JP2571562B2 - Water resistant tri-insulated wire - Google Patents
Water resistant tri-insulated wireInfo
- Publication number
- JP2571562B2 JP2571562B2 JP61235064A JP23506486A JP2571562B2 JP 2571562 B2 JP2571562 B2 JP 2571562B2 JP 61235064 A JP61235064 A JP 61235064A JP 23506486 A JP23506486 A JP 23506486A JP 2571562 B2 JP2571562 B2 JP 2571562B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- insulated wire
- butene
- water
- copolymer
- 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 - Lifetime
Links
Landscapes
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、耐水トリー性に優れた絶縁電線に関するも
のである。Description: TECHNICAL FIELD The present invention relates to an insulated wire having excellent water tree resistance.
［従来技術とその問題点］ ポリエチレンに代表されるポリオレフィンあるいはエ
チレン系共重合体、並びにこれらの架橋物は、優れた電
気絶縁性を示すことから、電力ケーブルを中心とする電
気絶縁材料として広く用いられてきている。[Prior art and its problems] Polyolefins represented by polyethylene or ethylene-based copolymers and crosslinked products thereof have excellent electrical insulation properties, and are widely used as electrical insulation materials mainly for power cables. Have been
しかし、これらの材料を湿潤若しくは浸水状態で使用
した場合、絶縁体中に水トリーが発生し、材料のもつ優
れた電気絶縁性能が大きく低下するという問題がある。However, when these materials are used in a wet or immersed state, there is a problem that water trees are generated in the insulator, and the excellent electrical insulation performance of the materials is greatly reduced.
この水トリーの問題については、各方面で種々研究が
なされており、例えば、エチレンビニルアセテートコポ
リマを単独あるいはブレンドして用いる方法は、特殊な
酸化防止剤やエステル基含有添加剤を配合する方法など
が提案されている。しかし、前者の方法では、水トリー
抑止効果を上げるためにビニルアセテート含有量を高く
すると電気的特性が低下するという問題がある。また、
後者の方法では、水トリー発生の抑止効果の上で不十分
である。Various studies have been made on the problem of water trees in various fields.For example, the method of using ethylene vinyl acetate copolymer alone or in a blend is a method of compounding a special antioxidant or an ester group-containing additive. Has been proposed. However, the former method has a problem in that when the vinyl acetate content is increased in order to increase the water tree deterrent effect, the electrical characteristics deteriorate. Also,
The latter method is insufficient in the effect of suppressing the occurrence of water trees.
［発明の目的］ 本発明は、上記に基づいてなされたものであり、耐水
トリー性を大幅に向上できる絶縁電線の提供を目的とす
るものである。[Object of the Invention] The present invention has been made based on the above, and an object of the present invention is to provide an insulated wire capable of greatly improving water tree resistance.
［発明の概要］ 本発明の耐水トリー性絶縁電線は、マグネシウムとチ
タン化合物および／またはバナジウム化合物とを含有す
る固体物質と有機アルミニウム化合物とを組合せた触媒
の存在下で、実質上溶媒の存在しない気相状態でエチレ
ンとブテン−１を共重合させて得られる密度が0.85〜0.
87、融点が110℃以上のエチレン−ブテン−１共重合体
を主体とする樹脂組成物からなる電気絶縁層を有するこ
とを特徴とするものである。[Summary of the Invention] The water-resistant tree-resistant insulated wire of the present invention has substantially no solvent in the presence of a catalyst in which a solid substance containing magnesium and a titanium compound and / or a vanadium compound is combined with an organoaluminum compound. The density obtained by copolymerizing ethylene and butene-1 in the gaseous phase is 0.85 to 0.8.
87, characterized by having an electrical insulating layer made of a resin composition mainly composed of an ethylene-butene-1 copolymer having a melting point of 110 ° C. or more.
本発明において、エチレン−ブテン−１共重合体の密
度を0.85〜0.87と規定したのは、0.85未満では機械的強
度の低下が大きく、0.87を越えると水トリーを抑止する
効果が低下するからである。また、融点（示差走査熱量
計で測定した場合のピーク温度）が110℃以上でないと
水トリー抑止効果が著しく低下する。メルトインデック
スは特に規定しないが、加工性を考慮すると、0.1〜10
の範囲が好ましい。In the present invention, the reason why the density of the ethylene-butene-1 copolymer is specified to be 0.85 to 0.87 is that if the density is less than 0.85, the mechanical strength is significantly reduced, and if it exceeds 0.87, the effect of suppressing water trees is reduced. is there. If the melting point (peak temperature as measured by a differential scanning calorimeter) is not higher than 110 ° C., the water tree suppressing effect is significantly reduced. Melt index is not specified, but considering workability, 0.1 ~ 10
Is preferable.
本発明における上記のようなエチレン−ブテン−１共
重合体は、例えば、マグネシウムとチタン化合物および
／またはバナジウム化合物とを含有する固体物質と有機
アルミニウム化合物とを組み合せた触媒の存在下で、実
質上溶媒の存在しない気相状態でエチレンとブテン−１
を共重合させることにより得られる。The ethylene-butene-1 copolymer as described above in the present invention can be substantially produced, for example, in the presence of a catalyst in which a solid substance containing magnesium and a titanium compound and / or a vanadium compound is combined with an organoaluminum compound. Ethylene and butene-1 in the solvent free gas phase
Are copolymerized.
固体物質としては、金属マグネシウム、水酸化マグネ
シウム、炭酸マグネシウム、酸化マグネシウム、塩化マ
グネシウムなど、また、けい素、アルミニウム、カルシ
ウムから選ばれる金属とマグネシウム原子とを含有する
複塩、複酸化物、炭酸塩、塩化物水酸化物など、さらに
はこれらの無機室固体担体を含酸素化合物、含硫黄化合
物、芳香属炭化水素、ハロゲン含有物質で処理または反
応させたもの等のマグネシウムを含む無機質固体担体に
チタン化合物および／またはバナジウム化合物を公知の
方法により担持させたものがあげられる。Solid substances include metal magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, and the like, and double salts, double oxides, and carbonates containing a metal selected from silicon, aluminum, and calcium and a magnesium atom. , Chloride hydroxide and the like, and furthermore, these inorganic chamber solid supports containing magnesium such as those treated or reacted with oxygen-containing compounds, sulfur-containing compounds, aromatic hydrocarbons, halogen-containing substances, etc. What carried a compound and / or a vanadium compound by a well-known method is mentioned.
有機アルミニウム化合物としては、一般式R3Al、R2Al
X、RAlX2、R2AlOR、RAl（OR）ＸおよびR3Al2X3であらわ
される化合物が好ましい。ここで、Ｒは炭素数１〜20の
アルキル基、アリール基またはアラルキル基、Ｘはハロ
ゲン原子を示し、Ｒは同一でも異なるものでもよい。As the organic aluminum compound, the general formulas R 3 Al and R 2 Al
X, RAlX 2, R 2 AlOR , compounds represented by RAl (OR) X and R 3 Al 2 X 3 is preferred. Here, R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and R may be the same or different.
上記の触媒系をブテン−１と接触させた後、気相重合
反応を用いることによって、その重合活性を大幅に向上
させ、未処理の場合よりも一層安定した運転ができる。By bringing the above catalyst system into contact with butene-1 and then using a gas phase polymerization reaction, the polymerization activity can be greatly improved, and a more stable operation can be achieved than in the case of untreated.
重合反応は、実質的に溶媒の存在しない気相状態で行
われ、使用する反応器としては、流動床、攪拌槽などの
公知のものが使用できる。重合反応温度は、通常０〜11
0℃、好ましくは20〜80℃であり、圧力は、常圧〜70kg/
cm2、好ましくは２〜60kg/cm2である。分子量の調節
は、重合温度、触媒のモル比、コモノマー量などによっ
ても調節することができるが、重合系中に水素を添加す
ることによっても効果的に行われる。The polymerization reaction is carried out in a gas phase state substantially free of a solvent, and a known reactor such as a fluidized bed and a stirring tank can be used as a reactor. The polymerization reaction temperature is usually 0 to 11
0 ° C., preferably 20 to 80 ° C., and the pressure is from normal pressure to 70 kg /
cm 2 , preferably 2 to 60 kg / cm 2 . The molecular weight can be adjusted by adjusting the polymerization temperature, the molar ratio of the catalyst, the amount of the comonomer, and the like, but can also be effectively adjusted by adding hydrogen to the polymerization system.
上記のようにして得られたエチレン−ブテン−１共重
合体には、配合剤としてポリエチレン、ポリプロピレ
ン、ポリブテン、ポリ−４メチル−ペンテン−１のよう
なポリオレフィン、エチレン−酢酸ビニル共重合体、エ
チレン−エチルアクリレート共重合体などのポリマをブ
レンドしても差支えない。また、適宜、酸化防止剤、滑
剤、あるいはケイ酸マグネシウムやケイ酸アルミニウム
などの充填剤を加えてもよい。更に、水トリー抑止効果
を一層高めるための含エステル系添加剤の使用も可能で
ある。In the ethylene-butene-1 copolymer obtained as described above, polyolefins such as polyethylene, polypropylene, polybutene and poly-4methyl-pentene-1; ethylene-vinyl acetate copolymer; -A polymer such as an ethyl acrylate copolymer may be blended. Further, an antioxidant, a lubricant, or a filler such as magnesium silicate or aluminum silicate may be appropriately added. Further, it is also possible to use an ester-containing additive for further enhancing the water tree deterrent effect.
エチレン−ブテン−１共重合体を主体とする樹脂組成
物は、導体外周に直接あるいは半導電層を介して被覆さ
れ、架橋あるいは非架橋の電気絶縁層を形成する。架橋
する場合は、ジクミルパーオキサイド、2,5−ジメチル
−2,5−ジ（第三ブチル・ペルオキシ）ヘキシン−３に
代表されるパーオキサイドを用いて加熱架橋するのが一
般的である。その他、ビニルトリエトキシシランのよう
な有機シランをポリマにグラフト後、水分と接触させて
架橋させるいわゆるシラン水架橋、あるいは電子線のよ
うな電離性放射線の照射による架橋でもよい。The resin composition mainly composed of an ethylene-butene-1 copolymer is coated on the outer periphery of the conductor directly or via a semiconductive layer to form a crosslinked or non-crosslinked electric insulating layer. In the case of cross-linking, it is general to heat cross-link using a peroxide represented by dicumyl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3. Other than the above, so-called silane water crosslinking, in which an organic silane such as vinyltriethoxysilane is grafted onto a polymer and then brought into contact with moisture to perform crosslinking, or crosslinking by irradiation with ionizing radiation such as an electron beam may be used.
［発明の実施例］ 実質的に無水の塩化マグネシウム、1,2−ジクロルエ
タンおよび四塩化チタンよりなる固体触媒成分とトリエ
チルアルミニウムよりなる触媒を用いてエチレンとブテ
ン−１の共重合を行い、第１表の各例に示すような密
度、融点を有するエチレン−ブテン−１共重合体を得
た。各例のエチレン−ブテン−１共重合体100重量部に
対して、ジクミルパーオキサイド0.2重量部、および4,
4′−チオビス（６−ターシャリブチル−３−メチルフ
ェノール）0.2重量部を配合した樹脂組成物を調整し
た。Embodiments of the Invention Ethylene and butene-1 were copolymerized using a solid catalyst component consisting of substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride and a catalyst consisting of triethylaluminum. An ethylene-butene-1 copolymer having a density and a melting point as shown in each example of the table was obtained. With respect to 100 parts by weight of the ethylene-butene-1 copolymer in each case, 0.2 parts by weight of dicumyl peroxide, and 4,
A resin composition containing 0.2 parts by weight of 4'-thiobis (6-tert-butyl-3-methylphenol) was prepared.
断面積80mm2の撚線導体上に厚さ1mmの半導電層を設
け、この外周に上記樹脂組成物を厚さ4mmに押出被覆
後、13気圧の水蒸気雰囲気中に３分間保持して架橋絶縁
層を形成することにより絶縁電線を作製した。A semiconductive layer having a thickness of 1mm provided on stranded conductor cross-sectional area 80 mm 2, after extrusion coated to a thickness of 4mm the resin composition in the outer peripheral, crosslinked insulation and held in a water vapor atmosphere at 13 atm for 3 minutes The insulated wire was produced by forming a layer.
この絶縁電線を水中に浸漬し、50Hz、3kVの交流電圧
を18ヶ月課電し、絶縁体中に発生した0.2mm以上の水ト
リーを数えた結果を第１表に示した。This insulated wire was immersed in water, an AC voltage of 50 Hz and 3 kV was applied for 18 months, and the number of water trees of 0.2 mm or more generated in the insulator was counted.
［発明の効果］ 以上の説明から明らかな通り、本発明によれば耐水ト
リー性に優れた絶縁電線を実現できるようになる。 [Effects of the Invention] As is clear from the above description, according to the present invention, an insulated wire having excellent water tree resistance can be realized.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−99614（ＪＰ，Ａ) 特開 昭61−27006（ＪＰ，Ａ) 特開 昭56−147838（ＪＰ，Ａ) 特開 昭57−5206（ＪＰ，Ａ) 「電力ケーブル技術ハンドブック」昭 和49年６月10日第１版第１刷発行（株) 電気書院発行Ｐ．137〜138 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-99614 (JP, A) JP-A-61-27006 (JP, A) JP-A-56-1447838 (JP, A) 5206 (JP, A) “Electrical Cable Technology Handbook”, June 10, 1974, First Edition, First Edition, published by Denki Shoin Co., Ltd. 137-138
Claims (1)
はバナジウム化合物とを含有する固体物質と有機アルミ
ニウム化合物とを組合せた触媒の存在下で、実質上溶媒
の存在しない気相状態でエチレンとブテン−１を共重合
させて得られる密度が0.85〜0.87、融点が110℃以上の
エチレン−ブテン−１共重合体を主体とする樹脂組成物
からなる電気絶縁層を有することを特徴とする耐水トリ
ー性絶縁電線。(1) Ethylene and butene-1 in a gas phase substantially free of a solvent in the presence of a catalyst in which a solid substance containing magnesium and a titanium compound and / or a vanadium compound is combined with an organoaluminum compound. A water-resistant tree-insulated wire having an electrical insulating layer made of a resin composition mainly composed of an ethylene-butene-1 copolymer having a density of 0.85 to 0.87 and a melting point of 110 ° C. or higher obtained by copolymerization. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61235064A JP2571562B2 (en) | 1986-10-02 | 1986-10-02 | Water resistant tri-insulated wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61235064A JP2571562B2 (en) | 1986-10-02 | 1986-10-02 | Water resistant tri-insulated wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6388707A JPS6388707A (en) | 1988-04-19 |
| JP2571562B2 true JP2571562B2 (en) | 1997-01-16 |
Family
ID=16980537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61235064A Expired - Lifetime JP2571562B2 (en) | 1986-10-02 | 1986-10-02 | Water resistant tri-insulated wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2571562B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220040944A (en) * | 2020-09-24 | 2022-03-31 | 주식회사 모노리스 | Processing method of polyolefin elastomer copolymer having ultra low density and high elastic property and polyolefin elastomer copolymer produced thereby |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2880725B2 (en) * | 1988-06-14 | 1999-04-12 | 三井化学株式会社 | Method for producing crosslinked polyolefin |
| CZ285069B6 (en) * | 1989-07-26 | 1999-05-12 | Union Carbide Chemicals And Plastics Company Inc., | Insulating composition resistant to water tree-like effect |
| JPH0443506A (en) * | 1990-06-08 | 1992-02-13 | Sumitomo Chem Co Ltd | Electric insulating sheet and electrothemal sheet using electric insulating sheet |
| DE4107665A1 (en) * | 1991-03-09 | 1992-09-10 | Basf Ag | PARTLY NETWORKED PLASTIC MATERIAL FROM PROPYLENE AND ETHYLENE POLYMERS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5999614A (en) * | 1982-11-30 | 1984-06-08 | 住友電気工業株式会社 | Electrically insulating cable |
| JPS6127006A (en) * | 1984-07-16 | 1986-02-06 | 株式会社フジクラ | Power cable |
-
1986
- 1986-10-02 JP JP61235064A patent/JP2571562B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 「電力ケーブル技術ハンドブック」昭和４９年６月１０日第１版第１刷発行（株）電気書院発行Ｐ．１３７〜１３８ |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220040944A (en) * | 2020-09-24 | 2022-03-31 | 주식회사 모노리스 | Processing method of polyolefin elastomer copolymer having ultra low density and high elastic property and polyolefin elastomer copolymer produced thereby |
| KR102505939B1 (en) | 2020-09-24 | 2023-03-03 | 주식회사 모노리스 | Processing method of polyolefin elastomer copolymer having ultra low density and high elastic property and polyolefin elastomer copolymer produced thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6388707A (en) | 1988-04-19 |
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