JPH0784548B2 - Chlorosulfonated polyethylene composition - Google Patents
Chlorosulfonated polyethylene compositionInfo
- Publication number
- JPH0784548B2 JPH0784548B2 JP61201761A JP20176186A JPH0784548B2 JP H0784548 B2 JPH0784548 B2 JP H0784548B2 JP 61201761 A JP61201761 A JP 61201761A JP 20176186 A JP20176186 A JP 20176186A JP H0784548 B2 JPH0784548 B2 JP H0784548B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- parts
- weight
- composition
- general formula
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、クロロスルフォン化ポリエチレン組成物に関
し、永久歪みが少なく且つ耐熱性とスコーチ性及び蒸気
加硫物の引張強さや耐オゾン性が優れたクロロスルフォ
ン化ポリエチレン組成物に関するものである。TECHNICAL FIELD The present invention relates to a chlorosulfonated polyethylene composition, which has a low permanent set and is excellent in heat resistance and scorch property and tensile strength and ozone resistance of a steam vulcanized product. And a chlorosulphonated polyethylene composition.
クロロスルフォン化ポリエチレンは、その優れた耐熱性
と耐油性及び耐候性の故に、電線及びLPGホースなど屋
外で使用するゴム部品の表皮材として広く用いられてい
る。クロロスルフォン化ポリエチレンの架橋剤として
は、酸化マグネシウム又は酸化鉛とチラウムポリスルフ
ィド系化合物の組み合わせが一般的であるが、この組成
物は永久歪みが大きく、密閉性が要求される用途、例え
ば自動車用ホースなどには、あまり使用されていない。Chlorosulfonated polyethylene is widely used as a skin material for rubber parts used outdoors such as electric wires and LPG hoses because of its excellent heat resistance, oil resistance and weather resistance. As a cross-linking agent for chlorosulphonated polyethylene, a combination of magnesium oxide or lead oxide and a thallium polysulfide-based compound is generally used, but this composition has a large permanent set and is used in applications that require hermeticity, such as automobiles. Not used much for hoses.
クロロスルフォン化ポリエチレンにジアミンマレイミド
化合物とアルカリ土類金属の酸化物または水酸化物とア
ミン化合物を架橋剤として添加してなるクロロスルフォ
ン化ポリエチレン組成物は、上記問題点を改善した組成
物として公知であるが、スコーチが短く、引張強度がで
ない。しかも蒸気加硫では耐オゾン性の低下が激しく、
ホースなど長尺ゴム部品にはあまり応用されていない。A chlorosulphonated polyethylene composition obtained by adding a diamine maleimide compound and an oxide or hydroxide of an alkaline earth metal and an amine compound to chlorosulphonated polyethylene as a crosslinking agent is known as a composition in which the above problems are improved. However, the scorch is short and the tensile strength is not. Moreover, steam vulcanization causes a sharp decrease in ozone resistance,
It is not often used for long rubber parts such as hoses.
これまで公知の酸化マグネシウムや酸化鉛などの金属酸
化物とチウラムポリスルフィドを架橋剤とするクロロス
ルフォン化ポリエチレン組成物は、優れた引張強さやス
コーチ安定性を示すが耐永久歪み性がおとる。一方、金
属の酸化物又は水酸化物とジアミンマレイミド化合物を
架橋剤とするクロロスルフォン化ポリエチレン組成物は
優れた耐永久歪み性を示すものの、スコーチ安定性と引
張強さ及び蒸気加硫物の耐オゾン性に問題がある。引張
強さと耐永久歪み性及びスコーチ安定性や蒸気加硫物の
耐オゾン性をバランスよく生かす方策は未だ知られてい
ない。The chlorosulphonated polyethylene composition containing a conventionally known metal oxide such as magnesium oxide or lead oxide and thiuram polysulfide as a cross-linking agent exhibits excellent tensile strength and scorch stability, but has low permanent set resistance. On the other hand, although the chlorosulphonated polyethylene composition using a metal oxide or hydroxide and a diamine maleimide compound as a cross-linking agent shows excellent permanent set resistance, scorch stability and tensile strength and resistance to steam vulcanizates. There is a problem with ozone property. A method of utilizing tensile strength, permanent set resistance, scorch stability, and ozone resistance of steam vulcanizates in a well-balanced manner has not yet been known.
本発明は上記にかんがみでなされたものであって優れた
引張特性やスコーチ安定性を維持しつつ耐永久歪み性や
蒸気加硫物の耐オゾン性を損なわないクロロスルフォン
化ポリエチレン組成物の提供を目的とする。そして、本
発明の組成物はクロロスルフォン化ポリエチレン100重
量部に対し、金属酸化物又は金属水酸化物３〜20重量
部、一般式（Ｉ） （但し、R1はアルキレン基、及びフェニレン基を示す）
であらわされるジアミンマレイミド化合物１〜５重量
部、一般式（II） （但し、R2はアルキレン基、アリル基を示す）であらわ
されるジチオカルバミン酸ニッケル及び一般式（III） （但し、ｎは２〜７で、R3はアルキル基、アリル基を示
す） 又は一般式（IV） （但し、ｎは２〜７で、R4はアルキル基を示す） であらわされるチラウムポリスルフィド化合物を１〜５
重量部添加してなる組成物である。The present invention has been made in view of the above, and provides a chlorosulfonated polyethylene composition that does not impair the permanent set resistance and the ozone resistance of steam vulcanizates while maintaining excellent tensile properties and scorch stability. To aim. Then, the composition of the present invention has 3 to 20 parts by weight of a metal oxide or a metal hydroxide based on 100 parts by weight of chlorosulfonated polyethylene, and has the general formula (I). (However, R 1 represents an alkylene group and a phenylene group)
1 to 5 parts by weight of a diamine maleimide compound represented by the general formula (II) (However, R 2 represents an alkylene group or an allyl group) and nickel dithiocarbamate represented by the general formula (III) (However, n is 2 to 7 and R 3 represents an alkyl group or an allyl group) or the general formula (IV) (Provided that n is 2 to 7 and R 4 is an alkyl group) and is 1 to 5
It is a composition obtained by adding parts by weight.
また、この組成物にペンタエリスリトールをくわえて金
属酸化物の添加量を１〜９重量部に減量してもよい。ま
た、この組成物における金属酸化物、又は水酸化物の好
ましい具体例として、酸化マグネシムウ，酸化カルシウ
ム，酸化鉛，水酸化カルシウムなどが挙げられる。一般
式（Ｉ）であらわされるジアミンマレイミド化合物の好
ましい具体例としてN,N′−フェニレンジアミンマレイ
ミド,N,N′−エチレンジアミンマレイミド、N,N′−プ
ロピレンジアミンマレイミドなどが挙げることができ
る。一般式（II）であらわされるジチオカルバミン酸ニ
ッケルにおいて、R2は好ましくは炭素数２〜５のアルキ
ル基であり、好ましい具体例として、ジエチルジチオカ
ルバミン酸ニッケル、ジーイソープロピルジチオカルバ
ミン酸ニッケル、ジブチルジチオカルバミン酸ニッケル
などが挙げることができる。また、一般式（III）又は
（IV）はあらわされるチウラムポリスルフィド化合物の
好ましい具体例としてジペンタメチレンチウラムテトラ
スルフィドやテトラメチルチウラムジスルフィドなどを
挙げることができる。これはクロロスルフォン化ポリエ
チレン組成物を形成する配合物の配合順序，配合条件は
特に限定されるものではない。Further, the amount of the metal oxide added may be reduced to 1 to 9 parts by weight by adding pentaerythritol to this composition. Further, preferred specific examples of the metal oxide or hydroxide in this composition include magnesium oxide, calcium oxide, lead oxide, calcium hydroxide and the like. Preferred specific examples of the diamine maleimide compound represented by the general formula (I) include N, N'-phenylenediamine maleimide, N, N'-ethylenediamine maleimide, N, N'-propylenediamine maleimide and the like. In the nickel dithiocarbamate represented by the general formula (II), R 2 is preferably an alkyl group having 2 to 5 carbon atoms, and preferable specific examples thereof include nickel diethyldithiocarbamate, nickel diiso-propyldithiocarbamate, and nickel dibutyldithiocarbamate. And so on. Further, preferred specific examples of the thiuram polysulfide compound represented by the general formula (III) or (IV) include dipentamethylene thiuram tetrasulfide and tetramethyl thiuram disulfide. The compounding order and compounding conditions of the compound forming the chlorosulfonated polyethylene composition are not particularly limited.
本発明組成物、すなわち金属酸化物又は金属水酸化物と
ジアミンマレイミド化合物、ジチオカルバミン酸ニッケ
ル化合物及びチラウムポリスルフィド化合物を添加した
組成物、或いは金属酸化物とペンタエリスリトール、ジ
アミンマレイミド化合物、ジチオカルバミン酸ニッケル
化合物及びチラウムリポリスルフィド化合物を添加した
組成物は、従来知られている金属酸化物又は金属水酸化
物とチラウムポリスルフィド化合物を添加した組成物、
或いは金属酸化物又は金属水酸化物とペンタエリスリト
ール及びチラウムポリスルフィド化合物を架橋剤とする
組成物と比較し良好な耐永久歪み性と水蒸気加硫物の耐
オゾン性を有している。また耐永久歪み性を改良した組
成物として公知のジマレイミド化合物を架橋剤とする、
すなわち、金属酸化物又は水酸化物とジマレイミド化合
物とアミン化合物を架橋剤とする組成物と比較し、良好
なスコーチ安定性と引張強度及び水蒸気加硫物の耐オゾ
ン性を有している。The composition of the present invention, that is, a composition containing a metal oxide or metal hydroxide and a diaminemaleimide compound, a nickel dithiocarbamate compound, and a thallium polysulfide compound, or a metal oxide and pentaerythritol, a diaminemaleimide compound, and a nickel dithiocarbamate compound. And, the composition containing the thallium polysulfide compound is a composition containing a conventionally known metal oxide or metal hydroxide and a thallium polysulfide compound,
Alternatively, it has good permanent set resistance and ozone resistance of a steam vulcanizate as compared with a composition using a metal oxide or metal hydroxide and a pentaerythritol and a thallium polysulfide compound as a crosslinking agent. Further, using a known dimaleimide compound as a crosslinking agent as a composition having improved permanent set resistance,
That is, it has good scorch stability, tensile strength, and ozone resistance of a steam vulcanizate as compared with a composition containing a metal oxide or hydroxide, a dimaleimide compound and an amine compound as a crosslinking agent.
金属酸化物又は金属水酸化物とジアミンマレイミド化合
物、ジチオカルバミン酸ニッケル化合物及びチウラムポ
リスルフィド化合物の四成分の内のどの成分を除いても
本発明が有する効果を得ることはできない。The effect of the present invention cannot be obtained by removing any of the four components of the metal oxide or metal hydroxide and the diamine maleimide compound, the nickel dithiocarbamate compound and the thiuram polysulfide compound.
実施例１〜６及び比較例１〜７ 表−１の配合成分をロール上で混練し、150℃で表−１
に示す所定時間プレス加硫及び蒸気加硫を行って得た成
形物の諸物性及び未加硫コンパウンドの諸物性につき比
較例と実施例の比較を以下に記す。Examples 1 to 6 and Comparative Examples 1 to 7 The ingredients shown in Table 1 were kneaded on a roll, and the mixture was mixed at 150 ° C.
Comparative properties of Comparative Examples and Examples are described below with respect to various physical properties of molded articles obtained by press vulcanization and steam vulcanization for a predetermined period of time and various physical properties of unvulcanized compounds.
比較例１は、CSM組成物の最も標準的配合例でスコーチ
安定性及び引張強さに優れるが、Ｃ−セットに代表され
る耐永久歪み性に劣っている。比較例３はマレイミド加
硫として公知の配合であり、Ｃ−セットは比較例１より
優れるがスコーチタイムが短く引張強さも劣っている。
比較例２は、比較例３のAWを本発明の一成分であるNBC
と置き換えた例であるが、なんら改良点を見出せない。
また、上記加硫物の耐オゾン性が著しく劣っている。Comparative Example 1 is the most standard compounding example of the CSM composition and is excellent in scorch stability and tensile strength, but inferior in permanent set resistance represented by C-set. Comparative Example 3 is a compound known as maleimide vulcanization, and C-set is superior to Comparative Example 1 but has a short scorch time and a poor tensile strength.
Comparative Example 2 uses the AW of Comparative Example 3 as NBC, which is a component of the present invention.
It is an example of replacing with, but I can not find any improvement.
Further, the ozone resistance of the vulcanized product is remarkably inferior.
これに対し実施例１〜６は、比較例１と同様なスコーチ
タイムと引張強さを示しながら良好なＣ−セットを高温
下でも低温下でも示しており、且つ蒸気加硫物の耐オゾ
ン性に著しい改良が認められる。On the other hand, Examples 1 to 6 show good C-set both at high temperature and at low temperature while showing the same scorch time and tensile strength as Comparative Example 1, and the ozone resistance of the steam vulcanizate. Markedly improved.
比較例４〜７は、実施例に示す四成分の内の一成分を除
いたり他成分に置き換えた例であるが、本発明の効果が
認められない。Comparative Examples 4 to 7 are examples in which one of the four components shown in the examples is removed or replaced with another component, but the effect of the present invention is not recognized.
尚、加硫物の試験はJIS Ｋ 6301に、未加硫物の試験
はJIS Ｋ 6300に準じて行った。The vulcanized product was tested according to JIS K 6301, and the unvulcanized product was tested according to JIS K 6300.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 5:3415 5:39 5:40） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area C08K 5: 3415 5:39 5:40)
Claims (1)
部に対して、一般式（Ｉ） （但し、R1はアルキレン基、及びフェニレン基を示す）
であらわされるジアミンマレイミド化合物１〜５重量
部、金属酸化物または水酸化物３〜20重量部及び一般式
（II） （但し、R2はアルキル基、アリル基を示す）であらわさ
れるジチオカルバミン酸ニッケル１〜５重量部と一般式
（III）又は（IV） （但し、ｎは２〜７で、R3はアルキル基、アリル基を示
す） （但し、ｎは２〜７で、R4はアルキレン基を示す） であらわされるチウラムポリスルフィド化合物を１〜５
重量部添加してなるクロロスルフォン化ポリエチレン組
成物。1. A compound of the general formula (I) with respect to 100 parts by weight of chlorosulfonated polyethylene. (However, R 1 represents an alkylene group and a phenylene group)
The diamine maleimide compound represented by 1 to 5 parts by weight, the metal oxide or hydroxide 3 to 20 parts by weight, and the general formula (II) (Wherein R 2 represents an alkyl group or an allyl group) and 1 to 5 parts by weight of nickel dithiocarbamate and the general formula (III) or (IV) (However, n is 2 to 7, and R 3 is an alkyl group or an allyl group.) (Provided that n is 2 to 7 and R 4 is an alkylene group).
A chlorosulphonated polyethylene composition obtained by adding parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61201761A JPH0784548B2 (en) | 1986-08-29 | 1986-08-29 | Chlorosulfonated polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61201761A JPH0784548B2 (en) | 1986-08-29 | 1986-08-29 | Chlorosulfonated polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6357654A JPS6357654A (en) | 1988-03-12 |
| JPH0784548B2 true JPH0784548B2 (en) | 1995-09-13 |
Family
ID=16446496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61201761A Expired - Lifetime JPH0784548B2 (en) | 1986-08-29 | 1986-08-29 | Chlorosulfonated polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784548B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03100035A (en) * | 1989-09-14 | 1991-04-25 | Showa Denko Du Pont Kk | Chlorosulfonated polyethylene composition |
| JPH0593114A (en) * | 1991-10-01 | 1993-04-16 | Tatsuta Electric Wire & Cable Co Ltd | Radiation-resistant resin composition |
| JP2983894B2 (en) * | 1995-11-27 | 1999-11-29 | バンドー化学株式会社 | Transmission belt |
| JP7243239B2 (en) * | 2019-01-23 | 2023-03-22 | 東ソー株式会社 | Chlorosulfonated polyolefin composition and vulcanizate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3891725A (en) * | 1974-10-04 | 1975-06-24 | Du Pont | Vulcanizable chlorinated elastomer composition |
| JPS5930180B2 (en) * | 1978-11-22 | 1984-07-25 | 三菱電線工業株式会社 | Rubber composition for vulcanization under atmospheric pressure and method for producing vulcanized molded products |
| JPS5613608A (en) * | 1979-07-13 | 1981-02-10 | Showa Electric Wire & Cable Co | Electric field alleviating selffadhesive tape |
| JPS61136538A (en) * | 1984-12-05 | 1986-06-24 | Furukawa Electric Co Ltd:The | Rubber composition |
| US4698392A (en) * | 1986-05-02 | 1987-10-06 | E. I. Du Pont De Nemours And Company | Blend of chlorinated polyolefin elastomer and ethylene-containing terpolymer |
-
1986
- 1986-08-29 JP JP61201761A patent/JPH0784548B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6357654A (en) | 1988-03-12 |
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