JPH0626164B2 - Self-bonding insulated electric wire and its coil - Google Patents

Description

TECHNICAL FIELD The present invention relates to a self-welding insulated electric wire in which an enameled wire used for a motor, a transformer, a magnetic coil, and the like is provided with a self-bonding function, and a coil manufactured from the same. It is a thing.

(Prior Art and Problems Thereof) Conventionally, a coil molded body of an electric device, a communication device or the like has been used in which an insulated wire is wound into a predetermined shape and then varnished to bond and solidify the wires. However, recently, self-fusing insulated electric wires, which can be fused and solidified between electric wires by only heating or solvent treatment, are being used instead of the impregnating varnish treatment.

Self-fusing insulated wire is a self-fusing layer consisting mainly of a thermoplastic material provided on the enamel wire and insulating layer.After winding the wire into a coil, or while winding it into a coil, heat or solvent treatment By doing so, the wires are fixed to each other and the coil can be obtained, so that the impregnating varnish treatment can be omitted, which brings many advantages to the user as follows.

There is no need to worry about pollution or safety and health due to the use of impregnated varnish.

As represented by electric heating, the coil forming cycle is accelerated, and the impregnating varnish is not used, so the manufacturing cost is reduced.

It is possible to solidify complex coil shapes and those that impregnated coils do not penetrate.

For this reason, the demand for self-bonding insulated electric wires is increasing, and it is desired to develop materials having various characteristics so as to meet the customer's process and use conditions. Among them, the deflection yoke coil used in televisions and the like has been much demanded by the winding manufacturer from the consumer because of its special shape and dimensional accuracy.

A few years ago, the heating deformation of the coil was small due to the increase of the deflection angle, it had a sticking force even at high temperature (for example, about 130 ° C), and the fluidity of the self-fusing material during the heating process during coil manufacturing However, the winding manufacturer has responded by changing the self-bonding material from polyvinyl butyral to copolymer nylon.

Recently, with the development of computers and the like, higher precision CRTs are required, and deflection yoke coils that are not deformed more than before are required. The current co-polymerized nylon-based self-fusing material has strong adhesion at high temperatures,
Although it is a fluid material, the material itself is soft.
Therefore, when a deflection yoke coil is manufactured using a copolymer nylon self-bonding insulated wire, there is a drawback that the coil is slightly deformed by the springback force of the coil after manufacturing the deflection yoke coil. The above modification is a problem for the current high-precision CRT requirements.

On the other hand, a self-bonding insulated electric wire using phenoxy as a self-bonding material is known, and when a deflection yoke coil is formed using this, a coil with less deformation can be obtained. However, since phenoxy has a poor fluidity of the material during heat treatment, it requires a large current at the time of energization and fusion compared to the co-polymerized nylon type. I can't get it. Therefore, multiple heat energy is required as compared with the case where the conventional copolymer nylon system is used, and the manufacturing cost of the coil increases. In addition, there is a drawback in that a large current for a long time causes thermal deterioration of the insulating layer and short circuit between the wires.

As a result of diligent studies to eliminate these drawbacks, the inventors of the present invention can manufacture a deflection yoke coil that is as good as the conventional copolymerized nylon system in fluidity and has little deformation after molding. Find a self-bonding insulated wire
The present invention has been reached.

Recently, electric appliances have become smaller and smaller, high reliability is required, and manufacturing cost is also reduced.

Self-fusing insulated electric wire of the present invention, the material is easily fused,
It has excellent resistance to deformation and hardness after fusion, and can be applied not only to deflection yoke coils but also to other coils.

(Structure of the Invention) The present invention provides a polyhydroxy compound obtained by reacting a compound having two epoxy groups in a molecule (component A) with a compound having two phenolic OH groups in a molecule (component B). In ethers, the A and B components have the following chemical formula
The structural unit represented by (C) or (D) Of a compound having a structural unit represented by (C) in an amount of 25% by weight or more based on the total amount of the compound having a polyhydroxyether-based coating material directly on a conductor or another insulating material. The present invention relates to a self-fusion-bonded insulated electric wire coated and baked through a coil and a coil obtained by using the same.

In the present invention, a molecule of a polyhydroxy ether obtained by reacting a compound having two epoxy groups in the molecule (component A) with a compound having two phenolic OH groups in the molecule (component B) Chemical formula in structure It is important to include. Phenoxy, which is currently used as a self-bonding material in polyhydroxy ethers, has the following chemical formula: It has a repeating structural unit represented by.

On the other hand, as in the present invention, the chemical formula in the molecular structure For example, the following chemical formula When a polyhydroxy ether having a repeating structural unit represented by is used, the fluidity of the material is improved by the amount of the reduced CH ₃ groups and the material is easily fused. (CH ₃ group causes steric hindrance to impair the rotation of the main chain skeleton, resulting in poor fluidity.) However, since the density of aromatics does not change, the hardness of the material, which has excellent phenoxy characteristics, is The deformation resistance of No. 2 is not so different from that of phenoxy, and it is an excellent self-bonding material, and is most suitable for use in the deflection yoke coil.

In the present invention, the chemical formula The method of introducing the structural unit represented by the formula into the polyhydroxy ether is as a compound having two epoxy groups in the molecule (component A) as at least one component A compound having two phenolic OH groups in the molecule It may be introduced as at least one component in (Component B), or may be introduced into both as a matter of course.

Chemical formula with a compound (component A) having two epoxy groups in the molecule The following general formulas are typical of those containing the structural unit For example, Dainippon Ink and Chemicals, Inc. trade name Epicron 830 Tohto Kasei trade name Epotote YDF-170, 190
Etc.

On the other hand, a compound having two phenolic OH groups in the molecule (component B) has the chemical formula Including the structural unit shown by There is bis (hydroxyphenyl) methane represented by.

Here, in the present invention, the chemical formula It is necessary to use the compound containing the structural unit represented by the formula above in an amount of 25% by weight or more based on the resulting polyhydroxy ether. This is because when the amount is less than 25% by weight, the effect of improving the fluidity of the obtained polyhydroxy ether is small, and the effect is not sufficiently exhibited in the case of heat fusion by energization.

Chemical formula among compounds having two epoxy groups in the molecule (component A) Those not containing the structural unit shown by are chemical formulas It includes a structural unit represented by the following general formula (1) It is preferable to use the epoxy compound represented by the following in terms of raw material price and availability.

Specifically, Ciel Chemical Company trade name Epicote # 828,834,
1001,1004,1007 Dow Chemical Company trade name DER330,331,332,
337,557,660,661,662,664 Ciba Geigy Product name Araldite 6004,6005,6010,6020,6030,6040,6060,6071,607
5,6084 Dainippon Ink and Chemicals, Inc. Trade name Epicron 840,8
50,860,1050,3050,4050 Toto Kasei Co., Ltd. Trade name Epototo YD
-128,134,011,013,014 etc.

Compounds having two phenolic OH groups in the molecule (B
Component) out of chemical formula Those not containing the structural unit represented by Including the structural unit shown in, the following chemical formula It is preferable to use bis (hydroxyphenyl) propane represented by the following in terms of raw material price and availability.

The polyhydroxy ethers referred to in the present invention include 2 in the molecule.
The presence of a basic catalyst in a solvent or without solvent between a compound having one phenolic OH group (component B) and a diepoxy side obtained from a compound having two phenolic OH groups in the molecule (component A) It is obtained by a lower reaction.

The reaction is based on the epoxy group of component A and the phenolic O of component B.
More preferably, the equivalence ratio with the H group is in the range of 0.95 to 1.05.
It is performed in the range of 0.98 to 1.02 without solvent or in the following solvents.

As the reaction solvent, cellosolve acetate, phenyl cellosolve, cellosolve, carbitol, methyl carbitol,
Glycol ethers typified by butyl carbitol, ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone; aldehydes such as furfural; nitriles such as acetonitrile, phenylacetonitrile, propanedinitrile, and benzonitrile; and nitrobenzene. , Nitro compounds such as 1-chloro-2-nitrobenzene and 1-chloro-3-nitrobenzene, sulfoxides such as dimethyl sulfoxide, and sulfones such as cyclotetramethylene sulfone.

However, it goes without saying that those that react with epoxy groups or phenolic OH groups and those that cause side reactions are not suitable.

As the reaction catalyst, alkali metal phenoxides such as sodium phenoxide, monosodium salt of 2.2-bis (4-hydroxyphenyl) propane and monosodium salt of 4.4'-dihydroxydiphenylsulfone, sodium methoxide, sodium ethoxide. , Alkali metal alkoxides, sodium hydride, metal hydrides such as sodium borohydride, triethylamine, n-propylamine, iso-propylamine, n-
Butylamine, tert-butylamine, n-hexylamine, n-octylamine, cyclohexylamine, guanidine, guanidine derivative, methylamine, methylamine derivative, ethylamine, ethylamine derivative, piperidine, piperidine derivative pyrrolidone, N-methylpyrrolidone, morpholine, triethylamine Organic bases such as ethylenediamine, hexamethylenediamine, pyridine, imidazoles, 1.8-diazabicyclo [5.4.0] undecene-7, or phenol salts of 1.8-diazapicyclo [5.4.0] undecene-7, 2-ethylhexanoic acid Salt, oleate, etc. can be mentioned. The catalyst is used in the range of 0.01 to 10 mole percent with respect to the bisphenols, 0.02
To 5 mole percent is preferred.

The reaction temperature is preferably between 80 ° C. and 200 ° C., but may be outside this range, and if necessary, the solution reaction can be carried out under pressure at a temperature not lower than the boiling point of the solvent.

The polymerized polymer preferably has a reduced specific viscosity [ηsp / c] of 0.2 to 1.0 dl / g measured at a concentration of 0.5 g / dl in m · cresol. When the reduced specific viscosity is 0.2 or less, it becomes poor in flexibility when used as an electric wire, and when it is 1.0 or more, fluidity becomes poor at the time of fusing and the fusing property deteriorates.

When it is desired to obtain a high-concentration paint due to regulations on discharged organic solvents for environmental protection or economic reasons, the polymerization degree is set relatively low, and when the epoxy group and the phenolic OH group are present in the same amount, When either one is in excess, the epoxy resin and the phenolic OH group are used in an equivalent amount, and
It is also possible to add a compound represented by the above chemical formula and a compound having two phenolic OH groups in the molecule to the coating material, and to continue the reaction at the time of coating and baking during the production of electric wire to obtain a high degree of polymerization. Ah

Next, the coating composition containing the polyhydroxyethers of the present invention as the main component includes polyether sulfone resin, polysulfone resin, phenoxy resin, polycarbonate resin, polyphenylene oxide resin, polystyrene resin, polyureta resin, polyamide resin, polyester resin, It is also possible to add polyvinyl formal resin, silicone resin, phenol resin, melamine resin, urea resin, etc. to an extent that does not adversely affect the fluidity of the material, and further plasticizer, silicone, low molecular weight polyethylene, surfactant, By adding an appropriate amount of one or more of pigments, dyes, organic-inorganic fillers, etc., it is possible to improve the electric wire characteristics to some extent.
This is also included in the scope of the present invention.

In the case of producing a coating composition containing the polyhydroxyether of the present invention as a main component, the above-mentioned reaction solvent can be used as a solvent and a dispersant for the coating composition. In addition, m-cresol, NN-dimethylformamide, N-methylpyrrolidone , Methyl ethyl ketone, xylene, naphtha, etc. are soluble in some cases,
It can be used to adjust viscosity.

The paint can be used in any concentration, but from 5% to
A range of 95% is preferred and a range of 20% to 80% is used more effectively.

The coating composition is formed on the conductor directly or through another insulating material to form a film, thereby producing the self-bonding insulated electric wire of the present invention.

The method of forming the film is to apply a solution or molten paint to the wire and adjust the film thickness with a die, felt, etc.
Alternatively, it is carried out by forming and drying a film in a coagulation bath, or when a solvent is not contained, simply by coating the molten paint and then cooling.

The fusion method of the self-fusing insulated wire of the present invention is preferably fusion by heating, and in particular, it is fused by heating by energization, and a coil requiring hardness after fusion, specifically a deflection yoke coil Great effect when used.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. The reduced specific viscosity (ηsp / c) in the following examples is 0.5 g of the obtained polyhydroxyether solution of the present invention with m-cresol.
Resin / 100 ml, diluted to a solvent concentration and measured at 30 ° C.

[Example 1] 173.0 g of trade name Epiclon 830 (hereinafter abbreviated as Epicron 830, epoxy equivalent 173) of Dainippon Ink and Chemicals, Inc., bisphenol A (2.2-bis (4-hydroxydiphenyl))
Propane, reagent primary molecular weight 228.3) 114.1 g, tri-n-
Butylamine (reagent primary molecular weight 185.4) 4.6 g, diethylene glycol monomethyl ether (hereinafter abbreviated as DM) 28
7 g and 7 g were mixed and dissolved in a round bottom flask equipped with a thermometer, a stir bar and a condenser, the temperature was raised to 150 ° C., and the reaction was carried out for 10 hours. After completion of the reaction, the heating was stopped and 400 g of DM was added to obtain a yellowish brown transparent solution having a resin content of 30%. The reduced specific viscosity (ηsp / c) of this resin was 0.42. Then, in a enamel wire baking furnace, a class H polyester imide (trade name Isomid LV manufactured by Nippon Schenectady Co., Ltd.) is applied 7 times onto a 0.5 mm diameter copper wire, and this resin solution is applied 3 times under the baking conditions of a polyester imide insulating paint. A self-bonding insulated electric wire was obtained.

The electric wire characteristics of the self-fusing insulated electric wire of this example are shown in Table 1.

Example 2 173.0 g of Epicron 830, bisphenol F (bis (4
-Hydroxyphenyl) methane, molecular weight 200.2) 100.1
g, tri-n-butylamine 4.6 g DM273 g were reacted in the same manner as in Example 1, DM364 g was added, and the resin content 3
A 0% yellow-black transparent solution was obtained. The reduced specific viscosity (ηsp / c) of this resin was 0.39. Then, it carried out similarly to Example 1, and obtained the self-bonding insulated electric wire.

The electric wire characteristics of the self-fusing insulated electric wire of this example are shown in Table 1.

[Example 3] Epoxy resin trade name Epicoat # 828 manufactured by Ciel Chemical Co., Ltd.
(Epoxy equivalent 186 or less abbreviated as Epicoat # 828) 186.0
g, bisphenol F (100.1 g), tri-n-butylamine (4.6 g) and DM286 (g) were reacted in the same manner as in Example 1, and DM381 g was added to obtain a yellow cutish transparent solution having a resin content of 30%. The reduced specific viscosity (ηsp / c) of this resin was 0.36. Then, it carried out similarly to Example 1, and obtained the self-bonding insulated electric wire.
The electric wire characteristics of the self-fusing insulated electric wire of this example are shown in Table 1.

[Example 4] Epiclon 830 86.5 g, Epicoat # 828 93.0 g, bisphenol A 114.1 g, tri-n-butylamine 4.6 g,
After reacting with 294 g of DM in the same manner as in Example 1, 390 g of DM
Was added to obtain a black transparent solution having a resin content of 30%. The reduced specific viscosity (ηsp / c) of this resin was 0.44. Then, it carried out similarly to Example 1, and obtained the self-bonding insulated electric wire.

The electric wire characteristics of the self-fusing insulated electric wire of this example are shown in Table 1.

[Comparative Example 1] 300 g of phenoxy resin (Phenoxy PKHH having a trade name of Union Carbide, average molecular weight of about 40,000) was dissolved in 700 g of DM to obtain a light yellow transparent solution having a resin content of 30%.

Then, it carried out similarly to Example 1, and obtained the self-bonding insulated electric wire.

The electric wire characteristics of the self-bonding insulated electric wire of this comparative example are shown in Table 1.

[Comparative Example 2] 12-6 copolymerized polyamide (1) having a reduced specific viscosity (ηsp / c) of 1.71 (the weight composition ratio of the 12-nylon component and the 6-nylon component constituting the copolymerized polyamide was 8). : 2; same hereafter) 240gr and reduced specific viscosity of 1.24 12-6-6.
6 (weight composition ratio 1: 1: 1) copolyamide (II) 16
A polymer solution obtained by heating and reacting 0 gr with 1200 gr of a mixed solvent of phenol and m-cresol (weight ratio 2: 8) at 170 ° C. for 5 hours was diluted with 750 gr of xylol to give a concentration of 17% and a viscosity ( A uniform transparent coating of 1640 cps was obtained, which was measured with a B-type viscometer at 30 ° C., the same applies hereinafter.

Then, it carried out similarly to Example 1, and obtained the self-bonding insulated electric wire. The electric wire characteristics of the self-bonding insulated electric wire of this comparative example are shown in Table 1.

[Example 5] The self-fusing insulated electric wires obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tightly wound around a mandrel having a diameter of 5.0 mmφ 125 gr.
The sample was left for 20 minutes in a constant temperature bath under a predetermined load, and the adhesion was measured according to ASTM-D2519.

Table 2 shows the relationship between the fusing temperature and the fastening force of the self-fusing insulated electric wires of the respective examples and comparative examples.

Example 6 The self-fusing insulated electric wires obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tightly wound around a mandrel having a diameter of 5.0 mm for 175 turns, and a constant current of 10 A was set under a load of 125 gr. It was energized and heated for an hour.

The coil obtained by heating is used as a sample, and the adhesion strength is determined by ASTM-D251.
It measured based on 9. Table 3 shows the relationship between the energizing time and the fixing force of the self-fusing insulated electric wires of Examples and Comparative Examples.

[Example 7] The self-fusing coating films obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were prepared by baking for 2 hours in a constant temperature bath at 200 ° C.

The elastic modulus-temperature characteristics of the films of Examples and Comparative Examples were measured at a frequency of 11 Hz by a dynamic viscoelasticity measuring device (Vibron) manufactured by Toyo Baldwin. The obtained elastic modulus temperature characteristics are shown in Table 4.

[Example 8] The self-bonding insulated electric wires produced in Examples 1 to 4 and Comparative Examples 1 and 2 were coiled by a deflection yoke coil winding machine to produce a deflection yoke coil. The obtained deflection yoke coil was allowed to stand still on a smooth plate, and the gap (Δh: take-out deformation) between the deflection yoke coil and the plate as shown in FIG. 2 was measured. The results are shown in Table 5.
It was shown to.

The manufactured deflection yoke coil is shown in FIG. a,
b and c had a size of 40 mm, 90 mm and 60 mm, respectively.

(Effects of the invention) From Tables 2 and 3, the self-bonding insulated electric wire of the present invention is phenoxy,
It can be seen that the fusion can be performed at a lower temperature than that of the copolymer nylon type, and that the current fusion can be performed in about the same time as the copolymer nylon type. Further, as shown in Table 4, it is harder from room temperature to 90 ° C. than the copolymerized nylon type, and almost the same hardness from room temperature to 70 ° C. as that of phenoxy. When a deflection yoke coil is actually manufactured, the amount of deformation of the coil is smaller than that of the current copolymer nylon type, as shown in Table 5. Therefore, the self-bonding insulated wire of the present invention is suitable for a deflection yoke coil which is used in a high precision CRT and has a small deformation. Of course, it can be applied to a coil manufactured by other heat fusion, and its industrial value is great as a novel self-fusing insulated wire.

[Brief description of drawings]

1 and 2 show a deflection yoke coil according to the present invention. Fig. 1 shows the outline of the deflection yoke coil. In this coil, a, b and c in the figure are 40 mm, 90 mm and 60 mm, respectively.
Is the size of. FIG. 2 shows the take-out deformation amount (Δh). 1. Deflection yoke coil, 2. Smooth plate

Claims (7)

[Claims] 1. A polyhydroxyether obtained by reacting a compound having two epoxy groups in a molecule (component A) with a compound having two phenolic OH groups in a molecule (component B). A component and B component are the following chemical formulas
The structural unit represented by (C) or (D) A coating containing polyhydroxy ethers as a main component, which comprises 25% by weight or more of the compound containing the structural unit represented by (C), directly on the conductor or other insulating material. A self-fusing insulated electric wire that is applied and baked through an object. 2. The chemical formula in component A As a compound having a structural unit represented by the following chemical formula The self-bonding insulated electric wire according to claim 1, wherein a compound represented by the formula (n is an integer from 0 to 10) is used. 3. The chemical formula in component B As a compound having a structural unit represented by the following chemical formula The self-bonding insulated electric wire according to claim 1, which uses a compound represented by: 4. The equivalent ratio of the epoxy group of the component A to the phenolic OH group of the component B is in the range of 0.95 to 1.05, and the polyhydroxy ether obtained by the reaction has a degree of polymerization of 0.2 to 1.0 dl in terms of reduced specific viscosity. The self-bonding insulated electric wire according to claim 1, which is / g. 5. A polyhydroxyether obtained by reacting a compound having two epoxy groups in the molecule (component A) with a compound having two phenolic OH groups in the molecule (component B), Ingredients and B ingredients are the following chemical formulas
(C), from a compound having a structural unit represented by (D) Of which the compound containing the structural unit represented by (C) is used in an amount of 25% by weight or more of the whole, and a coating containing polyhydroxyethers as a main component is applied directly on the conductor or through another insulator. A coil manufactured by heat fusion using a self-fusing insulated electric wire that is applied and baked. 6. The coil according to claim 5, which is manufactured by heat fusion by energization. 7. The coil according to claim 6, wherein the coil is a deflection yoke coil.