JPH021865B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a self-fusing insulated wire that is an enameled wire used in motors, transformers, magnetic coils, etc. and is provided with a self-fusing function. (Prior art and its problems) Conventionally, coil molded bodies for electrical equipment, communication equipment, etc. have been made by winding insulated wires into a predetermined shape and then applying varnish treatment to bond and solidify the wires. However, recently, self-bonding insulated wires, which can fuse and solidify the wires by heating or solvent treatment alone, are being used instead of impregnated varnish treatment. Self-bonding insulated wire has a self-bonding layer mainly made of thermoplastic material on the insulating layer of enamelled wire, and is heated or treated with a solvent after or while winding the wire into a coil. As a result, the wires are bonded to each other and a coil is obtained, so that the impregnating varnish treatment can be omitted, and the following advantages are brought to the user. There is no need to worry about pollution or safety and health caused by the use of impregnated varnish. The coil shape cycle is faster, as exemplified by electrical heating, and manufacturing costs are reduced because impregnated varnish is not used. It is also possible to solidify coils with complex shapes and those that cannot be impregnated with varnish. For this reason, there has been a growing demand for self-bonding insulated wires, and there has been a desire to develop materials with various characteristics to suit the process and usage conditions of customers. In particular, the deflection yoke coils used in televisions and the like have a special shape and strict dimensional accuracy, so customers have placed many demands on winding manufacturers. A few years ago, we focused on increasing the deflection angle so that the heating deformation of the coil is small, the ability to maintain adhesion even at high temperatures (e.g. around 130°C), and the fluidity of self-fusing materials during heat treatment by energization during coil manufacturing. In response to demands for better performance, winding wire manufacturers have responded by changing the self-bonding material from polyvinyl butyral to copolymerized nylon. Recently, with the development of computers,
As CRTs with higher precision are required, deflection yoke coils that do not deform are required even more than before. Current copolymerized nylon-based self-fusing materials have strong adhesion at high temperatures and have good fluidity, but the material itself is soft. For this reason, when a deflection yoke coil is manufactured using a copolymerized nylon self-bonding insulated wire, there is a drawback that the coil is slightly deformed due to the spring back force of the coil after the deflection yoke coil is manufactured. The above-mentioned deformation poses a problem in response to the current demand for high-precision CRTs. On the other hand, a self-bonding insulated wire using phenoxy as a self-bonding material is known, and if a deflection yoke coil is made using this, a coil with little deformation can be obtained. However, phenoxy has poor fluidity as a material during heat treatment, so compared to copolymerized nylon-based materials, it requires a larger current to fuse when energized, and unless the energization time is lengthened, the coils cannot fully adhere to each other between the wires. I can't get it. Therefore, a larger amount of thermal energy is required than when conventional copolymerized nylon is used, increasing the manufacturing cost of the coil. Another disadvantage is that passing a large current for a long period of time causes thermal deterioration of the insulating layer and short circuits between wires. As a result of intensive studies to eliminate these drawbacks, the inventors of the present invention have found that it is possible to manufacture a deflection yoke coil that has good fluidity similar to conventional copolymerized nylon systems and that has minimal deformation after molding. The present invention was achieved by discovering a self-bonding insulated wire. BACKGROUND OF THE INVENTION Recently, electrical equipment has become smaller and smaller, and higher reliability is required, as well as lower manufacturing costs. The self-bonding insulated wire of the present invention has materials that are easy to fuse, and has excellent deformation resistance and hardness after welding, and can be applied not only to deflection yoke coils but also to other coils. It is possible. (Structure of the Invention) The present invention relates to a compound having two phenolic OH groups in the molecule (component A) and the following chemical formula: Polyhydroxyethers obtained by reacting the compound represented by (component B), whose main component is a polyhydroxyether characterized by at least 25 mol% of mononuclear dihydric phenol in component A. This invention relates to a self-bonding insulated wire made by applying a coating material on a conductor through another insulating material and baking it. Mononuclear 2 used as component A in the present invention
For example, valent phenols have the general formula

[ka]
Representative examples include hydroquinone in which the OH group is in the para position, resorcinol in which the OH group is in the meta position, and catechol in which the OH group is in the ortho position. Of course, these compounds may be substituted with an alkyl group, an alkenyl group, a halogen, or the like. Among them, hydroquinone and resorcinol are suitable because they are easily available industrially. Compounds having two phenolic OH groups in the molecule and other than mononuclear dihydric phenols used as component A in the present invention include, for example, the general formula
(Y is −CH ₂ −,

【C】−CH ₂ CH ₂ −

【C】-O-,

【C】-S-,

[C] etc., and H in the benzene nucleus is one or more alkyl groups (CH ₃ , C ₂ H ₅ etc.) halogen
(Cl, Br, I, etc.) may be substituted. )
More specifically, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)
-hydroxyphenyl)methane, 2,2-bis(4
-hydroxyphenyl)ethane, 4.4'-dihydroxydiphenyl sulfone, 4.4'dihydroxyphenyl ether, 2.2'-bis(4-hydroxy-
Examples include 3.5-dibromophenyl)propane, 2.2'-bis(4-hydroxy-3-bromophenyl)propane, and 4.4'-(α-methylbenzylidene) diphenol. Furthermore, other compounds having two phenolic OH groups in the molecule include dihydroxynaphthalene,
etc. can also be used. Among them, 2,2'-bis(4-hydroxyphenyl)propane is preferred because it is industrially easily available and inexpensive. Chemical formula of the following formula used as component B in the present invention Examples of compounds represented by are as follows. The most common epoxy compounds in which R ₁ is H and R ₂ is CH ₃ include Ciel Chemical Company's product name Epicote #828, 834, 1001, 1004, 1007, Dow Chemical Company's product name DER330, 331, 332, 337, 557,
660, 661, 662, 664 Ciba Geigy product name Araldite 6004, 6005, 6010, 6020, 6030, 6040,
6060, 6071, 6075, 6084 Dainippon Ink Chemical Industry Co., Ltd. Product name Epicron 840, 850, 860, 1050, 3050,
4050 Toto Kasei Co., Ltd. Product name: Epotote YD-128,
There are 134, 011, 013, 014, etc. Examples of those in which R ₁ is H and R ₂ are H include Toto Kasei's Epotote YDF-170 and 190, Dainippon Ink and Chemicals' trade name Epicron 830, and the like. Among the above, compounds in which R ₁ is H and R ₂ is CH ₃ are the most industrially produced, and are easy to obtain.
Favorable in terms of price. As component B used in the present invention, in addition to the compound represented by the above chemical formula, some of these may be substituted with other similar chemicals, for example, R ₁ is H, R ₂ is CH ₃ , and some of the hydrogens in the benzene nucleus are replaced with bromine. The substituted compound is Dainippon Ink Chemical Industry Co., Ltd. trade name Epicron 152,
1120 Toto Kaseisha Product name YDB-340, 400, 500,
700, R ₁ is H and R ₂ is CH ₃ to hydrogenate the benzene nucleus to form a cyclohexane ring, Dainippon Ink Chemical Co., Ltd. trade name Epicron 750, Toto Kasei Co. Ltd. trade name Santoto 1000,3000, and other polypropylene glycols. Compounds such as Dow Chemical Company's product name DER732, which is a diepoxide of linole dimer acid, Ciel Chemical Company's product name Epicote #871, which is a diepoxide of linoleic dimer acid, and Asahi Denka Company's product name Epu6,10,15, which is a diepoxide with a urethane bond. Of course, partial substitution is also possible within a range that does not significantly affect the properties of the material. The polyhydroxyethers referred to in the present invention are compounds having two phenolic OH groups in the molecule (component A) and a compound represented by the chemical formula shown above (component B) in a solvent or without a solvent. It is obtained by reacting in the presence of a neutral catalyst. The reaction is carried out in the absence of a solvent or in the following solvent at an equivalent ratio of the epoxy group of component B to the phenolic OH group of component A in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02. Examples of reaction solvents include glycol ethers such as acetic acid cellosolve, phenyl cellosolve, cellosolve, carbitol, methyl carbitol, and butyl carbitol, ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone, and furfural. Aldehydes, nitriles such as acetonitrile, phenylacetonitrile, propandinitrile, benzonitrile, nitrobenzene, 1-chloro-2-
Examples of nitrobenzene and 1-chloro-3-nitrobenzene include nitro compounds, sulfoxides such as dimethyl sulfoxide, and sulfones such as diclotetramethylene sulfone. However, it goes without saying that those that react with epoxy groups or phenolic OH groups or those that cause side reactions are not suitable. As a reaction catalyst, sodium phenoxide,
Alkali metal phenoxides such as monosodium salt of 2.2-bis(4-hydroxyphenyl)propane and monosodium salt of 4.4′-dihydroxydiphenylsulfone; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; 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 pyrrolidine, N-methylpyrrolidine, morpholine , triethylenediamine, hexamethylenediamine, pyridine, imidazoles, 1.8−
Diazabicyclo [5.4.0] Organic base such as undecene-7, or 1,8-diazabicyclo [5.4.0]
Examples include phenol salt, 2-ethylhexanoate, and chelate of undecene-7. The catalyst is used in a range of 0.01 to 10 mole percent, preferably 0.02 to 5 mole percent, based on the bisphenols. The reaction temperature is preferably between 80°C and 200°C,
The temperature may be outside this range, and if necessary, the solution reaction can be carried out under pressure at a temperature higher than the boiling point of the solvent. The degree of polymerization of the polymer is 0.5 in m-cresol.
Reduced viscosity (ηsp/c) measured at a concentration in g/dl
It is desirable that the amount is 0.2 to 0.5 dl/g. If the reduced specific viscosity is 0.2 or less, the wire will have poor flexibility when used as an electric wire, and if it is 0.5 or more, the fluidity will be poor during fusion, resulting in poor fusion properties. If you want to obtain a highly concentrated paint due to regulations on emitted organic solvents for environmental protection or for economic reasons, the degree of polymerization should be relatively low, and when equivalent amounts of epoxy groups and phenolic OH groups are present,
If either one is in excess, add the compound represented by the above chemical formula and a compound having two phenyl OH groups in the molecule to paint the remaining amount so that the epoxy group and the phenolic OH group are equivalent. It would also be possible to achieve a high degree of polymerization by adding it to the inside and continuing the reaction during coating and baking during the manufacture of electric wires. In the present invention, the proportion of mononuclear divalent phenol in the compound having two phenyl OH groups in the molecule must be 25 mol% or more. If it is less than 25 mol%, the effect of using mononuclear divalent phenol will not be apparent. Next, paints containing polyhydroxyethers as a main component include polyether sulfone resins, polysulfone resins, phenoxy resins, polycarbonate resins, polyphenylene oxide resins, polystyrene resins, polyurethane resins, polyamide resins, polyester resins, It is also possible to add polyvinyl formal resin, silicone resin, phenolic resin, melamine resin, urea resin, etc. to an extent that does not adversely affect the fluidity of the material, and it is also possible to add plasticizers, silicone, low molecular weight polyethylene, surfactants, etc. By adding appropriate amounts of one or more of pigments, dyes, organic and inorganic fillers, etc., it is possible to improve the wire characteristics to some extent, and this is also within the scope of the present invention. When producing the paint containing polyhydroxyethers as the main component of the present invention, the above-mentioned reaction solvents can be used as the solvent and dispersant for the paint components, and in addition, m-
Cresol, NN-dimethylformamide, N
- Methylpyrrolidone, methylethylketone, xylene, naphtha, etc. may also be used to adjust solubility and viscosity. This paint can be used in any concentration, but
A range of % to 95% is preferred, and a range of 20% to 80% is used more effectively. The paint is formed into a film via another insulator to produce the self-bonding insulated wire of the present invention. The film is formed by applying a solution or molten paint onto the wire, adjusting the film thickness with a die, felt, etc., forming a film in a baking oven or coagulation bath, or drying it, or without using a solvent. In this case, this is simply done by applying a molten paint and then cooling it. The method for fusing the self-fusing insulated wire of the present invention is preferably fusing by heating, and in particular, fusing by heating by energization is used for coils that require hardness after fusing, specifically deflection yoke coils. It is very effective when used. EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, the reduced specific viscosity (ηsp/
c) was measured at 30°C after diluting the obtained polyhydroxyether solution of the present invention with m-cresol to a concentration of 0.5g resin/100ml solvent. Example 1 Epoxy resin manufactured by Ciel Chemical Co., Ltd., trade name Epicote #828 (hereinafter abbreviated as Epicote #828, epoxy equivalent weight 186) 186.0 g, hydroquinone (primary reagent molecular weight 110.1) 55.0 g, tri-n-butylamine (primary reagent, molecular weight 185.4) 4.6 g and 240 g of diethylene glycol monomethyl ether using a thermometer, stirring rod,
Mixing and melting temperature was increased to 80℃ in a round bottom flask equipped with a cooling tube, and the temperature was increased from 80℃ to 140℃ at 10℃/hr.
The temperature was raised at a temperature increase rate of 1, and the reaction was allowed to proceed for 6 hours. After the reaction was completed, heating was stopped and 320 g of diethylene glycol monomethyl ether was added to obtain a black transparent solution with a resin content of 30%. The reduced specific viscosity (ηsp/c) of this resin is
It was 0.38. Then 0.5 in an enameled wire baking furnace.
After applying and baking the H class polyester imide insulation paint (trade name Isomid LV, manufactured by Nissho Makenectaday Co., Ltd.) on the mm diameter copper wire 7 times under the baking conditions for polyester imide insulation paint, the resin solution of this example was applied. The coating was applied and baked three times under the same baking conditions to obtain a self-fused wire. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 2 A black transparent solution with a resin content of 30% was obtained using the same reaction method as in Example 1, except that 55.0 g of resorcinol (primary molecular weight of the reagent: 110.1) was used instead of hydroquinone. The reduced specific viscosity (ηsp/c) of this resin was 0.29. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 3 A black transparent solution containing 30% resin component was obtained by the same reaction method as in Example 1, using a mixture of 27.5 g of resorcinol and 27.5 g of hydroquinone instead of 55.0 g of hydroquinone. Reduced specific viscosity of this resin (ηsp/c)
was 0.39. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 4 Epicote #1001 (epoxy equivalent: 513) 205.2g
and hydroquinone 22.0g, tri-n-butylamine
After reacting in the same manner as in Example 1 using 1.85 g of diethylene glycol monomethyl ether and 227.2 g of diethylene glycol monomethyl ether, 303 g of diethylene glycol monomethyl ether was added to obtain a black transparent solution with a resin content of 30%. The reduced specific viscosity (ηsp/c) of this resin was 0.42. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 5 Epicote #828 186.0g, hydroquinone
27.5g, bisphenol A (reagent primary molecular weight
228.3), 4.6 g of tri-n-butylamine, and 270 g of diethylene glycol monomethyl ether were reacted in the same manner as in Example 1, and then 360 g of diethylene glycol monomethyl ether was added to obtain a black transparent solution with a resin content of 30%. The reduced specific viscosity (ηsp/c) of this resin was 0.35. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 6 Epicote #828 186.0g, hydroquinone
After reacting 13.8 g of bisphenol A, 85.6 g of tri-n-butylamine, and 285 g of diethylene glycol monomethyl ether in the same manner as in Example 1, 380 g of diethylene glycol monomethyl ether was added to form a black transparent solution with a resin content of 30%. Obtained. The reduced specific viscosity (ηsp/c) of this resin was 0.32. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Example 7 After reacting 253.0 g of Epicote #834 (epoxy equivalent weight 253), 55.0 g of catechol (reagent primary molecular weight 110.1), 4.6 g of tri-n-butylamine, and 308 g of diethylene glycol monomethyl ether in the same manner as in Example 1, 410 g of diethylene glycol monomethyl ether was added to obtain a black transparent solution with a resin content of 30%. Reduced specific viscosity of this resin (ηsp/c)
was 0.37. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this example. Comparative Example 1 A pale yellow transparent solution with a resin content of 30% was obtained by dissolving 300 g of phenoxy resin (Union Carbide Co., Ltd. trade name Phenoxy PKHH, average molecular weight approximately 40,000) in 700 g of diethylene glycol monomethyl ether.
Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this comparative example. Comparative example 2 Reduced specific viscosity (ηsp/c), m-cresol 0.5%
12-6 copolyamide (1) whose solution, at 30°C, the same below) is 1.71 (the weight composition ratio of the 12-nylon component and the 6-nylon component constituting the copolyamide is 8:2, the same below) ) 240gr and the reduced specific viscosity is 1.24 12-6-6.6 (weight composition ratio 1:
1:1) copolymerized polyamide (II) 160gr,
A polymer solution obtained by heating and reacting in 1200gr of a mixed solvent of phenol and m-cresol (2:8 by weight) at 170℃ for 5 hours was diluted with xylol 750gr to give a concentration of 17% and a viscosity (B-type viscometer). Measured in AT30
℃, same below) A uniform transparent paint of 1640 cps was obtained. Subsequently, a self-bonding insulated wire was obtained in the same manner as in Example 1. Table 1 shows the wire characteristics of the self-bonding insulated wire of this comparative example.

[Table] Example 8 The self-bonding insulated wires obtained in Examples 1, 2, and 5 and Comparative Examples 1 and 2 were wrapped tightly around a mandrel with a diameter of 5.0 mm and placed in a thermostatic oven at a predetermined temperature under a load of 125 gr. A sample was left standing for 20 minutes, and the adhesion strength was measured based on ASTM-D2519. Table 2 shows the relationship between the fusing temperature and the adhesion strength of the self-fusing insulated wires of each Example and Comparative Example.

[Table] Example 9 The self-bonding insulated wires obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were tightly wrapped around a mandrel with a diameter of 5.0 mmφ.
It was heated by applying a constant current of 10A for a predetermined time under a turn winding load of 125gr. The coil obtained by heating was used as a sample, and the adhesion force was measured based on ASTM-D2519. Each example,
Table 3 shows the relationship between the current application time and the adhesion strength of the self-bonding insulated wire of the comparative example. Example 10 Films of the self-adhesive paints obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were prepared by baking them in a constant temperature bath at 200°C for 2 hours. The elastic modulus-temperature characteristics of the films of each Example and Comparative Example were measured at a frequency of 11 Hz using a dynamic elasticity measuring device (Viblon) manufactured by Toyo Baldwin. Table 4 shows the obtained elastic modulus temperature characteristics.

[Table] Example 11 The self-bonding insulated wires produced in Examples 1 to 7 and Comparative Examples 1 to 2 were wound with a deflection yoke coil winding machine to produce a deflection yoke coil. The obtained deflection yoke coil was placed on a smooth plate, and the gap (Δh: extraction deformation) between the deflection yoke coil and the plate as shown in FIG. 2 was measured. The results are shown in Table 5. Incidentally, the deflection yoke coil produced is shown in FIG. The sizes of a, b, and c were 40 mm, 90 mm, and 60 mm, respectively.

[Table] (Effects of the invention) From Tables 2 and 3, the self-fusing insulated wire of the present invention can be fused at a lower temperature than phenoxy and copolymerized nylon wires, and it takes about the same amount of time to conduct electricity as the copolymerized nylon wires. It turns out that it can be fused. As shown in Table 4, it is harder than copolymerized nylon from room temperature to 90°C, and is almost as hard as phenoxy from room temperature to 70°C. When a deflection yoke coil is actually manufactured, as shown in Table 5, the amount of deformation of the coil is smaller than that of the current copolymerized nylon-based coil. Therefore, the self-fusing insulated wire of the present invention is suitable for use in deflection yoke coils with little deformation used in high-precision CRTs. Naturally, it can be applied to coils manufactured by other heat-fusion methods, and its industrial value as a new self-bonding insulated wire is great.

[Brief explanation of the drawing]

1 and 2 show a deflection yoke coil according to the present invention. Figure 1 shows an outline of the deflection yoke coil. In this coil, a, b, and c in the figure are each 40 mm.
They are 90mm and 60mm in size. FIG. 2 illustrates the amount of deformation (Δh) taken out. 1... Deflection yoke coil, 2... Smooth plate.

Claims (1)

[Claims] 1. A compound having two phenolic OH groups in the molecule (component A) and the following chemical formula: Polyhydroxyethers obtained by reacting the compound represented by (component B), whose main component is a polyhydroxyether characterized by at least 25 mol% of mononuclear dihydric phenol in component A. A self-bonding insulated wire made by applying a coating material to the conductor through another insulating material and baking it. 2. The self-bonding insulated wire according to claim 1, wherein the mononuclear divalent phenol is hydroquinone. 3. The self-bonding insulated wire according to claim 1, wherein the mononuclear divalent phenol is resorcinol. 4. The self-bonding insulated wire according to claim 1, wherein the mononuclear divalent phenol is catechol. 5 The B component has the following chemical formula The self-bonding insulated wire according to claim 1, which is a compound represented by: