JPH07288039A - Electrical insulation resin composition, wire, and cable - Google Patents

Electrical insulation resin composition, wire, and cable

Info

Publication number
JPH07288039A
JPH07288039A JP6078495A JP7849594A JPH07288039A JP H07288039 A JPH07288039 A JP H07288039A JP 6078495 A JP6078495 A JP 6078495A JP 7849594 A JP7849594 A JP 7849594A JP H07288039 A JPH07288039 A JP H07288039A
Authority
JP
Japan
Prior art keywords
resin composition
cable
water
polyethylene
electrical insulation
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
Application number
JP6078495A
Other languages
Japanese (ja)
Inventor
Shinya Morishita
信哉 森下
Takanori Yamazaki
孝則 山崎
Kiyoshi Watanabe
清 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Cable Ltd
Original Assignee
Hitachi Cable Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Cable Ltd filed Critical Hitachi Cable Ltd
Priority to JP6078495A priority Critical patent/JPH07288039A/en
Publication of JPH07288039A publication Critical patent/JPH07288039A/en
Pending legal-status Critical Current

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  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

PURPOSE:To suppress generation of water-trees by adding acrylate of specific composition to a base resin composed of polyethylene, ethylene copolymer, or these mixture to provide an electrical insulation resin composition. CONSTITUTION:An electrically insulating resin composition is provided by adding 0.005-1.51-A of acrylate having a formula to 100wt.% of base resin composed of polyethylene, ethylene copolymer, or these mixture. In the formula, R1, R2 are hydrogen or hydrocarbon radicals and it is acceptable that oxygen, nitrogen, sulfur, and silicon atoms or an atomic group thereof are contained in the R1, R2 structure. This electrical insulating resin composition is made to cover on a conductor and bridge so as to provide a wire and a cable. Employment of the electrical insulation composition can improves durability under wet environment.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は架橋ポリエチレン絶縁電
力・ケーブルなどの絶縁体内に発生する水トリー、特に
ボウタイトリーの発生を大巾に抑止することができる電
気絶縁樹脂組成物及びこれを被覆した電線・ケーブルに
関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrically insulating resin composition capable of greatly suppressing the generation of water trees, especially bow tie tree, generated in insulators such as cross-linked polyethylene insulated power cables and the like, and a coating thereof. It relates to electric wires and cables.

【0002】[0002]

【従来の技術】一般に電線・ケーブル用電気絶縁体の材
料としてはポリオレフィン、特にポリエチレンを架橋し
たいわゆる架橋ポリエチレンが広く使用されている。こ
の架橋ポリエチレンを被覆した絶縁電線・ケーブルは優
れた電気絶縁性及び耐熱性を有する反面、湿潤環境下も
しくは浸水雰囲気で使用した場合に、絶縁体に水トリー
と呼ばれる電気化学的劣化が発生し、電気絶縁性能が著
しく低下するという欠点を有している。
2. Description of the Related Art Generally, as a material for electric insulators for electric wires / cables, polyolefin, particularly so-called cross-linked polyethylene obtained by cross-linking polyethylene is widely used. Insulated wires and cables coated with this crosslinked polyethylene have excellent electrical insulation and heat resistance, but when used in a humid environment or in a flooded atmosphere, electrochemical deterioration called water tree occurs in the insulator, It has the drawback that the electrical insulation performance is significantly reduced.

【0003】例えば、高圧用絶縁ケーブルの一般的構成
は図1に示すように導体1の上に内部半導電層2を介し
て絶縁層3が設けられ、さらにこの絶縁層3の外周に外
部半導電層4が設けられた構成をしており、この絶縁層
3の内部にボウタイ状水トリーが発生したり、内部半導
電層2または外部半導電層4の界面に界面水トリーが発
生すると、最悪の場合には絶縁層3を貫通して絶縁破壊
に至ることすらある。
For example, the general structure of an insulated cable for high voltage is that an insulating layer 3 is provided on a conductor 1 via an inner semiconductive layer 2 as shown in FIG. The conductive layer 4 is provided, and when a bowtie-shaped water tree is generated inside the insulating layer 3 or an interfacial water tree is generated at the interface of the inner semiconductive layer 2 or the outer semiconductive layer 4, In the worst case, it may even penetrate the insulating layer 3 and cause dielectric breakdown.

【0004】この水トリーは絶縁体中のボイド、異物、
並びに絶縁体と半導電層界面の不整などの局所的高電界
部に水が凝集し、水との親和性が低い非極性の架橋ポリ
エチレンが、この凝集した水の圧力上昇によってその周
辺に発生する力学的ヒズミによって発生する。
The water tree is a void in the insulator, foreign matter,
In addition, non-polar cross-linked polyethylene, which has a low affinity for water, is generated around the local high electric field part such as irregularity of the interface between the insulator and the semiconductive layer due to the increase in pressure of the condensed water. Caused by mechanical strain.

【0005】そこで、この水トリーの発生を防止するた
めに、発生の原因となるボイド、異物並びに突起物等を
減少すべくレジンの細心にわたる品質管理や製造ライン
のクリーンルーム化等の電線・ケーブルの製造技術の改
善あるいは絶縁体中への極性基の導入による親水性の向
上等の手段が講じられている。
Therefore, in order to prevent the generation of this water tree, in order to reduce the voids, foreign matters, and protrusions that cause the generation, meticulous quality control of the resin and the use of electric wires and cables for making the production line a clean room, etc. Measures have been taken to improve the manufacturing technique or improve the hydrophilicity by introducing a polar group into the insulator.

【0006】[0006]

【発明が解決しようとする課題】しかしながら、各方面
にわたる努力が重ねられているのに拘らず、上述したよ
うな技術のみではこの水トリーの発生原因となる欠陥を
完全に除去できるまでには至っていないのが現状であ
る。
However, in spite of efforts to be made in various fields, it is not possible to completely eliminate the defect that causes the generation of the water tree by the above-mentioned technique alone. The current situation is not.

【0007】本発明は上記の課題を有効に解決するため
に案出されたものであり、その目的は絶縁体中にボイ
ド、異物並びに絶縁体と半導電層との界面における不整
といった水トリーの原因となる欠陥が不可避的に存在し
ていても、水トリーの発生を大幅に抑止できる新規な電
気絶縁組成物及び電線・ケーブルを提供するものであ
る。
The present invention has been devised in order to effectively solve the above-mentioned problems, and its purpose is to eliminate voids, foreign matters, and irregularities at the interface between the insulator and the semiconductive layer in the insulator. It is intended to provide a novel electrical insulating composition and a wire / cable capable of significantly suppressing the generation of a water tree even if the causative defect is unavoidably present.

【0008】[0008]

【課題を解決するための手段】上記課題を解決するため
に本発明は、ポリエチレンまたはエチレン系共重合体あ
るいはこれらの混合物からなるベースレジン100重量
部に対し、次式
In order to solve the above problems, the present invention provides the following formula based on 100 parts by weight of a base resin made of polyethylene, an ethylene copolymer or a mixture thereof.

【0009】[0009]

【化1】 [Chemical 1]

【0010】(ここで、R1 ,R2 は水素または炭化水
素基であり、また、このR1 ,R2 の構造中に一部酸
素、窒素、硫黄、珪素等の原子またはこれらからなる原
子団が含まれていても良い)を有するアクリレートを
0.005〜1.5重量部添加してなる電気絶縁樹脂組
成物であり、また、これら電気絶縁樹脂組成物を導体上
に被覆し、架橋処理してなる電線・ケーブルである。
(Here, R 1 and R 2 are hydrogen or a hydrocarbon group, and in the structure of R 1 and R 2 , atoms such as oxygen, nitrogen, sulfur, silicon, etc., or atoms composed of these atoms are partially contained. An electrically insulating resin composition containing 0.005 to 1.5 parts by weight of an acrylate having a group), and a conductor is coated with the electrically insulating resin composition and crosslinked. It is a wire or cable that has been processed.

【0011】本発明に用いることができるベースレジン
としては、低密度ポリエチレン、中密度ポリエチレン及
びエチレン−プロピレン共重合体の他に、エチレン−エ
チルアクリレート共重合体、エチレン−酢酸ビニル共重
合体等のエチレンを過半に含むポリオレフィンが該当
し、これらは必要に応じてそれぞれ単独あるいは2種以
上を組み合わせて用いても良い。
Examples of the base resin which can be used in the present invention include low density polyethylene, medium density polyethylene and ethylene-propylene copolymer, as well as ethylene-ethyl acrylate copolymer and ethylene-vinyl acetate copolymer. A polyolefin containing a majority of ethylene is applicable, and these may be used alone or in combination of two or more, if necessary.

【0012】このベースレジンに添加する上記アクリレ
ートとしては2,2,6,6,−テトラメチルピペリジ
ニルメタクリレート、N−メチル−2,2,6,6−テ
トラメチルピペリジニルメタクリレート等が挙げられ、
これらはそれぞれ単独2種以上を組み合わせて用いても
良い。
Examples of the acrylate added to the base resin include 2,2,6,6, -tetramethylpiperidinyl methacrylate and N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate. The
These may be used alone or in combination of two or more.

【0013】また、本発明において、この添加量を0.
005〜1.5重量部としたのは、0.005重量部未
満では目的とするボウタイトリー発生抑止効果が不十分
であり、反対に1.5重量部を越えると相溶性の上限か
ら絶縁体表面に析出し(この現象をブルームという)、
製品の品質を低下させてしまうからである。
Further, in the present invention, this addition amount is 0.
The amount of 005 to 1.5 parts by weight means that if the amount is less than 0.005 parts by weight, the desired effect of suppressing the formation of boutite trie is insufficient, and if the amount exceeds 1.5 parts by weight, the compatibility is higher than the upper limit of the insulator. Deposited on the surface (this phenomenon is called bloom),
This is because it deteriorates the quality of the product.

【0014】この電気絶縁樹脂組成物を架橋するための
架橋剤としては、通常使用されているジクミルパーオキ
サイド、1,3−ビス−(ターシャリーブチルパーオキ
シーイソプロピル)ベンゼン、2,5−ジメチル−2,
5−(tーブチルパーオキシ)−ヘキシン3等が挙げら
れる。そして、架橋法としては、有機過酸化物による化
学架橋の他に、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し、水分と接触させてシラノ
ール縮合触媒によりシランを縮合させて架橋させる、い
わゆるシラン水架橋、あるいは電離性放射線によるもの
がある。
As a cross-linking agent for cross-linking the electrically insulating resin composition, dicumyl peroxide, 1,3-bis- (tert-butylperoxy-isopropyl) benzene, and 2,5-dimethyl, which are commonly used, are used. -2
5- (t-butylperoxy) -hexyne 3 and the like can be mentioned. Then, as the cross-linking method, in addition to the chemical cross-linking with an organic peroxide, an organic silane such as vinyltriethoxysilane is grafted to a polymer, and the silane is condensed by contacting with a silanol condensation catalyst to cross-link, There are so-called silane water crosslinks or ionizing radiation.

【0015】尚、この組成物中には、その他必要に応じ
て、滑剤、着色剤、充填剤、架橋促進剤等を添加するこ
とは一考に差し支えない。
Incidentally, it is possible to add a lubricant, a coloring agent, a filler, a crosslinking accelerator, etc. to the composition, if necessary.

【0016】[0016]

【作用】本発明は上述したように、ポリエチレンまたは
エチレン系共重合体あるいはこれらの混合物からなるベ
ースレジンに対し、上記アクリレートを混合してなる電
気絶縁組成物及び、この電気絶縁組成物を導体上に被覆
し架橋処理してなるものであるため、十分なボウタイト
リー特性を発揮する。従って、絶縁体中に水トリーの発
生原因となるボイド、異物、突起等の欠陥が生じていて
も水トリーの発生が大巾に抑止される。
As described above, the present invention provides an electrical insulating composition obtained by mixing the above acrylate with a base resin made of polyethylene, an ethylene copolymer or a mixture thereof, and the electrical insulating composition on a conductor. Since it is coated with and cross-linked, it exhibits sufficient bowtley characteristics. Therefore, even if a defect such as a void, a foreign substance, or a protrusion that causes a water tree is generated in the insulator, the generation of the water tree is greatly suppressed.

【0017】[0017]

【実施例】以下、本発明の具体的実施例を詳述する。EXAMPLES Hereinafter, specific examples of the present invention will be described in detail.

【0018】先ず、表1に示す配合成分からなる各組成
物をそれぞれ120℃に加熱した熱ロールによって混練
し、シート状にしたものをペレタイザを用いてペレット
化した後、これらを図1に示すように外径3mmの導体
1上に、厚さが0.5mmの内部半導電層2及び外部半
導電層4と共に、厚さが2mmの絶縁層3となるように
同時押出法により押出し被覆し、その後、直ちに加熱媒
体として窒素ガスを用いた乾式架橋法により、架橋管内
で連続架橋を行った後、加圧冷却して9種類の試料電線
を作製した。そして、これら各試料電線についてそれぞ
れボウタイトリー発生数及びブルームの発生の有無を調
べ、その結果を表1の下欄に示す。
First, each composition consisting of the compounding ingredients shown in Table 1 was kneaded by a hot roll heated to 120 ° C. and formed into a sheet, which was then pelletized using a pelletizer. On the conductor 1 having an outer diameter of 3 mm, together with the inner semi-conductive layer 2 and the outer semi-conductive layer 4 having a thickness of 0.5 mm by extrusion extrusion coating so as to form the insulating layer 3 having a thickness of 2 mm. Immediately thereafter, continuous cross-linking was performed in a cross-linking tube by a dry cross-linking method using nitrogen gas as a heating medium, and then pressure cooling was performed to produce 9 types of sample electric wires. Then, with respect to each of these sample electric wires, the number of occurrence of boutrite and the presence or absence of occurrence of bloom were examined, and the results are shown in the lower column of Table 1.

【0019】尚、このボウタイトリー発生数の評価につ
いては、各試料電線を90℃の温水中に浸漬し、導体1
と水との間にAC3kVの交流電圧を500日間印加し
た後、これを薄くスライスしてメチレンブルー水溶液で
煮沸染色し、光学顕微鏡を用いて0.2mm以上のボウ
タイトリーの発生の有無とその個数を計数した。一方、
ブルームの有無については、電線を作製する前のペレッ
トを80℃の恒温槽内に10日間保持した後、その表面
を観察し、目視によって評価した。
For the evaluation of the number of occurrence of bow tie tree, each sample electric wire was immersed in warm water at 90 ° C.
After applying AC3kV AC voltage between water and water for 500 days, thinly slice this and boil it with methylene blue aqueous solution. Counted. on the other hand,
The presence or absence of bloom was evaluated by visually observing the surface of the pellet after holding it in a thermostat at 80 ° C. for 10 days before producing the electric wire.

【0020】[0020]

【表1】 [Table 1]

【0021】この結果、表1からも明らかなように、本
発明に規定する配合成分からなる実施例1〜8は、いず
れもボウタイトリーの発生が十分抑止されていると共に
ブルームの発生がみられなかった。
As a result, as is clear from Table 1, in Examples 1 to 8 which consisted of the compounding components defined in the present invention, the occurrence of boutite tree was sufficiently suppressed and the occurrence of bloom was observed. There wasn't.

【0022】これに対し、2,2,6,6−テトラメチ
ルピペリジニルメタクリレート等のメタクリレートを全
く添加しない比較例1及びこれらメタクリレートの添加
量が本発明の規定量以下の比較例2、4はいずれも多量
のボウタイトリーが発生した。また、このこれらメタク
リレートの添加量が本発明の規定量を越える比較例3,
5はいずれもブルームがみられた。
On the other hand, Comparative Example 1 in which no methacrylate such as 2,2,6,6-tetramethylpiperidinyl methacrylate was added, and Comparative Examples 2, 4 in which the amount of these methacrylates was less than the specified amount of the present invention. In each case, a large amount of boutite tree was generated. In addition, Comparative Example 3 in which the amount of addition of these methacrylates exceeds the specified amount of the present invention
Bloom was seen in all of No. 5.

【0023】このように本発明はポリエチレン等からな
るベースレジン中に、上記メタクリレートを所定量、添
加することにより、ボウタイトリーの発生数が大巾に減
少するため、絶縁体中に水トリーの発生原因となるボイ
ド、異物、突起等の欠陥が生じていても水トリーの発生
が大巾に抑止される。
As described above, according to the present invention, by adding a predetermined amount of the above-mentioned methacrylate to the base resin made of polyethylene or the like, the number of generation of the bow tie tree is greatly reduced, so that generation of water tree in the insulator is caused. Even if defects such as voids, foreign matter, and protrusions that cause the problem occur, the generation of water trees is greatly suppressed.

【0024】なお、ボウタイトリーに及ぼす水分の影響
は極めて大きく、気中で課電したケーブルや金属シース
などで遮水したケーブルにもボウタイトリーが見出ださ
れる。これらは外部から浸透した水分によるものではな
く、ケーブル製造時に架橋ポリエチレンの内部に含まれ
る微量の水分によるものであると考えられる。このよう
なボウタイトリーに対しても、本発明にかかる絶縁体が
有効な水トリー抑止効果を発揮することはいうまでもな
い。
The influence of water on the bow tie tree is extremely large, and the vault tie tree is also found in a cable charged in the air or a cable shielded by a metal sheath. It is considered that these are not due to water permeating from the outside, but due to a small amount of water contained inside the cross-linked polyethylene during cable production. It is needless to say that the insulator according to the present invention also exerts an effective water tree suppressing effect against such a bowtie tree.

【0025】[0025]

【発明の効果】以上要するに本発明によれば、絶縁体中
に水トリーの発生原因となるボイド、異物、突起等の欠
陥が生じていても水トリーの発生は大巾に抑止されるた
め、湿潤環境下での耐久性が向上し、信頼性の高い電線
・ケーブルが得られる等といった優れた効果を発揮する
ことができる。
In summary, according to the present invention, the generation of water trees is greatly suppressed even if defects such as voids, foreign matters, and protrusions that cause water trees are generated in the insulator. The durability in a wet environment is improved, and excellent effects such as obtaining highly reliable electric wires and cables can be exhibited.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の一実施例を示す拡大横断面図である。FIG. 1 is an enlarged cross-sectional view showing an embodiment of the present invention.

【符号の説明】[Explanation of symbols]

1 導体 2 内部半導電層 3 絶縁層 4 外部半導電層 1 conductor 2 inner semiconductive layer 3 insulating layer 4 outer semiconductive layer

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 ポリエチレンまたはエチレン系共重合体
あるいはこれらの混合物からなるベースレジン100重
量部に対し、次式 【化1】 (ここで、R1 ,R2 は水素または炭化水素基であり、
また、このR1 ,R2 の構造中に一部酸素、窒素、硫
黄、珪素等の原子またはこれらからなる原子団が含まれ
ていても良い)を有するアクリレートを0.005〜
1.5重量部添加してなることを特徴とする電気絶縁樹
脂組成物。
1. To 100 parts by weight of a base resin composed of polyethylene, an ethylene copolymer or a mixture thereof, the following formula: (Wherein R 1 and R 2 are hydrogen or a hydrocarbon group,
In addition, 0.005 of an acrylate having an oxygen atom, a nitrogen atom, a sulfur atom, an atom atom such as silicon, or an atomic group consisting of these atoms may be contained in the structure of R 1 and R 2.
An electrically insulating resin composition comprising 1.5 parts by weight.
【請求項2】 請求項1記載の電気絶縁樹脂組成物を導
体上に被覆し、架橋処理してなることを特徴とする電線
・ケーブル。
2. An electric wire / cable comprising a conductor coated with the electrically insulating resin composition according to claim 1 and crosslinked.
JP6078495A 1994-04-18 1994-04-18 Electrical insulation resin composition, wire, and cable Pending JPH07288039A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6078495A JPH07288039A (en) 1994-04-18 1994-04-18 Electrical insulation resin composition, wire, and cable

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6078495A JPH07288039A (en) 1994-04-18 1994-04-18 Electrical insulation resin composition, wire, and cable

Publications (1)

Publication Number Publication Date
JPH07288039A true JPH07288039A (en) 1995-10-31

Family

ID=13663558

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6078495A Pending JPH07288039A (en) 1994-04-18 1994-04-18 Electrical insulation resin composition, wire, and cable

Country Status (1)

Country Link
JP (1) JPH07288039A (en)

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