JPS5989345A - Electrical insulating composition - Google Patents
Electrical insulating compositionInfo
- Publication number
- JPS5989345A JPS5989345A JP19953982A JP19953982A JPS5989345A JP S5989345 A JPS5989345 A JP S5989345A JP 19953982 A JP19953982 A JP 19953982A JP 19953982 A JP19953982 A JP 19953982A JP S5989345 A JPS5989345 A JP S5989345A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- aromatic vinyl
- crosslinking
- ethylene
- vinyl monomer
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は電気絶縁組成物、特に耐放射線性ならびに高電
圧特性に優れた電気絶縁組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrical insulating composition, particularly an electrical insulating composition having excellent radiation resistance and high voltage characteristics.
リ
エチレン系ポマーは電気特性、耐熱性、機械強度、低温
特性などにおいてバランスのとれた材料であり、電気絶
縁物として多用されている。Liethylene-based polymers are materials with well-balanced electrical properties, heat resistance, mechanical strength, low-temperature properties, etc., and are widely used as electrical insulators.
しかしながら、エチレン系ポリマーを原子力発電所など
の放射線環境下において使用すると劣化により脆くなっ
たり、表面がべとついたりするという問題がある。However, when ethylene-based polymers are used in a radiation environment such as a nuclear power plant, they deteriorate and become brittle and have a sticky surface.
また、電気絶縁物は高電圧下での使用が多くなってきて
おり、高い絶縁破壊電圧が要求されてきている。In addition, electrical insulators are increasingly being used under high voltage, and a high dielectric breakdown voltage is required.
本発明は上記に基いてなされたもので、エチレン系ポリ
マーの有する本来の特性を損うことなく耐放射線性およ
び高電圧特性を改善した電気絶縁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 an electrical insulating composition that has improved radiation resistance and high voltage characteristics without impairing the original properties of ethylene polymers.
この目的を達成するため本発明者はエチレン系ポリマー
の改質を種々試みた結果、エチレン系ポリマー（ニー期
ａ−
１
１
（式中Ｒ１は水素原子または炭素数１〜４のアルキル基
、Ｒ２−Ｒ６はそれぞれ水素原子、塩素原子またはＦＡ
素数１〜４のアルキル基である。）
で示される芳香族ビニルモノマーをグラフトしてなり、
該芳香族ビニルモノマーの含有割合が１０〜７０重Ｍ％
であるポリマーを主体とした混和物を架橋してなる組成
物が耐放射線性に優れ、しかも高電圧特性に優れている
ことを見出し、本発明に到った。In order to achieve this objective, the present inventors attempted various modifications of ethylene polymers and found that ethylene polymers (knee period a-11 (wherein R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 -R6 is a hydrogen atom, a chlorine atom or FA, respectively
It is an alkyl group having a prime number of 1 to 4. ) is grafted with an aromatic vinyl monomer represented by
The content ratio of the aromatic vinyl monomer is 10 to 70% by weight
It has been discovered that a composition obtained by crosslinking a mixture mainly composed of a polymer has excellent radiation resistance and high voltage characteristics, and has led to the present invention.
本発明におけるエチレン系ポリマーとしては、ポリエチ
レン、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、エチレン・プロピレン共重合
体、エチレン・ブデン共重合体といったものがあげられ
る。Examples of the ethylene polymer in the present invention include polyethylene, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/propylene copolymer, and ethylene/butene copolymer.
芳香族ビニルモノマーとしては、スチレン、メチルスチ
レン、イソプロピルスチレン、クロルスチレン、α−メ
チルスチレン、α−エチルスチレンといったものがあげ
られる。Examples of aromatic vinyl monomers include styrene, methylstyrene, isopropylstyrene, chlorstyrene, α-methylstyrene, and α-ethylstyrene.
芳香族ビニル千ツマ−のエチレン系ポリマーへのグラフ
トは一般のグラフ（・重合法、例えばジクミルパーオキ
サイド、ｔ−ブチルパーオキサイドなどの有機過酸化物
やアゾビスイソブチロニトリルなどのアゾ化合物のよう
なラジカル重合開始剤を用いる水性懸濁重合法などによ
り行われる。Grafting of aromatic vinyl chloride onto ethylene polymers is carried out using general polymerization methods, such as organic peroxides such as dicumyl peroxide and t-butyl peroxide, and azo compounds such as azobisisobutyronitrile. This is carried out by an aqueous suspension polymerization method using a radical polymerization initiator such as.
エチレン系ポリマーに芳香族ビニルモノマーをグラフト
したポリマーに１おける芳香族ビニルモノマーの含有割
合は１０〜７０重量％の範囲とする必要があり、１０重
量％未満では耐放射線性や高電圧特性を十分に改善でき
ず、７０重量％を越えると脆くなって伸び特性や加工性
が低下する。The content of aromatic vinyl monomer in the polymer obtained by grafting an aromatic vinyl monomer to an ethylene polymer must be in the range of 10 to 70% by weight, and if it is less than 10% by weight, radiation resistance and high voltage characteristics may not be sufficient. If it exceeds 70% by weight, it becomes brittle and the elongation properties and workability deteriorate.
グラフトしたポリマーは単独でも使用可能であるが、ケ
イ酸塩を主体とするタルク、クレーなどの充填剤、ある
いは炭酸塩、サーマルカーボンなどの充填剤を加えて使
用してもよい。また加工性を良くするために石油系のプ
ロセス油を加えてもＪ：い。The grafted polymer can be used alone, but it may also be used in addition to a filler such as talc or clay, which is mainly composed of silicate, or a filler such as carbonate or thermal carbon. Also, petroleum-based process oil may be added to improve workability.
更に、酸化防止剤を一種または二種以上組合せて加えて
もよく、酸化防止剤としては、アミン系のＮ−Ｎ−−ジ
フェニル−Ｐ−フェニレンジアミン、フェニル−α−ナ
フチルアミン、Ｎ−フェニル−Ｎ−−イソプロピル−Ｐ
−フェニレンジアミン、ポリ（２，２，４−１−ツメチ
ル−１，２ジヒドロキノリン）など、フェノール系の２
，２−−メチレンビス（４−メチル−６−ｔｅｒｔ−ブ
チルフェノール）、２．６−シーｔｅｒｔ−ブチル−４
−メチルフェノール）４．４′−チオビス＜ ６− ｔ
ｅｒｔ−フ゛チルー３−メチルフェノール）など、イミ
ダゾール系の２−メルカプトベンゾイミダゾール−メル
カプトベンゾイミダゾールの亜鉛塩などがあげられる。Furthermore, one kind or a combination of two or more kinds of antioxidants may be added. Examples of the antioxidants include amine-based N-N--diphenyl-P-phenylenediamine, phenyl-α-naphthylamine, N-phenyl-N --isopropyl-P
-Phenyl diamine, poly(2,2,4-1-methyl-1,2 dihydroquinoline), etc.
, 2-methylenebis(4-methyl-6-tert-butylphenol), 2.6-tert-butyl-4
-methylphenol)4.4'-thiobis<6-t
Examples include zinc salts of imidazole-based 2-mercaptobenzimidazole-mercaptobenzimidazole, such as ert-butyl-3-methylphenol).
架橋方法としては、有機過酸化物による化学架橋、電離
性放射線による架橋、シラン化合物をポリマーにグラフ
トした後シラノール縮合触媒の存在下で水により架橋す
るシラン水架橋といったものがある。Crosslinking methods include chemical crosslinking using organic peroxides, crosslinking using ionizing radiation, and silane water crosslinking in which a silane compound is grafted onto a polymer and then crosslinked with water in the presence of a silanol condensation catalyst.
化学架橋の場合に使用される架橋剤としてはジクミルパ
ーオキサイド、１・３−ビス（ｔ−ブチル・パーオキシ
・インプロピル）ベンゼンに代表される有機過酸化物が
最も適切であり、これを単独あるいは助剤としてイオウ
、エチレンジメタアクリレート、シアｌノルフタレート
、Ｐ−キノンジオキシムなどを併用して使用してもよい
。The most suitable crosslinking agents used in chemical crosslinking are organic peroxides such as dicumyl peroxide and 1,3-bis(t-butyl peroxy impropyl)benzene. Alternatively, sulfur, ethylene dimethacrylate, sial norphthalate, P-quinone dioxime, etc. may be used in combination as an auxiliary agent.
以下、本発明の実施例について説明する。Examples of the present invention will be described below.
第１表に示す通り、各種成分を所定量配合した混合物を
１５０＃φミキシングロールを用い、温度８０〜１２０
℃で均一に混練した後ゲージ圧力８０Ｋｇ／ ｍＡ 、
温度１８０℃の条件で１０分間プレス加硫し、厚さ０．
５＃の絶縁シートを作成した。As shown in Table 1, a mixture containing predetermined amounts of various components was mixed using a 150#φ mixing roll at a temperature of 80 to 120.
Gauge pressure 80Kg/mA after uniformly kneading at ℃,
Press vulcanization was performed at a temperature of 180°C for 10 minutes to a thickness of 0.
A #5 insulation sheet was created.
また、実施例１〜４、比較例１，２については絶縁電線
を作成した。Moreover, insulated wires were created for Examples 1 to 4 and Comparative Examples 1 and 2.
ジクミルパーオキサイドを除いた各種成分を容量２００
１のパンバリミキサを用いて混練し、５５０＃φミキシ
ングロールを用いジクミルパーオキサイドを加え混練し
た。得られた混合物を断面積２−の導体上に厚さ０．５
層に押出被覆し、１７気圧の水蒸気中を５分間で通過さ
せることにより連続加硫して絶縁電線を得た。Capacity 200 of various ingredients except dicumyl peroxide
The mixture was kneaded using Panbury mixer No. 1, and dicumyl peroxide was added and kneaded using a 550 #φ mixing roll. The resulting mixture is spread on a conductor with a cross-sectional area of 2- to a thickness of 0.5
The layer was extrusion coated and continuously vulcanized by passing through steam at 17 atmospheres for 5 minutes to obtain an insulated wire.
かくして得られた絶縁シートの耐放射線性、および絶縁
電線の耐放射線性と絶縁破壊電圧を試験したところ、第
１表の下欄に示すような結果が得られた。When the radiation resistance of the thus obtained insulating sheet and the radiation resistance and dielectric breakdown voltage of the insulated wire were tested, the results shown in the lower column of Table 1 were obtained.
ポリエチレンやエチレン酢酸ビニル共重合体は、γ線照
射により硬化が優先する劣化を起こし、クラックが生じ
るが、スチレンモノマーをグラフトすることにより防止
されている。エチレン・プロピレン共重合体やエチレン
・ブテン共重合体は、γ線照射により分子が切断する劣
化を示し、表面がベトついてくる。しかしスチレンモノ
マーをグラフトすることによりベトッキが生じなくなる
。Polyethylene and ethylene-vinyl acetate copolymers deteriorate when exposed to gamma rays, favoring curing, and cracks occur, but this can be prevented by grafting styrene monomers. Ethylene-propylene copolymers and ethylene-butene copolymers exhibit deterioration when irradiated with gamma rays, in which molecules are cut, resulting in sticky surfaces. However, by grafting styrene monomer, stickiness does not occur.
また、絶縁電線の絶縁破壊電圧もスチレ〕ノモノマーを
グラフトすることにより大幅に向上している。Furthermore, the dielectric breakdown voltage of insulated wires has been significantly improved by grafting styrene monomer.
以上説明してきた通り、本発明によればエチレン系ポリ
マーの耐放射線性および高電圧特性が大幅に改善された
電気絶縁組成物が得られることになり、その工業的価値
は極めて大きいといえる。As explained above, according to the present invention, it is possible to obtain an electrical insulating composition in which the radiation resistance and high voltage characteristics of ethylene-based polymers are significantly improved, and the industrial value thereof can be said to be extremely large.
Claims (1)
、Ｒ２−Ｒ６はそれぞれ水素原子、塩素原子または炭素
数１〜４のアルキル基である。） で示される芳香族ビニルモノマーをグラフトしてなり、
該芳香族ビニルモノマーの含有割合が１０〜７０重量％
であるポリマーを主体とした混和物を架橋してなること
を特徴とする電気絶縁組成物。[Claims] The ethylene polymer has the general formula: (wherein R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 to R6 are each a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms. ) is obtained by grafting an aromatic vinyl monomer shown in
The content of the aromatic vinyl monomer is 10 to 70% by weight
An electrical insulating composition characterized by being formed by crosslinking a mixture mainly composed of a polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19953982A JPS5989345A (en) | 1982-11-12 | 1982-11-12 | Electrical insulating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19953982A JPS5989345A (en) | 1982-11-12 | 1982-11-12 | Electrical insulating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5989345A true JPS5989345A (en) | 1984-05-23 |
Family
ID=16409510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19953982A Pending JPS5989345A (en) | 1982-11-12 | 1982-11-12 | Electrical insulating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5989345A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0482108A (en) * | 1990-07-24 | 1992-03-16 | Hitachi Cable Ltd | Electric insulator for wire, cable and their accessories |
| JP2017014446A (en) * | 2015-07-06 | 2017-01-19 | 日油株式会社 | Polycarbonate resin composition and resin molded article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495473A (en) * | 1972-05-08 | 1974-01-18 | ||
| JPS4985187A (en) * | 1972-12-21 | 1974-08-15 | ||
| JPS5418760A (en) * | 1977-07-13 | 1979-02-13 | Oki Electric Ind Co Ltd | Optical fiber connector and production of the same |
-
1982
- 1982-11-12 JP JP19953982A patent/JPS5989345A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495473A (en) * | 1972-05-08 | 1974-01-18 | ||
| JPS4985187A (en) * | 1972-12-21 | 1974-08-15 | ||
| JPS5418760A (en) * | 1977-07-13 | 1979-02-13 | Oki Electric Ind Co Ltd | Optical fiber connector and production of the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0482108A (en) * | 1990-07-24 | 1992-03-16 | Hitachi Cable Ltd | Electric insulator for wire, cable and their accessories |
| JP2814715B2 (en) * | 1990-07-24 | 1998-10-27 | 日立電線株式会社 | Electric wires and cables |
| JP2017014446A (en) * | 2015-07-06 | 2017-01-19 | 日油株式会社 | Polycarbonate resin composition and resin molded article |
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