JPH0144249B2 - - Google Patents
Info
- Publication number
- JPH0144249B2 JPH0144249B2 JP59116245A JP11624584A JPH0144249B2 JP H0144249 B2 JPH0144249 B2 JP H0144249B2 JP 59116245 A JP59116245 A JP 59116245A JP 11624584 A JP11624584 A JP 11624584A JP H0144249 B2 JPH0144249 B2 JP H0144249B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- parts
- crosslinking
- oxide
- 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
Links
- 238000004132 cross linking Methods 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 4
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001954 samarium oxide Inorganic materials 0.000 description 2
- 229940075630 samarium oxide Drugs 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- VOSUIKFOFHZNED-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,3,5-tricarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=CC(C(=O)OCC=C)=C1 VOSUIKFOFHZNED-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、高温雰囲気下における機械的特性に
優れたふつ素樹脂架橋成形体を得ることができる
電子線等の放射線の照射によつて架橋可能なふつ
素樹脂組成物に関するものである。
〔従来の技術〕
エチレン−フルオロオレフイン共重合体は、一
般にふつ素樹脂の中でも特に機械的性質や加工性
に優れ、また電気的特性、耐薬品性および耐熱性
にも優れており、バランスのとれた材料である。
このため、電線被覆材料をはじめ、フイルムやチ
ユーブに成形して各種分野に使用されている。し
かしながら、融点を越えるような高温雰囲気にお
かれた場合、外力により変形してしまい、高温で
の使用には限界があつた。
これを改善するため、電子線等の放射線を照射
して架橋することが知られているが、放射線の照
射により架橋と崩壊が同時に進行し、十分な架橋
効率を達成できない。
従つて、アリル型化合物のような架橋促進剤を
添加して架橋効率を向上することが試みられてい
るが、単に架橋促進剤を添加して押出成形する
と、高温での押出のため架橋促進剤の分解および
局所的な凝集等により、架橋促進剤とふつ素樹脂
とが反応を起し、成形品の外観が荒れ、良好な製
品を得られないという問題がある。
〔発明が解決しようとする問題点〕
本発明は上記に基いてなされたものであり、良
好な外観を有する成形品を得ることが可能であ
り、しかも高温雰囲気下における機械的特性に優
れた成形品を得られる含ふつ素樹脂組成物の提供
を日的とするものである。
〔問題点を解決するための手段〕
本発明のふつ素樹脂組成物は、エチレン−フル
オロオレフイン共重合体100重量部に対して、酸
化ビスマス（Bi2O3）、酸化サマリウム
（Sm2O3）、酸化ジスプロシウム（Dy2O3）の中か
ら選ばれた少なくとも一種を0.05〜10重量部、架
橋形成剤を0.5重量部以上含有することを特徴と
するものである。
〔作用〕
本発明において、エチレン−フルオロオレフイ
ン共重合体としては、エチレン−テトラフルオロ
エチレン共重合体あるいはエチレン−クロロトリ
フルオロエチレン共重合体といつたものがあげら
れ、これらは単独でもあるいは２種以上混合して
も使用可能である。
酸化ビスマス、酸化サマリウム、酸化ジスプロ
シウムにはエチレン−フルオロオレフイン共重合
体と架橋形成剤との化学反応を抑制する働きがあ
り、これらは単独使用又は２種以上の併用が可能
である。添加量はエチレン−フルオロオレフイン
共重合体100重量部に対して0.05〜10重量部とす
る必要があり、0.05重量部未満では上記の化学反
応を抑制する働きが十分でなく、10重量部を越え
るとこれら添加剤自身の凝集によりツブを発生し
やすくなる。
架橋形成剤としてはアリル型化合物（アリル基
を含有する化合物）があげられ、トリアリルシア
ヌレート、アリアリルイソシアヌレート、トリア
リルトリメリテート、トリアリルトリメゼート、
テトラアリルピロメリテートといつたものがあげ
られる。
架橋形成剤は、エチレン−テトラフルオロエチ
レン共重合体100重量部に対して0.5重量部以上と
する必要があり、これ未満では高温雰囲気におい
て良好な機械的特性を有する成形品を得ることが
できない。通常は１〜20重量部の範囲である。
本発明においては、上記成分以外に適宜、無機
充填剤、着色剤等を加えてもよく、またテトラフ
ルオロエチレン−プロピレン系共重合体、ポリふ
つ化ビニリデン等をブレンドしてもよい。
〔実施例〕
各種成分を第１表の各例に示すような配合割合
でもつて、バレル帯域１の温度260℃、バレル帯
域２の温度270℃、バレル帯域３の温度300℃、ク
ロスヘツド部温度320℃、ダイ部温度320℃、スク
リユウ回転数15r.p.mに設定した押出機（40ｍ／
ｍ、Ｌ／Ｄ＝20、圧縮比＝３）に導入し、外径
0.8mmの導体外周に、厚さ0.2mmに押出被覆し、続
いて10Mradの電子線を照射して架橋絶縁電線を
作成した。
各例の絶縁電線について評価結果は第１表およ
び第２表の下欄に示す通りである。
なお、押出外観は押出後の絶縁電線表面のツブ
の数を目視により観察した結果であり、加熱変形
率はJISC3005に準拠し300℃で測定した結果であ
る。
[Industrial Application Field] The present invention relates to a fluororesin composition that can be crosslinked by irradiation with radiation such as an electron beam, which can yield a fluororesin crosslinked molded product with excellent mechanical properties in a high-temperature atmosphere. It is related to. [Prior art] Ethylene-fluoroolefin copolymers generally have particularly excellent mechanical properties and processability among fluororesins, as well as excellent electrical properties, chemical resistance, and heat resistance, and are well-balanced. The material is
For this reason, it is used in various fields, including as a material for covering electric wires, and in the form of films and tubes. However, when placed in a high-temperature atmosphere that exceeds the melting point, it deforms due to external force, and there is a limit to its use at high temperatures. In order to improve this, it is known to perform crosslinking by irradiating with radiation such as an electron beam, but crosslinking and collapse proceed simultaneously due to radiation irradiation, making it impossible to achieve sufficient crosslinking efficiency. Therefore, attempts have been made to improve the crosslinking efficiency by adding a crosslinking accelerator such as an allyl type compound, but if the crosslinking accelerator is simply added and extruded, the crosslinking accelerator is removed due to extrusion at high temperature. There is a problem in that the crosslinking accelerator and the fluororesin react with each other due to decomposition and local aggregation, resulting in a rough appearance of the molded product and a failure to obtain a good product. [Problems to be Solved by the Invention] The present invention has been made based on the above, and it is possible to obtain a molded product having a good appearance and also having excellent mechanical properties in a high temperature atmosphere. The purpose of this invention is to provide a fluorine-containing resin composition that can be used as a commercially available product. [Means for Solving the Problems] The fluororesin composition of the present invention contains bismuth oxide (Bi 2 O 3 ), samarium oxide (Sm 2 O 3 ), and 100 parts by weight of the ethylene-fluoroolefin copolymer. ), dysprosium oxide (Dy 2 O 3 ) in an amount of 0.05 to 10 parts by weight, and a crosslinking agent in an amount of 0.5 parts by weight or more. [Function] In the present invention, examples of the ethylene-fluoroolefin copolymer include ethylene-tetrafluoroethylene copolymer and ethylene-chlorotrifluoroethylene copolymer, which may be used alone or in combination of two types. It is also possible to use the above mixtures. Bismuth oxide, samarium oxide, and dysprosium oxide have the function of suppressing the chemical reaction between the ethylene-fluoroolefin copolymer and the crosslinking agent, and these can be used alone or in combination of two or more. The amount added must be 0.05 to 10 parts by weight per 100 parts by weight of the ethylene-fluoroolefin copolymer; if it is less than 0.05 parts by weight, the effect of suppressing the above chemical reaction will not be sufficient, and if it exceeds 10 parts by weight. The agglomeration of these additives themselves tends to cause lumps. Examples of the crosslinking agent include allyl type compounds (compounds containing an allyl group) such as triallyl cyanurate, allaryl isocyanurate, triallyl trimellitate, triallyl trimesate,
Examples include tetraallyl pyromellitate. The amount of the crosslinking agent must be 0.5 parts by weight or more based on 100 parts by weight of the ethylene-tetrafluoroethylene copolymer, and if it is less than this, it will not be possible to obtain a molded article with good mechanical properties in a high-temperature atmosphere. It is usually in the range of 1 to 20 parts by weight. In the present invention, in addition to the above-mentioned components, inorganic fillers, colorants, etc. may be added as appropriate, and tetrafluoroethylene-propylene copolymers, polyvinylidene fluoride, etc. may be blended. [Example] With the various components in the proportions shown in each example in Table 1, the temperature in barrel zone 1 was 260°C, the temperature in barrel zone 2 was 270°C, the temperature in barrel zone 3 was 300°C, and the crosshead temperature was 320°C. ℃, die temperature 320℃, screw rotation speed 15rpm (40m/
m, L/D = 20, compression ratio = 3), and the outer diameter
A crosslinked insulated wire was created by extrusion coating the outer periphery of a 0.8 mm conductor to a thickness of 0.2 mm, and then irradiating it with a 10 Mrad electron beam. The evaluation results for the insulated wires of each example are shown in the lower columns of Tables 1 and 2. Note that the extruded appearance is the result of visually observing the number of lumps on the surface of the insulated wire after extrusion, and the thermal deformation rate is the result of measurement at 300°C in accordance with JISC3005.
【表】【table】
【表】【table】
以上説明してきた通り、本発明はエチレン−フ
ルオロオレフイン共重合体に酸化ビスマス、酸化
サマリウム、酸化ジスプロシウムから選ばれた少
なくとも一種、及び架橋形成剤を含有した組成物
を提供するものであり、これにより、高温での機
械的特性に優れ、しかも外観の良好な架橋成形品
を得ることが可能となり、ふつ素樹脂の使用分野
が更に拡大されることになる。
As explained above, the present invention provides a composition containing an ethylene-fluoroolefin copolymer, at least one selected from bismuth oxide, samarium oxide, and dysprosium oxide, and a crosslinking agent. This makes it possible to obtain crosslinked molded products with excellent mechanical properties at high temperatures and a good appearance, further expanding the fields of use of fluororesins.
Claims (1)
重量部に対して、酸化ビスマス（Bi2O3）、酸化
サマリウム（Sm2O3）、酸化ジスプロシウム
（Dy2O3）の中から選ばれた少なくとも一種を
0.05〜10重量部、架橋形成剤を0.5重量部以上含
有することを特徴とする放射線照射架橋可能なふ
つ素樹脂組成物。 ２ エチレン−フルオロオレフイン共重合体は、
エチレン−テトラフルオロエチレン共重合体であ
る特許請求の範囲第１項記載の放射線照射架橋可
能なふつ素樹脂組成物。 ３ 架橋形成剤は、アリル型化合物である特許請
求の範囲第１項又は第２項記載の放射線照射架橋
可能なふつ素樹脂組成物。[Claims] 1. Ethylene-fluoroolefin copolymer 100
At least one selected from bismuth oxide (Bi 2 O 3 ), samarium oxide (Sm 2 O 3 ), and dysprosium oxide (Dy 2 O 3 ) is added to the weight part.
A fluororesin composition capable of crosslinking by radiation, characterized in that it contains 0.05 to 10 parts by weight and 0.5 parts by weight or more of a crosslinking agent. 2 Ethylene-fluoroolefin copolymer is
The radiation crosslinkable fluororesin composition according to claim 1, which is an ethylene-tetrafluoroethylene copolymer. 3. The radiation crosslinkable fluororesin composition according to claim 1 or 2, wherein the crosslinking agent is an allyl type compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11624584A JPS60260636A (en) | 1984-06-06 | 1984-06-06 | Radiation crosslinkable fluororesin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11624584A JPS60260636A (en) | 1984-06-06 | 1984-06-06 | Radiation crosslinkable fluororesin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60260636A JPS60260636A (en) | 1985-12-23 |
| JPH0144249B2 true JPH0144249B2 (en) | 1989-09-26 |
Family
ID=14682370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11624584A Granted JPS60260636A (en) | 1984-06-06 | 1984-06-06 | Radiation crosslinkable fluororesin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60260636A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011122112A (en) * | 2009-12-14 | 2011-06-23 | Mitsubishi Cable Ind Ltd | Rubber composition, and electric wire, cable and rubber molded article, using the same |
| US8309641B2 (en) * | 2010-08-13 | 2012-11-13 | E I Du Pont De Nemours And Company | Curable fluoroelastomer compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49107350A (en) * | 1973-01-30 | 1974-10-11 | ||
| JPS50148453A (en) * | 1974-05-21 | 1975-11-28 |
-
1984
- 1984-06-06 JP JP11624584A patent/JPS60260636A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49107350A (en) * | 1973-01-30 | 1974-10-11 | ||
| JPS50148453A (en) * | 1974-05-21 | 1975-11-28 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60260636A (en) | 1985-12-23 |
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