JPS58163108A - Method of producing magnet 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 improved method for manufacturing magnet wire by extrusion.

The method of manufacturing a magnet wire according to the present invention is extremely effective in solving the various drawbacks described below.

Currently, magnet wires are manufactured by using an insulating paint made by dissolving a polymer or prepolymer in an organic solvent, applying this to a conductor by squeezing it with a die or felt, and baking it in a baking oven, which is repeated several times. This method uses large amounts of highly toxic organic solvents, so
It causes air pollution, creating a poor working environment, has poor energy efficiency, and cannot be manufactured at high speed due to solvent removal and curing.

Recently, the extrusion method has attracted attention as a method for manufacturing magnet wire that does not require any solvent and can be produced at a manufacturing speed of several hundred meters.
Applications have been proposed for various thermoplastic resins.

However, magnet wires made by extrusion and simply coated with thermoplastic resin are inferior in heat resistance, such as deterioration resistance and overload resistance.

In this regard, the present inventors have proposed a method in which a thin film of a condensed thermoplastic resin composition is applied by extrusion and then crosslinked by irradiation with ionizing radiation. According to this method, the heat resistance of extruded magnet wire is greatly improved and reaches the level of conventional polyester wire.

Furthermore, magnet wires obtained by conventionally proposed extrusion methods are significantly inferior in mechanical properties, such as surface hardness and abrasion resistance, when compared with ordinary magnet wires.

A method in which a thin film of a condensed thermoplastic resin composition is applied by extrusion and then crosslinked by irradiation with ionizing radiation improves the mechanical properties slightly, but it is still insufficient. In particular, recently there has been a trend towards speeding up the winding process, and there is an extremely strong demand for improved resistance to processing deterioration. Therefore, it is presumed that magnet wires produced by extrusion, which have poor surface hardness and wear resistance, suffer from severe processing deterioration during the winding process and cannot withstand use.

The present inventors have arrived at the present invention as a result of intensive studies on the resistance to processing deterioration, which is a major drawback of the extrusion method for producing magnet wire. That is, the present invention involves applying a thin film of a composition containing a condensed thermoplastic resin as a main component by an extrusion method, applying a compound that is irradiated and cured by ionizing radiation or ultraviolet rays to a thickness of 10 μm or less, and then irradiating the composition with ionizing radiation or ultraviolet rays. This manufacturing method is characterized by the following.

By using the manufacturing method of the present invention, the processing deterioration resistance of a magnet wire coated with a thin film of a composition mainly composed of a condensed thermoplastic resin by an extrusion method is greatly improved, and becomes almost equivalent to that of ordinary polyester wire. .

Furthermore, when polyester resin is used in a composition whose main component is a condensed thermoplastic resin, it is possible to prevent the occurrence of crazing, which is minute cracks that occur due to stretching or bending, which is a drawback of polyester magnet wires. can.

In the present invention, it is important to apply a compound that is irradiated and cured by ionizing radiation or ultraviolet rays to a thickness of 10 μm or less. In the present invention, a compound that is irradiated and cured by ionizing radiation or ultraviolet rays is used to improve the processing deterioration resistance, that is, the mechanical strength, of magnet wires coated with a thin film of a composition mainly composed of thermoplastic resin by extrusion. Since this is the main purpose, higher surface hardness is preferred. Generally, in order to harden a compound that is irradiated and cured by ionizing radiation or ultraviolet rays, it is necessary to increase the crosslinking density. In this case, as the crosslinking density increases, the hardness increases, but curing shrinkage increases and flexibility and adhesion tend to deteriorate. Also in the present invention, if a compound that is irradiated and cured by ionizing radiation or ultraviolet rays is applied thickly to a thickness of 10 μm or more, the adhesion and flexibility will deteriorate. However, surprisingly, when the coating thickness is 10μ or less, both adhesion and flexibility can satisfy the required characteristics of the magnet wire, and even with such a thin coating thickness, it is possible to use a composition whose main component is a thermoplastic resin. It has been found that the process deterioration resistance, that is, the mechanical strength, of magnet wire coated with a thin film by the extrusion method can be significantly improved. As mentioned above, the coating thickness of the compound that can be cured by ionizing radiation or ultraviolet rays is 10 μm.
If it is within that range, it will be effective. However, if it is too thin, the effect will be small and it will be difficult to apply it evenly, and if it is too thick, it will begin to affect the toughness and adhesion. Therefore about 3
A coating thickness of about μ to 8 μ is appropriate.

In the present invention, a composition containing a condensed thermoplastic resin as a main component refers to a condensed thermoplastic resin itself, or a condensed thermoplastic resin to which crosslinking aids, dyes, pigments, fillers, etc. are added.

Examples of condensation thermoplastic resins include polyester resins such as aromatic polyesters represented by polyethylene, etc.
6-Nylon, Clause 6.6-Iron, amide resin, phenoxy resin, polyether resin such as polyphenylene oxide, polysulfone, polysulfone resin such as polyethersulfone, other polycarbonate resins, polyester amide resins, polyether ester resins and so on.

Furthermore, it is also possible to use two or more of the condensed thermoplastic resins described in "-" as a blend, or as a single or multilayer structure film.

Among these, from the viewpoint of heat resistance as a magnet wire, it is preferable to use a condensed thermoplastic resin having a melting point or flow temperature of 170'C or higher.

Examples of crosslinking aids include compounds with terminal groups such as acrylic ester groups and methacrylic ester groups; unsaturated polyesters with unsaturated bonds derived from maleic acid, fumaric acid, itaconic acid, etc. in the molecule; Compounds with allyl groups are known. However, compounds with terminal acrylic ester groups, methacrylic ester groups, etc., and the unsaturated polyesters mentioned above are all thermally unstable at high temperatures (for example, 170°C or higher).
It is impossible to perform extrusion processing with the condensed thermoplastic resin used in the present invention. In comparison, compounds having allyl groups are stable even at high temperatures (for example, 170"C or higher) and can be extruded together with the condensation thermoplastic resin used in the present invention.

Examples of compounds having such an allyl group include the following.

l-diallyl isocyanurate, diallylmethylisocyanurate, diallylhydroxyethyl isocyanurate, l-diallyl cyanurate-1, diallylmethyl cyanurate, diallylhydroxyethyl cyanurate, diallylcarboethoxycyanurate-1, diallylpoetoxyisocyanurate nurate, diallylchloroethyl isocyanurate diallylchloroethyl isocyanurate,
Compounds having two or more allyl groups adjacent to a triazine ring, such as ethylene bismodiallylisocyanurate), ethylene bismodiallylisocyanurate), hexaallylmelamine, N, N, diallylmelamine, and prepolymers thereof.

Diallyl isofucurate, diallyl terephthalate.

8- Diallyl adipate, diallyl azelaate, diallyl trimellitate, tetraallyl pyromellitate, l
- Allyl esters such as diallyl rimellitate and diallyl pyromellitate, or prepolymers thereof.

Allylamines such as triallylamine, diallylamine, diallylmethylamine, diallylphenylamine, and their prepolymers.

Tetraallylammonium chloride, triallylmethylammonium chloride, triallylammonium chloride, diallyldimethylammonium chloride,
Allyl ammonium salts such as l-diallylphenylammonium chloride and diallylphenylmethylammonium chloride, and prepolymers thereof.

Allylamides and prepolymers thereof, such as N,N diallylacetamide, N,N diallylformamide, N,N diallyl-2-chloroacetamide.

Allyl phosphate esters such as diallyl diphenyl phosphate, triallyl phosphate, diallylphenyl phosphonate, ) and realyl phosphite, and their prepolymers.

Furthermore, it is also possible to use two or more kinds of compounds having two or more allyl groups in the molecule.

Among these, it is preferable to use triallyl isocyanurate, triallyl cyanurate, and prepolymers thereof, since the allyl group is adjacent to the triazine ring from the viewpoint of heat resistance, and it is commercially easy to use.

It is also possible to add dyes and pigments for coloring.
Silicon dioxide,
An inorganic filler whose main component is calcium acid, magnesium oxide, calcium carbonate, aluminum oxide, iron oxide, titanium dioxide, etc. may be added.

Compounds that are irradiated and cured by ionizing radiation or ultraviolet rays include the following:

(1) At the molecular end of ester acrylate oligomer, ester meccrylate oligomer, urethane acrylate oligomer, urethane methacrylate oligomer-1, epoxy acrylate-1-, epoxy methacrylate-1-, polyether acrylate, polyether methacrylate, etc. An oligomer having an acryloyl group or a methacryloyl group.

Prepolymers of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and acrylic acid or methacrylic acid derivatives.

(2) Allyl ester oligomers, allyl ether oligomers, allyl urethane oligomers, allyl epoxy oligomers, etc. with allyl groups at the molecular ends, such as sulfur oligomers, diallyl phthalate, l-lylylisocyanurate, and triallyl cyanurate. An oligomer with an allyl group at the end of the molecule, which is made of a prepolymer of a compound that has an allyl group.

(3) Polyester oligomers, polyether oligomers, polyurethane oligomers, and epoxy oligomers having an epoxy ring at the molecular end.

-11~ However, in order to use an epoxy compound, it cannot be cured by high-energy rays as it is, so cationic polymerization catalyst Lewis, acid A compound that generates is necessary.

(4) Unsaturated polyester oligomers, unsaturated polyesters, imide oligomers, and unsaturated polyamide oligomers having unsaturated bonds induced by maleic acid, faric acid, itaconic acid, etc. in their molecular chains.

(5) Polybutadiene, polythiol, polyene type resins, and Spirois cool resins having unsaturated double bonds in their molecular chains or side chains.

It is also possible to use a compound having two or more types of the above-mentioned compound structures in its molecular chain, or a mixture of two or more types of the above-mentioned compounds.

Furthermore, among the compounds of (1) to (5), methyl acrylate, methyl methacrylate-1-, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylene glyco-12-7, etc. Place °〒′, 7f. -7゜7.2.71 Acrylates, acrylic esters and methacrylic esters such as trimethylolpropane trimethacrylate, triallyl isocyanurate, triallyl cyanurate, diallylamine-1, allyl glycidyl ether, diallylamine, N,N diallyl Compounds with allyl groups such as heptamide, known reactive diluents such as styrene, divinylbenzene, and vinylpyrrolidone are added, dyes or pigments are added for coloring, and viscosity is increased to improve workability during application. It is also possible to add agents, leveling agents, antifoaming agents, etc.

Ionizing radiation includes electron beams, β rays, γ rays, neutron beams,
Although X-rays and the like can be used, it is convenient to use electron beams as a normal industrial radiation source.

The appropriate amount of irradiation dose varies depending on the composition whose main components are a compound cured by ionizing radiation or ultraviolet rays and a condensed thermoplastic resin, but the appropriate amount is generally 50 Mrad or less.

Ultraviolet sources include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps, but high-pressure mercury lamps are effective for industrial use. When curing is carried out with ultraviolet rays, it is necessary to add a photosensitizer to the compound that is irradiated and cured with ionizing radiation or ultraviolet rays. Examples of photosensitizers include benzoin alkyl ethers such as benzoin ethyl ether and benzoin n-butyl ether, acetophenone derivatives such as diethoxytophenone, amyloxime esters, ketals such as benzyl methyl ketal, and xanthone such as 2-fluorothioxanthone. There are many known ones. Furthermore, known sensitizing aids such as triethylamine and triethanolamine may be added.

As for the amounts of the sensitizer and sensitizing aid, the total amount of both is 0.1 to 15 parts per 100 parts of nonvolatile content, and the ratio of the photosensitizer to the sensitizing aid is 1 part of the photosensitizer. Sensitizer 0.3-3 per mole
The molar ratio is appropriate.

In carrying out the present invention, there are a step of applying a thin film of a composition mainly composed of a condensed thermoplastic resin using an extrudate, a step of applying a compound that is cured by irradiation with ionizing radiation or ultraviolet rays, and a step of applying a compound that is cured by irradiation with ionizing radiation or ultraviolet rays. The irradiation step may be performed continuously or by analysis, but it is more efficient to perform it continuously.

The present invention will be explained below with reference to Examples and Comparative Examples, but the present discovery is not limited by these Examples.

Comparative Example 1.2 Polyethylene terephthalate resin (hereinafter PE manufactured by Toyo Keisha)
(abbreviated as T) using an extruder at an extrusion temperature of 310°C,
It was applied by extrusion onto a 7 mm diameter annealed copper wire. Film thickness is 33μ
(Comparative Example 1) and 4.5μ (Comparative Example 2).

Table 1 shows the properties of this extruded wire.

Examples 1 to 3 PET resin was extruded using an extruder at an extrusion temperature of 310°C.
After extrusion coating on annealed copper wire of 7 mmφ, Q, 78
mmφ (Example 1), 0.79 mmφ (Example 2), Q
, 13Qmmφ (Example 3) using a die, 2 wt% of photosensitizer was added to Aronix 6] 00 (ester acrylate oligomer manufactured by Toagosei Co., Ltd. hereinafter abbreviated as Aronix).
Sunray #1O00 (manufactured by Mitsubishi Yuka Co., Ltd.) was applied once and then passed through a so-called high-pressure mercury lamp at a line speed of 50 m/min three times at a position of 50 mm for curing. Table 1 shows the characteristics of the extruded wire whose surface was modified with this UV curing paint.

Comparative Example 3 PET resin was extruded using an extruder at an extrusion temperature of 810'C.
'0.82 after extrusion coating on 7mmφ annealed copper wire? ? 2
Using a 77Zφ die, apply 2wt% Sunray $1000 to Aronix and harden it by passing it under a high-pressure mercury lamp at 5(1) three times at a linear speed of 5 om/min. I let it happen. Table 1 shows the characteristics of the extruded wire whose surface was modified with this UV curing paint.

Table 1 Characteristics of PET extruded wire (*1) Number of pinballs after stretching 1 meter of sample by 3 inches.

(*2) After winding the sample around a 25111111 mandrel, wash it with ethanol and check for the occurrence of sharpness.

Other tests were conducted in accordance with JIS O3003.

As is clear from Table 1, the magnet obtained by the present invention
The mechanical strength (abrasion resistance, pencil hardness) of J/Twire is improved by 11] compared to the conventional method.

Comparative Examples 4 and 5 5 parts by weight of triallylisocyanure-1 was added to 100 parts by weight of polybutylene terephthalate resin (manufactured by Toyo Keisha, trade name TUFFENOL-PBT, hereinafter abbreviated as PBT) and mixed uniformly. After that, use an extruder to increase the extrusion temperature to 2.
It was extruded and coated onto a Q, 7 m, mφ annealed copper wire at 50°C. The film thickness was 28 no. This extruded wire was irradiated with an electron beam irradiation device at a dose of 18 Mrad (Comparative Example 3).
a d (Comparative Example 4) Irradiated. Table 2 shows the properties of this irradiated extruded wire.

Examples 4 and 5 After finely pulverizing 100 parts by weight of PBT resin, 5 parts by weight of triallyl isocyanurate-1 was added and mixed uniformly, and then annealed copper with a diameter of 07 mm was extruded using an extruder at an extrusion temperature of 250°C. Extrusion coating was applied to the line. The film thickness was 29μ. This extruded wire was exposed to an electron beam irradiation device at a dose of 10 Mrad (
Example 4. ) After irradiation with a dose of 22 Mrad (Example 5), the weight ratio of VR-90 (epoxy acrylate oligomer manufactured by Showa Kobunshi Co., Ltd.) and Aroex, 1:
] was applied with felt, and then irradiated with an electron beam irradiation device at a dose of 8M rad under a nitrogen gas atmosphere.

Table 2 shows the properties of this irradiated extruded wire.

Comparative Example 6 Polyester varnish (Nitto Electric Industry Co., Ltd. Delaco-1-E)
220G) on Q, 7 mm TFR copper wire with furnace length 9
,5m.

Furnace temperature: Upper part 360°C1 Middle part 320°C1 Lower part 260°C
Coating and baking was performed seven times at a linear speed of 15 m/min using a vertical furnace. Table 2 shows the characteristics of this polyester baked wire.

19- Table 2 Characteristics of polyester magnet wire and others (-, J, Tested according to JIS 0300g.

20- As is clear from Table 2, the mechanical strength (abrasion resistance, pencil hardness) of the magnet wire obtained by the present invention is greatly improved compared to the conventional method.

Comparative Example 7 6.10 nylon resin (trade name CM2O01 manufactured by Toshisha)
using an extruder at an extrusion temperature of 280°C.
extrusion coating onto annealed copper wire. The film thickness was 30μ.

Table 3 shows the properties of this extruded wire.

Example 6 6.0 nylon resin was extruded using an extruder at a temperature of 280
After extrusion coating Q on a mild steel wire with a diameter of 7 mm at
A mixture of 00L) and Aroex in a weight ratio of 1:1 was applied on a felt and irradiated with an electron beam irradiation device at a dose of 8 Mrad in a nitrogen gas atmosphere.

The film thickness of the 6.10 nylon resin was 30μ, and the thickness of the upper film was 6μ. Table 3 shows the properties of this extruded wire.

Comparative Example 8 6.61 nylon resin (trade name CM3001 manufactured by Toshisha Co., Ltd.
') using an extruder at an extrusion temperature of 300°C, Q, 7
The extrusion coating was applied to annealed copper wire-1 having a diameter of mmφ. Film thickness is 25
It was μ.

Table 3 shows the properties of this extruded wire.

Example 7 6.6 Nylon resin was extruded using an extruder at a temperature of 300°.
O4υ in C? After extrusion coating on 7n7φ annealed copper wire,
The epoxy resin was irradiated with ultraviolet rays at a dose of 4 M r a d in a nitrogen gas atmosphere using an AZOCA Ultraset machine manufactured by Jinka Co., Ltd.

The film thickness of the 6,6 nylon resin was 30μ, and the film thickness was 5p. Table 3 shows the properties of this extruded wire.

Table 3 Properties of extruded nylon wire (Note) All were tested in accordance with J'IS C 3003.

As is clear from Table 3, the mechanical strength (abrasion resistance, pencil hardness) of the magnet wire according to the present invention is significantly improved compared to the conventional method.

As is clear from the following two examples, the magnet wire obtained by the present invention has excellent magnetic properties and is of great industrial value.

Agent: Patent Attorney Tetsu Kamiyo

Claims (1)

[Scope of Claims] (1) A thin film of a composition containing a condensed thermoplastic resin as a main component is applied by extrusion, and a compound that is cured by irradiation with ionizing radiation or ultraviolet rays is applied to a thickness of 10μ or less, followed by ionizing radiation. Or a manufacturing method for magnet wire characterized by irradiation with ultraviolet rays. (2) The method for producing a magnet wire according to claim 1, wherein the condensed thermoplastic resin is a polyester resin. (3) The method for producing a magnet wire according to claim 2, wherein the polyester resin is polyethylene terephthalate. (4) Ho! J-1-The method for producing a magnet wire according to claim 2, wherein the stell resin is polybutylene terephthalate. (5) The method for producing a magnet wire according to claim 1, wherein the condensed thermoplastic resin is a polyamide resin. (6) The method for manufacturing a magnet wire according to claim 5, wherein the polyamide resin is 6,6 nylon. (A method for manufacturing a magnet wire according to claim 6, characterized in that the capolyamide resin is 6,10 nylon. A method for producing a magnet wire according to claim 1, characterized in that the magnet wire is an oligomer having an allyl group at the molecular end. A method for manufacturing a magnet wire according to claim 1, characterized in that α0) the compound that is irradiated and cured by ionizing radiation or ultraviolet rays is an oligomer having an epoxy ring at the molecular end. manufacturing method of magnet wire.