JPH01144509A - Electric wire/cable - Google Patents

Abstract

PURPOSE:To prevent bow-tie tree from occurring and to obtain electric wires and cables excellent in resistance against both bow-tie tree and heat-aging by forming a cover layer made by a resin composition containing a specified amount of phosphor-based anti-oxidation agent with its fundamental frame being triphenyl phosphatide relative to a specified amount of polyolefine on the circumference of a conductor and by cross-linking the cover layer. CONSTITUTION:A cover layer of a resin composition is formed on a conductor, with the composition made of 100 weight parts of polyolefine containing phosphor-based antioxidation agent with its fundamental frame being triphenyl phosphatide by the amounts of 0.05-3weight parts. The coverlayer is further heated and cross-linked so that a cable or wire having excellent resistances against both bow-tie tree and heat-aging with the circumference of the wire covered with an electric insulation layer either directly or with an intermediate semiconductor layer interposed in between, with the cover layer of polyolefine containing an antioxidation agent and a cross-linking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to electric wires and cables that can suppress the occurrence of bow tie tree and have excellent heat resistance.

[Prior Art] Polyolefin, especially so-called cross-linked polyethylene, which is made by cross-linking polyethylene, is widely used as an insulating material for electric wires and cables because of its excellent electrical insulation and heat resistance. It is recognized that when used in wet or wet conditions, insulation may deteriorate due to water treeing. Therefore, in order to improve the reliability of electric wires and cables, a major issue is how to suppress the occurrence of water trees and bow trees.

On the other hand, it is common to add antioxidants to crosslinked polyolefins to prevent heat aging;
, 4'-thiobis(6-t-butyl-3-methylphenol) is frequently used.

[Problems to be solved by the invention] However, 4,4'-thiobis(6-t-butyl-
Although 3-methylphenol (3-methylphenol) has poor compatibility with polyolefins, it is usually added at least 0.2 parts by weight per 100 parts by weight of polyolefins to maintain heat resistance, and its melting point is 161'C. Because of the high compatibility, there is a concern that the amount exceeding the compatibility limit will bloom and become the core of bow tite tree.

The present invention has been made based on the above, and aims to provide electric wires and cables that are excellent in both bow tie resistance and heat aging resistance.

[Summary of the Invention] The electric wire/cable of the present invention has a coating made of a resin composition containing 0.05 to 3 parts by weight of a phosphorous antioxidant having triphenylphosphite as its basic skeleton, based on 100 parts by weight of polyolefin. It is characterized in that a layer is formed around the outer periphery of the conductor and is crosslinked.

In the present invention, polyolefins include polyethylenes such as low-density polyethylene and medium-density polyethylene;
Examples include ethylene copolymers containing ethylene in the majority, such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, which can be used alone or in combination of two or more. Can be used together.

The phosphorus-based antioxidant having triphenylphosphite as its basic skeleton, which is added to the polyolefin, is represented by the following structural formula.

(R1, R2 are H or C, H, .) It has been found that by using such an antioxidant, both the bow tie resistance and the heat aging resistance are significantly improved.

Specific examples include tris (mixed mono and di-nonylphenyl) phosphite, tris nonylphenyl phosphite, triphenyl phosphite, and the like.

The phosphorus antioxidant having triphenylphosphite as its basic skeleton is 0.0% per 100 parts by weight of polyolefin.
It is necessary to add in the range of 0.05 to 3 parts by weight, and 0.05
If it is less than 3 parts by weight, heat aging resistance is insufficiently imparted, and if it exceeds 3 parts by weight, the bow tie resistance is reduced due to bloom.

In the present invention, it is possible to use one type or a combination of two or more of the above antioxidants and phenolic antioxidants. As a phenolic antioxidant,
Pentaerythrityl-tetrakis [3-(3,5-di-
t-butyl-4-hydroxyphenyl)propione)
], ]2-thiodiethylenebis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionate, 3,9-bis-[2-(3-(3-t-butyl-4-hydroxy-5
-methylphenyl)propionyloxy) -1,1-dimethylethyl]-2,4,8,to-tetraoxaspiro(5,5)andecane.

The crosslinking was carried out using dicumyl peroxide, 1,3-bis-(t
-butyl peroxy-isopropyl)benzene, 2,
It is common to carry out thermal crosslinking using a peroxide typified by 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3. Other methods include silane water crosslinking, in which an organic silane such as vinyltriethoxysilane is grafted onto a polymer and then brought into contact with water in the presence of a silanol condensation catalyst, or crosslinking by irradiation with ionizing radiation such as electron beams. .

A resin composition containing a polyolefin, the above-mentioned antioxidant, and a crosslinking agent is coated on the outer periphery of a conductor directly or via a semiconductive layer and then crosslinked to form an electrically insulating layer. In the present invention, in addition to the above-mentioned components, a lubricant, a coloring agent, a filler, a crosslinking accelerator, etc. may be added as necessary.

[Examples of the Invention] The components shown on each side of Table 1 were kneaded using hot rolls at 120°C to form a sheet, and then pelletized. This pellet was introduced into an extruder and placed on a copper conductor with an outer diameter of 3 mm to a thickness of 0.5 mm.
The wire was extruded and coated with a polyethylene semiconductive layer of 2 mm thick to a thickness of 2 mm, and then crosslinked in a dry crosslinking tube using nitrogen gas as a heating medium to produce an insulated wire.

The produced insulated wires were evaluated for bow tie resistance, heat aging resistance, and bloom, and the results are shown in the lower column of Table 1. In addition, the evaluation was performed based on the following.

Bow tie resistance: An insulated wire was immersed in water at 90° C., and an AC voltage of 3 kV and 50 Hz was applied between the conductor and water for 500 days. After the electrification was completed, the sample was sliced, boiled and stained with a methylene blue aqueous solution, and the number of pockmarks (0.2 mm or more) generated was examined using an optical microscope.

Heat aging resistance: A tube-shaped insulator obtained by removing the conductor from an insulated wire was punched into the shape of a No. 3 dumbbell, and heated in an aging tester at 150°C. The number of days until brown spots appear on the sample (aging limit) was measured.

Bloom: Pellets before wire production are placed in a constant temperature bath at 80℃.
After holding for 0 days, the surface was observed and evaluated.

As is clear from Table 1, Example 1 within the scope of the present invention
-5 has excellent bow tie resistance and heat aging resistance, and no blooming occurs. Comparative Example 1 is a case in which no antioxidant is used, and Comparative Example 2 is a case in which the content of antioxidant is less than the prescribed value of the present invention, and both have poor heat aging resistance. Comparative Example 3 is a case where the content of the antioxidant exceeds the specified value of the present invention, and Comparative Example 4 is a case where a conventional antioxidant is used, and in both cases, blooming occurs and the occurrence of bow tree is also significant.

[Effects of the Invention] As is clear from the above description, according to the present invention, it is possible to realize electric wires and cables with excellent bow tie resistance and heat aging resistance.

Claims (1)

[Claims] (1) A coating layer made of a resin composition containing 0.05 to 3 parts by weight of a phosphorous antioxidant having a basic skeleton of triphenylphosphite based on 100 parts by weight of polyolefin is formed on the outer periphery of the conductor. An electric wire/cable characterized in that the layers are cross-linked.