JPH03241613A - Heat-proof cross-linking electric wire - Google Patents
Heat-proof cross-linking electric wireInfo
- Publication number
- JPH03241613A JPH03241613A JP2037108A JP3710890A JPH03241613A JP H03241613 A JPH03241613 A JP H03241613A JP 2037108 A JP2037108 A JP 2037108A JP 3710890 A JP3710890 A JP 3710890A JP H03241613 A JPH03241613 A JP H03241613A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- electric wire
- aromatic
- thermoplastic resin
- resin
- 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.)
- Granted
Links
- 238000004132 cross linking Methods 0.000 title description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000010884 ion-beam technique Methods 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004696 Poly ether ether ketone Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002530 polyetherether ketone Polymers 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006162 poly(etherimide sulfone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明はエンジニアリングプラスチック電線などの耐
熱架橋電線に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to heat-resistant crosslinked electric wires such as engineering plastic electric wires.
〈従来の技術〉
一般に電線の被覆にはポリエチレン樹脂やポリ塩化ビニ
ル樹脂が用いられているが、これらは融点が１００℃程
度と低いため、これ以上の高温になると絶縁層が溶けて
しまう欠点がある。<Conventional technology> Generally, polyethylene resin or polyvinyl chloride resin is used to cover electric wires, but since these have a low melting point of about 100°C, they have the disadvantage that the insulating layer will melt if the temperature is higher than this. be.
このような欠点をなくすために、電子線照射やその他架
橋剤を用いる化学的方法によって架橋したポリエチレン
架橋電線やポリ塩化ビニル架橋電線が用いられている。In order to eliminate such drawbacks, polyethylene crosslinked electric wires and polyvinyl chloride crosslinked electric wires are used, which are crosslinked by electron beam irradiation or other chemical methods using crosslinking agents.
更に、高い耐熱性を必要とする分野では、例えば、実開
平１−１０３２１５号のようにポリエーテルエーテルケ
トンまたはそれを主体とする高耐熱性の芳香族系熱可塑
性樹脂を絶縁層とした電線が用いられている。Furthermore, in fields that require high heat resistance, for example, electric wires with an insulating layer made of polyether ether ketone or a highly heat resistant aromatic thermoplastic resin mainly composed of polyether ether ketone, as disclosed in Utility Model Application Publication No. 1-103215, are used. It is used.
又、本発明者は芳香族または複素環を分子内に有する高
耐熱性の熱可塑性樹脂をイオン照射により架橋してさら
に耐熱性の向上した耐熱架橋電線をさきに提案した（特
開平１−１８６００号）。In addition, the present inventor previously proposed a heat-resistant cross-linked electric wire with further improved heat resistance by cross-linking a highly heat-resistant thermoplastic resin having aromatic or heterocycles in the molecule by ion irradiation (Japanese Patent Application Laid-Open No. 1-18600). issue).
〈発明が解決しようとする課題〉
しかしながら、ポリエーテルイミドやポリエーテルサル
フォンなどの非晶性の芳香族熱可塑性樹脂は耐ストレス
クラツキング性が悪く、このため、このような樹脂で被
覆した電線はストレスがかかった状態で溶剤に触れると
容易にクラックが発生するという欠点があった。また、
ポリエーテルエーテルケトンなどの芳香族の熱可塑性樹
脂は、電子線照射や架橋剤による化学的方法では架橋で
きない。<Problem to be solved by the invention> However, amorphous aromatic thermoplastic resins such as polyetherimide and polyethersulfone have poor stress cracking resistance, and therefore Electric wires have the disadvantage that they easily crack when exposed to solvents under stress. Also,
Aromatic thermoplastic resins such as polyetheretherketone cannot be crosslinked by electron beam irradiation or chemical methods using crosslinking agents.
このため、これらの樹脂で被覆した電線は、樹脂の融点
以上に温度が上がると被覆層が流れるという欠点があっ
た。For this reason, electric wires coated with these resins have the disadvantage that the coating layer flows when the temperature rises above the melting point of the resin.
更に、ポリエーテルエーテルケトンやポリフェニレンサ
ルファイドなと結晶性の芳香族熱可塑性樹脂で被覆した
電線は、熱履歴により結晶化度が変化するため、熱履歴
による物性の変化が大きいという欠点を有している。Furthermore, electric wires coated with crystalline aromatic thermoplastic resins such as polyetheretherketone and polyphenylene sulfide have the disadvantage that their physical properties change significantly due to thermal history, since the degree of crystallinity changes with thermal history. There is.
〈課題を解決するための手段〉
本発明者は上記に鑑みて、エンジニアリングプラスチッ
クを被覆した電線の熱変形性向上をはかるべく検討した
結果、この発明に至ったものである。<Means for Solving the Problems> In view of the above, the present inventors conducted studies to improve the thermal deformability of electrical wires coated with engineering plastics, and as a result, they arrived at the present invention.
即ち、この発明は芳香族あるいは複素環を分子内に有す
る非晶性の熱可塑性樹脂１００重量部とフッ素樹脂５〜
７０重量部よりなる樹脂混合物を絶縁層とし、該絶縁層
を０．１ＭｅＶより大なるエネルギーに加速されたイオ
ンビームの照射により架橋してなる耐熱架橋電線を提供
するものである。That is, this invention consists of 100 parts by weight of an amorphous thermoplastic resin having an aromatic or heterocyclic ring in its molecule and 5 to 5 parts by weight of a fluororesin.
The present invention provides a heat-resistant crosslinked electric wire in which an insulating layer is made of a resin mixture containing 70 parts by weight, and the insulating layer is crosslinked by irradiation with an ion beam accelerated to an energy greater than 0.1 MeV.
く作用〉
この発明は、芳香族あるいは複素環を分子内に有する熱
可塑性樹脂のうち、特に非晶性のタイプを用いることに
より、熱履歴による物性変化をなくしたものである。Effect> The present invention eliminates changes in physical properties due to thermal history by using a particularly amorphous type of thermoplastic resin having an aromatic or heterocyclic ring in the molecule.
結晶性の熱可塑性樹脂をガラス転移点以上に加熱し、再
び冷却すると、冷却速度の違いにより結晶化度が変わる
。このため、結晶性の熱可塑性樹脂で被覆された電線を
ガラス転位点以上に加熱すると、物性が大きく変わるこ
とがある。例えばポリエーテルエーテルケトンは完全に
結晶化した時の物性は非常にすぐれているが、結晶化の
度合いが小さいと、ストレスクラッキングを起こしたり
、破断伸びが小さくなったりする。When a crystalline thermoplastic resin is heated above its glass transition point and cooled again, the degree of crystallinity changes depending on the cooling rate. For this reason, when an electric wire coated with a crystalline thermoplastic resin is heated above its glass transition point, its physical properties may change significantly. For example, polyetheretherketone has very good physical properties when completely crystallized, but if the degree of crystallization is small, it may cause stress cracking or have a low elongation at break.
そこでこの発明は結晶性でない非晶性の熱可塑性樹脂を
用いることにより、この問題を解決したのである。Therefore, the present invention solves this problem by using a non-crystalline thermoplastic resin.
非晶性の熱可塑性樹脂は、一般に耐溶剤性が悪（、スト
レスのかかった状態で溶剤に触れると、クラックを発生
するという問題があったが、この発明は芳香族あるいは
複素環を分子内に有する非晶性の熱可塑性樹脂１００重
量部に対してフッ素樹脂５〜７０重量部（好ましくは１
０〜３０重量部）を混合することにより、耐ストレスク
ラツキング性が改善されることを見出したものである。Amorphous thermoplastic resins generally have poor solvent resistance (and cracks occur when they come into contact with solvents under stress), but this invention solves the problem of 5 to 70 parts by weight (preferably 1 part by weight of fluororesin) per 100 parts by weight of amorphous thermoplastic resin.
It has been discovered that stress cracking resistance can be improved by mixing 0 to 30 parts by weight).
フッ素樹脂の使用量を５〜７０重量部とするのは、５重
量部より少ないと、耐ストレスクラツキング性が改善さ
れず、また７０重量部より多いと非晶性の熱可塑性樹脂
とフッ素樹脂との相溶性が悪（なって物性が著しく低下
して好ましくないためである。The reason why the amount of fluororesin used is 5 to 70 parts by weight is that if it is less than 5 parts by weight, the stress cracking resistance will not be improved, and if it is more than 70 parts by weight, the amorphous thermoplastic resin and fluorine This is because the compatibility with the resin is poor (and the physical properties are significantly deteriorated, which is undesirable).
このように、非晶性の熱可塑性樹脂とフッ素樹脂の混合
樹脂よりなる絶縁層に０．１ＭｅＶより大なるエネルギ
ーに加速されたイオンビームな照射することにより架橋
が起こり、耐熱性が向上するのである。In this way, by irradiating an insulating layer made of a mixed resin of an amorphous thermoplastic resin and a fluororesin with an ion beam accelerated to an energy greater than 0.1 MeV, crosslinking occurs and heat resistance is improved. be.
芳香族あるいは複素環を分子内に有する熱可塑性樹脂は
、電子線やγ線では架橋せず、イオンビームを用いた場
合のみ架橋する。これはイオンビーム照射の方が電子線
照射よりも単位体積当たりに与えるエネルギーがはるか
に大きい（電子の数１０００倍）ために、電子線では起
きない反応が起きているものと考えられる。Thermoplastic resins having aromatic or heterocycles in their molecules do not crosslink with electron beams or gamma rays, but only with ion beams. This is thought to be because ion beam irradiation provides much more energy per unit volume than electron beam irradiation (several thousand times that of electrons), so reactions that do not occur with electron beams occur.
照射するイオンビームの種類としてはＨ′″１８２ＺＨ
ｅ”、 Ｎ”、Ｎ２″″、Ａｒ＋などが使用可能である
が、特にこれらのイオン種に限定されるものではない。The type of ion beam to be irradiated is H'''182ZH.
e'', N'', N2'''', Ar+, etc. can be used, but the ion species are not particularly limited to these.
照射するイオンの質量が小さいものほどイオンビームの
透過距離が長くなるので肉厚の厚い絶縁層をもつ電線の
照射に適当である。The smaller the mass of the ions to be irradiated, the longer the transmission distance of the ion beam, so it is suitable for irradiating electric wires with thick insulating layers.
イオンビームのエネルギーは０．１ＭｅＶ〜５０ＭｅＶ
が適当である。０．１ＭｅＶより小さいと、イオンが表
面で止まってしまうため、被覆層の内部まで架橋するこ
とができないので、熱変形性を向上させることができず
、また５０ＭｅＶよりも大きいとイオンビームにより被
覆層が劣化し、電線の機械的強度が低下するので好まし
くない。The energy of the ion beam is 0.1 MeV to 50 MeV
is appropriate. If it is less than 0.1 MeV, the ions will stop at the surface and cannot crosslink to the inside of the coating layer, making it impossible to improve thermal deformability. This is undesirable because it deteriorates the mechanical strength of the wire.
イオンビームの照射量としては、１ ｘ １０”７０ｍ
”〜Ｉ Ｘ １０”／ＣＩｌ＋” （好ましくはｌ Ｘ
１０”７ｃｍ２〜５ Ｘｔｏ”７０ｍ”）が適当であ
る。The irradiation amount of the ion beam is 1 x 10”70m
"~I X 10"/CIl+" (preferably l
10"7cm2~5Xto"70m") is appropriate.
これはＩ Ｘ １０”７０ｍ”より小さいと架橋が起こ
らないので耐熱性向上の効果が得られない。また、Ｉ
Ｘ １０”７０ｍ”より大きいと、被覆層の劣化が進み
、強度が低下して好ましくないためである。If this is smaller than I x 10"70 m", crosslinking will not occur and the effect of improving heat resistance will not be obtained. Also, I
This is because if it is larger than X 10"70 m", the coating layer will deteriorate and the strength will decrease, which is not preferable.
この発明で芳香族または複素環を分子内に有する非晶性
の熱可塑性樹脂としては、ポリエーテルイミド、ポリエ
ーテルサルフオン、ポリサルフオン、ポリアリレートな
どを用いることができる。In this invention, polyetherimide, polyethersulfone, polysulfone, polyarylate, etc. can be used as the amorphous thermoplastic resin having an aromatic or heterocycle in its molecule.
フッ素樹脂としては、四フッ化エチレンーエチレン共重
合体、四フッ化エチレンー六フッ化プロピレン共重合体
、四フッ化エチレンーパーフルオロビニルエーテル共重
合体、三フッ化塩化エチレン樹脂、フッ素ゴムなどがあ
る。Examples of fluororesins include tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer, trifluorochloroethylene resin, fluororubber, etc. be.
〈実施例〉 以下、この発明を実施例により説明する。<Example> This invention will be explained below with reference to Examples.
下記第１表に示す樹脂混合物を用いて０．５ｍｍφの導
体にそれぞれ絶縁層を被覆し、イオン照射を行なった。Conductors each having a diameter of 0.5 mm were coated with an insulating layer using the resin mixture shown in Table 1 below, and ion irradiation was performed.
被覆層の厚み、イオン照射の条件は第１表に示した。The thickness of the coating layer and the conditions of ion irradiation are shown in Table 1.
得られた被覆電線について、ストレスクラッキング、ゲ
ル分率、３８０℃半田浸漬後の形状の状態等をみたとこ
ろ第１表に示す結果が得られた。The obtained covered wires were examined for stress cracking, gel fraction, shape after being immersed in solder at 380° C., and the results shown in Table 1 were obtained.
それぞれの試験方法は次の通りである。The respective test methods are as follows.
（１） ストレスクラッキング：電線を２．５ｍｍφ
の金属棒に巻き付けた状態でアセトン溶液に１０秒間浸
漬し、クラック発生の有無をみた。(1) Stress cracking: 2.5mmφ wire
The sample was wrapped around a metal rod and immersed in an acetone solution for 10 seconds to check for cracks.
（２） ゲル分率＝１２０℃のジメチルホルムアルデヒ
ドで測定した。(2) Gel fraction = Measured using dimethyl formaldehyde at 120°C.
（３） ３８０℃半田浸漬：電線から導体を引抜き、
３８０℃の半田に１０秒間浸漬し、絶縁層が溶融しない
かどうか、形状の状態をみ
た。(3) 380℃ solder immersion: Pull out the conductor from the wire,
It was immersed in solder at 380°C for 10 seconds, and the shape was checked to see if the insulating layer would melt.
尚、比較例として、ポリエーテルイミド樹脂のみの絶縁
層のもの、ポリエーテルイミドとフッ素樹脂の混合樹脂
を用いたが、イオン照射なしのものなどを示した。As comparative examples, examples were shown in which an insulating layer was made only of polyetherimide resin, and a mixture resin of polyetherimide and fluororesin was used, but without ion irradiation.
第 １ 表
〈発明の効果〉
以上説明したように、芳香族または複素環を分子内に有
する非晶性の熱可塑性樹脂とフッ素樹脂の混合樹脂にイ
オンビームを照射して得た耐熱架橋電線は耐ストレスク
ラツキング性に優れ、なおかつ、高温でも溶融しない耐
熱性に優れていることが認められた。Table 1 <Effects of the invention> As explained above, a heat-resistant cross-linked electric wire obtained by irradiating a mixed resin of an amorphous thermoplastic resin and a fluororesin having an aromatic or heterocycle in the molecule with an ion beam is It was recognized that it has excellent stress cracking resistance and also has excellent heat resistance that does not melt even at high temperatures.
Claims (2)
熱可塑性樹脂１００重量部とフッ素樹脂５〜７０重量部
よりなる樹脂混合物を絶縁層とし、該絶縁層を０．１Ｍ
ｅＶより大なるエネルギーに加速されたイオンビームの
照射により架橋してなる耐熱架橋電線。(1) The insulating layer is made of a resin mixture consisting of 100 parts by weight of an amorphous thermoplastic resin having an aromatic or heterocyclic ring in the molecule and 5 to 70 parts by weight of a fluororesin, and the insulating layer is 0.1M
A heat-resistant cross-linked electric wire that is cross-linked by irradiation with an ion beam accelerated to an energy greater than eV.
ｅＶでその照射量が１×１０＾１＾１／ｃｍ＾２〜１×
１０＾１＾５／ｃｍ＾２である請求項（１）記載の耐熱
架橋電線。（３）芳香族あるいは複素環を分子内に有す
る非晶性の熱可塑性樹脂がポリエーテルイミド、ポリエ
ーテルサルフォン、あるいはポリアリレートである請求
項（１）記載の耐熱架橋電線。(2) Energy of irradiated ions is 0.1MeV to 50M
The irradiation amount in eV is 1×10^1^1/cm^2~1×
The heat-resistant crosslinked electric wire according to claim (1), which has a thickness of 10^1^5/cm^2. (3) The heat-resistant crosslinked electric wire according to claim (1), wherein the amorphous thermoplastic resin having an aromatic or heterocyclic ring in the molecule is polyetherimide, polyether sulfone, or polyarylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2037108A JP2890610B2 (en) | 1990-02-16 | 1990-02-16 | Heat-resistant bridge wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2037108A JP2890610B2 (en) | 1990-02-16 | 1990-02-16 | Heat-resistant bridge wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03241613A true JPH03241613A (en) | 1991-10-28 |
| JP2890610B2 JP2890610B2 (en) | 1999-05-17 |
Family
ID=12488406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2037108A Expired - Lifetime JP2890610B2 (en) | 1990-02-16 | 1990-02-16 | Heat-resistant bridge wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2890610B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082730A (en) * | 2022-11-01 | 2023-05-09 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking type composition containing ECTFE and application thereof |
-
1990
- 1990-02-16 JP JP2037108A patent/JP2890610B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082730A (en) * | 2022-11-01 | 2023-05-09 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking type composition containing ECTFE and application thereof |
| CN116082730B (en) * | 2022-11-01 | 2023-11-03 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking type composition containing ECTFE and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2890610B2 (en) | 1999-05-17 |
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