JPS62165807A - Resin-covered wire cable - 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 [Industrial Field of Application] The present invention is directed to a method of manufacturing a 4-methyl-1-pentene copolymer coated with a specific 4-methyl-1-pentene copolymer which has excellent cold flow resistance and crack resistance.
! , related to wires and cables.

[Conventional technology]

Wires and cables coated with 4-methyl-1-pentene polymers or copolymers have already been patented in British Patent No.
No. 074241. , 4-methyl-
1-pentene polymer.

Because of its high melting point, it is suitable as a bean resin for coating electric wires and cables that are used at high temperatures or in areas that may be exposed to high temperatures.

However, the 4-
Electric wires coated with methyl-1-pentene polymer or copolymer have heat resistance of 1 and bending strength.

The impact resistance strength was not satisfactory, and it was also insufficient for industrial production.

As a resin liquid wits/cable that has improved this drawback, we have developed an electric wire coated with a random copolymer of 4-methyl-1-pentene and 1-olefin having 16 to 22 carbon atoms.
The applicant had previously applied for the cable (Japanese Patent Laid-Open No. 11/1989).
Publication No. 0085 However, for applications that are used under extremely high temperatures, such as oil well exploration cables, the intrinsic viscosity [η] specified therein is 2.3 d (1/g). It has been found that the cracking resistance may be insufficient depending on the application.

[Problem that the invention seeks to solve]

In view of this situation, the present inventor conducted various studies to develop a resin for covering electric wires that does not cause cold flow even under high temperatures and has excellent crack resistance.
] It was found that a random copolymer of 4-methyl-1-pentene and an α-olefin having 12 to 22 carbon atoms has the above characteristics, and the present invention was completed.

[Means for solving problems]

That is, 1 the present invention has an intrinsic viscosity [η] of 2.5 to s,
Cold flow resistance characterized by being coated with a 4-methyl-1-pentene random copolymer having oaff/g and a content of α-olefin having 12 to 22 carbon atoms in the range of 1 to 20% by weight. The present invention provides resin-coated electric wires and cables with excellent crack resistance and shock resistance.

[For production]

The 4-methyl-1-pentene random copolymer used in the present invention has an intrinsic viscosity [η] of decalin solvent at 135°C.
is 2.5 to 5.0 dl/g, preferably 2nia to 4.3 J/g, and the content of α-olefin having 12 to 22 carbon atoms is 1 to 20% by weight, preferably 272
It is a 4-methyl-1-pentene random copolymer in the range of 18% by weight, and has a content of 1% by weight (usually 1% by weight) 70-1/-
) (MAR: load 5kQ, temperature 260℃) is 1 to 20 g/10 win, preferably 2 to 15 g
/ 10mln, normal melting point ('ASTM D 3418
) is a crystalline resin with a temperature of 200°C or higher.

Those with an intrinsic viscosity [η] of 2.5 a5/g5/ have poor cold flow resistance, crack resistance, and impact resistance, while those exceeding 5.04117 g have too high a melt viscosity and cannot be used as copper wire, etc. Extrusion coating cannot be performed and N-covered electric wires cannot be obtained.

In addition, those whose intrinsic viscosity [η] is within the above range are usually 50 to 250 m/m at the normal molding temperature of 260 to 300°C.
min, preferably a molding speed of 100 to 2QOm/min, when the conductor described below is extruded and coated with a surface roughness of 0.0.
It also has the characteristic of being roughened in the range of 5 to 1 am.

A copolymer with an olefin having less than 12 carbon atoms has poor crack resistance and impact resistance, and when the number of carbon atoms exceeds 22, it is not only difficult to produce the copolymer, but also the melting point of the copolymer is poor. This is not preferable because it lowers the oil resistance and has poor oil resistance. If the content of α-olefin having 12 to 22 carbon atoms is less than 1 mol%, crack resistance and S impact resistance will not be improved, and 2
If it exceeds 0% by weight, the cold flow resistance will be poor, the melting point will be low, and the oil resistance will be poor. Carbon number is 12 to 2
Specifically, the α-olefin in No. 2 is 1-dodecene.

These include 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-dofusene.

These α-olefins may be used alone or as a mixture of two or more.

Random copolymers used in the present invention include: 1. Heat-resistant stabilizers, weather-resistant stabilizers, lubricants, copper damage-resistant stabilizers, antifogging agents, etc., to the extent that the purpose of the present invention is not impaired; 1. Usually added to polyolefins. Compounding agents may be added.

The method for coating electric wires and cables with the random copolymer is a known method 9, such as polychlorination using a wire coating device consisting of a wire feeder, an extruder, a cross-layer die, a cooling water tank, a pulling device, a winding device, etc. vinyl.

This is carried out in a manner similar to the coating method using conventional thermoplastic resins such as polyethylene.

The resin-coated tR cable of the present invention has the above-mentioned 4-methyl-1
- The pentene random copolymer can be used in steel, copper alloys such as silver-containing copper, chromium copper, zirconium steel and tin-containing copper,
- Aluminum, No. 1 aluminum alloy - A conductor such as aluminum-covered steel wire coated as an insulating material. The thickness of the resin coating is usually in the range of 0.5 to 2 Qmm. Also, the surface of the resin coating material becomes rough.

Preferable surface roughness meter (Koita Labora) 'l-Todoroki 5E
-3A, RJ 27 type) surface roughness measured with 0.05
Roughening in the range of ~4 mm is preferable because when the coated conductors are bundled to form a cable, the coated conductors will not be misaligned with each other and/or the coated conductors with an intervening material such as cotton, cloth, jute, etc.

〔Effect of the invention〕

Electric wires and cables coated with the 4-methyl-1-pentene random copolymer of the present invention have better cold flow resistance, crack resistance, and impact resistance than conventional resin-coated electric wires, and have low NvD resistance. Since the surface of the oil is appropriately roughened, it can be firmly fixed without twisting when multiple coated S7P cables are bundled together to form a cable, making it ideal for oil wells used under high temperatures. Suitable for test drilling cables, video cables, and communication cables.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way unless the gist of the invention is exceeded.

Example 1 Intrinsic viscosity (77): 6.5d6/g1MFR: 0
．． 4-methyl-1-pentene random copolymer powder (hereinafter referred to as M Omitted) 1
00 parts by weight of two volatile heat-resistant stabilizers (trade name: Irganox 1010, manufactured by Musashino Geigy Co., Ltd., and trade name: Sandstub P-KPQ, manufactured by Sandoz Co., Ltd.) and zinc stearate.
．． 02.0.01 and 0.003 parts by weight of H were mixed in a Henschel mixer, and then melt-kneaded and extruded in a 6Q mmφj1i axial extrusion chamber (molding temperature 260°C) to obtain Sample-1. Next, sample-1 was put into a 65 mmφ extruder and a diameter of 2.10 mm.
A resin-coated electric wire with a coating thickness Q of 5 mm and a surface roughness of 0.25 mm is made by coating a copper wire with an outer diameter of 0.2 mmφ using a wire-coated N forming machine equipped with a radiator for a φ solid cross. I got it. Intrinsic viscosity [η
] was 3.61/g and MFR was 4 g/10 mtn. Next, the low-temperature cracking resistance of the resin-coated wire was measured by the following method: Low-humidity crack test: A 2 m long resin coating was placed on one end of the wire (2 kq-1) in an o'c atmosphere.
Kq and 0.5 nig) are tied together, passed through an iron pulley with a diameter of 60 holes, and the other end is moved up and down for 1 m to measure the number of times (one reciprocating movement) until cracks occur in the coating resin. did.

In addition, in order to separately evaluate cold-flow properties and impact resistance, an injection molding machine with a mold clamping pressure of 100 tons (molding temperature 2
Izot impact test pieces (thickness 178 inches, no notch) and 12c1HX having the same intrinsic viscosity [η] and MFR as N resin-r from sample-1 (80°C) and 12c1HX
12CMX 8mm square plate for compression test is molded, ■〕J
I performed the test below.

High temperature compression test (cold resistance 70 - resistance): A rectangular parallelepiped made of iron with a tip shape of 5 mm x 5 mm was placed on a square plate in an air chamber at 170°C, a load was applied to the rectangular parallelepiped, a compression test was performed, and Young's modulus and compressive yield point stress were measured. Measure cold 7
It was used as a measure of 0-ness.

In other words, pressure! ? 4. The larger the yield point stress, the better the cold flow resistance.

Isot impact test: As'1゛MD 256 results are shown in Table 11.

Example 2 Instead of Sample-1 used in Example 1, Sample-2 obtained by melt-kneading and extrusion using the single-screw extruder of Example PI at 280'C was used. The process was carried out in the same manner as in Example 1, and the limiting viscosity "η" of the target fat-■ was 2.9'dd/g.
A resin-coated electric wire with an MFR of 10 g/10 mtn and a surface roughness of 0.15 mm was obtained. The results are shown in Table 1.

Example 3 Instead of MPR-1 used in Example 1, intrinsic viscosity [7
71' 6.7i/g-MFR: 0.4g/IQmi
n and 1-dodecene/1-tetradecene = 50150
(weight ratio) of 4-methyl-1-pentene random containing 5% by weight of mixed α-olefin, 1/14 (MpR
-2) except rJ was carried out in the same manner as in Example 1, and the limiting viscosity [η] of the coating layer resin-i [1] was 3.4 dd/g.

MFR is 5g/10m1n and surface roughness is 0-23mm
A resin-coated electric wire was obtained. The results are shown in Table 1.

Example 4 Intrinsic viscosity C7) instead of MPR-1 used in Example 2
)' 6.5de/g, MFR: 0.5g/10
a+in and 1-dodecene/1-tetradecene = 501
4-methyl-1-pentene random copolymer K (MF
The process was carried out in the same manner as in Example 2 except that R-3) was used, and the limiting viscosity of the coating resin
A resin-coated electric wire having an IQmin and a surface roughness of 0 to 25 mm was obtained. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that Sample-5 obtained by melt-kneading and extrusion using the single-screw extruder of Example 1 at 320°C was used in place of Sample-1 used in Example 1. The same procedure was carried out, and the limiting viscosity [η] of coating resin-V was 2.3 ag/g, MF
R is 28g/10m1n and surface roughness is Q, 31mm
A resin-coated N electric wire was obtained. The results are shown in Table 1.

Comparative Example 2 Instead of MPR-i used in Example 1, @limiting viscosity Cη
): 6.5J'/g, MPR: 3.5g/10
4-methyl- containing m1n and 1-decene
The procedure was carried out in the same manner as in Example 1 except that 1-pentene random copolymer (MPR-4) was used, and the intrinsic viscosity [η] of the coating resin -① was 3.4 de/g, and the MFR was 5 g/10 m1n.
A resin-coated electric wire with a surface roughness of 0.20 ml was obtained.

The results are shown in Table 1.

Comparative example 3

Claims (1)

[Claims] (1) The intrinsic viscosity [η] is 2.5 to 5.0 dl/g and the content of α-olefin having 12 to 22 carbon atoms is 1
A resin-coated electric wire/cable characterized by being coated with a 4-methyl-1-pentene random copolymer in a range of 20% by weight.