JPS59185648A - Composite body of ethylene group polymer composition and metal - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite of an ethylene polymer composition having excellent resistance to deterioration due to contact with metals, and specifically relates to a composite of an ethylene polymer composition in which the metal conductor is made of an ethylene polymer composition. It is a cable covered with a certain primary insulating layer, and a semiconductive ethylene polymer composition layer containing a conductive material such as carbon black is interposed between the two-dimensional metal conductor and the insulating layer, and each of these layers The cables are made of ethylene-based polymer compositions that both prevent deterioration accelerated by contact with metals.Other uses include 1) foaming agents and/or crosslinking agents containing metals with excellent deterioration resistance. 1. A foam insulation blanket coated with an ethylene-based polymer composition.

A thermally insulated metal pipe or plate that also contains powdered or fibrous metal. The surface of the sword was coated with metal. It is a composite of an ethylene polymer composition and metal that has excellent resistance to metal deterioration. The ethylene polymer composition that prevents the acceleration of deterioration due to metals contains 0.01 to 2.0 parts by weight, preferably 0.02 to 1.0 parts by weight of a phenolic antioxidant to the ethylene polymer. Chemical structural formula.

(R-8-C2H, -Coo-CH2+4C antioxidant 001-2.0 parts by weight, favorable index 0.02-1
．． This composition is characterized by consisting of 0 parts by weight of the combination, and other necessary additives are added depending on the purpose.

In the present invention, the ethylene polymer is a polymer containing ethylene as a main component, and is produced using a high-pressure method.

Including medium and low pressure method, and when there is a copolymerization component, td,,
'tJLutd, α-olefin, vinyl ester.

Selected from acrylic ester, acrylic acid 2, etc.

Furthermore, these ethylene polymers may be ones obtained by graft polymerizing organic acids or their anhydrides, if necessary.

One of the antioxidants of the present invention is commonly referred to as a phenol type antioxidant, and it is desirable that a plurality of phenol groups exist and that the phenol groups are hindered phenols. A specific antioxidant that can be combined with Kadakore is a thioether having a pentaerythritol type skeleton, and the alkyl group or unsaturated alkyl group is C10 to C2.
□ is desirable, and stearyl, lauri oleyl, etc. are practical.

As an additive for stabilizing polyolefins in the presence of metals, i.e. in contact or encapsulation,
Nhitrazone derivatives (Special Publication No. 4'l-1940),
Hydroxy-substituted benozoyl hydrazide (Special Publication No. 43-3
965. % Kosho 43-18607. Special Public Service Showa 43=z37
A technique is known in which a heterocyclic compound having two or more 6sl nitrogen atoms and a compound containing at least an amine group are used in combination with other antioxidants (Japanese Patent Publication No. 46-22574). However, the polyolefin referred to in these prior art refers to a futile effort to make polypropylene molded products, which deteriorate significantly even at temperatures around room temperature due to contact with copper, into practical use, and now 10 years have passed since then. too.

Polypropylene, which has excellent electrical properties, is rarely used as an insulating material that requires durability, such as for electric wires.

On the other hand, electric wires and cables using ethylene polymer as an insulating material have been extremely popular, and in response to recent industrial trends that demand improved heat resistance, they have been made in the high temperature range of 50 to 90 degrees Celsius.

It became necessary to solve the problem that oxidative deterioration of molded products is accelerated by contact between metals such as copper and ethylene polymers. As a countermeasure to this problem, phenolic stabilizers, sulfur, and di(orthobenzamidophenyl) disulfide are used.
Although a technique for adding seeds (Japanese Patent Publication No. 49-18461) has been disclosed, it is said that the prevention of document deterioration at high temperatures is insufficient. Additionally, US Pat.
No. 1, US Pat. No. 3,826,781, etc., all of which are techniques for selecting a hydranode-based compound as a metal deactivator. These substances have higher melting points than ethylene polymers.

It has disadvantages such as not being compatible with ethylene polymers and not being uniformly dispersed, and also decomposes when kneaded at high temperatures and generates gas, creating bubbles in the molded product, which can affect the quality of the molded product. This causes deterioration, especially the deterioration of electrical insulation properties, and since it is necessary to add about 50% of the additive, the additive itself causes an increase in energy loss under an electric field. Therefore, it is desired to develop additives that are effective even when added in small amounts.

Polyolefin has two electrical properties (contract properties).

Propylene-based polymers are widely used as molding materials due to their excellent chemical properties, but in applications that require contact with metals, especially copper, metals act catalytically and cause severe deterioration. Despite the development of many record deterioration inhibitors, it is difficult to use them in applications that come into contact with electric wires, cables, and other networks. On the other hand, compared to propylene polymers, ethylene polymers are more stable with respect to copper near room temperature, and deterioration is less likely to be accelerated by other metals. For this reason, it is widely used as an insulating material for electric wires and cables.

However, as conditions for using electric wires and cables, polyethylene insulated wires that can withstand use in high-temperature environments are now required. Moreover, even in ethylene polymers, which were conventionally thought to have little acceleration of deterioration due to metals such as copper, it has become impossible to ignore the acceleration of deterioration caused by ions of metals such as copper acting as catalysts.

The present invention not only prevents oxidative deterioration in a high-temperature atmosphere, but also makes it possible to obtain an ethylene polymer composition that does not easily deteriorate even when used at high temperatures in the presence of metal ions such as copper.

This made it possible to create a composite of this composition and metal.

The ethylene polymer composition contains 0.001 to 2.0 parts of a phenolic antioxidant per 100 parts by weight of the ethylene polymer.
parts by weight, preferably 0.02 to 1.0 parts by weight, and the chemical structure is (R-8-C2H4-COO-CH2-)4C, where R is saturated or unsaturated alkyl or cyclo It contains at least a small amount of an antioxidant selected from alkyl in an amount of 0.01 to 20 parts by weight, preferably 0.02 to 1.0 parts by weight. Even if an appropriate amount of crosslinking agent or crosslinking auxiliary agent is added to this composition depending on the intended use, the effect will not be inhibited.

In the case where a semiconductive ethylene polymer composition mixed with a conductive agent such as a conductive carbon blank is interposed between the metal used as a trench electrical conductor, the insulator, and the ethylene polymer molded article used, The heat resistance of the semiconductive ethylene polymer composition can also be improved by containing the combination of the two oxidation stabilizers that are excellent in preventing deterioration caused by metal ions as disclosed in the present invention. The combination of the stabilizers of the present invention is also effective in other uses such as adhesives and electromagnetic shielding materials used in contact with metal surfaces.

The next thing to note is that the combination of an ethylene polymer and a phenolic antioxidant, or an ethylene polymer and an antioxidant whose chemical structural formula is (R, -8-C2H4-CoO-CH2-), is C. Compositions consisting of the combination are known and also known for their antioxidant effect. However, it is completely inadequate in its ability to prevent accelerated deterioration caused by contact with metals or the inclusion of metal ions. (See Comparative Example)-1: Combinations of each of these antioxidants and other antioxidants are also ineffective in promoting metal-induced deterioration.

However, in the case of a combination of a phenolic antioxidant and an antioxidant whose chemical structural formula is (R-5-C2H4-COO-CH2÷4C) as in the composition constituting the present invention, it is clear from the results of the examples that Thus, we have discovered the existence of a synergistic effect that effectively suppresses deterioration even in contact with metals and in the presence of metal ions, and significantly prolongs the time for signs of deterioration to appear, and has thus arrived at the present invention.

These antioxidants combined in the present invention are:
The amount added is 0.01 to 2.0 parts by weight, preferably 0.02 to 1.0 parts by weight. Both are 0.
0.01 parts by weight or less, the synergistic effect is not clear, and 2.
On the other hand, when 0 part by weight or more is added, the rate of improvement in metal damage deterioration resistance is small.

Other adverse effects 2 For example, leaching of antioxidants onto the surface.

This is due to the appearance of suppression of the reaction of the crosslinking agent, increase in dielectric loss, etc.

The typical effects of the present invention will be explained below using Examples and Comparative Examples. To prepare the samples shown in Table 1, first, a predetermined amount of polyethylene was melted and kneaded using two kneading rolls kept at 120°C, and a predetermined amount of each antioxidant shown in Table 1 was added thereto.
Knead for a minute to uniformly disperse and then form into a sheet. In the case of Examples 3 and 4 in which dicumyl peroxide is blended as a crosslinking agent, dicumyl peroxide is mixed following the above-mentioned kneading for 15 minutes, and after kneading for an additional 3 minutes, a sheet is formed. Next, this sheet was heated to 180°C for 15 minutes using a mold.
Pressure molding was carried out for 1 minute to obtain a sheet with a thickness of 1. The sheet obtained by these operations is punched out using a punching cutter to obtain a disk-shaped specimen with a diameter of 40 holes. Using this specimen, a deterioration test using copper ions, which has a remarkable deterioration reaction even among metals, will be conducted. The method involved placing the specimen on fresh copper foil and placing it in a constant temperature bath with air circulation at 150°C to accelerate deterioration, and measuring the time it took for brown spots to appear. judge. This determination method is an extremely sensitive measuring method that can detect signs of deterioration at a time when no signs of deterioration are observed using various mechanical measuring methods. What is the deterioration symptom onset time in Table 1?

This refers to the time until the brown spots are clearly recognized. As an electric wire/cable insulator that comes into direct contact with copper conductors,
In the accelerated deterioration test described above, those with no discoloration or spotting for 72 hours or more were judged to have passed. The use of copper as a metal is not only because it significantly accelerates deterioration, but also because it is often used as an electrical conductor and as a building material in contact with ethylene polymers.

From the results in Table 1, phenolic antioxidants.

Amine antioxidant, quinoline antioxidant.

The antioxidants represented by the chemical formulas % and %) are all compounded in the prior art using only single substances, and have insufficient resistance to deterioration from metal damage such as mountains and copper (see Comparative Examples 1.23 and 4). ) is a combination of a phenolic antioxidant and an antioxidant having a structure of (C to R-8-C2H4-COO-CH2) (see Examples 1.2.3 and 4), copper, etc. It has remarkable resistance to metal damage deterioration.In this case, dicumyl oxide may be added as a crosslinking agent, or a different type of phenolic antioxidant may be used. I understand what happened.

However, combinations of phenolic antioxidants and amine-based or quinoline-based antioxidants, as well as combinations of antioxidants with the chemical structure formula % and amine-based or quinoline-based antioxidants, are both copper-based. There is no effect of suppressing the acceleration of deterioration caused by metals such as metals.

As described above, the ethylene polymer composition disclosed in the present invention has extremely excellent resistance to metal damage and deterioration, so it can be used as a composite that comes into direct contact with metals.

Dog is effective in suppressing deterioration even when used at relatively high temperatures, and its utility value is dog.

The specific uses of the present invention will be easily understood from the above description, but a summary thereof will be listed below.

1) Electric wires and cables that have a structure in which an ethylene polymer composition is in direct contact with a metal conductor. (Low voltage cables, communication cables, etc.) 2) High voltage cables that are electric wires and cables and have a structure in which a semiconductive ethylene polymer composition is in contact with a metal conductor, and semiconductive crosslinked ethylene polymer compositions. A high-voltage cable that comes in contact with a metal conductor.

3) Cross-linked and/or foamed ethylene polymer moldings and related parts for thermal energy-related equipment, which primarily function as heat insulating materials for steel pipes, copper plates, etc.

4) A construction material that is a laminated composite material of copper plates, etc. and ethylene polymer.

5) 7.Ujinda for electronics, electrical products, etc.

A semiconductive ethylene polymer composition, a metallized ethylene polymer sheet, a composite of metal foil and an ethylene polymer adhesive, a composite of a magnetic material and an ethylene polymer, is applied to the front or back surface of the substrate. What you have.

What is important about the above-mentioned composites of ethylene polymer and metal is that they are often exposed to high temperatures.

The point is that it is required to withstand acceleration of oxidative deterioration caused by metals.

Patent applicant: Nippon Unicar Co., Ltd.

Claims (1)

[Claims] 1. A composite of an ethylene polymer composition and a metal that has excellent resistance to deterioration due to contact with metal, wherein the ethylene polymer composition contains 100 parts by weight of the ethylene polymer. In contrast, phenolic antioxidant o, oi ~ 2.0
It is characterized by containing 0.01 to 2.0 parts by weight of an antioxidant having the structure of the general formula (% by weight), and may also contain other additives. Composite of ethylene polymer composition and metal. 2. The metal is an electrical conductor such as copper, and the ethylene polymer composition is an electrical insulator mainly composed of polyethylene or an ethylene-α olefin copolymer. A composite of the ethylene polymer composition according to claim 1 and a metal. 3. The metal is an electrical conductor such as copper, and the ethylene polymer composition is an electrical insulator mainly composed of crosslinkable polyethylene or ethylene-α-olefin copolymer. A composite of the ethylene polymer composition according to claim 1 and a metal. 4 The metal is an electrical conductor such as copper, the ethylene polymer composition is polyethylene containing conductive carbon black as an additive, ethylene-α olefin copolymer, ethylene vinyl ester copolymer, ethylene-acrylic acid It consists of at least a semiconductive layer containing an ester copolymer layer/and an ethylene-acrylic acid copolymer as main components, and an electrically insulating layer as described in claim 2.3. A composite of the ethylene polymer composition according to claim 1 and a metal. 5. The metal is a plate or pipe, and the additives of the ethylene polymer composition are a blowing agent and/or a crosslinking agent. A composite of the ethylene polymer composition according to claim 1 and a metal. 6. The metal is in the form of powder, fine particles, or fibers and is preferably dispersed in the ethylene polymer. A composite of the ethylene polymer composition according to claim 1 and a metal. 7. The metal is in the form of a fibrous fabric, a cloak, or a felt, and is embedded in a molded article made of an ethylene polymer composition or laminated with a folded piece. A composite of an ethylene polymer and a metal according to claim 1. 8 Metal is vacuum-deposited, plated, or adhered in the form of a foil to the surface of the molded article of the ethylene polymer composition. A composite of an ethylene polymer and a metal according to claim 1.