JPH07179705A - Method for crosslinking fluororubber composition and its crosslinked molded product - Google Patents
Method for crosslinking fluororubber composition and its crosslinked molded productInfo
- Publication number
- JPH07179705A JPH07179705A JP5324187A JP32418793A JPH07179705A JP H07179705 A JPH07179705 A JP H07179705A JP 5324187 A JP5324187 A JP 5324187A JP 32418793 A JP32418793 A JP 32418793A JP H07179705 A JPH07179705 A JP H07179705A
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- fluororubber composition
- crosslinked
- composition
- propylene
- 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
【０００１】[0001]
【産業上の利用分野】本発明はフッ素ゴム組成物の架橋
方法に関し、さらに詳しくは電気絶縁被覆材、ホース、
チューブ等への適用が可能なフッ素ゴム組成物の架橋方
法およびその架橋成形体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for crosslinking a fluororubber composition, and more particularly to an electrical insulation coating material, a hose,
The present invention relates to a method for crosslinking a fluororubber composition applicable to tubes and the like and a crosslinked molded article thereof.
【０００２】[0002]
【従来の技術】テトラフルオロエチレンおよびプロピレ
ンを共重合して得られるフッ素ゴムは電気絶縁性、耐熱
性、耐油性、耐薬品性、耐候性等に優れるため、幅広い
分野で用いられている。しかし、例えば電線等の電気絶
縁材料に用いた場合には該フッ素ゴム単独の成形体では
機械的特性が不十分であるためそれを改善する目的で、
電気絶縁性、機械的特性がバランスよく優れ、また安価
であるポリオレフィン等とブレンドした組成物を有機過
酸化物で架橋する方法が提案されている（特公昭６０−
４６４８６）。2. Description of the Related Art Fluorine rubber obtained by copolymerizing tetrafluoroethylene and propylene is used in a wide range of fields because it is excellent in electric insulation, heat resistance, oil resistance, chemical resistance, weather resistance and the like. However, in the case of being used as an electrical insulating material such as an electric wire, for example, in order to improve the mechanical properties of the fluororubber molded product alone, the mechanical properties are insufficient.
A method has been proposed in which a composition blended with a polyolefin or the like, which has excellent electric insulation and mechanical properties in a well-balanced manner and is inexpensive, is crosslinked with an organic peroxide (Japanese Patent Publication No. 60-
46486).
【０００３】[0003]
【発明が解決しようとする課題】しかし、有機過酸化物
により架橋する方法では、フッ素ゴムと熱可塑性ポリオ
レフィン樹脂とのブレンド物に有機過酸化物を混合する
際、またはそのブレンド物を成形する際にポリオレフィ
ンの溶融温度の１５０℃以上に加熱する必要がある。し
かし、それにより成形前に有機過酸化物が分解してしま
う、あるいは該ブレンド物の一部が架橋するため成形が
容易ではなく、良好な架橋成形体が得られないという問
題があった。However, in the method of crosslinking with an organic peroxide, when the organic peroxide is mixed with the blend of the fluororubber and the thermoplastic polyolefin resin, or when the blend is molded. In addition, it is necessary to heat the polyolefin to a melting temperature of 150 ° C. or higher. However, there is a problem in that the organic peroxide is decomposed before molding, or a part of the blend is crosslinked, so that molding is not easy and a good crosslinked molded article cannot be obtained.
【０００４】[0004]
【課題を解決するための手段】本発明は、前述の問題点
を解決すべくなされたものであり、テトラフルオロエチ
レンおよびプロピレンを共重合して得られるフッ素ゴ
ム、熱可塑性ポリオレフィン樹脂、および不飽和多官能
性化合物からなるフッ素ゴム組成物を電離放射線照射に
より架橋させることを特徴とするフッ素ゴム組成物の架
橋方法およびその架橋成形体を提供するものである。The present invention has been made to solve the above-mentioned problems, and is a fluororubber obtained by copolymerizing tetrafluoroethylene and propylene, a thermoplastic polyolefin resin, and an unsaturated compound. The present invention provides a method for crosslinking a fluororubber composition, which comprises crosslinking a fluororubber composition comprising a polyfunctional compound by irradiation with ionizing radiation, and a crosslinked molded article thereof.
【０００５】本発明に用いられるテトラフルオロエチレ
ンおよびプロピレンを共重合して得られるフッ素ゴム
は、テトラフルオロエチレンとプロピレンとが３０／７
０〜７０／３０（モル比）の割合で共重合されたもの
で、さらに１種またはそれ以上のフッ素含有オレフィン
や炭化水素系オレフィンが共重合されてもよい。The fluororubber obtained by copolymerizing tetrafluoroethylene and propylene used in the present invention has tetrafluoroethylene and propylene of 30/7.
Copolymerized at a ratio of 0 to 70/30 (molar ratio), and one or more kinds of fluorine-containing olefins or hydrocarbon-based olefins may be further copolymerized.
【０００６】本発明に用いられるフッ素ゴムの製造に
は、塊状重合、懸濁重合、乳化重合、溶液重合等の従来
公知の各種重合方法を採用することが可能である。ま
た、本発明に用いられるフッ素ゴムは任意の分子量の範
囲において使用可能であるが、成形性や成形物の機械的
強度等を満足させるためには１〜３０万程度の分子量の
ものが好ましく用いられる。In the production of the fluororubber used in the present invention, various conventionally known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization can be adopted. Further, the fluororubber used in the present invention can be used in an arbitrary molecular weight range, but in order to satisfy the moldability and the mechanical strength of the molded product, one having a molecular weight of about 1 to 300,000 is preferably used. To be
【０００７】本発明に用いられる熱可塑性ポリオレフィ
ン樹脂としては、ポリエチレン、ポリプロピレン、エチ
レン−プロピレン共重合体、ポリスチレン等のポリ−α
−オレフィン類が挙げられる。The thermoplastic polyolefin resin used in the present invention includes poly-α such as polyethylene, polypropylene, ethylene-propylene copolymer and polystyrene.
-Olefins are mentioned.
【０００８】テトラフルオロエチレンおよびプロピレン
を共重合して得られるフッ素ゴム／熱可塑性ポリオレフ
ィン樹脂の混合割合は、特に限定されないが、好ましく
は４０／６０〜９０／１０、さらに好ましくは５０／５
０〜８０／２０（重量比）の範囲である。The mixing ratio of fluororubber / thermoplastic polyolefin resin obtained by copolymerizing tetrafluoroethylene and propylene is not particularly limited, but is preferably 40/60 to 90/10, more preferably 50/5.
It is in the range of 0 to 80/20 (weight ratio).
【０００９】本発明に用いられる不飽和多官能性化合物
はフッ素ゴム組成物を架橋させる際の架橋助剤として用
いられるもので、トリアリルイソシアヌレート、ポリブ
タジエン、ジアリルフタレート、トリメチロールプロパ
ントリメタクリレート等が好ましく用いられる。フッ素
ゴム１００重量部に対する不飽和多官能性化合物の使用
量は０．５〜２０重量部、好ましくは１〜１０重量部の
範囲である。The unsaturated polyfunctional compound used in the present invention is used as a cross-linking aid when the fluororubber composition is cross-linked, and examples thereof include triallyl isocyanurate, polybutadiene, diallyl phthalate and trimethylolpropane trimethacrylate. It is preferably used. The amount of the unsaturated polyfunctional compound used with respect to 100 parts by weight of the fluororubber is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight.
【００１０】本発明のフッ素ゴム組成物は、上記フッ素
ゴム、熱可塑性ポリオレフィン樹脂、および不飽和多官
能性化合物を溶融混合することにより得られる。本発明
のフッ素ゴム組成物は、その性能を損なわない範囲にお
いてカーボン、シリカ等の充填剤やガラス繊維、炭素繊
維、金属酸化物、顔量、内部離型剤、その他用途に応じ
て任意の添加剤を混合することが可能である。また、他
の合成ゴム、フッ素樹脂や熱可塑性樹脂等とブレンドし
て使用してもよい。The fluororubber composition of the present invention can be obtained by melt-mixing the fluororubber, the thermoplastic polyolefin resin, and the unsaturated polyfunctional compound. The fluororubber composition of the present invention is carbon, filler such as silica, glass fiber, carbon fiber, metal oxide, face amount, internal release agent, and other additives within a range not impairing its performance, depending on other applications. It is possible to mix the agents. Further, it may be used by blending with other synthetic rubber, fluororesin, thermoplastic resin and the like.
【００１１】フッ素ゴム組成物は押し出し成形、カレン
ダー成形、射出成形やプレス成形等の金型を用いる方法
や従来公知の方法により成形することが可能である。こ
うして得られたフッ素ゴム組成物成形体の架橋は電離放
射線を照射することにより容易に行うことができる。架
橋条件は成形物の形状や厚さ等にもよるが一般的には１
〜２０Ｍｒａｄ、好ましくは３〜１０Ｍｒａｄ程度の線
量を照射することで架橋可能である。The fluororubber composition can be molded by a method using a die such as extrusion molding, calender molding, injection molding or press molding, or a conventionally known method. The fluororubber composition molded body thus obtained can be easily crosslinked by irradiation with ionizing radiation. The crosslinking condition depends on the shape and thickness of the molded product, but is generally 1
Crosslinking is possible by irradiating with a dose of about 20 Mrad, preferably about 3 to 10 Mrad.
【００１２】[0012]
【作用】テトラフルオロエチレンおよびプロピレンを共
重合して得られるフッ素ゴム、熱可塑性ポリオレフィン
樹脂および不飽和多官能性化合物を溶融混合して得られ
るフッ素ゴム組成物は、電離放射線により架橋すること
により成形性が改良され、機械的特性に優れた成形体を
与えるものと考えられる。[Function] A fluororubber obtained by copolymerizing tetrafluoroethylene and propylene, a thermoplastic polyolefin resin, and a fluororubber composition obtained by melt-mixing an unsaturated polyfunctional compound are molded by crosslinking with ionizing radiation. It is considered that the molded product has improved properties and excellent mechanical properties.
【００１３】[0013]
【実施例】実施例中、部とは重量部を示す。EXAMPLES In the examples, “parts” means “parts by weight”.
【００１４】［実施例１］アフラス１５０Ｅ（テトラフ
ルオロエチレン／プロピレン＝５５／４５（モル比）、
旭硝子製フッ素ゴム）５０部、Ｍ９０Ｍ（三菱油化製ポ
リエチレン）５０部、トリアリルイソシアヌレート５
部、炭酸カルシウム粉末４０部をニーダーを用い１５０
℃で３分間混練し、フッ素ゴム組成物を得た。これを押
出機（シリンダー温度１６０℃、ダイス温度１８０℃）
により錫メッキ銅集合撚線上に０．５ｍｍの厚さに押出
被覆し、その後５Ｍｒａｄの電離放射線を照射し架橋し
た。成形物の表面に発泡はなく、また、その引張強さは
２６０ｋｇ／ｃｍ2 、伸びは２２０％であった。Example 1 Aflas 150E (tetrafluoroethylene / propylene = 55/45 (molar ratio),
Asahi Glass Fluororubber) 50 parts, M90M (Mitsubishi Yuka Polyethylene) 50 parts, Triallyl isocyanurate 5
Parts, calcium carbonate powder 40 parts using a kneader 150
The mixture was kneaded at 3 ° C for 3 minutes to obtain a fluororubber composition. Extruder (cylinder temperature 160 ℃, die temperature 180 ℃)
By extrusion coating on a tin-plated copper aggregate stranded wire to a thickness of 0.5 mm, followed by irradiation with 5 Mrad of ionizing radiation for crosslinking. There was no foaming on the surface of the molded product, the tensile strength was 260 kg / cm 2 , and the elongation was 220%.
【００１５】［比較例１］アフラス１５０Ｅの５０部、
Ｍ９０Ｍの５０部、トリアリルイソシアヌレートの５
部、ライトンＡの４０部をニーダーを用い１５０℃で３
分間混練し、フッ素ゴム組成物を得た。このフッ素ゴム
組成物を冷却後、ニーダーで冷却しながらパーカドック
ス１４（日本油脂製有機過酸化物）を１．５部混合し
た。これを押出機（シリンダー温度１６０℃、ダイス温
度１８０℃）により錫メッキ銅集合撚線上に０．５ｍｍ
の厚さに押出被覆しようとしたが、フッ素ゴム組成物が
押出機のシリンダー中で架橋してしまい良好な成形体が
得られなかった。[Comparative Example 1] 50 parts of Aflas 150E,
50 parts of M90M, 5 of triallyl isocyanurate
Parts, 40 parts of Ryton A at 150 ° C. for 3 times with a kneader
The mixture was kneaded for a minute to obtain a fluororubber composition. After cooling this fluororubber composition, 1.5 parts of Perkadox 14 (organic peroxide manufactured by NOF CORPORATION) was mixed while cooling with a kneader. 0.5mm on the tin-plated copper aggregate stranded wire with an extruder (cylinder temperature 160 ° C, die temperature 180 ° C)
However, the fluororubber composition was crosslinked in the cylinder of the extruder and a good molded product could not be obtained.
【００１６】[0016]
【発明の効果】本発明の電離放射線によるフッ素ゴム組
成物の架橋方法は、成形加工が容易であり、得られる成
形体の機械的特性が改善され、電気絶縁性、耐熱性、耐
油性、耐薬品性、耐候性等に優れ電気絶縁被覆、ホー
ス、チューブ等への適用に好適で工業的に極めて有用で
ある。INDUSTRIAL APPLICABILITY According to the method for crosslinking a fluororubber composition by ionizing radiation of the present invention, the molding process is easy, the mechanical properties of the resulting molded article are improved, and the electrical insulation, heat resistance, oil resistance and resistance are improved. It has excellent chemical resistance and weather resistance and is suitable for electrical insulation coatings, hoses, tubes, etc., and is extremely useful industrially.
Claims (2)
を共重合して得られるフッ素ゴム、熱可塑性ポリオレフ
ィン樹脂、および不飽和多官能性化合物からなるフッ素
ゴム組成物を電離放射線照射により架橋させることを特
徴とするフッ素ゴム組成物の架橋方法。1. A fluororubber composition comprising a fluororubber obtained by copolymerizing tetrafluoroethylene and propylene, a thermoplastic polyolefin resin, and an unsaturated polyfunctional compound is crosslinked by irradiation with ionizing radiation. A method for crosslinking a fluororubber composition.
素ゴム組成物の架橋成形体。2. A crosslinked molded article of a fluororubber composition crosslinked by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324187A JPH07179705A (en) | 1993-12-22 | 1993-12-22 | Method for crosslinking fluororubber composition and its crosslinked molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324187A JPH07179705A (en) | 1993-12-22 | 1993-12-22 | Method for crosslinking fluororubber composition and its crosslinked molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07179705A true JPH07179705A (en) | 1995-07-18 |
Family
ID=18163051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5324187A Pending JPH07179705A (en) | 1993-12-22 | 1993-12-22 | Method for crosslinking fluororubber composition and its crosslinked molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07179705A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7220788B2 (en) | 2003-02-28 | 2007-05-22 | Nichias Corporation | Fluororubber molded article and method for producing the same |
| US8426527B2 (en) | 2009-10-01 | 2013-04-23 | Asahi Glass Company, Limited | Crosslinkable fluororubber composition and crosslinked rubber article |
| JP2013170259A (en) * | 2012-02-22 | 2013-09-02 | Asahi Glass Co Ltd | Fluorine-containing elastomer composition and crosslinked article of the same |
| WO2014010508A1 (en) * | 2012-07-09 | 2014-01-16 | 住友電気工業株式会社 | Heat-resistant flame-retardant resin composition, insulated electric wire, and tube |
| JP2015003985A (en) * | 2013-06-20 | 2015-01-08 | 日立金属株式会社 | Fluorine-containing elastomer composition, and insulated electric wire and insulated cable each using the same |
-
1993
- 1993-12-22 JP JP5324187A patent/JPH07179705A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7220788B2 (en) | 2003-02-28 | 2007-05-22 | Nichias Corporation | Fluororubber molded article and method for producing the same |
| US8426527B2 (en) | 2009-10-01 | 2013-04-23 | Asahi Glass Company, Limited | Crosslinkable fluororubber composition and crosslinked rubber article |
| JP2013170259A (en) * | 2012-02-22 | 2013-09-02 | Asahi Glass Co Ltd | Fluorine-containing elastomer composition and crosslinked article of the same |
| WO2014010508A1 (en) * | 2012-07-09 | 2014-01-16 | 住友電気工業株式会社 | Heat-resistant flame-retardant resin composition, insulated electric wire, and tube |
| CN103842431A (en) * | 2012-07-09 | 2014-06-04 | 住友电气工业株式会社 | Heat-resistant flame-retardant resin composition, insulated electric wire, and tube |
| JP2015003985A (en) * | 2013-06-20 | 2015-01-08 | 日立金属株式会社 | Fluorine-containing elastomer composition, and insulated electric wire and insulated cable each using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2525968B2 (en) | Process for producing flame-retardant resin composition, flame-retardant resin composition produced therefrom and insulating tube using the same | |
| JP2000212291A (en) | Preparation of nonhalogen flame-retardant silane- crosslinked polyolefin composition | |
| US3845166A (en) | Curable composition comprising polyvinyl chloride,chlorinated polyolfin and an ethylene polymer,and the cured product thereof | |
| JPS63503148A (en) | Heat recoverable article comprising a fluoropolymer composition | |
| JPH06256567A (en) | Resin composition and insulated wire and insulating tube produced therefrom | |
| WO2020013187A1 (en) | Heat-resistant crosslinked fluororubber molded product and production method thereof, and heat-resistant product | |
| JPH07179705A (en) | Method for crosslinking fluororubber composition and its crosslinked molded product | |
| JPS6116910A (en) | Fluororesin composition crosslinkable with radiation | |
| JP7426876B2 (en) | Crosslinked fluororubber composition, wiring material using the same, and manufacturing method thereof | |
| JP3555628B2 (en) | Method for producing fluoroelastomer molded article, method for producing insulated wire using same, method for producing insulated tube | |
| JPS6116911A (en) | Fluororesin composition crosslinkable with radiation | |
| JP3224015B2 (en) | Crosslinkable vinyl chloride resin composition for covering electric wires and method for producing crosslinked vinyl chloride resin for covering electric wires | |
| JPH0463849A (en) | Fluorocarbon resin composition | |
| JPS5844700B2 (en) | Method for manufacturing flame-retardant molded products | |
| JPS59100141A (en) | Production of crosslinked fluorocarbon resin molding | |
| JP3603965B2 (en) | Heat resistant insulating composition | |
| JP2005206763A (en) | Molded material of silane-crosslinked polymer and electric wire/cable using the same | |
| JP3003837B2 (en) | Crosslinkable polyethylene composition and electric wires and cables | |
| JPH04335055A (en) | Production of water-crosslinked resin molding | |
| JPH10334738A (en) | Wire/cable covered with elastomer containing fluorine | |
| JP2654666B2 (en) | Heat resistant insulating composition | |
| JP2644340B2 (en) | Heat resistant wire | |
| JPH08143736A (en) | Crosslinking of fluororubber and crosslinked molding thereof | |
| JP2595255B2 (en) | Radiation resistant insulation composition | |
| JP3269847B2 (en) | Polyolefin resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |