JPS604A - Insulated wire - 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 an insulated wire useful as a heat-resistant flexible wire having a specific fluorine-containing elastomer coating layer.

Fluorine-containing elastomer copolymers, especially copolymers of propylene and tetrafluoroethylene, have excellent heat resistance, oil resistance, and chemical resistance, and have low electrical insulation properties, making them useful as insulating materials for electric wires. It is also a material with high IIIJ retention.

The present inventors have made various studies on the application of a copolymer of propylene and tetraful A-L tyrene to electric wire coatings, but such baton bodies have poor extrudability, and in order to improve this, Practical use has been achieved by lowering the molecular weight.

However, we discovered a new problem: lowering the molecular weight reduces the toughness of the coating layer, which limits its use in some applications.

The present invention is based on the above, and aims to provide an insulated wire that is excellent in production efficiency J'3 and appearance by using white clay as the extrusion 1, and also has toughness.

That is, the insulated wire of the present invention has a number average molecular weight of 20,000 to 20,000.
70,000, and forming an extrusion coating layer of an elastomer composition containing a copolymer of propylene, tetrafluoroethylene, and glycidyl vinyl ether on the circumference of the body,
And the coating layer is crosslinked to give MI#/&.

In the present invention, it is important to use a material having a number average molecular weight of 20,000 to 70,000, preferably 30,000 to 50,000. If the number average molecular weight is too large, cracks are likely to occur in the coating layer, and the surface smoothness of the coating layer will be lost. If the number average molecular weight is too small, the toughness of the crosslinked coating layer will be lost.

In the present invention, the method for producing a copolymer having a number average molecular weight within the preferred range described above is not particularly limited. Although it is possible to directly adjust the molecular weight of the polymer produced by controlling the copolymerization reaction conditions such as the degree of polymerization and the use of a chain transfer agent, it is also possible to directly adjust the molecular weight of the polymer produced during the copolymerization reaction. It is also possible to easily employ a method in which a polymer is produced and then heated in the presence of oxygen to reduce the molecular weight.

The number average molecule M of a copolymer can be measured by the osmotic pressure method, but for relative comparison between copolymers with the same structure, a value converted from the measured value of intrinsic viscosity can be used, and it can be calculated using the following formula. The number average molecule jJ Mn can be calculated from the intrinsic viscosity [η] (cL&/g) measured in Te1-rahydrofuran at 30°C.

Mn = [77 co”' 4N rack without compromising chemical properties etc.
The reaction can be significantly slowed down, thereby ensuring sufficient toughness even when the number average molecular weight of the copolymer is reduced.

The molar ratio of propylene/tetrafluoro-1-dylene is 5/95 to 70/30. Preferably 10/90~
It is preferable to select from the range of 55/45 from the viewpoint of heat resistance, extrusion moldability, etc.

It is preferable to contain glycidyl vinyl ether in an amount of 0.1 to 10 mol%, preferably 2 to 5 mol%.
If the amount of 1 is too little, the toughness will be lost, and if it is too much, the heat aging resistance will be impaired.

In addition to the main components of propylene, difluoroethylene, and glycidyl vinyl ether, there are also components copolymerizable with these, such as ethylene, isobutylene, vinyl fluoride, vinylidene trifluoride, propylene hexafluoride, and fluoropropylene.
Even if vinyl ether, al:dolvinyl ether, chlorotrifluoroethylene, etc. are not included, k <
It is preferable that the content of these is selected from a range of 15 mol% or less.

The copolymer thus obtained is introduced into an extruder alone or together with other ingredients, extruded and coated on the outer periphery of the conductor, and then crosslinked.

As the crosslinking means, chemical means using organic peroxides, amines, etc., crosslinking by irradiation with ionizing radiation such as gamma rays or electron beams, etc. can be employed, and there is no particular limitation.

Among them, combinations with hydroxy compounds containing one or more -01-1 groups in the molecule, such as tertiary amines or salts thereof, tertiary amines or salts thereof, which react with glycidyl vinyl ether and increase the crosslinking rate. ``A scented polyamide or its salt can be preferably used.

Examples of tertiary amines include hexyl benzoate, benzyldimethylamine, α-malebenzene dimethylamine, dimedylaminomethylphenol, tris(dimethylaminomethyl)phenol, diethylaminopropylamine, N-amine ethyl Piperazine, ethylmethylimidazole, triethylenediamine, N, N=-bis(alkyl)piperazine, 4,4'-1-rimethylenediviridine, 2,3-bis(2-pyridyl)-5,6-cyhydrovirazine, N Examples include -ethylmorboline, 1°8-diaza-bicyclo(5,4,O)lambrene-7 and salts thereof.

Hydroxy compounds used in combination with tertiary amines include octatool, cyclohexanol, phenol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, hydroquinone, catechol, resorcinol, 2,2--
Bis(4-hydroxyphenyl)propane (bisphenol A), 1, . 3.5-1-lihyde [1-xybenzene, dihydroxyno-phthalene, 4,4-dihydroxydiphenyl, 4,4'-dihydroxystilbene, 2°2'-bis<4-hydroxyphenyl)butane (bisphenol B), 2.4-dihydroxybenzophenone,
Examples include 2,4-dihydroxybenzoic acid, 4,4'-diaminodiphenylsulfone, 2-methylresorcinol, trimethylolallyloxyphenol, and tris(4-hydroxyphenyl)methane.

Examples of aromatic polyamines include xylylene diamine, metaphenylene diamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

Ingredients other than those listed above may include polyvinylisone fluoride, fluororesins such as vinylidene fluoride-hexafluoropropene copolymer, carbon black such as MT carbon, magnesium silicate, etc., to the extent that the properties are not degraded by one micron.
White fillers such as calcium carbonate may be added, and additives, processing aids, stabilizers such as metal oxides, etc. may also be added.

Various components including the copolymer are uniformly mixed using a Banbury mixer, rolls, etc., and then introduced into the extruder as a crosslinkable elastomer composition.

Mouni viscosity ML+ 10, s (100°
C) is preferably 10 to 1001, especially 20 to 60, from the viewpoint of extrusion moldability, surface condition of the coating layer, etc.

Examples of the present invention will be described below along with comparative examples.

As shown in Table 1, pyrene/tetrafluoroethylene/glycidyl vinylconyl copolymers 1 with different glycidyl vinyl ether contents and number average molecules m
A predetermined amount of a crosslinking agent and a filler were added to 00 parts by weight and kneaded for 15 minutes using an 8-inch roll kept at a temperature of 50 to 60°C to obtain a crosslinkable Elas 1 to 72 composition. .

Head: 100°C, cylinder 1:10
Using a 40mmφ extruder (L/D=22) set at 0'C and cylinder 2 and 80℃, it was coated to a thickness of 1 mm on a tin-plated copper single wire with an outer diameter of 1.6+++m, and then heated at 13 atm. The wire was held in water vapor (190° C.) for 3 minutes to crosslink and tighten to obtain a crosslinked insulated wire.

Table 1: Data on the appearance (surface smoothness) and toughness (tensile strength) of the electrically insulated JSI prepared with a propylene/tetrafluoroethylene ratio of -45155 are shown in Table 2.

As is clear from Table 2, Examples 1 to 5 within the scope of the present invention achieved a score of 1 in both the appearance and toughness of the insulated wire.

On the other hand, in Comparative Example 1, in which the number average molecular jjl is below the range of the present invention, there is almost no improvement in toughness, and in Comparative Example 2, in which the number average molecular jjl is above the range of the present invention, cracks occur on the surface and the appearance deteriorates. suddenly stops.

In addition, Comparative Example 3, which does not contain glycidyl vinyl ether,
No. 4 has a good appearance but poor toughness.

As explained above, the insulated wire of the present invention is made of propylene tetrafluor 7 having a number average molecular weight in the range of 20,000 to 70,000.
A coating layer is provided by crosslinking a composition having 8% of the IJ soil glycidyl vinyl vinyl copolymer, and thereby the original 9% of the propylene/detrafluoroethylene copolymer is This makes it possible to modify the toughness of the coating layer without impairing its properties, further expanding the scope of use of the 114 thermoplastic insulated wire.

Claims (3)

[Claims] (1) The number average molecular weight is in the range of 20,000 to 70,000, and is a combination of propylene, tetrafluoroethylene, and glycidyl vinyl ether! : An insulated wire characterized in that an extruded coating layer of an elastomer composition containing a polymer is formed on the circumference of a conductor, and the coating layer is crosslinked. (2) A patent characterized in that the molar ratio of propylene/tetrafluoroethylene in the copolymer is 5/95 to 70/30, and glycidyl vinyl ether is contained in an amount of 0.1 to 10°E. An insulated wire according to claim 1. (3) Claim 1 or 2 is characterized in that it is crosslinked in the presence of a tertiary amine or a salt thereof.
Insulated wire as described in section. The insulated wire according to claim 1 or 2, wherein the aromatic polyamine or Iζ is crosslinked in the presence of a salt thereof.