JPS63286456A - Fluororesin composition for crosslinking with radiation - Google Patents
Fluororesin composition for crosslinking with radiationInfo
- Publication number
- JPS63286456A JPS63286456A JP12154287A JP12154287A JPS63286456A JP S63286456 A JPS63286456 A JP S63286456A JP 12154287 A JP12154287 A JP 12154287A JP 12154287 A JP12154287 A JP 12154287A JP S63286456 A JPS63286456 A JP S63286456A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- crosslinking
- ethylene
- weight
- parts
- 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
- 238000004132 cross linking Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title abstract description 6
- 230000005855 radiation Effects 0.000 title description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 7
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims abstract description 5
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001954 samarium oxide Inorganic materials 0.000 claims abstract description 5
- 229940075630 samarium oxide Drugs 0.000 claims abstract description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 abstract description 2
- -1 etc. Chemical compound 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 238000010894 electron beam technology Methods 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
- 229920001780 ECTFE Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 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
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、高温における機械的強度に優れたふっ素樹脂
成形体を得るための放射線照射架橋用ふっ素樹脂組成物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluororesin composition for crosslinking by radiation irradiation to obtain a fluororesin molded article having excellent mechanical strength at high temperatures.
［従来の技術］
エチレン−フルオロオレフィン共重合体は、ふっ素樹脂
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
のとれた材料であり、電線被覆材料をはじめフィルムや
チューブに成形して各種分野に使用されている。[Prior art] Ethylene-fluoroolefin copolymers have particularly excellent mechanical properties and processability among fluororesins, as well as excellent electrical properties, chemical resistance, and heat resistance. It is used in various fields as a material for covering electric wires, as well as in the form of films and tubes.
しかし、融点を越えるような高温雰囲気下においた場合
、外力により容易に変形してしまい、高温での使用には
限界があった。However, when placed in a high-temperature atmosphere that exceeds the melting point, it easily deforms due to external force, and there is a limit to its use at high temperatures.
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。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.
このため、アリル型化合物のような架橋助剤を添加して
架橋効率を上げることが検討されている。For this reason, it is being considered to increase the crosslinking efficiency by adding a crosslinking aid such as an allyl type compound.
［発明が解決しようとする問題点］
しかしながら、単に架橋助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、架橋助剤とふっ素樹脂とが反応を起こし
、成形品の外観が荒れ、良好な製品を得られないとうい
う問題がある。[Problems to be Solved by the Invention] However, if the crosslinking promoter is simply added and extruded, the crosslinking promoter will decompose and locally aggregate due to extrusion at high temperatures, causing the crosslinking promoter and the fluororesin to separate. This causes a reaction, which results in a rough appearance of the molded product, making it difficult to obtain a good product.
本発明は、上記に基づいてなされたものであり、高温で
の機械的特性に優れ、しかも良好な外観を有する成形品
を得ることができる放射線照射架橋用ふっ素樹脂組成物
の提供を目的とするものである。The present invention has been made based on the above, and aims to provide a fluororesin composition for crosslinking by radiation irradiation, which can provide molded products having excellent mechanical properties at high temperatures and a good appearance. It is something.
［問題点を解決するための手段］
本発明のふっ素樹脂組成物は、エチレン−フルオロオレ
フィン共重合体１００重量部に対し、酸化ビスマス（Ｂ
ｉ、Ｏ，）、酸化サマリウム（Ｓｍ、α）、酸化ジスプ
ロシウム（Ｄ ｙ２０３ ）から選ばれた少なくとも一
種を０．０５〜１０重量部、酸化チタンを０．０５〜１
０重量部および架橋助剤を０．５重量部以上含有するこ
とを特徴とするものである。[Means for Solving the Problems] The fluororesin composition of the present invention contains bismuth oxide (B
0.05 to 10 parts by weight of at least one selected from samarium oxide (Sm, α), dysprosium oxide (D y203 ), and 0.05 to 1 part of titanium oxide.
0 parts by weight and 0.5 parts by weight or more of a crosslinking aid.
本発明において、エチレン−フルオロオレフィン共重合
体としては、エチレン−テトラフルオロエチレン共重合
体やエチレン−クロロトリフルオロエチレン共重合体と
いったものがあげられ、単独あるいは２種混合して使用
可能である。In the present invention, examples of the ethylene-fluoroolefin copolymer include ethylene-tetrafluoroethylene copolymer and ethylene-chlorotrifluoroethylene copolymer, which can be used alone or in combination.
酸化ビスマス、酸化サマリウム、酸化ジスプロシウムは
、エチレン−フルオロオレフィン共重合体と架橋助剤と
の押出成形時における化学反応を抑制する働きがある。Bismuth oxide, samarium oxide, and dysprosium oxide have the function of suppressing the chemical reaction between the ethylene-fluoroolefin copolymer and the crosslinking aid during extrusion molding.
これらは単独使用でもよく、２種以上の併用でもよい。These may be used alone or in combination of two or more.
添加量は、エチレン−フルオロオレフィン共重合体１０
０重量部に対し、０゜０５〜１０重量部の範囲とする必
要があり、０．０５重量部未満では上記の化学反応を抑
制する効果が不十分であり、１０重量部を越えるとこれ
ら添加剤自身の凝集によりつぶを生じ易くなる。The amount added is ethylene-fluoroolefin copolymer 10
The amount must be in the range of 0.05 to 10 parts by weight, and if it is less than 0.05 parts by weight, the effect of suppressing the above chemical reaction will be insufficient, and if it exceeds 10 parts by weight, these additions will be Clumping is likely to occur due to aggregation of the agent itself.
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に加えて酸化チタンを添加す
ることにより、これらの相乗作用によってより大きな効
果が達成される。酸化チタンの添加量は、上記の場合と
同様な理由によりエチレン−フルオロオレフィン共重合
体１００重量部に対して０．０５〜１０重量部である。By adding titanium oxide in addition to at least one selected from bismuth oxide, samarium oxide, and dysprosium oxide, a greater effect can be achieved due to their synergistic action. The amount of titanium oxide added is 0.05 to 10 parts by weight based on 100 parts by weight of the ethylene-fluoroolefin copolymer for the same reason as in the above case.
架橋助剤としては、アリル型化合物が特に好ましく、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等があげられる。架橋助剤
の添加量は、エチレン−フルオロオレフィン共重合体１
００重量部に対し０．５重量部以上とする必要があり、
これ未満では高温での機械的強度を向上する効果が不十
分である。上限は特に規定しないが、２０重量部程度で
架橋助剤の添加による効果が飽和する。As the crosslinking aid, allyl type compounds are particularly preferred, including triallyl cyanurate, triallyl isocyanurate,
triallyl trimellitate, triallyl trimesate,
Examples include tetraallyl pyromellitate. The amount of crosslinking aid added is 1 ethylene-fluoroolefin copolymer.
It is necessary to make it 0.5 parts by weight or more per 00 parts by weight,
If it is less than this, the effect of improving mechanical strength at high temperatures is insufficient. Although there is no particular upper limit, the effect of adding the crosslinking aid is saturated at about 20 parts by weight.
上記成分以外に必要に応じて無機充填剤、着色剤、酸化
防止剤、滑剤等を配合してもよ（、また、テトラフルオ
ロエチレン−プロピレン系共重合体やポリふっ化ビニリ
デン等の他のふっ素糸樹脂を配合してもよい。In addition to the above ingredients, inorganic fillers, colorants, antioxidants, lubricants, etc. may be blended as necessary. A thread resin may also be blended.
［発明の実施例］
第１表の各側に示す各種成分を均一に混練し、これをバ
レル帯域ｌの温度２６０℃、バレル帯域２の温度２７０
℃、バレル帯域３の温度３００°Ｃ１クロスヘッド部温
度３２０℃、ダイ部温度３２０℃、スクリュウ回転数１
５ｒｐｍに設定した押出機（４０ｍｍ、Ｌ／Ｄ＝２０、
圧縮比＝３）に導入し、外径０．８ｍｍの導体周上に厚
さ０．２ ｍ ｍに押出被覆し、続いて比較例３を除い
てｌＯＭｒａｄの電子線を照射して架橋絶縁電線を製造
した。[Embodiments of the Invention] Various components shown on each side of Table 1 are uniformly kneaded, and the mixture is heated at a temperature of 260°C in barrel zone 1 and a temperature of 270°C in barrel zone 2.
℃, Barrel zone 3 temperature 300℃ 1 Crosshead temperature 320℃, Die portion temperature 320℃, Screw rotation speed 1
Extruder set at 5 rpm (40 mm, L/D=20,
The wires were extruded and coated to a thickness of 0.2 mm on the circumference of a conductor with an outer diameter of 0.8 mm, and then, except for Comparative Example 3, they were irradiated with an electron beam of lOMrad to form crosslinked insulated wires. was manufactured.
各側の絶縁電線の押出外観、加熱変形率について評価し
た結果を第１表の下欄に示す。なお、押出外観は絶縁電
線の長さ１ｍ当りの粒の個数を目視により数えた結果で
あり、加熱変形率はＪＩＳＣ３００５に準拠して３００
℃で３００ｇの荷重をかけて測定した結果である。The results of evaluating the extrusion appearance and heat deformation rate of the insulated wire on each side are shown in the lower column of Table 1. The extruded appearance is the result of visually counting the number of grains per 1 meter length of the insulated wire, and the heat deformation rate is 300 in accordance with JISC3005.
This is the result of measurement at ℃ under a load of 300 g.
本発明の範囲にある実施例１〜５ではいずれも優れた押
出外観および加熱変形率である。比較例１は酸化ビスマ
スの添加量が本発明の規定値に満たない場合、比較例２
は規定値を越える場合であり、粒が発生して外観が悪（
なっている。比較例３は架橋しない場合であり、３００
℃で溶融してしまう。Examples 1 to 5 within the scope of the present invention all have excellent extrusion appearance and thermal deformation rate. In Comparative Example 1, when the amount of bismuth oxide added is less than the specified value of the present invention, Comparative Example 2
is when the specified value is exceeded, and grains are generated and the appearance is poor (
It has become. Comparative Example 3 is a case without crosslinking, and 300
It melts at ℃.
［発明の効果］
以上説明してきた通り、本発明によれば、押出外観が良
好で、高温での機械的特性に優れた架橋成形品を得るこ
とができるようになる。[Effects of the Invention] As explained above, according to the present invention, it is possible to obtain a crosslinked molded product with a good extrusion appearance and excellent mechanical properties at high temperatures.
Claims (1)
量部に対し、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を０．０５〜１
０重量部、酸化チタンを０．０５〜１０重量部および架
橋助剤を０．５重量部以上含有することを特徴とする放
射線照射架橋用ふっ素樹脂組成物。(1) 0.05-1% of at least one selected from bismuth oxide, samarium oxide, and dysprosium oxide is added to 100 parts by weight of the ethylene-fluoroolefin copolymer.
0 parts by weight of titanium oxide, 0.05 to 10 parts by weight of titanium oxide, and 0.5 parts by weight or more of a crosslinking aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12154287A JPS63286456A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12154287A JPS63286456A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63286456A true JPS63286456A (en) | 1988-11-24 |
Family
ID=14813825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12154287A Pending JPS63286456A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63286456A (en) |
Cited By (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 |
| JP2013534271A (en) * | 2010-08-13 | 2013-09-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Curable fluoroelastomer composition |
-
1987
- 1987-05-19 JP JP12154287A patent/JPS63286456A/en active Pending
Cited By (3)
| 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 |
| JP2013534271A (en) * | 2010-08-13 | 2013-09-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Curable fluoroelastomer composition |
| EP2603557A4 (en) * | 2010-08-13 | 2015-08-26 | Du Pont | Curable fluoroelastomer compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6116910A (en) | Fluororesin composition crosslinkable with radiation | |
| JPS6116911A (en) | Fluororesin composition crosslinkable with radiation | |
| JPS63286456A (en) | Fluororesin composition for crosslinking with radiation | |
| JPS6030694B2 (en) | Method for manufacturing fluororesin crosslinked molded product | |
| JPH0463849A (en) | Fluorocarbon resin composition | |
| JPS63284247A (en) | Radiation-crosslinkable fluorocarbon resin composition | |
| JPS63286457A (en) | Fluororesin composition for crosslinking with radiation | |
| JPS6281440A (en) | Radiation-crosslinkable fluororesin composition | |
| JPS60260634A (en) | Radiation-crosslinkable fluorocarbon resin composition | |
| JPH0144249B2 (en) | ||
| JPS60260635A (en) | Radiation-crosslinkable fluororesin composition | |
| JP3603965B2 (en) | Heat resistant insulating composition | |
| JPH0551628B2 (en) | ||
| JPS6215250A (en) | Fluororesin composition crosslinkable by irradiation | |
| JPS63286455A (en) | Fluororesin composition for crosslinking with radiation | |
| JPH07179705A (en) | Method for crosslinking fluororubber composition and its crosslinked molded product | |
| JPH07278394A (en) | Cross-linkable resin composition containing fluorine | |
| JPS60170629A (en) | Production of crosslinked molded article of fluororesin | |
| JPH01118559A (en) | Radiation-crosslinkable fluorocarbon resin composition | |
| JPH03231952A (en) | Fluororesin composition | |
| JPS63235354A (en) | Crosslinkable fluororesin composition | |
| JPH09245526A (en) | Heat resistant insulation composition and wire | |
| JPS63284248A (en) | Radiation-crosslinkable fluorocarbon resin composition | |
| JPS60262845A (en) | Fluororesin composition crosslinkable by irradiation | |
| JPS5930178B2 (en) | polyethylene composition |