JP4978919B2 - New sulfenamide compounds - Google Patents
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- JP4978919B2 JP4978919B2 JP2005280755A JP2005280755A JP4978919B2 JP 4978919 B2 JP4978919 B2 JP 4978919B2 JP 2005280755 A JP2005280755 A JP 2005280755A JP 2005280755 A JP2005280755 A JP 2005280755A JP 4978919 B2 JP4978919 B2 JP 4978919B2
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- vulcanization
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- UBHUJVKAJQRWRR-UHFFFAOYSA-N CCCCC(CC)CN(CC(CC)CCCC)Sc1nc2ccccc2[s]1 Chemical compound CCCCC(CC)CN(CC(CC)CCCC)Sc1nc2ccccc2[s]1 UBHUJVKAJQRWRR-UHFFFAOYSA-N 0.000 description 1
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Description
本発明はゴムの加硫促進剤に用いられるＮ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（以下ＤＣＢＳと略す）よりも加硫反応に遅効性を与える新規に合成されたスルフェンアミド化合物に関する。The present invention relates to a newly synthesized sulfenamide which gives a delayed effect on the vulcanization reaction rather than N, N-dicyclohexyl-2-benzothiazolylsulfenamide (hereinafter abbreviated as DCBS) used as a rubber vulcanization accelerator. Relates to compounds.
スルフェンアミド化合物はゴム用加硫促進剤として用いられており、加硫反応に遅効性を与えることを特徴とし、一般的にスルフェンアミド系加硫促進剤と称する。
ゴムは熱伝導性が悪く、肉厚のゴム製品を製造する上で均一な加硫をすることが難しく、その場合、加硫反応に遅効性を与えるスルフェンアミド系加硫促進剤を用いることが有効とされている。
また、ゴムと金属を接着する場合、ゴムの加硫とゴムと金属の結合を同時に行う方法、即ち、直接加硫接着法があるが、その場合、ゴムの加硫とゴムと金属の結合を同時に行う上で、加硫反応に遅効性を与えるスルフェンアミド系加硫促進剤を用いることが有効とされている。
現在、市販されているスルフェンアミド系加硫促進剤の中で、最も加硫反応に遅効性を与える加硫促進剤として、ＤＣＢＳが挙げられる。
このＤＣＢＳの加硫反応の遅効性よりも更に遅効性が必要な場合は、スルフェンアミド系加硫促進剤とは別に、加硫遅延剤を併用する。
尚、市販されている代表的な加硫遅延剤としては、Ｎ−（シクロヘキシルチオ）フタルイミド（以下ＣＴＰと略す）が挙げられるが、ＣＴＰをゴムへ多量に添加すると、加硫ゴムの物理的特性に悪影響を及ぼし、且つ、加硫ゴムの外観の悪化および接着性に悪影響を及ぼすブルーミングの原因にもなることは既知である。
Rubber has poor thermal conductivity, and it is difficult to uniformly vulcanize it in the production of thick rubber products. In that case, use a sulfenamide-based vulcanization accelerator that gives a slow effect to the vulcanization reaction. Is valid.
In addition, when rubber and metal are bonded, there is a method in which rubber vulcanization and rubber and metal bonding are performed simultaneously, that is, a direct vulcanization bonding method. In this case, rubber vulcanization and rubber and metal bonding are performed. In carrying out simultaneously, it is effective to use a sulfenamide vulcanization accelerator which gives a slow effect to the vulcanization reaction.
Among the commercially available sulfenamide-based vulcanization accelerators, DCBS can be cited as a vulcanization accelerator that most delays the vulcanization reaction.
When the delayed action is required more than the delayed action of the vulcanization reaction of DCBS, a vulcanization retarder is used in combination with the sulfenamide vulcanization accelerator.
In addition, N- (cyclohexylthio) phthalimide (hereinafter abbreviated as CTP) is mentioned as a typical vulcanization retarder that is commercially available. When a large amount of CTP is added to rubber, physical properties of the vulcanized rubber are listed. It is known that it causes a blooming that adversely affects the appearance of the vulcanized rubber and deteriorates the appearance and adhesion of the vulcanized rubber.
尚、特許文献１〜３によれば、直鎖アルキル基または分岐アルキル基からなるモノスルフェンアミド化合物がゴムの加硫促進剤として有効であることを開示している。
しかし、本発明の特定されたスルフェンアミド化合物に関しての具体的な記載はない。
However, there is no specific description regarding the specified sulfenamide compound of the present invention.
加硫ゴムの物性低下、ブルーミング等、問題を生ずる可能性の高い加硫遅延剤を併用して加硫反応を遅延化することは、必ずしも推奨される方法ではない。
よって、加硫遅延剤を併用することなくＤＣＢＳ以上の加硫反応の遅効性を有する新規スルフェンアミド化合物を提供することを課題とした。It is not always a recommended method to delay the vulcanization reaction in combination with a vulcanization retarder that is likely to cause problems such as deterioration of physical properties of vulcanized rubber and blooming.
Therefore, an object of the present invention is to provide a novel sulfenamide compound having a retarding effect of a vulcanization reaction over DCBS without using a vulcanization retarder in combination.
本発明者らは、上記課題を解決すべく鋭意検討した結果、本発明を完成するに至った。
即ち、化１で示される新規スルフェンアミド化合物であるＮ，Ｎ−ビス（２−エチルヘキシル）−２−ベンゾチアゾリルスルフェンアミドの合成に成功し、ゴムの加硫促進剤として用いることでＤＣＢＳ以上の加硫反応の遅効性が得られることを確認した。
よって、上記課題を解決し、本発明を完成するに至った。
That is, N, N-bis (2-ethylhexyl) -2-benzothiazolylsulfenamide, which is a novel sulfenamide compound represented by Chemical Formula 1, was successfully synthesized and used as a rubber vulcanization accelerator. It was confirmed that the above-mentioned vulcanization reaction was delayed.
Therefore, the above problems have been solved and the present invention has been completed.
化１で示される新規スルフェンアミド化合物は、ＤＣＢＳ以上の加硫反応の遅効性を示すことから、肉厚のゴム製品の製造およびゴムと金属の直接加硫接着において有用と考える。The novel sulfenamide compound represented by Chemical Formula 1 is considered to be useful in the production of thick rubber products and in the direct vulcanization adhesion between rubber and metal since it exhibits a slow vulcanization effect over DCBS.
以下、本発明を具体的な実施形態にてより詳しく説明する。
Ｎ−クロロビス（２−エチルヘキシル）アミン ４０．１ｇを４０℃でアセトン６５ｍｌに混合する。そこに２−メルカプトベンゾチアゾールのナトリウム塩の４０％水溶液 ６８．３ｇを作用させ４時間攪拌する。その後有機層を分液し、有機溶媒を除去する。ここで得られた油状物を精製して、Ｎ，Ｎ−ビス（２−エチルヘキシル）−２−ベンゾチアゾリルスルフェンアミドの黄色油状物を得た。ＩＲ ３４３２、２９５８、２９２７、２８５７、１４５８、１４２７、１３７８、１３０９、１２３７、１０７８、９９９、９７１、７５５、７２６、６６８ ｃｍ−１。マススペクトルにて分子イオンピーク４０６を確認。Hereinafter, the present invention will be described in more detail with specific embodiments.
40.1 g of N-chlorobis (2-ethylhexyl) amine is mixed with 65 ml of acetone at 40 ° C. There, 68.3 g of a 40% aqueous solution of sodium salt of 2-mercaptobenzothiazole is allowed to act and stirred for 4 hours. Thereafter, the organic layer is separated and the organic solvent is removed. The oil obtained here was purified to give a yellow oil of N, N-bis (2-ethylhexyl) -2-benzothiazolylsulfenamide. IR 3432, 2958, 2927, 2857, 1458, 1427, 1378, 1309, 1237, 1078, 999, 971, 755, 726, 668 cm- 1 . Molecular ion peak 406 is confirmed by mass spectrum.
参考例として表１に化１の化合物のゴム試験結果を示す。
表１に示した配合処方を定法にて混練りを行い、ゴム組成物を得た。
得られた各ゴム組成物のムーニースコーチ試験をＪＩＳＫ６３００に準拠した上で行い、各配合ゴムの初期加硫特性を確認した。
また、ＭＤＲ（アルファ・テクノロジーズ社製）にて各配合ゴムの加硫特性を測定し確認した。
尚、比較例１にて市販されているスルフェンアミド系促進剤の中で最も加硫反応の遅効性が得られるＤＣＢＳの結果を示し、実施例１は、化１の化合物をＤＣＢＳと同量添加した場合、実施例２には、化１の化合物をＤＣＢＳと同モル量添加した場合の結果を各々示した。
その結果、実施例１および２は、比較例１と比較し、スコーチタイム（ｔ５）が長く且つ、Ｍ．Ｄ．Ｒ．の最適加硫時間（ｔ９０）も長い。
よって、化１の化合物は、ＤＣＢＳよりも加硫反応の遅効性が得られることが確認された。As a reference example, Table 1 shows the rubber test results of the compound of Chemical Formula 1.
The compounding formulation shown in Table 1 was kneaded by a conventional method to obtain a rubber composition.
The Mooney scorch test of each obtained rubber composition was conducted in accordance with JISK6300, and the initial vulcanization characteristics of each compounded rubber were confirmed.
Moreover, the vulcanization characteristics of each compounded rubber were measured and confirmed by MDR (manufactured by Alpha Technologies).
In addition, the result of DCBS that can obtain the slowest effect of the vulcanization reaction among the commercially available sulfenamide accelerators in Comparative Example 1 is shown. Example 1 shows the same amount of the compound of Chemical Formula 1 as that of DCBS. When added, Example 2 shows the results when the compound of Chemical Formula 1 was added in the same molar amount as DCBS.
As a result, Examples 1 and 2 had a longer scorch time (t5) and M.E. D. R. The optimum vulcanization time (t90) is long.
Therefore, it was confirmed that the compound of Chemical formula 1 has a slower vulcanization effect than DCBS.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005280755A JP4978919B2 (en) | 2005-08-30 | 2005-08-30 | New sulfenamide compounds |
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| JP2005280755A JP4978919B2 (en) | 2005-08-30 | 2005-08-30 | New sulfenamide compounds |
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| JP2007063245A JP2007063245A (en) | 2007-03-15 |
| JP4978919B2 true JP4978919B2 (en) | 2012-07-18 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8148452B2 (en) | 2007-06-01 | 2012-04-03 | Sumitomo Rubber Industries, Ltd. | Rubber composition for coating tire cord |
| JP4493712B2 (en) | 2007-12-05 | 2010-06-30 | 住友ゴム工業株式会社 | Rubber composition for tire |
| JP4750837B2 (en) * | 2007-12-07 | 2011-08-17 | 住友ゴム工業株式会社 | Rubber composition for breaker topping |
| KR20100103853A (en) * | 2007-12-27 | 2010-09-28 | 가부시키가이샤 브리지스톤 | Rubber composition |
| JP2010037547A (en) * | 2008-07-07 | 2010-02-18 | Bridgestone Corp | Rubber composition |
| JP5524522B2 (en) * | 2008-08-19 | 2014-06-18 | 株式会社ブリヂストン | Rubber composition |
| JP5632592B2 (en) * | 2008-08-19 | 2014-11-26 | 株式会社ブリヂストン | Rubber composition |
| JP2010070747A (en) * | 2008-08-19 | 2010-04-02 | Bridgestone Corp | Rubber composition |
| JP5395113B2 (en) | 2011-05-13 | 2014-01-22 | 住友ゴム工業株式会社 | Rubber composition for breaker topping and pneumatic tire |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658828A (en) * | 1969-11-19 | 1972-04-25 | Monsanto Co | Unsymmetrical dialkyl thiazole sulfenamides |
| JPS5128111B2 (en) * | 1972-08-10 | 1976-08-17 | ||
| US5272213A (en) * | 1992-05-14 | 1993-12-21 | Air Products And Chemicals, Inc. | Scorch retardant polyacrylate elastomers |
| JPH0971759A (en) * | 1995-09-07 | 1997-03-18 | Bridgestone Corp | Adhesive composition for tire repairing |
| JP2005139239A (en) * | 2003-11-04 | 2005-06-02 | Sanshin Chem Ind Co Ltd | Vulcanization accelerator using amine derived from natural fat and oil, and rubber composition |
| JP2005139082A (en) * | 2003-11-04 | 2005-06-02 | Sanshin Chem Ind Co Ltd | Sulfenamide compound |
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