JPS649337B2 - - Google Patents
Info
- Publication number
- JPS649337B2 JPS649337B2 JP11624484A JP11624484A JPS649337B2 JP S649337 B2 JPS649337 B2 JP S649337B2 JP 11624484 A JP11624484 A JP 11624484A JP 11624484 A JP11624484 A JP 11624484A JP S649337 B2 JPS649337 B2 JP S649337B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- ethylene
- crosslinking agent
- 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
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000002845 discoloration 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
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 230000000007 visual effect Effects 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遂行し、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形成剤を
添加して架橋効率を向上することが試みられてい
る。
［発明が解決しようとする問題点］
しかし、単に架橋形成剤を添加して押出成形す
ると、高温での押出のため架橋形成剤の分解およ
び局所的な凝集等により、架橋形成剤とふつ素樹
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。
［発明が解決するための手段］
本発明は上記に用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そ樹脂組成物の提供
を目的とするものである。
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
化ネオジウムを0.05〜10重量部、酸化チタンを
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。
酸化ネオジウムは、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
る働きがあるものであり、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、特に0.2〜２
重量部の範囲が好ましい。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、また
押出外観を改善できず、５重量部を起えると酸化
ネオジウムの凝集によりツブを発生しやすくな
る。
酸化チタンも酸化ネオジウムと同様の働きをす
るものであるが、双方を併用することにより相乗
作用によつて大きな効果を生むことが実験によつ
て確かめられている。
酸化チタルの含有量は酸化ネオジウムの場合と
同様な理由により0.05〜10重量部の範囲とする必
要がある。
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、ト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表および第２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の評価結果は第１表お
よび第２表の下欄に示す通りである。
なお、押出後の外観は絶縁電線の外観を目視に
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 disintegration occur 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 agent such as an allyl type compound. [Problems to be Solved by the Invention] However, if a crosslinking agent is simply added and extrusion molded, the crosslinking agent and fluororesin will decompose and locally aggregate due to extrusion at high temperatures. There is a problem in that the molded product has a rough appearance due to a reaction with the molded product, making it impossible to obtain a good product. [Means for Solving the Invention] The present invention has been made using the above, and provides a molded product that can obtain a molded product having a good appearance and has excellent mechanical properties in a high-temperature atmosphere. The object of the present invention is to provide a sulfur-containing resin composition that can be obtained. The fluororesin composition of the present invention contains 0.05 to 10 parts by weight of neodymium oxide and titanium oxide to 100 parts by weight of the ethylene-fluoroolefin copolymer.
It is characterized by containing 0.05 to 10 parts by weight and 0.5 parts by weight or more of a crosslinking agent. [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 a mixture of the above. Neodymium oxide has the function of suppressing the chemical reaction between the ethylene-fluoroolefin copolymer and the crosslinking agent, and the amount added is per 100 parts by weight of the ethylene-fluoroolefin copolymer.
It is necessary to make it 0.05 to 10 parts by weight, especially 0.2 to 2 parts by weight.
Parts by weight ranges are preferred. If it is less than 0.05 parts by weight, the effect of suppressing the above chemical reaction will not be sufficient, and the extrusion appearance cannot be improved, and if it is more than 5 parts by weight, the neodymium oxide will agglomerate, resulting in the formation of lumps. Titanium oxide also works in the same way as neodymium oxide, but experiments have confirmed that using both together produces a great effect due to their synergistic effect. The content of tital oxide needs to be in the range of 0.05 to 10 parts by weight for the same reason as in the case of neodymium oxide. Examples of crosslinking agents include allyl type compounds (compounds containing an allyl group) such as triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, triallyl trimesate,
Examples include tetraallyl pyromellitate. The amount of the crosslinking agent must be at least 0.5 parts by weight per 100 parts by weight of the ethylene-tetrafluoroethylene copolymer; 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] Even when the various ingredients were mixed in the proportions shown in the examples in Tables 1 and 2, the temperature in barrel zone 1 was 260°C.
The extruder (40 m/m, L/D= 20, compression ratio = 3), extrusion coating was applied to the outer periphery of a conductor with an outer diameter of 0.8 mm to a thickness of 0.2 mm, and then 10 Mrad electron beam was irradiated to create a crosslinked insulated wire. The evaluation results for the insulated wires of each example are shown in the lower columns of Tables 1 and 2. The appearance after extrusion is the result of visual observation of the appearance of the insulated wire, and the heat deformation rate is
These are the results measured at 300℃ in accordance with JISC3005.
【表】【table】
【表】
第１表から明らかな通り、本発明の範囲にある
実施例１〜４ではいずれも良好な押出外観であ
り、また300℃という高温においても変形しにく
いものである。
これに対し、酸化ネオジウムの添加量が本発明
で規定する量に満たない比較例１、酸化チタンの
みの比較例２、いずれもを含まない比較例３は表
面にツブが多く押出外観が劣る。架橋形成剤を含
まない比較例４は300℃で溶融してしまう。
比較例５〜10は、酸化ネオジウム以外の金属酸
化物を添加した場合であり、いずれも表面に多く
の粒を発生し、外観が劣る。なお、酸化マグネシ
ウムの場合は、粒の発生と共に絶縁体の劣化が激
しく黒変を生じた。
［発明の効果］
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ネオジウム、酸
化チタンおよ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。[Table] As is clear from Table 1, all of Examples 1 to 4 within the scope of the present invention had a good extrusion appearance and were resistant to deformation even at a high temperature of 300°C. On the other hand, Comparative Example 1 in which the amount of neodymium oxide added was less than the amount prescribed in the present invention, Comparative Example 2 in which only titanium oxide was added, and Comparative Example 3 in which neither was added had many lumps on the surface and poor extrusion appearance. Comparative Example 4, which does not contain a crosslinking agent, melts at 300°C. Comparative Examples 5 to 10 are cases in which a metal oxide other than neodymium oxide was added, and in all cases, many particles were generated on the surface and the appearance was poor. In the case of magnesium oxide, grains were generated and the insulator deteriorated severely, resulting in black discoloration. [Effects of the Invention] As explained above, the present invention provides a composition containing neodymium oxide, titanium oxide, and a crosslinking agent in an ethylene-fluoroolefin copolymer. This makes it possible to obtain crosslinked molded products with excellent physical properties and a good appearance, further expanding the field of use of fluororesins.
Claims (1)
重量部に対して、酸化ネオジウムを0.05〜10重量
部、酸化チタンを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
Based on the weight part, 0.05 to 10 parts by weight of neodymium oxide, 0.05 to 10 parts by weight of titanium oxide, and a crosslinking agent.
A radiation crosslinkable fluororesin composition containing 0.5 parts by weight or more. 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, wherein the crosslinking agent is an allyl type compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11624484A JPS60260635A (en) | 1984-06-06 | 1984-06-06 | Radiation-crosslinkable fluororesin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11624484A JPS60260635A (en) | 1984-06-06 | 1984-06-06 | Radiation-crosslinkable fluororesin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60260635A JPS60260635A (en) | 1985-12-23 |
| JPS649337B2 true JPS649337B2 (en) | 1989-02-17 |
Family
ID=14682351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11624484A Granted JPS60260635A (en) | 1984-06-06 | 1984-06-06 | Radiation-crosslinkable fluororesin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60260635A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2537620B2 (en) * | 1987-04-22 | 1996-09-25 | 三菱電線工業株式会社 | Heat-aging resin composition |
| JP2579765B2 (en) * | 1987-04-22 | 1997-02-12 | 三菱電線工業株式会社 | Resin composition |
| JPH03231952A (en) * | 1989-12-20 | 1991-10-15 | Hitachi Cable Ltd | Fluororesin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947525A (en) * | 1973-01-30 | 1976-03-30 | Allied Chemical Corporation | Melt-processable, radiation cross-linkable E-CTFE copolymer compositions |
| JPS52136251A (en) * | 1976-05-11 | 1977-11-14 | Asahi Glass Co Ltd | Fluorine-containing elastomer composition |
-
1984
- 1984-06-06 JP JP11624484A patent/JPS60260635A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60260635A (en) | 1985-12-23 |
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