JPH0510767B2 - - Google Patents
Info
- Publication number
- JPH0510767B2 JPH0510767B2 JP59151748A JP15174884A JPH0510767B2 JP H0510767 B2 JPH0510767 B2 JP H0510767B2 JP 59151748 A JP59151748 A JP 59151748A JP 15174884 A JP15174884 A JP 15174884A JP H0510767 B2 JPH0510767 B2 JP H0510767B2
- Authority
- JP
- Japan
- Prior art keywords
- silane compound
- water
- unsaturated silane
- ethylene
- acrylic ester
- 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
- -1 acrylic ester Chemical class 0.000 claims description 17
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 240000005572 Syzygium cordatum Species 0.000 description 13
- 235000006650 Syzygium cordatum Nutrition 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Insulating Materials (AREA)
Description
［産業上の利用分野］
本発明は、耐水トリー性にに優れた電線・ケー
ブルに関するものである。
［従来の技術］
ポリオレフイン、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は、電気絶縁性及び耐
熱性に優れているため、電線・ケーブルの絶縁材
料として広く用いられてきているが、ポリオレフ
イン系の絶縁材料を浸水、湿潤状態で使用する
と、水トリー発生による絶縁劣化を生じることが
認められている。
従つて、電線・ケーブルの信頼性を向上させる
ためには、水トリーの発生を如何に低下させるか
が大きな課題となり、過去数多くの研究が行われ
てきている。
例えば、特公昭57−57804号公報には、エチレ
ン重合体に特定の有機シラン化合物を添加するこ
とにより、耐水トリー性を向上できることが記載
されている。
［発明が解決しようとする問題点］
しかしながら、有機シラン化合物は添加剤的に
使用されており、マイグレーシヨン（移行）によ
り有機シラン化合物が経時的に目減りし、長期に
わたつて水トリーの発生を抑制し得ない難点があ
る。なお、添加された有機シラン化合物の一部は
架橋時にエチレン重合体にグラフトされるが、グ
ラフト量は架橋条件によつて左右され、長期にわ
たつて安定した水トリー抑止効果を実現すること
は困難な状況にある。
本発明は上記に基づいてなされたものであり、
長期にわたつて水トリーの発生を抑止できる電
線・ケーブルの提供を目的とするものである。
［問題点を解決するための手段］
本発明の電線・ケーブルは、エチレンとアクリ
ル酸エステルと不飽和シラン化合物とをラジカル
重合開始剤の存在下で共重合してなるアクリル酸
の含有量が0.5〜10重量％であるエチレン−アク
リル酸エステル−不飽和シラン化合物三元共重合
体を主体として含有する組成物の被覆層が導体若
しくは半導電層の外周に設けられ、該被覆層は架
橋されていることを特徴とするものである。
本発明においては、アクリル酸エステルの水ト
リー抑止効果に加えて不飽和シラン化合物の水ト
リー抑止効果が重畳され、しかも不飽和シラン化
合物は共重合によりポリマの構成成分として組み
込まれているためマイグレーシヨンによる水トリ
ー抑止効果の経時的な目減りがなくなり、長期に
わたり安定した水トリー抑止効果を実現できる。
本発明におけるエチレン−アクリル酸エステル
−不飽和シラン化合物三元共重合体は、エチレン
とアクリル酸エステルと不飽和シラン化合物とを
ラジカル重合開始剤、更に必要に応じ好ましくは
連鎖移動剤の存在下で共重合して得られるもので
ある。
アクリル酸エステルとしては、メチルアクリレ
ート、エチルアクリレート、プロピルアクリレー
ト、ブチルアクリレート、メチルメタアクリレー
ト、エチルメタアクリレートといつたものがあげ
られる。エチレン−アクリル酸エステル−不飽和
シラン化合物三元共重合体中におけるアクリル酸
エステルの含有量は0.5〜10重量％の範囲とする
必要があり、0.5重量％未満では水トリー抑止効
果が不十分であり、10重量％を越えると電気特性
が低下し、高電圧分野には適用できなくなる。
不飽和シラン化合物は次式で表わされるもので
ある。
CH2＝Ｃ（Ｒ）COO（CH2）xSiR′y（OCH3）5-y
（ＲはＨまたはCH3、R′はCH3またはC2H5、
ｘは１〜６好ましくは３〜５、ｙは０〜３好まし
くは０である。）
エチレン−アクリル酸エステル−不飽和シラン
化合物三元共重合体中における不飽和シランの含
有量は0.1〜15重量％、好ましくは0.2〜３重量％
である。
エチレン−アクリル酸エステル−不飽和シラン
化合物三元共重合体を主体として含有する組成物
は、導体外周に直接あるいは半導電層を介して押
出被覆され、その後架橋処理が行われる。架橋法
としてはジクミルパーオキサイドに代表される有
機過酸化物を添加し、押出後加熱架橋する方法が
最も代表的である。それ以外に、電離性放射線の
照射による照射架橋、シラノール縮合触媒の存在
下で水と接触させる水架橋といつたものがある。
［実施例］
第１表の各例に示すような配合に従い、８イン
チロールに投入して混練し、混練シートをペレタ
イザーでペレツト化した。このペレツトを押出機
に導入し、外径３mmの銅導体上に厚さ２mmで押出
被覆した。続いて窒素ガスを熱媒体とした乾式架
橋管内で架橋した。
上記のようにして作製した各種電線についての
評価結果は第１表の下欄に示す通りである。
なお、水トリー発生数の評価は次のようにして
行つた。電線を水中に浸漬し、導体と水との間に
3kV、50Hzの交流電圧を印加し、500日間課電を
行つた。このとき、水の温度は室温から90℃の間
で12時間周期で変化させた。課電終了後、試料を
スライスしてメチレンブルー水溶液で煮沸染色
し、発生した水トリーの数を観察した。
[Industrial Field of Application] The present invention relates to electric wires and cables with excellent water resistance. [Prior Art] Polyolefin, especially so-called cross-linked polyethylene, which is made by cross-linking polyethylene, has excellent electrical insulation and heat resistance, so it has been widely used as an insulating material for electric wires and cables. It is recognized that when used in wet or wet conditions, insulation may deteriorate due to water tree formation. Therefore, in order to improve the reliability of electric wires and cables, how to reduce the occurrence of water trees has become a major issue, and many studies have been conducted in the past. For example, Japanese Patent Publication No. 57-57804 describes that water resistance can be improved by adding a specific organic silane compound to an ethylene polymer. [Problems to be Solved by the Invention] However, organic silane compounds are used as additives, and the organic silane compounds decrease over time due to migration, which can prevent water tree formation over a long period of time. There are drawbacks that cannot be suppressed. A portion of the added organosilane compound is grafted onto the ethylene polymer during crosslinking, but the amount of grafting depends on the crosslinking conditions, making it difficult to achieve a stable water tree suppression effect over a long period of time. I am in a situation. The present invention has been made based on the above,
The purpose is to provide electric wires and cables that can prevent the occurrence of water trees over a long period of time. [Means for Solving the Problems] The electric wire/cable of the present invention has an acrylic acid content of 0.5 which is obtained by copolymerizing ethylene, an acrylic acid ester, and an unsaturated silane compound in the presence of a radical polymerization initiator. A coating layer of a composition mainly containing ~10% by weight of an ethylene-acrylic acid ester-unsaturated silane compound terpolymer is provided on the outer periphery of the conductor or semiconducting layer, and the coating layer is crosslinked. It is characterized by the presence of In the present invention, the water tree inhibiting effect of the unsaturated silane compound is superimposed on the water tree inhibiting effect of the acrylic acid ester, and the unsaturated silane compound is incorporated as a component of the polymer by copolymerization, so migration is prevented. This eliminates the loss of water tree deterrent effect over time, making it possible to achieve a stable water tree deterrent effect over a long period of time. The ethylene-acrylic ester-unsaturated silane compound terpolymer of the present invention is produced by combining ethylene, acrylic ester, and unsaturated silane compound in the presence of a radical polymerization initiator and, if necessary, preferably a chain transfer agent. It is obtained by copolymerization. Examples of acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate. The content of acrylic ester in the ethylene-acrylic ester-unsaturated silane compound terpolymer must be in the range of 0.5 to 10% by weight, and if it is less than 0.5% by weight, the water tree inhibiting effect is insufficient. If it exceeds 10% by weight, the electrical properties will deteriorate and it will no longer be applicable to high voltage fields. The unsaturated silane compound is represented by the following formula. CH 2 =C(R)COO(CH 2 ) x SiR′ y (OCH 3 ) 5-y (R is H or CH 3 , R′ is CH 3 or C 2 H 5 ,
x is 1-6, preferably 3-5, and y is 0-3, preferably 0. ) The content of unsaturated silane in the ethylene-acrylic acid ester-unsaturated silane compound terpolymer is 0.1 to 15% by weight, preferably 0.2 to 3% by weight.
It is. A composition mainly containing an ethylene-acrylic acid ester-unsaturated silane compound terpolymer is extrusion coated onto the outer periphery of the conductor either directly or via a semiconductive layer, and then crosslinked. The most typical crosslinking method is to add an organic peroxide such as dicumyl peroxide and heat crosslinking after extrusion. Other methods include irradiation crosslinking by irradiation with ionizing radiation and water crosslinking by contacting with water in the presence of a silanol condensation catalyst. [Example] According to the formulation shown in each example in Table 1, the mixture was put into an 8-inch roll and kneaded, and the kneaded sheet was pelletized using a pelletizer. The pellets were introduced into an extruder and extrusion coated onto a copper conductor having an outer diameter of 3 mm to a thickness of 2 mm. Subsequently, crosslinking was carried out in a dry crosslinking tube using nitrogen gas as a heat medium. The evaluation results for the various electric wires produced as described above are as shown in the lower column of Table 1. The number of water trees generated was evaluated as follows. Immerse the wire in water and connect it between the conductor and the water.
AC voltage of 3 kV, 50 Hz was applied, and electricity was applied for 500 days. At this time, the water temperature was varied from room temperature to 90°C in 12 hour cycles. After the electrification was completed, the sample was sliced, boiled and stained with a methylene blue aqueous solution, and the number of water trees generated was observed.
【表】【table】
【表】
第１表から明らかな通り、本発明の範囲にある
実施例１〜３ではいずれも耐水トリー性および電
気特性（誘電正接）に優れていることがわかる。
これに対し、エチルアクリレートの含有量が少
ない比較例１では耐水トリー性の向上効果は小さ
く、エチルアクリレートの含有量が多過ぎる比較
例２では電気特性（誘電正接）の低下が著しい
（高電圧用としては、誘電正接は0.1％以下とされ
ている）。
［発明の効果］
以上説明してきた通り、本発明によれば長期に
わたつて水トリーの発生を抑止できる電線・ケー
ブルを実現できるようになる。[Table] As is clear from Table 1, Examples 1 to 3 within the scope of the present invention are all excellent in water resistance and electrical properties (dielectric loss tangent). On the other hand, in Comparative Example 1, which has a small content of ethyl acrylate, the effect of improving water resistance is small, and in Comparative Example 2, which has an excessively large content of ethyl acrylate, the electrical properties (dielectric loss tangent) decrease significantly (for high voltage (The dielectric loss tangent is said to be 0.1% or less). [Effects of the Invention] As explained above, according to the present invention, it is possible to realize electric wires and cables that can suppress the occurrence of water tree over a long period of time.
Claims (1)
ン化合物とをラジカル重合開始剤の存在下で共重
合してなるアクリル酸エステルの含有量が0.5〜
10重量％であるエチレン−アクリル酸エステル−
不飽和シラン化合物三元共重合体を主体として含
有する組成物の被覆層が導体若しくは半導電層の
外周に設けられ、該被覆層は架橋されていること
を特徴とする電線・ケーブル。1 The content of acrylic ester obtained by copolymerizing ethylene, acrylic ester, and unsaturated silane compound in the presence of a radical polymerization initiator is 0.5 to
10% by weight of ethylene-acrylic ester-
1. An electric wire/cable, characterized in that a coating layer of a composition mainly containing an unsaturated silane compound terpolymer is provided around the outer periphery of a conductor or semiconductive layer, and the coating layer is crosslinked.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15174884A JPS6132307A (en) | 1984-07-20 | 1984-07-20 | Wire and cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15174884A JPS6132307A (en) | 1984-07-20 | 1984-07-20 | Wire and cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6132307A JPS6132307A (en) | 1986-02-15 |
| JPH0510767B2 true JPH0510767B2 (en) | 1993-02-10 |
Family
ID=15525416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15174884A Granted JPS6132307A (en) | 1984-07-20 | 1984-07-20 | Wire and cable |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6132307A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6132308A (en) * | 1984-07-20 | 1986-02-15 | 日立電線株式会社 | Wire and cable |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5757804A (en) * | 1980-09-22 | 1982-04-07 | Kobe Steel Ltd | Production of honeycomb-shaped molding made of metal |
| JPS6132308A (en) * | 1984-07-20 | 1986-02-15 | 日立電線株式会社 | Wire and cable |
-
1984
- 1984-07-20 JP JP15174884A patent/JPS6132307A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5757804A (en) * | 1980-09-22 | 1982-04-07 | Kobe Steel Ltd | Production of honeycomb-shaped molding made of metal |
| JPS6132308A (en) * | 1984-07-20 | 1986-02-15 | 日立電線株式会社 | Wire and cable |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6132307A (en) | 1986-02-15 |
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