (p-toluenesulfonylthio) methane, 1,2-bis (p-toluenesulfonylthio) ethane, 1,2-bis (2-benzothiazylsulfonylthio) ethane, 1,6-bis (p-toluenesulfonylthio) hexane, 1,5-bis (p-toluenesulfonylthio) diethyl ether, 1,2-bis (N-cyclohexyl) -P-toluenesulfonamidothio) ethane, 1,2-bis (N-methyl / p-toluenesulfonamidothio) ethane, 1,6-bis (Ncyclohexyl-p-toluenesulfonamidothio) hexane, 1,2 −
Bis (phenylsulfonthio) ethane, 1,3-bis (p-toluenesulfonylthio) benzene and the like can be mentioned.
【００１３】[0013]
【作用】本発明においては、係る化合物の原料ゴムへの
配合割合は、原料ゴム１００重量部に対し、０．１重量
部以上であるが、好ましくは、０．１〜１０重量部の範
囲である。この理由は０．１重量部以下であると、（ポ
リマ−）−Ｓ−Ｒ−Ｓ−（ポリマ−）という架橋構造の
架橋密度がほとんど上らず、架橋剤としての効果がな
く、一方、１０重量部以上であると、ブル−ミングが起
こり加工上好ましくない。更に言えば、個別のゴム組成
物により望ましい架橋密度が違うため、一概には規定で
きないが、例えば、タイヤトレッド等のゴム組成物に使
用される場合には、上記した化合物をゴム１００重量部
に対して、０．２〜５．０重量部である。In the present invention, the compounding ratio of the compound to the raw rubber is 0.1 part by weight or more with respect to 100 parts by weight of the raw rubber, preferably in the range of 0.1 to 10 parts by weight. is there. The reason for this is that when the amount is 0.1 part by weight or less, the cross-linking density of the cross-linked structure of (polymer) -S-R-S- (polymer) hardly increases, and there is no effect as a cross-linking agent. If the amount is more than 10 parts by weight, blooming occurs, which is not preferable in processing. Furthermore, since the desired crosslink density differs depending on the individual rubber composition, it cannot be specified unconditionally.For example, when used in a rubber composition such as a tire tread, the above compound is added to 100 parts by weight of rubber. On the other hand, it is 0.2 to 5.0 parts by weight.
【００１４】ゴム中にチオフタルイミド化合物を配合す
る例としては、米国特許３，５４６，１８５号明細書に
記載があるが、これはモノチオフタルイミドであり、効
果も加硫遅延効果であって、本発明のビス体とは構造上
も、効果も明らかに違うものである。An example of compounding a thiophthalimide compound in rubber is described in US Pat. No. 3,546,185, which is a monothiophthalimide and has an effect of retarding vulcanization. The structure and the effect are clearly different from those of the screw body of the present invention.
【００１５】[0015]
【実施例】以下、本発明を実施例に基づいて更に詳細に
説明する。即ち、表１及び表２にて示すように、天然ゴ
ムに通常のゴム配合剤及び本発明における化合物を配合
した。そして、得られた組成物を加硫処理し、同時に、
比較のため本発明における化合物を添加せず、電子線加
硫にしたもの、及び通常のコンベンショナル加硫処理し
たものを取り上げた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments. That is, as shown in Tables 1 and 2, a natural rubber compounding agent and a compound of the present invention were compounded with natural rubber. And vulcanizing the obtained composition, at the same time,
For comparison, those subjected to electron beam vulcanization without addition of the compound of the present invention and those subjected to ordinary conventional vulcanization were taken up.
【００１６】加硫中、レオメ−タ−によりその加硫性を
測定し、得られた結果を表１及び表２に示す。レオメ−
タ−は、日本合成ゴム社製オンレ−ティングディスクレ
オメ−タ−を用いた。又、表中、ＭＨは加硫ゴムの架橋
密度或いはモジュラスに相当する最大トルク値を、Ｔ−
９０はトルク値が［０．９×（最大トルク値−最小トル
ク値）÷最小トルク値］になるまでに要した時間（分）
を夫々示す。During the vulcanization, the vulcanizability was measured by a rheometer, and the results obtained are shown in Tables 1 and 2. Rheome
An on-disc disc rheometer manufactured by Nippon Synthetic Rubber Co., Ltd. was used. In the table, MH represents the maximum torque value corresponding to the crosslinking density or modulus of the vulcanized rubber, T-
90 is the time (minutes) required for the torque value to become [0.9 × (maximum torque value−minimum torque value) ÷ minimum torque value].
Are shown respectively.
【００１７】ゴムの評価として、加硫後のゴム組成物か
らそれぞれ材料を採取し、試料の耐熱性と耐屈曲疲労性
を評価した。得られた結果を各表中に併記した。尚、評
価方法は、耐熱性はＡＳＴＭ、Ｄ−６２３ブロ−アウト
テスト方法に準拠して行い、試料がブロ−アウトしたと
きのブロ−アウト温度を測定した。一方、耐屈曲疲労性
はＡＳＴＭＤ−４３０デマ−チャテストに準拠して行
い、亀裂が入るまでの寿命（回数）を測定した。As the evaluation of the rubber, materials were sampled from the rubber composition after vulcanization, and the heat resistance and the bending fatigue resistance of the sample were evaluated. The obtained results are shown in each table. In addition, the heat resistance was evaluated according to ASTM and the D-623 blow-out test method, and the blow-out temperature when the sample was blown out was measured. On the other hand, the bending fatigue resistance was measured in accordance with the ASTM D-430 demarcation test, and the life (number of times) until a crack was formed was measured.
【００１８】実施例１〜４、比較例１ 表１中、実施例１〜４は硫黄を併用しない例を示す。こ
の場合、本発明で特定した化合物は比較的多量の配合量
を要する。これら実施例より、特定した化合物を単独で
使用する場合は加硫速度も遅くなるが、加硫促進剤を併
用すると加硫速度はかなり早くなることがわかる。本実
施例にあっては、耐熱性及び耐屈曲疲労性は双方共に満
足できる改良結果であったが、電子線加硫である比較例
１ではこれら特性を同時に達成できないことを示してい
る。Examples 1 to 4 and Comparative Example 1 In Table 1, Examples 1 to 4 show examples in which sulfur is not used together. In this case, the compound specified in the present invention requires a relatively large amount. From these examples, it can be seen that when the specified compound is used alone, the vulcanization rate is reduced, but when the vulcanization accelerator is used in combination, the vulcanization rate is considerably increased. In this example, both the heat resistance and the bending fatigue resistance were satisfactory results, but Comparative Example 1, which is electron beam vulcanization, cannot achieve these characteristics at the same time.
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例５〜７、比較例２、３ 表２中、実施例５〜７には本発明で特定した化合物に対
して硫黄を併用した例を示す。この場合、少量の硫黄の
併用で大きく架橋密度が上昇し、本発明における化合物
の使用量は少量で良いことがわかる。又、耐熱性は比較
例２の電子線加硫と同等レベル、耐屈曲疲労性は比較例
３のコンベンショナル加硫と同等のレベルにある。即
ち、従来の電子線加硫やコンベンショナル加硫では同時
に高い耐熱性、耐屈曲疲労性が得られないが、本発明の
それにあっては、この両性能を十分満足する結果を得た
のである。Examples 5 to 7, Comparative Examples 2 and 3 In Table 2, Examples 5 to 7 show examples in which sulfur is used in combination with the compound specified in the present invention. In this case, it can be seen that the crosslink density is greatly increased by using a small amount of sulfur in combination, and the amount of the compound used in the present invention may be small. The heat resistance is equivalent to the electron beam vulcanization of Comparative Example 2, and the bending fatigue resistance is equivalent to the conventional vulcanization of Comparative Example 3. That is, high heat resistance and bending fatigue resistance cannot be obtained at the same time by conventional electron beam vulcanization or conventional vulcanization. However, in the case of the present invention, both of these performances are sufficiently satisfied.
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【発明の効果】本発明の化合物を架橋剤として得られた
ゴム組成物は、熱的に安定なモノスルフィドとアルキル
結合からなり、かつ、フレキシブルな架橋鎖を持ち、耐
熱性に優れ、耐屈曲疲労性を向上させる。The rubber composition obtained by using the compound of the present invention as a crosslinking agent is composed of a thermally stable monosulfide and an alkyl bond, has a flexible crosslinked chain, has excellent heat resistance, and is resistant to bending. Improves fatigue.
Claims (1)
し、式１〜式２にて示す化合物（式中、Ｒ1 、Ｒ2 はア
ルキル基、シクロアルキル基、フェニル基、ベンゾチア
ゾール基を表し、Ｒ1 、Ｒ2 は同一でも良く、異っても
良い。Ｒ3 、Ｒ4、Ｒ5 はアルキル基、シクロアルキル
基、フェニル基を表し、Ｒ3 、Ｒ4 、Ｒ5は同一でも良
く、異っても良い）より選ばれた少なくとも１種を、
０．１重量部以上配合したことを特徴とするゴム組成
物。 【式１】 【式２】 1. A compound represented by the formula ( 1) or (2) wherein R 1 and R 2 represent an alkyl group, a cycloalkyl group, a phenyl group or a benzothiazole group per 100 parts by weight of a vulcanizable raw rubber. R 1 and R 2 may be the same or different, and R 3 , R 4 and R 5 represent an alkyl group, a cycloalkyl group or a phenyl group, and R 3 , R 4 and R 5 may be the same. At least one selected from
A rubber composition characterized by being added in an amount of 0.1 part by weight or more. (Equation 1) (Equation 2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22807492A JP3295456B2 (en) | 1992-08-04 | 1992-08-04 | Rubber composition containing new crosslinking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22807492A JP3295456B2 (en) | 1992-08-04 | 1992-08-04 | Rubber composition containing new crosslinking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0657042A JPH0657042A (en) | 1994-03-01 |
| JP3295456B2 true JP3295456B2 (en) | 2002-06-24 |
Family
ID=16870791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22807492A Expired - Fee Related JP3295456B2 (en) | 1992-08-04 | 1992-08-04 | Rubber composition containing new crosslinking agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3295456B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5467068B2 (en) | 2010-06-29 | 2014-04-09 | 横河電機株式会社 | Wireless explosion-proof equipment |
| CN108689912A (en) * | 2018-07-30 | 2018-10-23 | 山东阳谷华泰化工股份有限公司 | A kind of multifunctional rubber chemicals and its preparation process |
-
1992
- 1992-08-04 JP JP22807492A patent/JP3295456B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0657042A (en) | 1994-03-01 |
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