JPS60250051A - Rubber deterioration inhibitor - Google Patents
Rubber deterioration inhibitorInfo
- Publication number
- JPS60250051A JPS60250051A JP10732484A JP10732484A JPS60250051A JP S60250051 A JPS60250051 A JP S60250051A JP 10732484 A JP10732484 A JP 10732484A JP 10732484 A JP10732484 A JP 10732484A JP S60250051 A JPS60250051 A JP S60250051A
- Authority
- JP
- Japan
- Prior art keywords
- deterioration
- rubber
- phenylenediamine
- phenyl
- dihydroquinoline
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はゴム用劣化防止剤に関し、さらに詳しくは特定
のジヒドロキノリン化合物と特定のp−フェニレンジア
ミン化合物とからなることを特徴とするゴムの劣化防止
、特にオゾン劣化防止に卓効を示すゴム用劣化防止剤に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber deterioration inhibitor, and more particularly to a rubber deterioration prevention agent, which is characterized by comprising a specific dihydroquinoline compound and a specific p-phenylenediamine compound, and in particular to an ozone deterioration prevention agent. This invention relates to a deterioration inhibitor for rubber that is highly effective.
一般筈ζ天然ゴムあるいは合成ゴム製品はオゾンおよび
くり返し屈曲さらには熱などによって劣化が進行し、つ
いには実用に耐えなくなることが良く知られている。It is well known that natural rubber or synthetic rubber products deteriorate due to ozone, repeated bending, and heat, and eventually become unusable.
かかる劣化を防止する目的で数多くの方法が提案されて
おり、その多くは種々の劣化防止剤、例えばオゾンによ
る劣化を防止する目的でN−フェニル−N′−アルキル
−p−フェニ物を使用するものである。A number of methods have been proposed to prevent such deterioration, and many of them use various deterioration inhibitors, such as N-phenyl-N'-alkyl-p-phenyls to prevent ozone-induced deterioration. It is something.
ところが、これらの劣化防止剤によってもオゾンによる
劣化の防止にまだ満足しうる性能が得られず、特に近年
ではタイヤのラジアル化、ベルトコンベアーの高速化な
どに伴なってゴム製品がより劣化し易い条件下で長寿命
を保持することが強く要求されていたのである。However, even with these deterioration inhibitors, satisfactory performance in preventing ozone-induced deterioration has not yet been achieved, and in recent years, rubber products have become more susceptible to deterioration due to the shift to radial tires and faster belt conveyors. There was a strong demand for long life under these conditions.
このようなことから、本発明者らは耐オゾン性に優れた
劣化防止剤に関し鋭意検討を重ねた結果、特定のジヒド
ロキノリン化合物と特定のp−フェニレンジアミン化合
物とからなることを特徴とする劣化防止剤が、従来得ら
れたことのない卓越したオソノ劣化防止性能を示すこと
を見出し、さらには耐屈曲性、耐熱性などにおいても優
れた性能を有することを見い出し本発明を完成したつ
すなわち本発明は6−アニソツー2.2−4−トリメチ
ル−1,2−ジヒドロキノリンと、1種または2種以上
のN−フェニル−N’ −アルキル−p−フェニレンジ
アミン(アルキルとは炭素数8〜6の非環状アルキル基
をいう)とからなることを特徴とする極めて優れたゴム
用劣化防止剤を提供するものである。In view of this, the present inventors have conducted extensive studies regarding anti-deterioration agents with excellent ozone resistance, and have found that anti-deterioration agents are characterized by being composed of a specific dihydroquinoline compound and a specific p-phenylenediamine compound. It has been discovered that the inhibitor exhibits outstanding performance in preventing osmotic deterioration, which has never been achieved before, and that it also has excellent performance in terms of bending resistance, heat resistance, etc., and has thus completed the present invention. The invention consists of 6-aniso2,2-4-trimethyl-1,2-dihydroquinoline and one or more N-phenyl-N'-alkyl-p-phenylene diamines (alkyl refers to carbon atoms of 8 to 6 carbon atoms). The object of the present invention is to provide an extremely excellent anti-deterioration agent for rubber, which is characterized by consisting of a non-cyclic alkyl group (a non-cyclic alkyl group).
本発明に用いられる6−アニリツー2,2゜4−トリメ
チル−1,2−ジヒドロキノリンは従来から知られてい
るジヒドロキノリン化合物9一般的な合成法、例えばp
−アミノジフェニルアミンにアセトン類(アセトン9.
メシチルオキシド、ジアセトンアルコールなど)を80
〜200℃、酸性触媒下で反応せしめて製造することが
できる。The 6-anilito-2,2゜4-trimethyl-1,2-dihydroquinoline used in the present invention can be synthesized by a conventionally known dihydroquinoline compound 9, for example, p
-Aminodiphenylamine and acetones (acetone 9.
Mesityl oxide, diacetone alcohol, etc.) 80
It can be produced by reacting at ~200°C under an acidic catalyst.
また本発明に特定するN−フェニル−N/−アルキル−
p−フェニレンジアミンとしては、例えばN−フェニル
−N′−イソプロピル−p−フェニレンジアミノ、N−
フェニル−N/−8ec−ブチル−p−フェニレンジア
ミン、N−フェニル−N’−1,2−ジメチルプロピル
−p−フェニレンジアミン、N−フェニル−Nt−i、
:q−ジメチルブチル−p−フェニレンジアミンなどが
例示され、これらは1種あるいは2種以上の混合物とし
て用いるっここで、アルキル基が炭素数8以上のもの、
あるいは環状アルキル基である場合、もしくはアルキル
基の代りにアリール基が置換されたもの1例えばN−フ
ェニル−N′−オクチル−p−フエニレンジアξン、N
−フェニル−N/−シクロへキシル−p−フェニレンジ
アミン、N、N’−ジフェニル−p−フェニレンジアミ
ンなどは本発明に特定するジヒドロキノリン化合物と併
用しても性能性は不充分である。Also specified in the present invention is N-phenyl-N/-alkyl-
Examples of p-phenylenediamine include N-phenyl-N'-isopropyl-p-phenylenediamino, N-
Phenyl-N/-8ec-butyl-p-phenylenediamine, N-phenyl-N'-1,2-dimethylpropyl-p-phenylenediamine, N-phenyl-Nt-i,
: q-dimethylbutyl-p-phenylenediamine is exemplified, and these can be used alone or as a mixture of two or more.
Alternatively, it is a cyclic alkyl group, or one in which an aryl group is substituted in place of the alkyl group 1 For example, N-phenyl-N'-octyl-p-phenylene diane, N
-Phenyl-N/-cyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, etc. have insufficient performance even when used in combination with the dihydroquinoline compound specified in the present invention.
本発明の劣化防止剤は上記したような特定のジヒドロキ
ノリン化合物と、特定のp−フェニレンジアミン化合物
との組合わせによってはじめて、従来得られたことのな
い極めて高い劣化防止性能が得られるものであるが。The anti-deterioration agent of the present invention is capable of achieving extremely high anti-deterioration performance that has not been previously achieved only by combining a specific dihydroquinoline compound as described above and a specific p-phenylenediamine compound. but.
ジヒドロキノリン化合物とp−フェニレンジアミン化合
物との比率は通常80〜20対20〜80、好ましくは
65〜85対35〜65である。The ratio of dihydroquinoline compound to p-phenylenediamine compound is usually 80-20:20-80, preferably 65-85:35-65.
本発明の劣化防止剤は天然ゴムは勿論のこ色合成コム、
例えばスチレン管ブタジェン共重合コム、アクリロニト
リル・ブタジェン共重合ゴム、エチレン・プロピレン共
重合ゴム、ポリブタジェンコム、ポリイソプレンコム、
ポリクロロプレンゴムなど、更にはこれらの混合物など
に添加される。コムへの添加量は、本発明の劣化防止剤
がゴムへの相溶性に優れゴム表面へのブルームが殆どな
いため通常の劣化防止剤より多鳳添加することも可能で
あるが、ゴム100重量部に対して通常0.1〜8重屋
部、好ましくは0.5〜5M紙部である。The anti-deterioration agent of the present invention can be applied not only to natural rubber but also to brown synthetic comb,
For example, styrene tube butadiene copolymer comb, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer rubber, polybutadiene comb, polyisoprene comb,
It is added to polychloroprene rubber and mixtures thereof. Since the deterioration inhibitor of the present invention has excellent compatibility with rubber and hardly blooms on the rubber surface, it is possible to add a larger amount to the rubber than ordinary deterioration inhibitors; It is usually 0.1 to 8 paper parts, preferably 0.5 to 5M paper parts.
ゴムへの添加は通常の方法、例えば、オーブンロール、
バンバリーミキサ−なトラ用いて添加され、その場合ジ
ヒドロキノリン化合物とp−フェニレンジアミン化合物
トは別々に添加しても良いし、あるいはあらかじめ混合
したものを用いても良い。また本発明の劣化防止剤の使
用にあたっては必要に応じ他の劣化防止剤、添加剤、例
えば2,2.4−1−ジメチル−1,2−ジヒドロキノ
リン重合物などを併用しても良いっ
次に実施例によって本発明を具体的に説明する。なお、
例中部とあるのは爪厭部を示す。Addition to rubber can be done in the usual way, e.g. oven roll,
The dihydroquinoline compound and the p-phenylenediamine compound may be added separately, or they may be mixed in advance. In addition, when using the deterioration inhibitor of the present invention, other deterioration inhibitors and additives, such as 2,2,4-1-dimethyl-1,2-dihydroquinoline polymer, may be used in combination, if necessary. Next, the present invention will be specifically explained with reference to Examples. In addition,
In the example, "middle part" indicates the part of the nail.
実施例1
天然コム100部、HAFカーボン45部、亜鉛華5部
、イオウ2.5部、ステアリン酸1部、プロセス油5部
、ワックス8Th、N−シクロへキシルベンゾチアジル
スルフェンアミド(加硫促進剤)0,5部および第1表
に示しrこ劣化防止剤2部を常法により6インチ〆オー
プンロールにて配合し140℃にて40分間加硫して試
料を作成した。Example 1 100 parts of natural comb, 45 parts of HAF carbon, 5 parts of zinc white, 2.5 parts of sulfur, 1 part of stearic acid, 5 parts of process oil, 8 Th wax, N-cyclohexylbenzothiazyl sulfenamide (added) A sample was prepared by blending 0.5 parts of sulfur accelerator and 2 parts of the deterioration inhibitor shown in Table 1 using a 6-inch open roll in a conventional manner and vulcanizing at 140° C. for 40 minutes.
この試料を用いてオゾン劣化、熱劣化、屈曲亀裂試験を
行った。Using this sample, ozone deterioration, thermal deterioration, and flex crack tests were conducted.
なお、それぞれの試験はJ I S K−6801に準
拠し、オゾン劣化試験はオゾンウェサーメーター中、オ
ゾン濃度50 pphm、温度40℃、動的伸張率20
%にて肉眼で測定可能なりラックが発生するまでの時曲
を測定した。熱劣化試験は試験管加熱老化機を用いて1
00℃下48時間熱劣化せしめた後、破断強度の保持率
(%)を測定した。屈曲亀裂試験は試料に原長2卵のキ
スを入れ1万回屈曲後のキズの長さを測定したつ結果を
第2表に示す。Each test was conducted in accordance with JIS K-6801, and the ozone deterioration test was conducted using an ozone weather meter at an ozone concentration of 50 pphm, a temperature of 40°C, and a dynamic elongation rate of 20.
%, the bending was measured until racking occurred which was measurable with the naked eye. The thermal aging test was performed using a test tube heating aging machine.
After thermally deteriorating at 00° C. for 48 hours, the retention rate (%) of breaking strength was measured. In the bending crack test, a kiss of two original lengths was placed on the sample and the length of the crack was measured after bending 10,000 times.The results are shown in Table 2.
実施例2
スチレンψブタジェンゴム10 ON、HAFカーボン
50部、プロセス油5部、亜鉛華5部、ステアリン酸8
部、イオウ2.5部、ワックス8部、N−ンクロへキシ
ルベンゾチアジルスルフェンアミド(加硫促進剤)1部
および第1表に示す老化防止剤2部を隼法により6イン
チ〆オープンロールで配合し、145℃にて80分間加
硫したものについて実施例1と同様な試験を行なったっ
なお、熱劣化条件は110℃×48時間、屈曲亀裂試験
は5千同屈曲後の長さを測定した。結果を第2表に示す
。Example 2 Styrene ψ butadiene rubber 10 ON, HAF carbon 50 parts, process oil 5 parts, zinc white 5 parts, stearic acid 8
1 part, 2.5 parts of sulfur, 8 parts of wax, 1 part of N-chlorohexylbenzothiazylsulfenamide (vulcanization accelerator), and 2 parts of the anti-aging agent shown in Table 1 were added to a 6-inch open tube using the Hayabusa method. The same test as in Example 1 was conducted on a product that was blended in a roll and vulcanized at 145°C for 80 minutes.The thermal deterioration conditions were 110°C x 48 hours, and the flex crack test was performed on the length after 5,000 yen bending. was measured. The results are shown in Table 2.
Claims (1)
ヒドロキノリンと、1種または2種以上のN−フェニル
−N′−アルキル−p−フェニレンジアミン(アルキル
とl[素数8〜6の非環状アルキル基をいう)とからな
ることを特徴とするゴム用劣化防止剤。6-anilino-2,2,4-1-limethyl-1,2-dihydroquinoline and one or more N-phenyl-N'-alkyl-p-phenylenediamines (alkyl and l [prime number 8 to 6).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10732484A JPS60250051A (en) | 1984-05-25 | 1984-05-25 | Rubber deterioration inhibitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10732484A JPS60250051A (en) | 1984-05-25 | 1984-05-25 | Rubber deterioration inhibitor |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS60250051A true JPS60250051A (en) | 1985-12-10 |
Family
ID=14456171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10732484A Pending JPS60250051A (en) | 1984-05-25 | 1984-05-25 | Rubber deterioration inhibitor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60250051A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5684073A (en) * | 1994-05-13 | 1997-11-04 | The Yokohama Rubber Co., Ltd. | Pneumatic tire having improved abrasion resistance |
JP2011521041A (en) * | 2008-05-15 | 2011-07-21 | ソシエテ ド テクノロジー ミシュラン | Tire rubber composition containing a novel antioxidant system |
US10766305B2 (en) * | 2014-12-16 | 2020-09-08 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5785835A (en) * | 1980-11-18 | 1982-05-28 | Sumitomo Chem Co Ltd | Rubber composition |
-
1984
- 1984-05-25 JP JP10732484A patent/JPS60250051A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5785835A (en) * | 1980-11-18 | 1982-05-28 | Sumitomo Chem Co Ltd | Rubber composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5684073A (en) * | 1994-05-13 | 1997-11-04 | The Yokohama Rubber Co., Ltd. | Pneumatic tire having improved abrasion resistance |
DE19517544B4 (en) * | 1994-05-13 | 2005-08-25 | The Yokohama Rubber Co., Ltd. | Pneumatic tire with improved abrasion resistance |
JP2011521041A (en) * | 2008-05-15 | 2011-07-21 | ソシエテ ド テクノロジー ミシュラン | Tire rubber composition containing a novel antioxidant system |
US10766305B2 (en) * | 2014-12-16 | 2020-09-08 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
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