JPH07292199A - Fluoropolymer composition and method for crosslinking the same - Google Patents
Fluoropolymer composition and method for crosslinking the sameInfo
- Publication number
- JPH07292199A JPH07292199A JP9220794A JP9220794A JPH07292199A JP H07292199 A JPH07292199 A JP H07292199A JP 9220794 A JP9220794 A JP 9220794A JP 9220794 A JP9220794 A JP 9220794A JP H07292199 A JPH07292199 A JP H07292199A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- fluororubber
- tetrafluoroethylene
- fluorine
- fluorosurfactant
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフッ素系ポリマー組成物
およびその架橋方法に関し、さらに詳しくは含フッ素界
面活性剤を含有せしめることにより架橋性が改善され、
押出加工性が優れたフッ素系ポリマー組成物およびその
架橋方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoropolymer composition and a method for crosslinking the same, and more specifically, the inclusion of a fluorine-containing surfactant improves the crosslinkability.
The present invention relates to a fluoropolymer composition having excellent extrusion processability and a method for crosslinking the same.
【０００２】[0002]
【従来の技術】テトラフルオロエチレン−エチレン系フ
ッ素樹脂（以下、ＥＴＦＥフッ素樹脂ともいう）または
テトラフルオロエチレン−プロピレン系フッ素ゴム（以
下、ＦＰフッ素ゴムともいう）とＥＴＦＥフッ素樹脂の
溶融混合物は、電線被覆等の電気絶縁材料として好適に
用いられている。これらのＥＴＦＥフッ素樹脂またはＥ
ＴＦＥフッ素樹脂とＦＰフッ素ゴムの混合物は、成形し
た後に電離性放射線を照射することにより架橋して実用
的な物性を得るために、トリアリルイソシアヌレート等
の架橋助剤が必要であった。2. Description of the Related Art A molten mixture of tetrafluoroethylene-ethylene fluororesin (hereinafter also referred to as ETFE fluororesin) or tetrafluoroethylene-propylene fluororubber (hereinafter also referred to as FP fluororubber) and ETFE fluororesin is used for electric wires. It is preferably used as an electric insulating material for coatings and the like. These ETFE fluororesins or E
The mixture of TFE fluororesin and FP fluororubber needs a crosslinking aid such as triallyl isocyanurate in order to crosslink by irradiating ionizing radiation after molding to obtain practical physical properties.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ＥＴＦＥフッ
素樹脂またはＥＴＦＥフッ素樹脂とＦＰフッ素ゴムの混
合物とトリアリルイソシアヌレートとの溶融混合が高温
であるために、成形加工の工程においてトリアリルイソ
シアヌレートの揮散により作業環境が悪化することや、
成形物の表面に揮散したトリアリルイソシアヌレートが
付着して成形物の外観を損なうなどの問題があった。However, since the melt mixing of ETFE fluororesin or a mixture of ETFE fluororesin and FP fluororubber and triallyl isocyanurate is at a high temperature, triallyl isocyanurate of The work environment may deteriorate due to volatilization,
There was a problem that the volatilized triallyl isocyanurate was attached to the surface of the molded product and the appearance of the molded product was impaired.
【０００４】[0004]
【課題を解決するための手段】本発明者は、含フッ素界
面活性剤がＥＴＦＥフッ素樹脂またはＥＴＦＥフッ素樹
脂とＦＰフッ素ゴムの混合物の電離性放射線架橋反応性
を著しく向上させる効果を有することを見出し、本発明
に至った。The present inventors have found that the fluorine-containing surfactant has the effect of significantly improving the ionizing radiation crosslinking reactivity of ETFE fluororesin or a mixture of ETFE fluororesin and FP fluororubber. The present invention has been reached.
【０００５】すなわち、本発明は、テトラフルオロエチ
レン−エチレン系フッ素樹脂に含フッ素界面活性剤を含
有せしめてなることを特徴とするフッ素系ポリマー組成
物である。That is, the present invention is a fluoropolymer composition comprising a tetrafluoroethylene-ethylene fluororesin containing a fluorosurfactant.
【０００６】また、本発明は、テトラフルオロエチレン
−エチレン系フッ素樹脂として、含フッ素界面活性剤を
乳化剤として用いて重合されたものを使用することによ
り、フッ素系ポリマー組成物に含フッ素界面活性剤を含
有せしめてなる上記フッ素系ポリマー組成物である。Further, according to the present invention, as the tetrafluoroethylene-ethylene-based fluororesin, one obtained by polymerizing using a fluorosurfactant as an emulsifier is used to give a fluoropolymer composition with a fluorosurfactant. The above-mentioned fluorine-containing polymer composition containing the above.
【０００７】また、本発明は、テトラフルオロエチレン
−プロピレン系フッ素ゴムをさらに含有せしめてなる上
記フッ素系ポリマー組成物である。Further, the present invention is the above-mentioned fluorine-containing polymer composition, which further contains tetrafluoroethylene-propylene-based fluorine-containing rubber.
【０００８】また、本発明は、テトラフルオロエチレン
−プロピレン系フッ素ゴムとして、含フッ素界面活性剤
を乳化剤として用いて重合されたものを使用することに
より、フッ素系ポリマー組成物に含フッ素界面活性剤を
含有せしめてなる上記フッ素系ポリマー組成物である。Further, according to the present invention, as the tetrafluoroethylene-propylene fluororubber, one obtained by polymerizing using a fluorosurfactant as an emulsifier is used, the fluoropolymer composition contains a fluorosurfactant. The above-mentioned fluorine-containing polymer composition containing the above.
【０００９】また、本発明は、上記フッ素系ポリマー組
成物を電離性放射線の照射により架橋せしめることを特
徴とする架橋方法である。Further, the present invention is a cross-linking method characterized in that the above-mentioned fluoropolymer composition is cross-linked by irradiation of ionizing radiation.
【００１０】本発明の含フッ素界面活性剤を含有するＥ
ＴＦＥフッ素樹脂またはＥＴＦＥフッ素樹脂とＦＰフッ
素ゴムの混合物は、その機構は明らかではないが、架橋
反応性が著しく向上し、トリアリルイソシアヌレート等
の架橋助剤を用いることなく、電離性放射線を照射する
ことにより架橋可能となる。E containing the fluorine-containing surfactant of the present invention
The mechanism of the mixture of TFE fluororesin or ETFE fluororesin and FP fluororubber is not clear, but the crosslinking reactivity is remarkably improved, and irradiation with ionizing radiation is performed without using a crosslinking auxiliary agent such as triallyl isocyanurate. By doing so, crosslinking becomes possible.
【００１１】本発明に用いられるＥＴＦＥフッ素樹脂
は、テトラフルオロエチレン／エチレンが７０／３０〜
３０／７０（モル比）の割合で共重合されたものが好ま
しい。また、ＥＴＦＥフッ素樹脂は、さらに１種または
それ以上のフッ素含有のモノマーや炭化水素系のモノマ
ーが共重合されてもよい。The ETFE fluororesin used in the present invention contains tetrafluoroethylene / ethylene of 70/30 or more.
Those copolymerized at a ratio of 30/70 (molar ratio) are preferable. Further, the ETFE fluororesin may be copolymerized with one or more kinds of fluorine-containing monomers or hydrocarbon-based monomers.
【００１２】共重合可能なモノマーとしては、フッ化ビ
ニリデン、ヘキサフルオロプロピレン、（ペルフルオロ
ブチル）エチレン、（ペルフルオロヘキシル）エチレ
ン、ペルフルオロ（メチルビニルエーテル）、ペルフル
オロ（プロピルビニルエーテル）等のフッ素含有のモノ
マーや、プロピレン、ブテン、メチルビニルエーテル、
エチルビニルエーテル等の炭化水素系のモノマーが挙げ
られる。The copolymerizable monomers include vinylidene fluoride, hexafluoropropylene, (perfluorobutyl) ethylene, (perfluorohexyl) ethylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether) and other fluorine-containing monomers. Propylene, butene, methyl vinyl ether,
Hydrocarbon type monomers such as ethyl vinyl ether may be mentioned.
【００１３】これらのモノマーを用いる際には、ＥＴＦ
Ｅフッ素樹脂中に５０モル％以内で共重合されているこ
とが好ましい。When using these monomers, ETF
It is preferable that the E fluoropolymer is copolymerized within 50 mol%.
【００１４】本発明に用いられるＥＴＦＥフッ素樹脂の
製造に際しては、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はすべて採用できる。For the production of the ETFE fluororesin used in the present invention, various conventionally known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization can be adopted.
【００１５】ここで、含フッ素界面活性剤を用いた乳化
重合を採用するときは、含フッ素界面活性剤をＥＴＦＥ
フッ素樹脂に残存せしめることができる。他の重合方法
を採用するときは、溶融混練する際に含フッ素界面活性
剤を添加できる。Here, when emulsion polymerization using a fluorine-containing surfactant is adopted, the fluorine-containing surfactant is replaced with ETFE.
It can remain in the fluororesin. When another polymerization method is adopted, a fluorine-containing surfactant can be added during melt kneading.
【００１６】本発明に用いられるＦＰフッ素ゴムは、テ
トラフルオロエチレン／プロピレンが３０／７０〜７０
／３０（モル比）の割合で共重合されたものが好まし
い。また、ＦＰフッ素ゴムは、さらに１種またはそれ以
上のフッ素含有のモノマーや炭化水素系のモノマーが共
重合されてもよい。The FP fluororubber used in the present invention contains tetrafluoroethylene / propylene of 30/70 to 70.
Those copolymerized at a ratio of / 30 (molar ratio) are preferable. Further, the FP fluororubber may be further copolymerized with one or more kinds of fluorine-containing monomers and hydrocarbon-based monomers.
【００１７】共重合可能なモノマーとしては、フッ化ビ
ニリデン、ヘキサフルオロプロピレン、ペルフルオロ
（メチルビニルエーテル）、ペルフルオロ（プロピルビ
ニルエーテル）等のフッ素含有のモノマーや、エチレ
ン、ブテン、メチルビニルエーテル、エチルビニルエー
テル等の炭化水素系のモノマーが挙げられる。Examples of the copolymerizable monomer include vinylidene fluoride, hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), and other fluorine-containing monomers, and ethylene, butene, methyl vinyl ether, ethyl vinyl ether, and other carbonized monomers. Examples thereof include hydrogen-based monomers.
【００１８】これらのモノマーは、ＦＰフッ素ゴム中
に、５０モル％以内で共重合されていることが好まし
い。These monomers are preferably copolymerized in FP fluororubber within 50 mol%.
【００１９】本発明に用いられるＦＰフッ素ゴムの製造
に際しては、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はすべて採用できる。In the production of the FP 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.
【００２０】ここで、含フッ素界面活性剤を用いた乳化
重合を採用するときは、含フッ素界面活性剤をＦＰフッ
素ゴムに残存せしめることができる。他の重合方法を採
用するときは、ＥＴＦＥフッ素樹脂と溶融混練する際に
含フッ素界面活性剤を添加できる。Here, when emulsion polymerization using a fluorine-containing surfactant is adopted, the fluorine-containing surfactant can be left in the FP fluororubber. When another polymerization method is adopted, a fluorine-containing surfactant can be added during melt-kneading with the ETFE fluororesin.
【００２１】本発明のフッ素系ポリマー組成物は、前述
のＥＴＦＥフッ素樹脂またはＥＴＦＥフッ素樹脂とＦＰ
フッ素ゴムの混合物と、さらに含フッ素界面活性剤とを
ＥＴＦＥフッ素樹脂の溶融温度以上で混合することによ
り容易に得られる。具体的には、ＥＴＦＥフッ素樹脂の
融点以下、例えば５０〜１５０℃の温度で、ＦＰフッ素
ゴムにＥＴＦＥフッ素樹脂をロールやバンバリーミキサ
ーで混練し、次いでＥＴＦＥフッ素樹脂の融点以上で成
形してもよいし、予めＥＴＦＥフッ素樹脂の融点以上の
温度でロールやバンバリーミキサー、押出機を用い、両
者を混練してもよい。The fluorine-containing polymer composition of the present invention comprises the above-mentioned ETFE fluororesin or ETFE fluororesin and FP.
It can be easily obtained by mixing the mixture of fluororubber and the fluorine-containing surfactant at the melting temperature of the ETFE fluororesin or higher. Specifically, at a temperature below the melting point of the ETFE fluororesin, for example, at a temperature of 50 to 150 ° C., the FP fluororubber may be kneaded with the ETFE fluororesin by a roll or a Banbury mixer, and then molded at the melting point or higher of the ETFE fluororesin. However, both may be kneaded in advance using a roll, a Banbury mixer, or an extruder at a temperature equal to or higher than the melting point of the ETFE fluororesin.
【００２２】本発明において、ＥＴＦＥフッ素樹脂とＦ
Ｐフッ素ゴムの混合物を用いる場合には、両者を任意の
割合で混合することができる。得られる成形体の機械的
強度および可撓性を考慮すると、ＦＰフッ素ゴム／ＥＴ
ＦＥフッ素樹脂の混合比率は８０／２０〜２０／８０
（重量比）の範囲が好ましい。ＥＴＦＥフッ素樹脂の含
有量が少な過ぎると機械的強度の改善効果が少なく、多
過ぎるとＦＰフッ素ゴムの本来の特徴である可撓性が損
なわれることになる。In the present invention, ETFE fluororesin and F
When a mixture of P fluororubber is used, both can be mixed at an arbitrary ratio. Considering the mechanical strength and flexibility of the obtained molded product, FP fluororubber / ET
The mixing ratio of FE fluororesin is 80/20 to 20/80
The range of (weight ratio) is preferable. If the content of the ETFE fluororesin is too small, the effect of improving the mechanical strength is small, and if it is too large, the original flexibility of the FP fluororubber is impaired.
【００２３】含フッ素界面活性剤としては、以下のもの
が好ましく例示できる。なお、以下においてＲf は炭素
数６〜１２のペルフルオロアルキル基である。As the fluorine-containing surfactant, the following can be preferably exemplified. In the following, R f is a perfluoroalkyl group having 6 to 12 carbon atoms.
【００２４】ペルフルオロオクタン酸ナトリウム、ペル
フルオロオクタン酸アンモニウム、ペルフルオロノナン
酸アンモニウム、ペルフルオロヘプタンスルホン酸ナト
リウム、ペルフルオロオクタンスルホン酸カリウム、Ｃ
8 Ｆ17ＳＯ2 Ｎ（Ｃ2 Ｈ5 ）ＣＨ2 ＣＯＯＫ、［（ＣＦ
3 ）2 ＣＦ］2 Ｃ＝Ｃ（ＣＦ3 ）ＯＣ6 Ｈ4 ＳＯ3 Ｎａ
等のアニオン系界面活性剤。Sodium perfluorooctanoate, ammonium perfluorooctanoate, ammonium perfluorononanoate, sodium perfluoroheptanesulfonate, potassium perfluorooctanesulfonate, C
8 F 17 SO 2 N (C 2 H 5 ) CH 2 COOK, [(CF
3 ) 2 CF] 2 C = C (CF 3 ) OC 6 H 4 SO 3 Na
Anionic surfactants such as.
【００２５】Ｃ8 Ｆ17ＣＨ2 ＣＨ（ＯＨ）ＣＨ2 Ｎ（Ｃ
2 Ｈ4 ＯＨ）2 （ＣＨ3 ）Ｃｌ、Ｒ f ＣＯＮＨ（ＣＨ
2 ）3 Ｎ（ＣＨ3 ）3 Ｉ等のカチオン系界面活性剤。C8 F17CH2 CH (OH) CH2 N (C
2 HFour OH)2 (CH3 ) Cl, R f CONH (CH
2 )3 N (CH3 )3 Cationic surfactants such as I.
【００２６】［（ＣＦ3 ）2 ＣＦ］2 Ｃ＝Ｃ（ＣＦ3 ）
ＯＣ6 Ｈ4 （ＯＣＨ2 ＣＨ2 ）n ＯＣＨ3 （ただし、ｎ
＝５〜３０の整数）、Ｃ6 Ｆ13Ｃ2 Ｈ4 ＳＣ2 Ｈ4 （Ｏ
ＣＨ2 ＣＨ2 ）m ＯＨ（ただし、ｍ＝１〜１５の整
数）、Ｒf ＣＯＮＨ（ＣＨ2 ＣＨ2 Ｏ）21ＣＨ3 、Ｒf
Ｃ2 Ｈ4 ＯＣＨ2 ＣＨ（ＯＨ）ＣＨ2 ＮＨ（ＣＨ2 ）3
Ｎ（ＣＨ3 ）2 、Ｒf Ｃ2 Ｈ4 ＯＣＯＣＨ2 Ｓ（ＣＨ2
Ｃ（ＣＯＮＨ2 ）Ｈ）10Ｈ等のノニオン系界面活性剤。[(CF 3 ) 2 CF] 2 C = C (CF 3 )
OC 6 H 4 (OCH 2 CH 2 ) n OCH 3 (however, n
= 5-30 integer), C 6 F 13 C 2 H 4 SC 2 H 4 (O
CH 2 CH 2 ) m OH (provided that m = 1 to an integer of 15), R f CONH (CH 2 CH 2 O) 21 CH 3 , R f
C 2 H 4 OCH 2 CH (OH) CH 2 NH (CH 2 ) 3
N (CH 3 ) 2 , R f C 2 H 4 OCOCH 2 S (CH 2
Nonionic surfactants such as C (CONH 2 ) H) 10 H.
【００２７】Ｃ7 Ｆ15Ｃ2 Ｈ4 Ｓ（ＣＨ2 ）3 Ｎ（ＣＨ
2 ＣＯＯ）（ＣＨ3 ）2 、Ｒf ＣＯＮＨ（ＣＨ2 ）3 Ｎ
（ＣＨ2 ＣＯＯ）（ＣＨ3 ）2 等の両性界面活性剤。C 7 F 15 C 2 H 4 S (CH 2 ) 3 N (CH
2 COO) (CH 3 ) 2 , R f CONH (CH 2 ) 3 N
Amphoteric surfactants such as (CH 2 COO) (CH 3 ) 2 .
【００２８】含フッ素界面活性剤の添加量は、ＥＴＦＥ
フッ素樹脂またはＦＰフッ素ゴムとＥＴＦＥフッ素樹脂
の混合物１００重量部に対し、０．００１〜１重量部が
好ましい。０．００１重量部未満では効果が低く、１重
量部を超えても添加効果は変わらない。より好ましいの
は０．００３〜０．５重量％である。The amount of the fluorine-containing surfactant added is ETFE.
0.001 to 1 part by weight is preferable to 100 parts by weight of the mixture of fluororesin or FP fluororubber and ETFE fluororesin. If it is less than 0.001 part by weight, the effect is low, and if it exceeds 1 part by weight, the effect of addition remains unchanged. More preferably, it is 0.003 to 0.5% by weight.
【００２９】本発明において、フッ素系ポリマー組成物
の特性を損なわない範囲において、充填剤、顔料、加工
助剤、安定剤等の任意の添加剤を混合できる。また、従
来より用いられているトリアリルイソシアヌレート等の
架橋助剤も使用できる。In the present invention, optional additives such as fillers, pigments, processing aids, stabilizers and the like can be mixed within a range that does not impair the characteristics of the fluoropolymer composition. Further, crosslinking aids such as triallyl isocyanurate that have been conventionally used can also be used.
【００３０】本発明のフッ素系ポリマー組成物は、押出
機や金型等で成形した後に、γ線、電子線、Ｘ線などの
電離性放射線を照射することにより架橋される。電離性
放射線の照射量は特には限定されないが、通常は１〜２
０Ｍｒａｄ程度である。The fluoropolymer composition of the present invention is molded by an extruder, a mold or the like and then crosslinked by irradiation with ionizing radiation such as γ-ray, electron beam or X-ray. The dose of ionizing radiation is not particularly limited, but is usually 1 to 2
It is about 0 Mrad.
【００３１】[0031]
［参考例１］含フッ素界面活性剤のペルフルオロノナン
酸アンモニウムを乳化剤として用い、乳化重合により、
テトラフルオロエチレン重合単位／プロピレン重合単位
＝５５／４５（モル比）の共重合体を分散液から凝集、
乾燥してフッ素ゴム−１を製造した。フッ素ゴム−１の
１００重量部中の含フッ素界面活性剤は０．０２重量部
であった。[Reference Example 1] Using fluorine-containing surfactant ammonium perfluorononanoate as an emulsifier, emulsion polymerization
A copolymer of tetrafluoroethylene polymer units / propylene polymer units = 55/45 (molar ratio) is aggregated from the dispersion liquid,
It was dried to produce fluororubber-1. The fluorosurfactant in 100 parts by weight of fluororubber-1 was 0.02 parts by weight.
【００３２】［参考例２］界面活性剤のラウリル硫酸ナ
トリウムを乳化剤として用い、乳化重合により、テトラ
フルオロエチレン重合単位／プロピレン重合単位＝５５
／４５（モル比）の共重合体を参考例１と同様にしてフ
ッ素ゴム−２を製造した。[Reference Example 2] Tetrafluoroethylene polymer units / propylene polymer units = 55 were obtained by emulsion polymerization using sodium lauryl sulfate as a surfactant as an emulsifier.
A fluororubber-2 was produced in the same manner as in Reference Example 1 using a copolymer of / 45 (molar ratio).
【００３３】［参考例３］界面活性剤を用いずに、溶液
重合により、テトラフルオロエチレン重合単位／エチレ
ン重合単位／（ペルフルオロブチル）エチレン重合単位
＝５３／４７／０．７（モル比）のフッ素樹脂−１を製
造した。Reference Example 3 Tetrafluoroethylene polymer units / ethylene polymer units / (perfluorobutyl) ethylene polymer units = 53/47 / 0.7 (molar ratio) were obtained by solution polymerization without using a surfactant. Fluororesin-1 was produced.
【００３４】［実施例１］フッ素ゴム−１／フッ素樹脂
−１が４０／６０（重量比）の混合物を３００℃で溶融
混合しフッ素系ポリマー組成物を得た。この組成物を３
００℃でプレスした後に冷却して１ｍｍの厚さのシート
を得た。このシートに１０Ｍｒａｄの電子線を照射して
架橋し、２３℃で物性を測定したところ、引張強度３．
９０ｋｇ／ｍｍ2 、引張伸度２３５％であった。また、
この組成物をシリンダ−１を２５０℃、シリンダ−２を
２７０℃、シリンダ−３を２８０℃、ヘッドを２７５
℃、ダイスを２７５℃に設定した３０ｍｍ押出機（Ｌ／
Ｄ＝３０）を用い、外径０．３６ｍｍの導体上に厚み
０．１８ｍｍで押出被覆した。この被覆物に１０Ｍｒａ
ｄの電子線を照射して架橋させた。この被覆物は、押出
被覆直後、架橋後ともに押出外観は良好であった。Example 1 A mixture of fluororubber-1 / fluororesin-1 (40/60 by weight) was melt-mixed at 300 ° C. to obtain a fluoropolymer composition. 3 of this composition
It was pressed at 00 ° C. and then cooled to obtain a sheet having a thickness of 1 mm. The sheet was cross-linked by irradiating it with an electron beam of 10 Mrad, and its physical properties were measured at 23 ° C.
It was 90 kg / mm 2 and the tensile elongation was 235%. Also,
This composition was used for cylinder-1 at 250 ° C, cylinder-2 at 270 ° C, cylinder-3 at 280 ° C, and head at 275 ° C.
C., 30 mm extruder with die set at 275.degree. C. (L /
D = 30) was used for extrusion coating with a thickness of 0.18 mm on a conductor having an outer diameter of 0.36 mm. 10 Mra for this coating
The electron beam of d was irradiated to crosslink. This coating had a good extrusion appearance both immediately after extrusion coating and after crosslinking.
【００３５】［実施例２］フッ素ゴム−１／フッ素樹脂
−１が３０／７０（重量比）の混合物を３００℃で溶融
混合してフッ素系ポリマー組成物を得た。この組成物
を、実施例１と同様にして電子線を照射して架橋したシ
ートを得た。２３℃での物性は引張強度３．１３ｋｇ／
ｍｍ2 、引張伸度２９３％であった。また、この組成物
を実施例１と同様にして、導体上に厚み０．１８ｍｍで
押出被覆し、電子線を照射して架橋させた。この被覆物
は、押出被覆直後、架橋後ともに押出外観は良好であっ
た。Example 2 A mixture of fluororubber-1 / fluororesin-1 of 30/70 (weight ratio) was melt-mixed at 300 ° C. to obtain a fluoropolymer composition. This composition was irradiated with an electron beam in the same manner as in Example 1 to obtain a crosslinked sheet. The physical properties at 23 ℃ are tensile strength 3.13kg /
It was mm 2 and the tensile elongation was 293%. Further, this composition was extrusion-coated on a conductor in a thickness of 0.18 mm in the same manner as in Example 1 and irradiated with an electron beam to be crosslinked. This coating had a good extrusion appearance both immediately after extrusion coating and after crosslinking.
【００３６】［実施例３］フッ素ゴム−２／フッ素樹脂
−１／ペルフルオロオクタン酸ナトリウムが３０／７０
／０．０１（重量比）の混合物を３００℃で溶融混合し
てフッ素系ポリマー組成物を得た。この組成物を実施例
１と同様にして電子線を照射して架橋したシートを得
た。２３℃での物性は引張強度３．３０ｋｇ／ｍｍ2 、
引張伸度２４４％であった。また、この組成物を実施例
１と同様にして、導体上に厚み０．１８ｍｍで押出被覆
し、電子線を照射して架橋させた。この被覆物は、押出
被覆直後、架橋後ともに押出外観は良好であった。[Example 3] Fluorine rubber-2 / fluorine resin-1 / sodium perfluorooctanoate 30/70
The mixture of /0.01 (weight ratio) was melt-mixed at 300 ° C. to obtain a fluoropolymer composition. This composition was irradiated with an electron beam in the same manner as in Example 1 to obtain a crosslinked sheet. The physical properties at 23 ° C are tensile strength of 3.30 kg / mm 2 ,
The tensile elongation was 244%. Further, this composition was extrusion-coated on a conductor in a thickness of 0.18 mm in the same manner as in Example 1 and irradiated with an electron beam to be crosslinked. This coating had a good extrusion appearance both immediately after extrusion coating and after crosslinking.
【００３７】［実施例４］フッ素ゴム−２／フッ素樹脂
−１／ペルフルオロオクタン酸ナトリウムが４０／６０
／０．０１（重量比）の混合物を３００℃で溶融混合し
てフッ素系ポリマー組成物を得た。この組成物を実施例
１と同様にして電子線を照射して架橋したシートを得
た。２３℃での物性は引張強度３．０５ｋｇ／ｍｍ2 、
引張伸度２２８％であった。また、この組成物を実施例
１と同様にして、導体上に厚み０．１８ｍｍで押出被覆
し、電子線を照射して架橋させた。この被覆物は、押出
被覆直後、架橋後ともに押出外観は良好であった。[Example 4] Fluorine rubber-2 / fluorine resin-1 / sodium perfluorooctanoate 40/60
The mixture of /0.01 (weight ratio) was melt-mixed at 300 ° C. to obtain a fluoropolymer composition. This composition was irradiated with an electron beam in the same manner as in Example 1 to obtain a crosslinked sheet. The physical properties at 23 ° C. are tensile strength of 3.05 kg / mm 2 ,
The tensile elongation was 228%. Further, this composition was extrusion-coated on a conductor in a thickness of 0.18 mm in the same manner as in Example 1 and irradiated with an electron beam to be crosslinked. This coating had a good extrusion appearance both immediately after extrusion coating and after crosslinking.
【００３８】［実施例５］フッ素樹脂−１／ペルフルオ
ロオクタン酸ナトリウムが１００／０．０２（重量比）
の混合物を３００℃でプレスした後に冷却して厚さ１ｍ
ｍのシートを得た。このシートに実施例１と同様にして
電子線を照射して架橋し、物性を測定した。このシート
の２３℃での物性は引張強度４．６１ｋｇ／ｍｍ2 、引
張伸度１５０％、２２０℃での物性は引張強度１．０６
ｋｇ／ｍｍ2 、引張伸度１７０％であった。[Example 5] Fluororesin-1 / sodium perfluorooctanoate 100 / 0.02 (weight ratio)
The mixture was pressed at 300 ° C and then cooled to a thickness of 1 m.
m sheets were obtained. This sheet was irradiated with an electron beam and crosslinked in the same manner as in Example 1, and the physical properties were measured. The physical properties of this sheet at 23 ° C. are a tensile strength of 4.61 kg / mm 2 , the tensile elongation is 150%, and the physical properties at 220 ° C. are a tensile strength of 1.06.
It was kg / mm 2 and the tensile elongation was 170%.
【００３９】［比較例１］フッ素ゴム−２／フッ素樹脂
−１が４０／６０（重量比）の混合物を３００℃で溶融
混合してフッ素系ポリマー組成物を得た。この際、溶融
押出物が破断しやすく、連続してペレット化するのが困
難であった。この組成物を実施例１と同様にして電子線
を照射して架橋したシートを得た。２３℃での物性は引
張強度１．６５ｋｇ／ｍｍ2 、引張伸度１２５％であっ
た。[Comparative Example 1] A mixture of fluororubber-2 / fluororesin-1 of 40/60 (weight ratio) was melt-mixed at 300 ° C to obtain a fluoropolymer composition. At this time, the melt extrudate was easily broken and it was difficult to pelletize it continuously. This composition was irradiated with an electron beam in the same manner as in Example 1 to obtain a crosslinked sheet. The physical properties at 23 ° C. were a tensile strength of 1.65 kg / mm 2 and a tensile elongation of 125%.
【００４０】［比較例２］フッ素樹脂−１を実施例１と
同様にしてシートを得た。このシートに実施例１と同様
にして電子線を照射して物性を測定した。２３℃では引
張強度５．３４ｋｇ／ｍｍ2 、引張伸度４５０％、２２
０℃では引張強度０．４１ｋｇ／ｍｍ2 、引張伸度７０
０％であった。[Comparative Example 2] A sheet was obtained in the same manner as in Example 1 except that the fluororesin-1 was used. This sheet was irradiated with an electron beam in the same manner as in Example 1 to measure the physical properties. At 23 ° C., tensile strength 5.34 kg / mm 2 , tensile elongation 450%, 22
Tensile strength 0.41 kg / mm 2 , tensile elongation 70 at 0 ° C
It was 0%.
【００４１】［比較例３］フッ素ゴム−２／フッ素樹脂
−１／トリアリルイソシアヌレートが４０／６０／４
（重量比）の混合物を３００℃で溶融混合してフッ素系
ポリマー組成物を得た。この際に、トリアリルイソシア
ヌレートが揮散し、周辺に付着した。この組成物を実施
例１と同様にして電子線を照射し、架橋したシートを得
た。２３℃での物性は引張強度２．７８ｋｇ／ｍｍ2 、
引張伸度１９５％であった。また、この組成物を導体上
に厚み０．１８ｍｍで押出被覆した。電線の表面には、
トリアリルイソシアヌレートによると思われるしみが多
数見られた。[Comparative Example 3] Fluorine rubber-2 / fluorine resin-1 / triallyl isocyanurate 40/60/4
The mixture (weight ratio) was melt-mixed at 300 ° C. to obtain a fluoropolymer composition. At this time, triallyl isocyanurate was volatilized and adhered to the periphery. This composition was irradiated with an electron beam in the same manner as in Example 1 to obtain a crosslinked sheet. The physical properties at 23 ° C. are tensile strength of 2.78 kg / mm 2 ,
The tensile elongation was 195%. Further, this composition was extrusion-coated on a conductor with a thickness of 0.18 mm. On the surface of the wire,
Many stains that were probably due to triallyl isocyanurate were found.
【００４２】[0042]
【発明の効果】少量の含フッ素界面活性剤を用いること
により、架橋助剤が不要で作業環境の悪化がなく、溶融
押出物が破断することなく連続したペレット化が可能
で、良好な外観を有する架橋成形物が得られる。電線用
途をはじめとして、各種の産業分野で用いることができ
る。EFFECTS OF THE INVENTION By using a small amount of fluorine-containing surfactant, a cross-linking aid is not required, the working environment is not deteriorated, and the melt extrudate can be continuously pelletized without breaking, resulting in a good appearance. A crosslinked molded product having the above is obtained. It can be used in various industrial fields including electric wire applications.
Claims (5)
素樹脂に含フッ素界面活性剤を含有せしめてなることを
特徴とするフッ素系ポリマー組成物。1. A fluoropolymer composition comprising a tetrafluoroethylene-ethylene fluororesin containing a fluorosurfactant.
素樹脂として、含フッ素界面活性剤を乳化剤として用い
て重合されたものを使用することにより、フッ素系ポリ
マー組成物に含フッ素界面活性剤を含有せしめてなる請
求項１のフッ素系ポリマー組成物。2. A tetrafluoroethylene-ethylene-based fluororesin, which is obtained by polymerizing using a fluorosurfactant as an emulsifier, to allow the fluoropolymer composition to contain the fluorosurfactant. The fluoropolymer composition according to claim 1, wherein
ッ素ゴムをさらに含有せしめてなる請求項１または２の
フッ素系ポリマー組成物。3. The fluoropolymer composition according to claim 1, which further comprises tetrafluoroethylene-propylene fluororubber.
ッ素ゴムとして、含フッ素界面活性剤を乳化剤として用
いて重合されたものを使用することにより、フッ素系ポ
リマー組成物に含フッ素界面活性剤を含有せしめてなる
請求項３のフッ素系ポリマー組成物。4. A fluoropolymer composition containing a fluorosurfactant by using a polymer obtained by polymerizing a tetrafluoroethylene-propylene fluororubber using a fluorosurfactant as an emulsifier. The fluoropolymer composition according to claim 3, wherein
ー組成物を電離性放射線の照射により架橋せしめること
を特徴とする架橋方法。5. A cross-linking method comprising cross-linking the fluoropolymer composition according to any one of claims 1 to 4 by irradiation with ionizing radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9220794A JPH07292199A (en) | 1994-04-28 | 1994-04-28 | Fluoropolymer composition and method for crosslinking the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9220794A JPH07292199A (en) | 1994-04-28 | 1994-04-28 | Fluoropolymer composition and method for crosslinking the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07292199A true JPH07292199A (en) | 1995-11-07 |
Family
ID=14048005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9220794A Pending JPH07292199A (en) | 1994-04-28 | 1994-04-28 | Fluoropolymer composition and method for crosslinking the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07292199A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011042714A (en) * | 2009-08-19 | 2011-03-03 | Mitsubishi Cable Ind Ltd | Fluororubber composition and rubber member |
| WO2013114981A1 (en) * | 2012-01-30 | 2013-08-08 | 旭硝子株式会社 | Optical member, method for producing same, and article provided with optical member |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
| WO2015129762A1 (en) * | 2014-02-26 | 2015-09-03 | 旭硝子株式会社 | Method for manufacturing electrical wire, method for manufacturing molded article, and method for manufacturing resin material that contains modified fluororesin |
| CN109337263A (en) * | 2018-10-08 | 2019-02-15 | 深圳市沃尔核材股份有限公司 | Can low temperature process cross-linking radiation high temperature-resistant cable attachment and production method |
| WO2019231404A1 (en) * | 2018-06-01 | 2019-12-05 | National University Of Singapore | A dielectric material |
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1994
- 1994-04-28 JP JP9220794A patent/JPH07292199A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011042714A (en) * | 2009-08-19 | 2011-03-03 | Mitsubishi Cable Ind Ltd | Fluororubber composition and rubber member |
| WO2013114981A1 (en) * | 2012-01-30 | 2013-08-08 | 旭硝子株式会社 | Optical member, method for producing same, and article provided with optical member |
| US9194982B2 (en) | 2012-01-30 | 2015-11-24 | Asahi Glass Company, Limited | Optical member, process for producing same, and article provided with optical member |
| WO2015129762A1 (en) * | 2014-02-26 | 2015-09-03 | 旭硝子株式会社 | Method for manufacturing electrical wire, method for manufacturing molded article, and method for manufacturing resin material that contains modified fluororesin |
| JPWO2015129762A1 (en) * | 2014-02-26 | 2017-03-30 | 旭硝子株式会社 | Manufacturing method of electric wire, manufacturing method of molded product, and manufacturing method of resin material containing modified fluororesin |
| EP3113193A4 (en) * | 2014-02-26 | 2017-10-25 | Asahi Glass Company, Limited | Method for manufacturing electrical wire, method for manufacturing molded article, and method for manufacturing resin material that contains modified fluororesin |
| US10144792B2 (en) | 2014-02-26 | 2018-12-04 | AGC Inc. | Method for producing electric wire, method for producing molded artile, and method for producing resin material containing modified fluororesin |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
| WO2019231404A1 (en) * | 2018-06-01 | 2019-12-05 | National University Of Singapore | A dielectric material |
| CN112292422A (en) * | 2018-06-01 | 2021-01-29 | 新加坡国立大学 | Dielectric material |
| CN109337263A (en) * | 2018-10-08 | 2019-02-15 | 深圳市沃尔核材股份有限公司 | Can low temperature process cross-linking radiation high temperature-resistant cable attachment and production method |
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