JPH07165989A - Synthetic rubber composition - Google Patents
Synthetic rubber compositionInfo
- Publication number
- JPH07165989A JPH07165989A JP31553693A JP31553693A JPH07165989A JP H07165989 A JPH07165989 A JP H07165989A JP 31553693 A JP31553693 A JP 31553693A JP 31553693 A JP31553693 A JP 31553693A JP H07165989 A JPH07165989 A JP H07165989A
- Authority
- JP
- Japan
- Prior art keywords
- trimellitic acid
- rubber composition
- synthetic rubber
- composition
- nitrile rubber
- 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]
【産業上の利用分野】本発明は、耐寒性および耐熱性に
優れた合成ゴム組成物、詳しくは、主として自動車用の
潤滑油ホースや燃料ホース等に使用され、水素化ニトリ
ルゴムに、特定のトリメリット酸エステル系可塑剤を添
加してなる、耐寒性および耐熱性に優れた合成ゴム組成
物に関するものである。FIELD OF THE INVENTION The present invention relates to a synthetic rubber composition having excellent cold resistance and heat resistance, and more specifically, it is mainly used for lubricating oil hoses and fuel hoses for automobiles, and is used for hydrogenated nitrile rubber. TECHNICAL FIELD The present invention relates to a synthetic rubber composition which is obtained by adding a trimellitic acid ester plasticizer and has excellent cold resistance and heat resistance.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】合成ゴ
ムの中でも水素化ニトリルゴムは、耐熱性、耐油性に優
れることから、自動車用の潤滑油ホースや燃料ホース等
に主に使用されている。このような用途に用いられるゴ
ム材料には柔軟性が必要であり、特に寒冷地での使用に
も耐えるために、良好な耐寒性、即ち、低温下において
も柔軟性を保持することが要求される。また、近年の自
動車技術の革新に伴うエンジン出力の増大により使用環
境の高温化が進んでおり、このような用途に用いられる
ゴム材料には高度の耐熱性、即ち、高温下に暴露された
場合にも初期の物性を維持することも必要とされてい
る。BACKGROUND OF THE INVENTION Among synthetic rubbers, hydrogenated nitrile rubber is mainly used for lubricating oil hoses and fuel hoses for automobiles because of its excellent heat resistance and oil resistance. . The rubber material used for such an application needs to have flexibility, and in order to withstand use especially in cold regions, it is required to have good cold resistance, that is, to retain flexibility even at low temperatures. R. In addition, as the engine output has increased due to recent innovations in automobile technology, the operating environment has become higher in temperature, and the rubber materials used for such applications have a high degree of heat resistance, that is, when exposed to high temperatures. It is also necessary to maintain the initial physical properties.
【０００３】従来、このような用途に用いられるゴム材
料に柔軟性を持たせる目的で、芳香族多塩基酸エステル
系可塑剤あるいはポリエステル系可塑剤などの通常塩化
ビニル系樹脂に使用される可塑剤が使用されてきた。し
かしながら、未だ耐寒性および耐熱性の両方の性能を満
足する合成ゴム組成物は得られていなかった。Conventionally, for the purpose of imparting flexibility to rubber materials used for such purposes, plasticizers usually used for vinyl chloride resins such as aromatic polybasic acid ester plasticizers or polyester plasticizers. Has been used. However, a synthetic rubber composition satisfying both cold resistance and heat resistance has not yet been obtained.
【０００４】従って、本発明の目的は、主として自動車
用の潤滑油ホースや燃料ホース等に使用され、水素化ニ
トリルゴムを主成分とする、耐寒性および耐熱性に優れ
た合成ゴム組成物を提供することにある。Therefore, an object of the present invention is to provide a synthetic rubber composition mainly used for lubricating oil hoses and fuel hoses for automobiles, which contains hydrogenated nitrile rubber as a main component and is excellent in cold resistance and heat resistance. To do.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、種々検討
を重ねた結果、水素化ニトリルゴムに、特定のトリメリ
ット酸エステル系可塑剤を添加してなる合成ゴム組成物
が、上記目的を達成し得ることを見出し、本発明を完成
した。As a result of various studies, the present inventors have found that a synthetic rubber composition obtained by adding a specific trimellitic acid ester plasticizer to hydrogenated nitrile rubber has the above-mentioned object. The inventors have found that the above can be achieved and completed the present invention.
【０００６】即ち、本発明は、水素化ニトリルゴムに、
下記〔化２〕（前記〔化１〕と同じ）の一般式（Ｉ）で
表されるトリメリット酸のアルキルエステル化合物の少
なくとも一種を添加してなる合成ゴム組成物を提供する
ものである。That is, the present invention provides a hydrogenated nitrile rubber,
The present invention provides a synthetic rubber composition obtained by adding at least one kind of an alkyl ester compound of trimellitic acid represented by the general formula (I) of the following [Chemical formula 2] (the same as the above [Chemical formula 1]).
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】以下、本発明の合成ゴム組成物について詳
述する。The synthetic rubber composition of the present invention will be described in detail below.
【０００９】本発明に用いられる水素化ニトリルゴムと
は、ニトリルゴムの耐熱性向上のため主鎖の不飽和結合
の一部もしくは全部を水素化したもので、その製造方法
については、例えば特開昭５２−３２０９５号公報、特
開昭５９−１１５３０３号公報、特開昭５９−１１７５
０１号公報等に種々の製造方法が開示されているが、特
に限定されるものではない。また、ここで言うニトリル
ゴムとは、アクリロニトリルとブタジエンとの共重合体
であるが、該アクリロニトリルおよびブタジエンの他に
ジビニルベンゼン、メタクリル酸、アクリル酸等の第三
成分との共重合体であってもよい。The hydrogenated nitrile rubber used in the present invention is obtained by hydrogenating a part or all of the unsaturated bonds of the main chain in order to improve the heat resistance of the nitrile rubber. JP-A-52-32095, JP-A-59-115303, JP-A-59-1175.
Various production methods are disclosed in Japanese Patent Publication No. 01, etc., but are not particularly limited. Further, the nitrile rubber referred to here is a copolymer of acrylonitrile and butadiene, and in addition to the acrylonitrile and butadiene, a copolymer with a third component such as divinylbenzene, methacrylic acid, acrylic acid, Good.
【００１０】本発明においては、上記一般式（Ｉ）で表
されるトリメリット酸のアルキルエステル化合物が用い
られる。上記一般式（Ｉ）中、R1、R2およびR3は炭素原
子数７または８の直鎖のアルキル基を表す。ここで炭素
原子数が６以下では組成物の耐熱性が劣り、炭素原子数
が９以上では水素化ニトリルゴムとの相溶性に劣り、分
子中に分岐を持つ場合は組成物の耐熱性、水素化ニトリ
ルゴムとの相溶性共に劣る。In the present invention, an alkyl ester compound of trimellitic acid represented by the above general formula (I) is used. In the above general formula (I), R 1 , R 2 and R 3 represent a linear alkyl group having 7 or 8 carbon atoms. Here, when the number of carbon atoms is 6 or less, the heat resistance of the composition is inferior, and when the number of carbon atoms is 9 or more, the compatibility with hydrogenated nitrile rubber is inferior. Poor compatibility with nitrile rubber.
【００１１】上記トリメリット酸のアルキルエステル化
合物は、トリメリット酸あるいはその無水物とアルコー
ル類とのエステル化反応によって容易に製造することが
できるが、製法については特に限定されるものではな
い。The alkyl ester compound of trimellitic acid can be easily produced by an esterification reaction of trimellitic acid or its anhydride with an alcohol, but the production method is not particularly limited.
【００１２】上記トリメリット酸のアルキルエステル化
合物の添加量は、用途によって異なるが、通常、ゴム成
分１００重量部に対して、２〜１００重量部、好ましく
は５〜７０重量部である。The addition amount of the alkyl ester compound of trimellitic acid varies depending on the use, but is usually 2 to 100 parts by weight, preferably 5 to 70 parts by weight, relative to 100 parts by weight of the rubber component.
【００１３】また、上記トリメリット酸のアルキルエス
テル化合物の他に、他の可塑剤、例えば、フタル酸エス
テル系可塑剤、ピロメリット酸エステル系可塑剤、ポリ
エステル系可塑剤、リン酸エステル系可塑剤、更に上記
条件を満たさないトリメリット酸エステル系可塑剤等を
併用して柔軟性を改善することもできる。但し、これら
の他の可塑剤の添加量が多くなりすぎると耐熱性等に悪
影響を及ぼすので、該添加量は全可塑剤成分に対して１
０重量％を超えないことが好ましい。In addition to the above-mentioned trimellitic acid alkyl ester compound, other plasticizers such as phthalic acid ester plasticizers, pyromellitic acid ester plasticizers, polyester plasticizers, and phosphoric acid ester plasticizers. Further, the flexibility can be improved by further using a trimellitic acid ester plasticizer which does not satisfy the above conditions. However, if the addition amount of these other plasticizers is too large, heat resistance and the like are adversely affected, so the addition amount is 1 with respect to the total plasticizer component.
It preferably does not exceed 0% by weight.
【００１４】本発明の合成ゴム組成物を得るためには、
通常のゴムの混練方法が適用でき、例えばオープンロー
ル、バンバリーミキサー、ニーダーブレンダーなどが目
的によって使用される。To obtain the synthetic rubber composition of the present invention,
A usual rubber kneading method can be applied, and for example, an open roll, a Banbury mixer, a kneader blender or the like is used depending on the purpose.
【００１５】本発明の合成ゴム組成物には、必要に応じ
て、ゴムに通常添加される添加剤、例えば、加硫剤、加
硫促進剤、老化防止剤、充填剤、軟化剤、加工助剤など
を添加することができる。If necessary, the synthetic rubber composition of the present invention contains additives such as vulcanizing agents, vulcanization accelerators, antioxidants, fillers, softening agents and processing aids. Agents and the like can be added.
【００１６】[0016]
【実施例】以下、実施例を挙げて、本発明の組成物及び
その効果を具体的に示す。しかしながら、本発明はこれ
らの実施例によって限定されるものではない。EXAMPLES Hereinafter, the composition of the present invention and its effect will be specifically described with reference to examples. However, the invention is not limited to these examples.
【００１７】実施例１ 各種エステル化合物の水素化ニトリルゴムとの相溶性を
確認するため、下記に示した〔配合〕の処方により、バ
ンバリー混練し、次いでプレス成型して得られたシート
からの滲み出し現象を観察した。その結果を下記〔表
１〕に示す。尚、プレス条件は１７５℃、１５分とし
た。また、滲み出しの評価基準は下記の通りである。Example 1 In order to confirm the compatibility of various ester compounds with hydrogenated nitrile rubber, bleeding from a sheet obtained by Banbury kneading followed by press molding according to the formulation of [compounding] shown below The start-up phenomenon was observed. The results are shown in [Table 1] below. The pressing conditions were 175 ° C. and 15 minutes. In addition, the evaluation criteria for bleeding are as follows.
【００１８】〔評価基準〕 ○ ： 滲み出しなし △ ： やや滲み出しあり × ： 激しい滲み出しあり[Evaluation Criteria] ○: No bleeding out △: Some bleeding out ×: Severe bleeding out
【００１９】 〔配合〕 重量部 ゼットポール２０１０ １００ （日本ゼオン製水素化ニトリルゴム） ＦＥＦカーボン ５０ ペロキシモンＦ−４０（日本油脂製過酸化物） ６ ナウガード４４５（ユニロイヤル製老化防止剤） ２ 可塑剤（下記〔表１〕および〔表２〕に示す） ５０[Compounding] Parts by weight Zetpol 2010 100 (hydrogenated nitrile rubber manufactured by Nippon Zeon) FEF carbon 50 Peroximon F-40 (peroxide manufactured by NOF Corporation) 6 Noward 445 (antiaging agent manufactured by Uniroyal) 2 Plasticizer (Shown in [Table 1] and [Table 2] below) 50
【００２０】[0020]
【表１】 [Table 1]
【００２１】実施例２ 実施例１の〔配合〕の処方により、１７０℃で１５分間
プレス加硫して試験片を作成した。その試験片を用い、
硬度の測定と、引っ張り試験による抗張力と伸びの測定
とを行なった。また、１７５℃、１６８時間の熱老化後
の硬度および抗張力と伸びの測定を行ない、硬度につい
てはその差を求めた。また、熱老化前後のねじれ温度の
測定を行なった。以上の試験はＪＩＳ Ｋ−６３０１に
従って行なった。Example 2 A test piece was prepared by press vulcanizing at 170 ° C. for 15 minutes according to the formulation of [Compounding] in Example 1. Using the test piece,
The hardness was measured and the tensile strength and elongation were measured by a tensile test. Further, the hardness, tensile strength and elongation after heat aging at 175 ° C. for 168 hours were measured, and the difference in hardness was determined. In addition, the twist temperature before and after heat aging was measured. The above test was conducted according to JIS K-6301.
【００２２】更に、熱老化後の可塑剤の重量減少を測定
した。評価方法は、厚さ２ｍｍのシートを１５０ｍｍ×
１５０ｍｍの試験片を作成し、１７５℃、１６８時間の
熱老化後の質量変化から計算した。Further, the weight loss of the plasticizer after heat aging was measured. The evaluation method is 150 mm x 2 mm thick sheet
A 150 mm test piece was prepared and calculated from the change in mass after heat aging at 175 ° C. for 168 hours.
【００２３】それらの結果をそれぞれ下記〔表２〕に示
す。The results are shown in Table 2 below.
【００２４】[0024]
【表２】 [Table 2]
【００２５】上記〔表１〕および〔表２〕の結果より、
トリメリット酸のアルキルエステル化合物の中でも、上
記一般式（Ｉ）で表される本発明に係る化合物と比較し
てアルキル基の大きいものでは、水素化ニトリルゴムと
の相溶性に劣り（比較例 1-4）、アルキル基の短いもの
は、該相溶性に優れるが（比較例 1-3）、組成物の耐熱
性に対して十分な性能を与えることができず（比較例 2
-3）、さらに分岐のアルキルを有する場合には水素化ニ
トリルゴムとの相溶性に劣り（比較例 1-2）、組成物の
耐熱性に関しても不十分である（比較例 2-2）。From the results of the above [Table 1] and [Table 2],
Among the alkyl ester compounds of trimellitic acid, those having a larger alkyl group than the compound of the present invention represented by the general formula (I) have poor compatibility with hydrogenated nitrile rubber (Comparative Example 1 -4), those having a short alkyl group are excellent in the compatibility (Comparative Example 1-3), but cannot give sufficient performance to the heat resistance of the composition (Comparative Example 2).
-3) Further, when it has a branched alkyl, the compatibility with hydrogenated nitrile rubber is poor (Comparative Example 1-2), and the heat resistance of the composition is also insufficient (Comparative Example 2-2).
【００２６】これに対し、上記一般式（Ｉ）で表される
本発明に係るトリメリット酸の炭素原子数７または８で
直鎖のアルキルエステル化合物は、水素化ニトリルゴム
との相溶性に優れ（実施例 1-1〜1-3 ）、さらに耐寒性
および耐熱性に優れた組成物を与える（実施例 2-1〜2-
3 ）ことが判る。On the other hand, the linear alkyl ester compound having 7 or 8 carbon atoms of trimellitic acid according to the present invention represented by the general formula (I) has excellent compatibility with hydrogenated nitrile rubber. (Examples 1-1 to 1-3) Further, compositions having excellent cold resistance and heat resistance are provided (Examples 2-1 to 2-).
3) It turns out.
【００２７】[0027]
【発明の効果】水素化ニトリルゴムに、特定のトリメリ
ット酸のアルキルエステル化合物を添加してなる本発明
の合成ゴム組成物は、主として自動車用の潤滑油ホース
や燃料ホース等に使用される、耐寒性および耐熱性に優
れたものである。Industrial Applicability The synthetic rubber composition of the present invention obtained by adding a specific alkyl ester compound of trimellitic acid to hydrogenated nitrile rubber is mainly used for lubricating oil hoses and fuel hoses for automobiles, It has excellent cold resistance and heat resistance.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年３月１５日[Submission date] March 15, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】本発明の合成ゴム組成物には、必要に応じ
て、ゴムに通常添加される添加剤、例えば、加硫剤、加
硫促進剤、老化防止剤、充填剤、軟化剤、加工助剤など
を添加することができる。本発明の合成ゴム組成物は、
耐寒性および耐熱性に優れたものであることから、潤滑
油ホース、燃料ホース、ダイヤフラム、パッキン、タイ
ミングベルト等の自動車用途に好適に使用されるもので
あるが、当然のことながら、その用途は自動車用途に限
定されるものではなく、オイルシール、ガスケット、印
刷用ロール、ブランケット、製鉄ロール等のその他の用
途にも使用することができる。If necessary, the synthetic rubber composition of the present invention contains additives such as vulcanizing agents, vulcanization accelerators, antioxidants, fillers, softening agents and processing aids. Agents and the like can be added. The synthetic rubber composition of the present invention,
Lubrication due to excellent cold resistance and heat resistance
Oil hose, fuel hose, diaphragm, packing, tie
Suitable for automotive applications such as ming belts
However, as a matter of course, its application is limited to automobile applications.
Not specified, but an oil seal, gasket, seal
Other uses such as printing rolls, blankets, and steelmaking rolls
It can also be used en route .
Claims (1)
一般式（Ｉ）で表されるトリメリット酸のアルキルエス
テル化合物の少なくとも一種を添加してなる合成ゴム組
成物。 【化１】 1. A synthetic rubber composition comprising a hydrogenated nitrile rubber and at least one alkyl ester compound of trimellitic acid represented by the following general formula (I). [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31553693A JP3469282B2 (en) | 1993-12-15 | 1993-12-15 | Synthetic rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31553693A JP3469282B2 (en) | 1993-12-15 | 1993-12-15 | Synthetic rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165989A true JPH07165989A (en) | 1995-06-27 |
| JP3469282B2 JP3469282B2 (en) | 2003-11-25 |
Family
ID=18066524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31553693A Expired - Fee Related JP3469282B2 (en) | 1993-12-15 | 1993-12-15 | Synthetic rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3469282B2 (en) |
-
1993
- 1993-12-15 JP JP31553693A patent/JP3469282B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3469282B2 (en) | 2003-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2007094158A1 (en) | Hydrogenated NBR composition | |
| JPS63270753A (en) | Vulcanizable rubber composition | |
| KR20080100424A (en) | Hydrogenated nbr composition | |
| JP2008195881A (en) | Hydrogenated nbr composition | |
| WO2019087788A1 (en) | Ethylene-acrylate rubber composition and molded article thereof | |
| JP2008106207A (en) | Crosslinkable rubber composition comprising hydrogenated acrylonitrile-butadiene rubber and one kind or mixture of two kinds selected from isoprene-isobutylene rubber and ethylene-propylene-diene rubber and crosslinked rubber product obtained by crosslinking the composition | |
| JP2739285B2 (en) | Rubber composition for molding seal member and use thereof | |
| JPH093246A (en) | Hydrogenated nbr composition | |
| JPH07149990A (en) | Synthetic rubber composition | |
| JPH07165989A (en) | Synthetic rubber composition | |
| AU2011311990A1 (en) | Accelerator composition for elastomers | |
| RU2304596C2 (en) | Vulcanizable rubber mixture on the basis of the hydrogenated butadiene-nitrile caoutchouck | |
| JP3452966B2 (en) | Nitrile rubber or acrylic rubber composition | |
| JPH10231389A (en) | Rubber composition improved in processability | |
| JPH0820693A (en) | Halogenated butyl rubber composition | |
| JPS626581B2 (en) | ||
| JPWO2019003917A1 (en) | Method for producing crosslinked acrylic rubber molded article, acrylic rubber composition and sealing material | |
| US5446098A (en) | Covulcanizable rubber composition of partially hydrogenated nitrile rubber and chlorinated ethylene-propylene copolymer | |
| JPH08269267A (en) | Oil-bleeding polyolefin rubber composition | |
| KR100341317B1 (en) | Rubber composition for contacting metal | |
| JPH0238104B2 (en) | GOMUNOTAIKANSEIKOJOZAI | |
| JP2001040158A (en) | Rubber composition and hose | |
| JP2721612B2 (en) | Synthetic rubber composition | |
| JPH07179710A (en) | Synthetic rubber composition | |
| JP2687998B2 (en) | Process for producing oil-resistant hydrogenated acrylonitosol butadiene rubber having improved heat resistance and process for producing vulcanized rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20080905 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20090905 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090905 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 7 Free format text: PAYMENT UNTIL: 20100905 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20110905 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20110905 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120905 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |