JP2011057768A - Acrylic rubber composition and molded article thereof - Google Patents

Acrylic rubber composition and molded article thereof Download PDF

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JP2011057768A
JP2011057768A JP2009206546A JP2009206546A JP2011057768A JP 2011057768 A JP2011057768 A JP 2011057768A JP 2009206546 A JP2009206546 A JP 2009206546A JP 2009206546 A JP2009206546 A JP 2009206546A JP 2011057768 A JP2011057768 A JP 2011057768A
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acrylic rubber
weight
parts
rubber composition
vulcanization
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Akimi Shibayama
亜季実 柴山
Tatsuo Katayama
竜雄 片山
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Uchiyama Manufacturing Corp
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Uchiyama Manufacturing Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic rubber composition that exhibits excellent scorch stability and a rapid vulcanization rate without detriment to heat resistance, oil resistance and permanent compression set resistance of an epoxy group-containing acrylic rubber, and a molded article thereof. <P>SOLUTION: The acrylic rubber composition comprises an epoxy group-containing acrylic rubber and, incorporated therewith, at least a sulfonamide compound in an amount of 0.04-3.0 pts.wt. and a dithiocarbamic acid metal salt in an amount of 0.5-6.0 pts.wt., each amount being based on 100 pts.wt. of the acrylic rubber. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、加硫スピードが速いものでありながら、耐熱性、耐油性、耐圧縮永久歪性、スコーチ安定性にも優れたアクリルゴム組成物及びその成形品に関する。   The present invention relates to an acrylic rubber composition excellent in heat resistance, oil resistance, compression set resistance and scorch stability, and a molded product thereof, while having a fast vulcanization speed.

従来より、エポキシ基含有アクリルゴムはスコーチ安定性については良好であるが、加硫スピードが遅いという問題点が指摘されている。   Conventionally, it has been pointed out that epoxy group-containing acrylic rubber has good scorch stability but has a slow vulcanization speed.

そこでエポキシ基含有アクリルゴムの加硫剤としては下記特許文献1に開示されているようにアミン化合物、或いはジチオカルバミン酸金属塩、などが知られている。   Therefore, as a vulcanizing agent for an epoxy group-containing acrylic rubber, an amine compound or a metal salt of dithiocarbamate is known as disclosed in Patent Document 1 below.

下記特許文献2には、(A)シード重合法によってえられる活性塩素基を0.1〜0.5重量%含有する加硫性アクリルゴム100重量部に対し、(C)ジチオカルバミン酸金属塩を0.5〜5.0重量部、(D)N−イソプロピルチオ−N−シクロヘキシル−ベンゾチアジル−2−スルホンアミド、N−シクロヘキシル−N−トリクロロメチルチオ−ベンジル−2−スルホンアミドからなるアミド誘導体を0.05〜1.5重量部など含有させたものが開示されている。ここでは前記アミド誘導体は早期加硫の抑制を目的とした加硫遅延剤として配合されている。   In Patent Document 2 below, (A) 100 parts by weight of a vulcanizable acrylic rubber containing 0.1 to 0.5% by weight of active chlorine groups obtained by seed polymerization, (C) a metal salt of dithiocarbamate 0.5 to 5.0 parts by weight of an amide derivative composed of (D) N-isopropylthio-N-cyclohexyl-benzothiazyl-2-sulfonamide and N-cyclohexyl-N-trichloromethylthio-benzyl-2-sulfonamide What is contained, such as 0.05-1.5 weight part, is disclosed. Here, the amide derivative is blended as a vulcanization retarder for the purpose of suppressing early vulcanization.

下記特許文献3には、塩素含有アクリルゴムと、該アクリル100重量部に対して0.01〜10重量部の量の酸化マグネシウムとを含有するものが開示されており、ここではスルホンアミド誘導体が加硫遅延剤或いはスコーチ防止剤として、配合されることが記載されている。   Patent Document 3 listed below discloses a chlorine-containing acrylic rubber and one containing 0.01 to 10 parts by weight of magnesium oxide with respect to 100 parts by weight of the acrylic. It is described that it is blended as a vulcanization retarder or a scorch inhibitor.

特公昭49−13215号公報Japanese Patent Publication No.49-13215 特公平7−68425号公報Japanese Examined Patent Publication No. 7-68425 特開平9−194670号公報JP 9-194670 A

しかしながら、上記特許文献1に記載のアミン化合物を用いた場合、加硫スピードは向上するが所望する常態物性が得られず、加工が困難になる。また、上記特許文献1に記載のジチオカルバミン酸金属塩を用いた場合にはスコーチ安定性は良好となるが、加硫スピードが非常に遅く、加工に時間を有するものとなってしまう。   However, when the amine compound described in Patent Document 1 is used, the vulcanization speed is improved, but desired normal physical properties cannot be obtained, and processing becomes difficult. Further, when the metal salt of dithiocarbamate described in Patent Document 1 is used, the scorch stability is good, but the vulcanization speed is very slow and processing takes time.

上記特許文献2の(D)アミド誘導体は、上述のように活性塩素基を含有するアクリルゴムに対して、早期加硫の抑制を目的として配合され、また上記特許文献3のスルホンアミド誘導体は加硫遅延剤或いはスコーチ防止剤として配合されており、加硫スピードを速めるためにアクリルゴム組成物にスルホンアミド誘導体を配合する点は開示されていない。   The (D) amide derivative of Patent Document 2 is blended for the purpose of suppressing early vulcanization with respect to the acrylic rubber containing an active chlorine group as described above, and the sulfonamide derivative of Patent Document 3 is added. It is blended as a sulfur retarder or a scorch inhibitor, and there is no disclosure of incorporating a sulfonamide derivative into the acrylic rubber composition in order to increase the vulcanization speed.

本発明は、上記実情に鑑みなされたものであり、エポキシ基含有アクリルゴムの耐熱性、耐油性及び耐圧縮永久歪性を損なうことなくスコーチ安定性に優れ、且つ加硫スピードが速いアクリルゴム組成物及びその成形品を提供することを目的としている。   The present invention has been made in view of the above circumstances, and is an acrylic rubber composition that has excellent scorch stability and high vulcanization speed without impairing the heat resistance, oil resistance and compression set resistance of the epoxy group-containing acrylic rubber. It aims at providing a thing and its molded article.

本発明に係るアクリルゴム組成物は、少なくともエポキシ基含有アクリルゴム100重量部に対して、スルホンアミド化合物を0.04〜3.0重量部、ジチオカルバミン酸金属塩を0.5〜6.0重量部配合してなることを特徴とする。
また本発明において前記に記載のアクリルゴム組成物を加硫成形して成形品とすることができる。
The acrylic rubber composition according to the present invention comprises 0.04 to 3.0 parts by weight of a sulfonamide compound and 0.5 to 6.0 parts by weight of a metal salt of dithiocarbamate with respect to at least 100 parts by weight of an epoxy group-containing acrylic rubber. It is characterized by being partly blended.
In the present invention, the acrylic rubber composition described above can be vulcanized and molded into a molded product.

本発明のアクリルゴム組成物によれば、アクリルゴム組成物の特性である耐熱性、耐油性及び耐圧縮永久歪性を損なうことなく、スコーチ安定性に優れ、且つ加硫スピードが速いアクリルゴム組成物とすることができる。
スルホンアミド化合物の配合量が、エポキシ基含有アクリルゴム100重量部に対して0.04重量部未満では、加硫スピード向上の十分な効果が得られない傾向となる。また4.0重量部を超えて配合すると、加硫スピードが速くなりすぎて、成形性が悪くなる傾向となる。
ジチオカルバミン酸金属塩の配合量が、エポキシ基含有アクリルゴム100重量部に対して0.5重量部未満では架橋密度が十分ではない傾向となり、6.0重量部を超えると所望する常態物性が得られない傾向となる。
また本発明のアクリルゴム組成物による成形品によれば、成形するに際して、加硫スピードが速いので、自動機での生産も可能となり、効率よく生産することが可能となる。
According to the acrylic rubber composition of the present invention, the acrylic rubber composition has excellent scorch stability and quick vulcanization speed without impairing the heat resistance, oil resistance and compression set resistance, which are the characteristics of the acrylic rubber composition. It can be a thing.
When the compounding amount of the sulfonamide compound is less than 0.04 parts by weight with respect to 100 parts by weight of the epoxy group-containing acrylic rubber, a sufficient effect of improving the vulcanization speed tends not to be obtained. Moreover, when it mix | blends exceeding 4.0 weight part, it will become a tendency for a vulcanization speed to become too quick and for a moldability to worsen.
When the blending amount of the metal salt of dithiocarbamate is less than 0.5 parts by weight with respect to 100 parts by weight of the epoxy group-containing acrylic rubber, the crosslinking density tends to be insufficient, and when it exceeds 6.0 parts by weight, the desired normal physical properties are obtained. It becomes a tendency not to be able to.
Further, according to the molded article of the acrylic rubber composition of the present invention, the vulcanization speed is high when molding, so that it can be produced with an automatic machine and can be produced efficiently.

実施例1、実施例2及び比較例1〜3の加硫トルク曲線を示した図である。It is the figure which showed the vulcanization torque curve of Example 1, Example 2, and Comparative Examples 1-3.

以下に本発明の実施の形態について、図面に基づいて説明する。
本発明のアクリルゴム組成物は、エポキシ基含有アクリルゴム100重量部に対して、少なくともスルホンアミド化合物を0.04〜3.0重量部、ジチオカルバミン酸金属塩を0.5〜6.0重量部配合してなるものである。
本発明に用いられるエポキシ基含有アクリルゴムとしては、例えば(a)アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸オクチルなどのような例えばアルキル基が1〜8個の炭素原子を有するアルキルアクリレート、またはアクリル酸メトキシメチル、アクリル酸メトキシエチル、アクリル酸エトキシエチル、アクリル酸ブトキシエチルなどのようなアルキル基とアルキレン基がそれぞれ例えば1〜4個の炭素原子を有するアルコキシアルキルアクリレートから選ばれる少なくとも1種類以上のアクリル酸エステルと(b)アクリル酸グリシジル、メタクリル酸グリシジル、グリシジルビニルエーテル、グリシジルアリルエーテルなどのような上記(a)成分と共重合可能な二重結合と架橋反応に供するエポキシ基を両方持つ化合物を1種類以上共重合したゴムが挙げられる。
また(c)アクリロニトリル、ヒドロキシエチルアクリレート、テトラフルオロエチレン、ヘキサフルオロプロピレン、スチレン、ジビニルベンゼンなどのような上記(a)(b)成分と共重合可能な二重結合をもつ化合物を任意に1種類以上共重合してもよい。
(c)の含有量は好ましくは、ポリマー全体の1〜20重量%であり、(c)の含有量が1重量%より少ないと単量体のもつ効果が得られず、20重量%を超えるとアクリルゴム組成物の耐熱性、耐油性等の諸物性が低下しまう。
Embodiments of the present invention will be described below with reference to the drawings.
In the acrylic rubber composition of the present invention, at least 0.04 to 3.0 parts by weight of the sulfonamide compound and 0.5 to 6.0 parts by weight of the metal salt of dithiocarbamate with respect to 100 parts by weight of the epoxy group-containing acrylic rubber. It is a blended product.
Examples of the epoxy group-containing acrylic rubber used in the present invention include (a) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like. For example, an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms, or an alkyl group and an alkylene group such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, At least one acrylic ester selected from alkoxyalkyl acrylates having 4 carbon atoms and (b) glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, glycidyl allyl ether, etc. A (a) above rubber component copolymerizable with the double bond with a compound having both an epoxy group is subjected to crosslinking reaction by copolymerizing one or more thereof.
In addition, (c) one arbitrary compound having a double bond copolymerizable with the above components (a) and (b), such as acrylonitrile, hydroxyethyl acrylate, tetrafluoroethylene, hexafluoropropylene, styrene, divinylbenzene, etc. You may copolymerize above.
The content of (c) is preferably 1 to 20% by weight of the whole polymer, and if the content of (c) is less than 1% by weight, the effect of the monomer cannot be obtained and exceeds 20% by weight. And various physical properties such as heat resistance and oil resistance of the acrylic rubber composition are lowered.

本発明に用いられる充てん剤としては、例えば一般的に使用されるカーボンブラック、シリカ、珪藻土、珪酸カルシウム、クレー、炭酸カルシウム、タルクなどが挙げられ、これらから選ばれる少なくとも一種類以上を含有し、その配合量はポリマー100重量部に対して20から200重量部、好ましくは40から130重量部である。20重量部未満ではゴム硬さが不十分な傾向となり、200重量部を超えると所望する常態物性が得られない傾向となる。   Examples of the filler used in the present invention include commonly used carbon black, silica, diatomaceous earth, calcium silicate, clay, calcium carbonate, talc and the like, containing at least one selected from these, The amount is 20 to 200 parts by weight, preferably 40 to 130 parts by weight, based on 100 parts by weight of the polymer. If it is less than 20 parts by weight, the rubber hardness tends to be insufficient, and if it exceeds 200 parts by weight, the desired normal physical properties tend not to be obtained.

本発明に用いられるジチオカルバミン酸金属塩の配合量は、ポリマー100重量部に対して、0.5重量部以上6.0重量部以下、好ましくは1.0重量部以上4.0重量部以下である。0.5重量部未満では架橋密度が十分とはいえない傾向となり、6.0重量部を超えると所望する常態物性が得られない傾向となる。ジチオカルバミン酸金属塩としては例えばジメチルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸鉄、ジメチルジチオカルバミン酸銅、ジエチルジチオカルバミン酸テリウム、エチルフェニルジチオカルバミン酸亜鉛などがある。   The compounding amount of the metal salt of dithiocarbamate used in the present invention is 0.5 parts by weight or more and 6.0 parts by weight or less, preferably 1.0 part by weight or more and 4.0 parts by weight or less with respect to 100 parts by weight of the polymer. is there. If the amount is less than 0.5 part by weight, the crosslinking density tends not to be sufficient. If the amount exceeds 6.0 parts by weight, the desired normal physical properties tend not to be obtained. Examples of the metal salt of dithiocarbamate include zinc dimethyldithiocarbamate, iron dimethyldithiocarbamate, copper dimethyldithiocarbamate, terium diethyldithiocarbamate, and zinc ethylphenyldithiocarbamate.

本発明に用いられるスルホンアミド化合物の配合量は、ポリマー100重量部に対して、0.04重量部以上4.0重量部以下、好ましくは0.1重量部以上2.0重量部以下である。0.04重量部未満では加硫スピード向上の十分な効果が得られない傾向となる。4.0重量部を超えて配合すると、加硫スピードが速くなりすぎて、成形性が悪くなる傾向となる。スルホンアミド化合物としては例えばN-トリル‐N‐(ジクロロメチルスルフェニル)‐ベンゼンスルホンアミド、N‐フェニル‐N‐(トリクロロメチルスルフェニル)‐p‐トルエンスルホンアミド、N‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミド、N‐キシリル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドなどがある。   The amount of the sulfonamide compound used in the present invention is 0.04 to 4.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the polymer. . If it is less than 0.04 parts by weight, a sufficient effect of improving the vulcanization speed tends not to be obtained. If it exceeds 4.0 parts by weight, the vulcanization speed becomes too fast and the moldability tends to deteriorate. Examples of the sulfonamide compounds include N-tolyl-N- (dichloromethylsulfenyl) -benzenesulfonamide, N-phenyl-N- (trichloromethylsulfenyl) -p-toluenesulfonamide, N-phenyl-N- (trichloro Methylsulfenyl) -benzenesulfonamide, N-xylyl-N- (trichloromethylsulfenyl) -benzenesulfonamide, and the like.

その他滑剤、加工助剤、可塑剤、加硫剤、加硫促進剤、老化防止剤,カップリング剤、着色剤等ゴムに使用される一般的な配合剤を配合してもよい。
本発明のアクリルゴム組成物の加硫条件は、150〜220℃、望ましくは170〜200℃が好ましく、また必要に応じて後加硫してもよい。
In addition, general compounding agents used for rubber such as lubricants, processing aids, plasticizers, vulcanizing agents, vulcanization accelerators, anti-aging agents, coupling agents, and coloring agents may be blended.
The vulcanization conditions of the acrylic rubber composition of the present invention are preferably 150 to 220 ° C, desirably 170 to 200 ° C, and may be post-cured as necessary.

以下、本発明のアクリルゴム組成物について、実施例を挙げて更に具体的に説明するが、これらは本発明の実施の一例であって、これらに限定されるものではない。
表1に記載の配合にて、密閉式混練機またはオープンロールを用いて混練し、得られた混合物を170℃×10分間圧縮成形し、さらに180℃×4時間後加硫して、厚さ2mmの加硫シートを得た。これにより得られた加硫シートを試験片として、JIS規格に準じて各物性測定を以下のようにして行った。
Hereinafter, the acrylic rubber composition of the present invention will be described more specifically with reference to examples. However, these are examples of the present invention and are not limited thereto.
The composition shown in Table 1 was kneaded using a closed kneader or an open roll, and the resulting mixture was compression molded at 170 ° C. for 10 minutes, and further vulcanized at 180 ° C. for 4 hours to obtain a thickness. A 2 mm vulcanized sheet was obtained. Using the vulcanized sheet thus obtained as a test piece, each physical property measurement was performed in accordance with JIS standards as follows.

Figure 2011057768
Figure 2011057768

(実施例1)
エポキシ基含有アクリルゴム・・・100重量部
シリカ・・・50重量部
ジメチルジチオカルバミン酸亜鉛・・・2重量部
N‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミド
・・・0.1重量部
(実施例2)
実施例1においてN‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドの量を1.0重量部へ変更した。
(比較例1)
実施例1においてN‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドを配合しなかった。
(比較例2)
実施例1においてN‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドの量を0.02重量部へ変更した。
(比較例3)
実施例1においてN‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドの量を5.0重量部へ変更した。
(比較例4)
ジチオカルバミン酸金属塩のかわりにヘキサメチレンカーバメード2重量部を配合した。
N‐フェニル‐N‐(トリクロロメチルスルフェニル)‐ベンゼンスルホンアミドを配合しなかった。
Example 1
Epoxy group-containing acrylic rubber: 100 parts by weight
Silica: 50 parts by weight Zinc dimethyldithiocarbamate: 2 parts by weight N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide: 0.1 part by weight (Example 2)
In Example 1, the amount of N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide was changed to 1.0 part by weight.
(Comparative Example 1)
In Example 1, N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide was not blended.
(Comparative Example 2)
In Example 1, the amount of N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide was changed to 0.02 parts by weight.
(Comparative Example 3)
In Example 1, the amount of N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide was changed to 5.0 parts by weight.
(Comparative Example 4)
Instead of the metal salt of dithiocarbamate, 2 parts by weight of hexamethylene carbamate was blended.
N-phenyl-N- (trichloromethylsulfenyl) -benzenesulfonamide was not incorporated.

(1)加硫特性:JIS K 6300‐2に準じて所定サイズの試験片を用い、温度200℃、5分間の条件で測定を行った。tc(10)min、tc(90)min、最低トルクML及び最大トルクMHを求めることにより、加硫特性を評価した。tc(10)minは最大トルクを100%としたとき、トルクが10%に達するまでの時間であり、この数値が小さすぎる場合は、スコーチ安定性が劣るといえる。tc(90)minは最大トルクを100%としたとき、トルクが90%に達するまでの時間であり、この数値が大きすぎる場合は、加硫スピードが遅いといえる。またMLの値が小さいほど、未加硫体が流れやすいといえ、MHの値が大きいほど、架橋密度が高く、加硫スピードが従来(スルホンアミド化合物を配合しない場合)に比べて速いことから成形性に優れているといえる。
図1は(1)の試験結果の加硫曲線を示したものである。
(2)常態物性:JIS K 6253、6251準拠
JIS K6253に準じて、所定サイズの試験片の硬さを測定した。
JIS K6251に準じて、所定サイズの試験片の引張り強さ及び伸びを測定した。引張強さは値が大きいほど破断しにくく、機械的強度が強いことを示している。
(3)空気加熱老化試験:JIS K 6257準拠(150℃×70時間)
試験片を空気加熱老化試験機を使用して150℃70時間熱処理を行った後、該試験片を取り出し、硬さ変化を測定した。変化が小さいほど、耐熱性に優れているといえる。
(4)耐油試験:JIS K 6258準拠(IRM903、150℃×70時間)
試験片をIRM#903号油に150℃70時間浸漬した後、硬さ変化を測定した。変化が小さいほど、耐油性に優れているといえる。
(5)圧縮永久歪試験:JIS K 6262準拠(150℃×70時間)
試験片を25%圧縮し、150℃とした空気中に70時間保持後、圧縮を開放し、圧縮永久歪を算出した値を示している。値が小さいほど、長時間圧縮したときに復元する力が高いといえる。
(1) Vulcanization characteristics: Using a test piece of a predetermined size according to JIS K 6300-2, measurement was performed under conditions of a temperature of 200 ° C. for 5 minutes. Vulcanization characteristics were evaluated by determining tc (10) min, tc (90) min, minimum torque ML, and maximum torque MH. tc (10) min is the time until the torque reaches 10% when the maximum torque is 100%. If this value is too small, it can be said that the scorch stability is inferior. tc (90) min is the time until the torque reaches 90% when the maximum torque is 100%. If this value is too large, it can be said that the vulcanization speed is slow. Moreover, it can be said that the smaller the ML value, the easier the unvulcanized product flows. The higher the MH value, the higher the crosslink density, and the faster the vulcanization speed (when no sulfonamide compound is blended). It can be said that the moldability is excellent.
FIG. 1 shows the vulcanization curve of the test result of (1).
(2) Normal state physical properties: JIS K 6253, 6251 conformity According to JIS K6253, the hardness of a test piece of a predetermined size was measured.
In accordance with JIS K6251, the tensile strength and elongation of a test piece of a predetermined size were measured. The larger the tensile strength, the more difficult it is to break, indicating that the mechanical strength is high.
(3) Air heating aging test: JIS K 6257 compliant (150 ° C x 70 hours)
The test piece was heat-treated at 150 ° C. for 70 hours using an air heating aging tester, and then the test piece was taken out and the change in hardness was measured. It can be said that the smaller the change, the better the heat resistance.
(4) Oil resistance test: JIS K 6258 compliant (IRM903, 150 ° C x 70 hours)
After the test piece was immersed in IRM # 903 oil at 150 ° C. for 70 hours, the change in hardness was measured. It can be said that the smaller the change, the better the oil resistance.
(5) Compression set test: JIS K 6262 compliant (150 ° C. × 70 hours)
A value obtained by compressing the test piece by 25% and holding in air at 150 ° C. for 70 hours, then releasing the compression and calculating the compression set is shown. It can be said that the smaller the value, the higher the restoring force when compressed for a long time.

[結果]
表1の測定結果からわかるように、実施例1及び実施例2の配合により得られたものによれば、耐熱性、耐油性、耐圧縮永久歪性を損なうことなくスコーチ安定性にも優れ、且つ加硫スピードが速いアクリルゴム組成物とすることができる。
特に加硫特性の測定結果から実施例1及び実施例2の配合により得られたものは、tc(90)minの数値が小さくなっており、この結果より加硫スピードが速いということがいえる。
加硫スピードについては図1の加硫曲線からも明らかである。
例えば実施例1及び実施例2は、100sec後の加硫トルクの値が比較例1及び比較例2に比べて倍以上高く、150sec以降は安定した加硫トルクを示していることから、加硫特性に優れていることがわかる。比較例3は加硫特性だけをみるとよい数値がでているが、後記するように物性面で実施例1及び実施例2より劣る結果となった。
また実施例1及び実施例2の配合により得られたものは、tc(10)minの数値が従来品と変わらない数値を示しており、上述のように加硫特性に優れ且つスコーチ安定性にも優れているものといえる。
さらにスルホンアミド化合物を配合させることにより、耐熱性、耐油性、耐圧縮永久歪性の低下が懸念されるところ、実施例1及び実施例2の配合により得られたものによれば、これらの低下がなく上述の諸物性を備えたものを得ることができた。
以上より、実施例1及び実施例2の配合により得られる成形品はガスケット、パッキン、オイルシール、ベアリングシール、ブッシュなどのゴム製品とすることができ、耐熱性、耐油性、耐圧縮永久歪性を備えたものとすることができる。
よって、特にオイルシール、ベアリングシールに必要とされる適性に優れたものとすることができる。
またスコーチ安定性にも優れ、且つ加硫が速いので、成形品の生産効率を向上させることができる。
[result]
As can be seen from the measurement results in Table 1, according to those obtained by blending Example 1 and Example 2, the scorch stability is excellent without impairing heat resistance, oil resistance, and compression set resistance, Moreover, an acrylic rubber composition having a high vulcanization speed can be obtained.
In particular, those obtained by the blending of Example 1 and Example 2 from the measurement results of the vulcanization characteristics have a small numerical value of tc (90) min. From this result, it can be said that the vulcanization speed is fast.
The vulcanization speed is also apparent from the vulcanization curve in FIG.
For example, Example 1 and Example 2 show that the value of vulcanization torque after 100 seconds is more than double that of Comparative Example 1 and Comparative Example 2, and shows a stable vulcanization torque after 150 seconds. It can be seen that the characteristics are excellent. In Comparative Example 3, only good vulcanization characteristics were obtained, but the results were inferior to those in Examples 1 and 2 in terms of physical properties as will be described later.
Moreover, what was obtained by the mixing | blending of Example 1 and Example 2 has shown the numerical value of tc (10) min which is not different from a conventional product, and is excellent in a vulcanization | cure characteristic as mentioned above, and in scorch stability. Can also be said to be excellent.
Further, by blending a sulfonamide compound, there is a concern about a decrease in heat resistance, oil resistance, compression set resistance. According to those obtained by blending Example 1 and Example 2, these decreases It was possible to obtain a product having the above-mentioned various physical properties.
From the above, the molded products obtained by the blending of Example 1 and Example 2 can be rubber products such as gaskets, packings, oil seals, bearing seals, bushes, and have heat resistance, oil resistance, compression set resistance. Can be provided.
Therefore, it can be made excellent in aptitude required especially for oil seals and bearing seals.
Moreover, since the scorch stability is excellent and the vulcanization is fast, the production efficiency of the molded product can be improved.

一方、実施例1及び実施例2と比較例1〜4を比較すると、比較例1及び比較例2はtc(90)minの値が大きく、成形に時間がかかってしまうことがわかる。比較例1のようにスルホンアミド化合物を配合しなかった場合は、上述の所望する諸物性を得ることはできても加硫スピードの向上は見込めない。また比較例2の数値からわかるようにスルホンアミド化合物を加えても、その量が0.02重量部では加硫スピード向上の十分な効果が見られない。
比較例3は、tc(10)minの値が小さく、成形性が悪い。また所望する常態物性、耐熱性、耐油性、耐圧縮永久歪性が得られない。
比較例4は、常態物性の伸びが「70」と小さく所望する常態物性が得られないことがわかる。
On the other hand, when Example 1 and Example 2 and Comparative Examples 1 to 4 are compared, it can be seen that Comparative Example 1 and Comparative Example 2 have a large value of tc (90) min and take a long time for molding. When the sulfonamide compound is not blended as in Comparative Example 1, it is not possible to improve the vulcanization speed even though the above-mentioned desired physical properties can be obtained. Further, as can be seen from the numerical values of Comparative Example 2, even when a sulfonamide compound is added, if the amount is 0.02 parts by weight, a sufficient effect of improving the vulcanization speed is not observed.
In Comparative Example 3, the value of tc (10) min is small and the moldability is poor. In addition, desired normal properties, heat resistance, oil resistance, and compression set resistance cannot be obtained.
It can be seen that Comparative Example 4 has a small normal property elongation of “70” and the desired normal property cannot be obtained.

Claims (2)

エポキシ基含有アクリルゴム100重量部に対して、少なくともスルホンアミド化合物を0.04〜3.0重量部、ジチオカルバミン酸金属塩を0.5〜6.0重量部配合してなることを特徴とするアクリルゴム組成物。   It is characterized by blending at least 0.04 to 3.0 parts by weight of a sulfonamide compound and 0.5 to 6.0 parts by weight of a metal salt of dithiocarbamate with respect to 100 parts by weight of an epoxy group-containing acrylic rubber. Acrylic rubber composition. 請求項1に記載のアクリルゴム組成物を加硫成形してなる成形品。   A molded article obtained by vulcanizing and molding the acrylic rubber composition according to claim 1.
JP2009206546A 2009-09-08 2009-09-08 Acrylic rubber composition and molded article thereof Pending JP2011057768A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150089029A (en) 2012-11-27 2015-08-04 도레이 카부시키가이샤 Polymer electrolyte composition, and polymer electrolyte membrane, membrane electrode complex and solid polymer-type fuel cell each produced using same
KR20160142289A (en) 2014-04-07 2016-12-12 도레이 카부시키가이샤 Polymer electrolyte composition and polymer electrolyte membrane, membrane-electrolyte assembly, and solid polymer fuel cell using same
JP2019011431A (en) * 2017-06-30 2019-01-24 株式会社オートネットワーク技術研究所 Seal member for vehicle and electric relay component for vehicle

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03109456A (en) * 1989-09-22 1991-05-09 Toa Paint Kk Acrylic rubber composition
JP2004182786A (en) * 2002-11-29 2004-07-02 Nippon Zeon Co Ltd Rubber composition for semiconductive rubber roll and semiconductive rubber roll

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03109456A (en) * 1989-09-22 1991-05-09 Toa Paint Kk Acrylic rubber composition
JP2004182786A (en) * 2002-11-29 2004-07-02 Nippon Zeon Co Ltd Rubber composition for semiconductive rubber roll and semiconductive rubber roll

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150089029A (en) 2012-11-27 2015-08-04 도레이 카부시키가이샤 Polymer electrolyte composition, and polymer electrolyte membrane, membrane electrode complex and solid polymer-type fuel cell each produced using same
KR20160142289A (en) 2014-04-07 2016-12-12 도레이 카부시키가이샤 Polymer electrolyte composition and polymer electrolyte membrane, membrane-electrolyte assembly, and solid polymer fuel cell using same
JP2019011431A (en) * 2017-06-30 2019-01-24 株式会社オートネットワーク技術研究所 Seal member for vehicle and electric relay component for vehicle

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