JP2014013710A - Insulation coating material, insulation electric wire, and coil using the same - Google Patents

Abstract

An object of the present invention is to provide an insulated wire having high adhesion between a conductor and an insulating coating and having sufficient adhesion even with heat for a long time.
A conductor 11 made of metal and an insulating coating covering the outer periphery of the conductor 11, wherein the insulating coating contains 1,3-bis (4-aminophenoxy) benzene and substantially contains an adhesion improver. An insulated wire comprising an insulating layer 12 made of a polyamideimide resin that does not contain and having an adhesion strength with respect to the conductor 11 of 50 g / mm or more in close contact with the surface of the conductor 11.
[Selection] Figure 1

Description

  The present invention relates to an insulated wire used in an electric device such as a motor, a coil using the insulated wire, and an insulating paint for providing an insulating layer.

  Insulated wires used in electrical equipment such as motors are coated with a single layer or multiple layers by applying and baking an insulating paint in which a resin such as polyimide, polyamideimide, or polyesterimide is dissolved in an organic solvent. Some of them are provided with an insulating coating having an insulating layer.

  In recent years, demands such as miniaturization and high efficiency have been increasing year by year in electric devices such as motors. In order to meet this requirement, a process of winding a large number of insulated wires around a motor core and a process of directly inserting an insulated wire into a slot of the core are performed. However, the more the insulated wire is wound or inserted, the greater the processing stress applied to the insulated wire in the process of processing the insulated wire, resulting in damage to the insulation coating provided on the outer periphery of the conductor. There is a risk of poor insulation such as rare shorts. For this reason, insulated wires used in electric devices such as motors are required to have no damage to the insulation coating even when the processing stress applied to the insulation coating during the machining process increases.

  In response to such demands, there is a method of improving resistance to processing stress by, for example, actively adding a component that improves adhesion in an insulating paint to make the insulating coating difficult to peel off from the conductor (for example, patents) Literatures 1-3). In addition, as a component which improves such adhesiveness, adhesion improving agents, such as mercaptans, thiazoles, melamines, cyano compounds, phenylenediamines, are known, for example.

JP 2001-11312 A JP 2007-246595 A JP 2007-106823 A

  Electric devices such as motors tend to be used by boosting the voltage for miniaturization and high efficiency. For this reason, an electric current larger than that in the prior art flows through the insulated wire constituting the coil, and the insulated wire is used in an environment where a large amount of heat is generated due to the increase in current. In addition, in order to improve the space factor of the insulated wire, it has been studied to arrange the insulated wire more densely. However, if the space factor is improved, the generated heat is difficult to escape, that is, the heat dissipation becomes worse. End up.

  In such an environment, if high-temperature heat is applied to the insulation coating for a long time, the adhesion of the insulation coating to the conductor is extremely reduced due to the influence of this heat, and the insulation coating is peeled off from the conductor. was there. If the insulation coating is peeled off in this way, the insulation performance cannot be sufficiently exhibited, resulting in dielectric breakdown. Therefore, the insulating coating needs to have sufficient adhesion even when heat is applied for a long time. In the conventional method in which an adhesion improver is added to the insulating paint, sufficient adhesion may not be obtained when such a long-time heat is applied.

  Accordingly, an object of the present invention is to provide an insulated wire having high adhesion between a conductor and an insulating coating and having sufficient adhesion even with heat for a long time, and a coil formed using the insulated wire.

  In order to achieve the above object, the present invention comprises a conductor made of metal and an insulating coating covering the outer periphery of the conductor, and the insulating coating contains 1,3-bis (4-aminophenoxy) benzene, Provided is an insulated wire which is made of a polyamide-imide resin substantially free from an adhesion improver and has an insulating layer having an adhesion strength of 50 g / mm or more to the conductor in close contact with the surface of the conductor.

In order to achieve the above object, the present invention can make the following improvements and changes in the insulated wire according to the present invention.
(1) In the insulating layer, the 1,3-bis (4-aminophenoxy) benzene is contained in a proportion of 30 mol% to 100 mol% in the diamine component constituting the polyamideimide resin.
(2) As for the said insulation coating, the outer layer is provided in the outer periphery of the said insulating layer.
(3) The outer layer is made of any resin selected from polyamide imide, polyester imide, and polyimide.

  Moreover, in order to achieve the said objective, this invention provides the coil formed using the insulated wire of said invention.

  Further, in order to achieve the above object, the present invention is an insulating paint for providing an insulating layer in close contact with the surface of a conductor made of metal, comprising 1,3-bis (4-aminophenoxy) benzene, Provided is an insulating paint composed of a polyamide-imide resin substantially free from an adhesion improver, wherein the adhesion strength of the insulating layer to the conductor is 50 g / mm or more.

In order to achieve the above object, the present invention can make the following improvements and changes in the insulated wire according to the present invention.
(1) The polyamideimide resin is composed of at least a diamine component, a diisocyanate component, and an acid component, and the 1,3-bis (4-aminophenoxy) benzene is 30 mol% or more and 100 mol% in the diamine component. It is included in the following proportions.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of a conductor and insulation coating is high, and the coil formed using the insulated wire which has sufficient adhesiveness even with the heat for a long time, and the insulated wire can be provided.

It is sectional drawing which shows an example of the insulated wire which concerns on embodiment of this invention. It is sectional drawing which shows an example of the insulated wire which concerns on embodiment of this invention. It is sectional drawing which shows an example of the insulated wire which concerns on embodiment of this invention. It is sectional drawing which shows an example of the insulated wire which concerns on embodiment of this invention.

  Hereinafter, modes for carrying out the present invention will be described with reference to the drawings and examples. However, the scope of the present invention is not limited to only the modes and examples taken here, and the gist of the present invention is not limited thereto. Various changes and improvements can be made without departing from the scope.

  FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention. As shown in FIG. 1, the insulated wire 10 according to the present embodiment is composed of a metal conductive wire made of copper, aluminum, or the like, and has a conductor 11 having a circular cross section and an insulating coating that covers the outer periphery of the conductor 11. And the insulating coating is composed of a polyamide-imide resin containing 1,3-bis (4-aminophenoxy) benzene and substantially not containing an adhesion improver, and the adhesion strength to the conductor 11 is 50 g / mm or more. The insulating layer 12 is provided in close contact with the surface of the conductor 11. That is, the insulating layer 12 functions as an insulating layer that electrically and mechanically insulates the conductor 11 and functions as an anti-peeling layer that is provided in close contact with the surface of the conductor 11 to prevent peeling from the conductor 11. Have both. In addition, the term “substantially free” as used herein means that an adhesion improver may be included in the polyamide-imide resin within a range that does not impair the effects of the present invention.

  The insulating layer 12 includes a layer made of a polyamide-imide resin containing 1,3-bis (4-aminophenoxy) benzene and substantially not containing an adhesion improver. By providing such an insulating layer 12 as a layer that adheres and covers the surface of the conductor 11, the adhesion between the conductor 11 and the insulating coating at room temperature is increased in a state that substantially does not contain an adhesion improver. In addition, sufficient adhesion can be exhibited even by heat for a long time, and the insulating coating can be prevented from peeling off from the conductor 11. Regarding the reason why the adhesion between the conductor 11 and the insulating coating can be increased without substantially containing the adhesion improving agent, and the reason why sufficient adhesion can be exhibited even by heat for a long time. Although it is not clear, it is considered that the benzene ring is more easily oriented on the surface of the conductor 11 in a planar form than in the past.

  The insulating layer 12 includes 1,3-bis (4-aminophenoxy) benzene in a proportion of 30 mol% or more and 100 mol% or less with respect to 100 mol% of the diamine component constituting the polyamideimide resin. preferable. In addition, the insulating layer 12 is a ratio in which 1,3-bis (4-aminophenoxy) benzene is less than 30 mol% with respect to 100 mol% of the diamine component in the diamine component of the polyamideimide resin constituting the insulating layer 12. If included, there is a possibility that the adhesion between the conductor 11 and the insulating layer 12 cannot be sufficiently exhibited.

  Further, the insulating layer 12 includes 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4-, as a diamine component other than 1,3-bis (4-aminophenoxy) benzene. (4-Aminophenoxy) phenyl] sulfone (BAPS), bis [4- (4-aminophenoxy) phenyl] ether (BAPE), fluorenediamine (FDA), 4,4′-bis (4-aminophenoxy) biphenyl ( BAPB), 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmethane (DAM), 4,4′-diaminodiphenyl ether (DPE) and other aromatic diamines are Polyamideimide resin used in combination with 4-aminophenoxy) benzene may be used. At this time, it is preferable that 1,3-bis (4-aminophenoxy) benzene is contained in the diamine component of the polyamideimide resin at a ratio of 30 mol% or more and less than 100 mol%. Although not particularly limited to these aromatic diamines, 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenyl ether are available as aromatic diamines used in combination with 1,3-bis (4-aminophenoxy) benzene. And from the viewpoint of heat resistance.

  The insulating layer 12 is formed by applying an insulating paint as a covering material for an insulated wire in which a polyamideimide resin containing 1,3-bis (4-aminophenoxy) benzene as a diamine component is dissolved in a solvent to the outer periphery of the conductor 11. 11 is formed by baking the insulating paint applied to the outer periphery of the iron 11 in a baking furnace or the like. The thickness of the insulating layer 12 is not less than 5 μm and not more than 30 μm, for example.

  The polyamide-imide resin containing 1,3-bis (4-aminophenoxy) benzene constituting the insulating layer 12 is, for example, a diamine component essentially containing 1,3-bis (4-aminophenoxy) benzene in a predetermined ratio Polyamideimide resin obtained by further synthesizing a diisocyanate component with a prepolymer (imidodicarboxylic acid) obtained by synthesizing an acid component composed of tricarboxylic acid anhydride or the like can be used.

  Examples of the acid component constituting the polyamide-imide resin include trimellitic anhydride (TMA), 3,4,4′-benzophenone tricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, and the like. It consists of an acid component that essentially contains a product. Of these, trimellitic anhydride is preferred. Moreover, tetracarboxylic dianhydride can also be used together with an acid component with a tricarboxylic anhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-. Fragrances such as diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4′-oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride (BPDA) Group tetracarboxylic dianhydride. If necessary, butane tetracarboxylic dianhydride or 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Cyclic tetracarboxylic dianhydrides or alicyclic tetracarboxylic dianhydrides hydrogenated with the aromatic tetracarboxylic dianhydrides exemplified above may be used in combination with tricarboxylic anhydrides. However, in this case, it is necessary to adjust the molar ratio so that the terminal is a dicarboxylic acid.

  Moreover, you may use together dicarboxylic acid for an acid component with a tricarboxylic acid anhydride. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid (TPA), isophthalic acid, and naphthalenedicarboxylic acid, or dimethyl terephthalate (DMT) that is an alkyl ester thereof, dimethyl isophthalate, and the like. Of these, dimethyl terephthalate is preferred. In some cases, tricarboxylic acid having an isocyanurate ring such as chic acid or aromatic tricarboxylic acid such as trimesic acid may be used.

  The diisocyanate component constituting the polyamide-imide resin includes diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, diphenyl ether diisocyanate and the like, and a large amount And aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and xylylene diisocyanate, or alicyclic diisocyanates and isomers obtained by hydrogenating the aromatic diisocyanates exemplified above.

  Solvents for dissolving the polyamideimide resin include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), dimethylimidazolidinone ( DMI), cyclohexanone, methylcyclohexanone and the like. These solvents may be used in combination as long as the synthesis reaction of the polyamideimide resin is not inhibited, or may be diluted. In addition, aromatic alkylbenzenes may be used in combination for dilution purposes. However, it is necessary to consider when there is a risk of lowering the solubility of the polyamideimide.

  The insulating coating used when the insulating layer 12 is provided in close contact with the surface of the conductor 11 made of metal is a polyamide containing 1,3-bis (4-aminophenoxy) benzene and substantially free of an adhesion improving agent. An insulating paint made of imide resin and having an adhesion strength of the insulating layer 12 to the conductor 11 of 50 g / mm or more is used.

  In this polyamideimide resin, for example, an acid component composed of a tricarboxylic acid anhydride or the like is added to a diamine component essentially containing 1,3-bis (4-aminophenoxy) benzene, and a dehydration imidation reaction is performed. After the first step of the synthesis step to obtain the dicarboxylic acid, the diimide component is added to the obtained imide dicarboxylic acid, and then obtained through the second step of synthesis step in which a decarboxylation amidation reaction is performed. Can be used.

  In the first-stage synthesis step, the mixing ratio of the diamine component essentially containing 1,3-bis (4-aminophenoxy) benzene and the acid component composed of tricarboxylic acid anhydride, etc. should be equal molar amount. Although desirable, the ratio of the molar amount of the other component to the molar amount of the one component can be appropriately adjusted within a range of −5 mol% to 5 mol%. Similarly, in the second stage synthesis step, it is desirable that the mixing ratio of the imide dicarboxylic acid and the diisocyanate component is an equal molar amount, but the ratio of the molar amount of the diisocyanate component to the molar amount of the imide dicarboxylic acid is Adjustments can be made as appropriate within the range of −5 mol% to 5 mol%.

  In addition, it is also possible to manufacture a diisocyanate component using phosgene based on a diamine component, and all or a part of the diamine component described above can be used in place of the diisocyanate component. When all of them are replaced with diisocyanate components, the synthesis can be performed by the decarboxylation reaction in the first-stage synthesis step without performing the second-stage synthesis step.

  In the synthesis of the insulating paint, a reaction catalyst such as amines, imidazoles, and imidazolines may be used, but those that do not inhibit the stability of the insulating paint are desirable. Moreover, when stopping reaction at the time of a synthesis | combination, you may use sealing agents, such as alcohol. Furthermore, the insulating paint may contain various additives such as pigments, dyes, inorganic or organic fillers, lubricants, antioxidants, and leveling agents.

  The insulated wire 10 has excellent adhesion between the conductor 11 and the insulation coating, can prevent the insulation coating from peeling off from the conductor 11, and has excellent mechanical properties such as wear resistance and flexibility. . For this reason, the insulated wire 10 is not susceptible to damage to the insulation coating even when the stress applied to the insulated wire 10 is increased in the process of processing the insulated wire 10 such as a winding process, and the motor is reduced in size and weight, and the height is increased. It can meet demands for efficiency and is industrially useful.

  FIG. 2 is a cross-sectional view showing an example of a modified example of the insulated wire according to the embodiment of the present invention. An insulated wire 20 shown in FIG. 2 has a multi-layer structure of the insulation coating of the insulated wire 10 shown in FIG. Specifically, the conductor 21 is made of a conductive wire made of a metal such as copper or aluminum, the conductor 21 having a circular cross-sectional shape, and the insulating layer 22 that covers the surface of the conductor 21 in close contact with the outer periphery of the conductor 21; And an outer layer 23 provided on the outer periphery of the insulating layer 22. As the insulating layer 22, the same polyamideimide resin as that of the insulating layer 12 shown in FIG. 1, that is, a polyamideimide resin containing 1,3-bis (4-aminophenoxy) benzene and substantially free of an adhesion improver. The adhesion strength to the conductor 21 is 50 g / mm or more.

  The outer layer 23 provided on the outer periphery of the insulating layer 22 includes a first outer layer 23a covering the surface of the insulating layer 22 in close contact with the outer layer 23, and a second outer layer 23b provided on the outer periphery of the first outer layer 23a. . The first outer layer 23a and the second outer layer 23b are made of, for example, a resin made of any one of a polyamideimide resin, a polyimide resin, a polyesterimide resin, and the like. The second outer layer 23b may be made of a resin to which a lubricant is added.

  In the insulated wire 20 shown in FIG. 2, the outer layer 23 has been described as having a layer structure including the first outer layer 23a and the second outer layer 23b. However, the present invention is not limited to this, and for example, the first outer layer 23a. Alternatively, it may have a layer structure in which any one of the second outer layers 23b is not provided, and a polyamide imide resin, a polyimide resin, a polyester imide resin, etc. are further provided on the outer periphery of the second outer layer 23b shown in FIG. The outer layer 23 having a layer structure in which one or more resin layers made of the above resin are provided may be used.

  FIG. 3 is a cross-sectional view showing an example of a modified example of the insulated wire according to the embodiment of the present invention. An insulated wire 30 shown in FIG. 3 is composed of a conductive wire made of a metal such as copper or aluminum, and a conductor 31 having a flat cross-sectional shape and an insulation covering the surface of the conductor 31 in close contact with the outer periphery of the conductor 31. And an insulating coating having at least a layer 32. The insulating layer 32 includes the same polyamideimide resin as that of the insulating layers 12 and 22 shown in FIGS. 1 and 2, that is, 1,3-bis (4-aminophenoxy) benzene, and substantially includes an adhesion improver. The adhesive strength with respect to the conductor 31 is 50 g / mm or more.

  FIG. 4 is a cross-sectional view showing an example of a modified example of the insulated wire according to the embodiment of the present invention. The insulated wire 40 shown in FIG. 4 is provided with an outer layer on the outer periphery of the insulating layer 32 of the insulated wire 30 shown in FIG. Specifically, a conductor 41 made of a metal such as copper or aluminum and having a circular cross-sectional shape, and an insulating layer 42 which is an outer periphery of the conductor 41 and covers the surface of the conductor 41 in close contact with each other, And an outer layer 43 provided on the outer periphery of the insulating layer 42. The insulating layer 42 includes a polyamideimide resin similar to the insulating layers 12, 22, and 32 shown in FIGS. 1 to 3, that is, 1,3-bis (4-aminophenoxy) benzene, and substantially includes an adhesion improver. It is comprised with the polyamidoimide resin which does not contain, and the adhesive strength with respect to the said conductor is 50 g / mm or more.

  The outer layer 43 provided on the outer periphery of the insulating layer 42 is made of, for example, a resin made of any one of polyamideimide resin, polyimide resin, polyesterimide resin, and the like. The outer layer 43 may be made of a resin to which a lubricant is added.

  In the insulated wire 40 shown in FIG. 4, the outer layer 43 has been described as a single layer structure. However, the outer layer 43 is not limited to this. For example, as in the insulated wire 20 shown in FIG. It may have a layer structure in which the first outer layer and the second outer layer are sequentially provided. Further, the outer periphery of the second outer layer is made of a resin such as a polyamideimide resin, a polyimide resin, or a polyesterimide resin. The outer layer 43 may have a layer structure in which one or more resin layers are provided.

  In the insulated wire according to the present embodiment, the conductors 11, 21, 31, 41 are copper wires made of low oxygen copper, oxygen free copper, or the like, or copper alloy wires, and other metal wires such as silver and aluminum. Etc. are also used. The cross-sectional shapes of the conductors 11, 21, 31, 41 are round shapes as shown in FIGS. 1-2, or quadrangular shapes with four corners curved as shown in FIGS. However, the present invention is not limited to this. For example, it may be an irregular shape or a polygonal shape having a cross-sectional shape in which corners in a quadrangular shape are tapered.

  In the insulated wire according to the present embodiment, the outer layer provided on the outer periphery of the peeling prevention layer as an insulation coating is made of a resin such as polyamide imide resin, polyimide resin, polyester imide resin, H-type polyester resin, silica, alumina, or the like. It may be composed of a resin layer to which inorganic fine particles are added. By setting it as the outer layer which consists of such a resin layer, the tolerance with respect to generation | occurrence | production of a partial discharge can be improved. Further, for the purpose of improving the lubricity of the surface of the insulating coating, the outer layer may be composed of a lubricating layer.

[Preparation of insulating paint]
In producing the insulated wires according to the examples and comparative examples, an insulating paint made of a polyamideimide resin for forming an insulating layer covering and covering the surface of a conductor made of metal was prepared by the method shown below. .

The insulating paint used for forming the insulating layers of Examples 1 to 6 was prepared by performing the following two-step synthesis.
First, a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer was prepared, and as a first-stage synthesis reaction, the diamine components, acid components, and solvents shown in Examples 1 to 6 to be post-treated About 50-80% was put into a prepared flask, heated to 180 ° C. in about 1 hour with stirring in a nitrogen atmosphere, and reacted at this temperature for 4 hours while taking out water generated by the dehydration reaction from the system. I let you. Next, after cooling to 60 ° C. while maintaining the nitrogen atmosphere, the diisocyanate component and the remaining solvent are added, and the second-stage synthesis reaction is heated to 140 ° C. in about 1 hour with stirring in the nitrogen atmosphere. In order to obtain a polyamideimide resin solution having a reduced viscosity of about 0.5 dl / g, an insulating coating made of polyamideimide resin was prepared by reacting at this temperature for 2 hours.

The insulating paint used to form a layer (a layer corresponding to an insulating layer) that adheres and covers the surfaces of the conductors of Comparative Examples 1 to 3 is synthesized with an acid component and a diisocyanate component as shown below. It was prepared with.
Into a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, the acid component, diisocyanate component, and solvent shown in Comparative Examples 1 to 3 to be post-treated are added at once, while stirring in a nitrogen atmosphere. Heating to 140 ° C. in 1 hour was carried out at this temperature for 2 hours so as to obtain a polyamideimide resin solution having a reduced viscosity of about 0.5 dl / g, thereby preparing an insulating paint made of polyamideimide resin.

Example 1
As a first stage synthesis, 146.0 g (0.5 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) as a diamine component and trimellitic anhydride as an acid component were added to a flask. 192.0 g (1.0 mol) of (TMA) and 1000 g of N-methyl-2-pyrrolidone (NMP) as a solvent were added, and synthesis was performed while discharging water outside the system at 180 ° C. After cooling to 60 ° C. while maintaining, as the synthesis of the second stage, 130.0 g (0.52 mol) of 4,4′-diphenylmethane diisocyanate (4,4′-MDI) as a diisocyanate component, and a solvent Insulating paint made of polyamide-imide resin with a reduced viscosity of about 0.5 dl / g and a resin concentration of about 25% by weight. Obtained.
An insulated wire made of polyamideimide resin is applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this is baked to form an insulating layer having a thickness of 30 μm, thereby obtaining an insulated wire. It was.

(Example 2)
In the first stage synthesis, 102.2 g (0.35 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) as a diamine component and 4,4′-diaminodiphenyl ether ( 4,4′-DPE) 30.0 g (0.15 mol), trimellitic anhydride (TMA) 192.0 g (1.0 mol) as the acid component, and N-methyl-2-pyrrolidone as the solvent (NMP) was added in 900 g, synthesis was performed while water was discharged out of the system at 180 ° C., and the mixture was cooled to 60 ° C. while maintaining the nitrogen atmosphere. 90.5 g (0.52 mol) of 4-tolylene diisocyanate (2,4-TDI) and 340 g of γ-butyrolactone as a solvent were added and synthesized at 140 ° C. An insulating paint made of polyamideimide resin having a degree of about 0.5 dl / g and a resin content concentration of about 25% by weight was obtained.
An insulated wire made of polyamideimide resin is applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this is baked to form an insulating layer having a thickness of 30 μm, thereby obtaining an insulated wire. It was.

(Example 3)
As a first stage synthesis, 43.8 g (0.15 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) and 4,4′-diaminodiphenylmethane ( DAM) is 69.3 g (0.35 mol), trimellitic anhydride (TMA) is 192.0 g (1.0 mol) as an acid component, and N-methyl-2-pyrrolidone (NMP) is 1000 g as a solvent. And after synthesizing while discharging water outside the system at 180 ° C. and cooling to 60 ° C. while maintaining the nitrogen atmosphere, as the second stage synthesis, 4,4′-diphenylmethane diisocyanate as the diisocyanate component (MDI) 130.0 g (0.52 mol) and N, N-dimethylformamide (DMF) 350 g as a solvent were added and synthesized at 140 ° C. Performed, a reduced viscosity of about 0.5 dl / g, to obtain an insulating coating resin concentration of about 25 wt% of polyamide-imide resin.
An insulated wire made of polyamideimide resin is applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this is baked to form an insulating layer having a thickness of 30 μm, thereby obtaining an insulated wire. It was.

Example 4
In the first stage synthesis, 146.0 g (0.50 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) as a diamine component and trimellitic anhydride as an acid component were added to a flask. 192.0 g (1.0 mol) of (TMA) and 1000 g of N-methyl-2-pyrrolidone (NMP) as a solvent were added, and synthesis was performed while discharging water outside the system at 180 ° C. After cooling to 60 ° C. while maintaining, 90.5 g (0.52 mol) of 2,4-tolylene diisocyanate (2,4-TDI) as a diisocyanate component and as a solvent were synthesized as the second stage synthesis. 280 g of N, N-dimethylformamide (DMF) was added, synthesized at 140 ° C., polyamide viscosity having a reduced viscosity of about 0.5 dl / g and a resin concentration of about 25% by weight. Obtain an insulation coating made of a resin.
An insulated wire made of polyamideimide resin is applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this is baked to form an insulating layer having a thickness of 30 μm, thereby obtaining an insulated wire. It was.

(Example 5)
The insulating paint made of polyamideimide resin obtained in Example 1 was applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this was baked to form an insulating layer having a thickness of 22 μm. An insulated wire made of a general-purpose polyamide-imide resin was applied on the insulating layer (HIC 406 manufactured by Hitachi Chemical Co., Ltd.), and this was baked to form an outer layer having a thickness of 8 μm to obtain an insulated wire. .

(Example 6)
The insulating paint made of polyamideimide resin obtained in Example 1 was applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this was baked to form an insulating layer having a thickness of 5 μm. An insulating paint made of general-purpose polyesterimide resin (EH402, manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied on the insulating layer, and this is baked to form a first outer layer having a thickness of 17 μm. Insulation is performed by applying an insulating paint made of general-purpose polyamideimide resin (HI406, manufactured by Hitachi Chemical Co., Ltd.) on the first outer layer and baking it to form a second outer layer having a thickness of 8 μm. I got an electric wire.

(Comparative Example 1)
In the flask, 255.0 g (1.02 mol) of 4,4′-diphenylmethane diisocyanate (4,4′-MDI) as a diisocyanate component and 192.0 g (1. 2) of trimellitic anhydride (TMA) as an acid component. 0 mol), and 1000 g of N-methyl-2-pyrrolidone (NMP) and 330 g of N, N-dimethylformamide (DMF) as a solvent were added and synthesized at 140 ° C., and the reduced viscosity was about 0.5 dl / g. An insulating paint made of a polyamideimide resin having a resin concentration of about 25% by weight was obtained.
The insulated wire made of this polyamideimide resin was applied to the surface of a conductor made of copper wire having a diameter of 0.8 mm, and this was baked to form a layer having a thickness of 30 μm to obtain an insulated wire. .

(Comparative Example 2)
In the flask, 255.0 g (1.02 mol) of 4,4′-diphenylmethane diisocyanate (MDI) as the diisocyanate component, 192.0 g (1.0 mol) of trimellitic anhydride (TMA) as the acid component, and As a solvent, 1000 g of N-methyl-2-pyrrolidone (NMP) and 330 g of N, N-dimethylformamide (DMF) were added and synthesized at 140 ° C., the reduced viscosity was about 0.5 dl / g, and the resin concentration was After obtaining a paint composed of about 25% by weight of polyamideimide resin, 1.34 g (0.3 phr) of aminobenzothiazole as an adhesion improver was added to the paint to obtain an insulating paint.
This insulating paint was applied to the surface of a conductor made of a copper wire having a diameter of 0.8 mm, and baked to form a layer having a thickness of 30 μm, thereby obtaining an insulated wire.

(Comparative Example 3)
In the flask, 255.0 g (1.02 mol) of 4,4′-diphenylmethane diisocyanate (MDI) as the diisocyanate component, 192.0 g (1.0 mol) of trimellitic anhydride (TMA) as the acid component, and 1330 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent, synthesized at 140 ° C., and a paint composed of polyamideimide resin having a reduced viscosity of about 0.5 dl / g and a resin concentration of about 25% by weight. Then, 1.34 g (3.0 phr) of melamine resin was added as an adhesion improver to the paint to obtain an insulating paint.
This insulating paint was applied to the surface of a conductor made of a copper wire having a diameter of 0.8 mm, and baked to form a layer having a thickness of 30 μm, thereby obtaining an insulated wire.

  Table 1 shows the raw material composition of the insulating paint used in Examples 1 to 6 and Comparative Examples 1 to 3, and the characteristics of the insulated wires.

  In addition, about the dimension and abrasion resistance of the insulated wire, it measured by the method based on JISC3216.

  The adhesion strength between the conductor and the insulating film was measured by the following method. First, a sample piece having a length of about 5 cm was cut from each insulated wire obtained. Thereafter, two notches extending in the longitudinal direction of the sample piece were formed at an interval of 1 mm on the insulating coating on the upper surface or the lower surface (one of the wider surfaces) of each sample piece using a cutter or the like. The end portion in the longitudinal direction of the insulating coating between the cuts was peeled off from the conductor using tweezers or the like to form a grip allowance. Thereafter, each sample piece was fixed to a jig, the gripping margin was sandwiched between chucks, and the insulation coating was peeled off from the conductor using a Tensilon universal testing machine. At this time, the strength (peeling strength) when the insulating coating was peeled from the end in the longitudinal direction to a length of 1 mm was measured as the adhesion strength.

  The adhesion strength between the conductor after thermal deterioration and the insulating film was measured by the following method. First, a sample piece having a length of about 5 cm was cut from each insulated wire obtained. Then, each cut sample piece was put into a thermostat and left at a temperature of 160 ° C. for 168 hours. After that, each sample piece is taken out from the thermostat, and a cut or the like extending in the longitudinal direction of the sample piece is applied to the insulating coating on the upper surface or lower surface (one of the wider surfaces) of each sample piece using a cutter or the like. Two were formed at 1 mm intervals. The end portion in the longitudinal direction of the insulating coating between the cuts was peeled off from the conductor using tweezers or the like to form a grip allowance. Thereafter, each sample piece was fixed to a jig, the gripping margin was sandwiched between chucks, and the insulation coating was peeled off from the conductor using a Tensilon universal testing machine. At this time, the strength (peeling strength) when the insulating coating was peeled from the end in the longitudinal direction to a length of 1 mm was measured as the adhesion strength.

  In addition, the adhesion (initial) is to fix a linear sample taken from an insulated wire between two coaxial clamps 250 mm apart, and to use an insulating coating on two sides parallel to the length of the sample as a conductor. Remove until it reaches. Thereafter, the other clamp was rotated while one clamp was fixed, and the number of rotations of the clamp when the insulating coating floated from the surface of the conductor was measured. The adhesion was tested both in the normal state and after heat deterioration (deterioration condition: 160 ° C. × 168 h).

  For adhesion (after heat deterioration), a linear sample taken from an insulated wire was placed in a thermostatic bath and left at a temperature of 160 ° C. for 168 hours. Then, the sample taken out from the thermostat is fixed between two coaxial clamps separated by 250 mm, and two insulating coatings parallel to the length direction of the sample are removed until reaching the conductor. Thereafter, the other clamp was rotated while one clamp was fixed, and the number of rotations of the clamp when the insulating coating floated from the surface of the conductor was measured.

  In the insulated wires of Examples 1 to 6, as is apparent from the results shown in Table 1, compared to Comparative Example 1 which is a general-purpose polyamideimide, initial adhesion and wear resistance are greatly improved. It can also be seen that it has good adhesion even after thermal degradation. On the other hand, in Comparative Examples 2 and 3 to which an adhesion improver for improving the adhesion was added, the initial adhesion and wear resistance showed values close to those of Examples 1 to 6, but the adhesion after heat deterioration It can be seen that the performance is greatly reduced.

  As described above, according to the present invention, it is provided with a conductor made of metal and an insulating coating covering the outer periphery of the conductor, and the insulating coating contains 1,3-bis (4-aminophenoxy) benzene and substantially contains the adhesion improver. By using an insulated wire that is made of a polyamide-imide resin that does not contain a conductive material and that has an insulating layer having an adhesion strength to the conductor of 50 g / mm or more in close contact with the surface of the conductor, In addition to improving the adhesiveness, good adhesiveness can be exhibited even when heat is applied for a long time.

10, 20, 30, 40 Insulated wire 11, 21, 31, 41 Conductor 12, 22, 32, 42 Insulating layer 23, 43 Outer layer 23a First outer layer 23b Second outer layer

Claims (7)

A conductor made of metal;
An insulating coating covering the outer periphery of the conductor,
The insulating coating includes 1,3-bis (4-aminophenoxy) benzene, is composed of a polyamide-imide resin substantially free of an adhesion improver, and has an adhesion strength of 50 g / mm or more with respect to the conductor. Is an insulated wire provided in close contact with the surface of the conductor.   The insulating layer contains the 1,3-bis (4-aminophenoxy) benzene in a proportion of 30 mol% or more and 100 mol% or less in the diamine component constituting the polyamideimide resin. Insulated wire as described.   The insulated wire according to claim 1, wherein the insulating coating is provided with an outer layer on an outer periphery of the insulating layer.   The insulated wire according to any one of claims 1 to 3, wherein the outer layer is made of any one of polyamideimide, polyesterimide, and polyimide.   The coil formed using the insulated wire of any one of Claims 1-4. An insulating paint for providing an insulating layer in close contact with the surface of a conductor made of metal,
An insulating coating comprising 1,3-bis (4-aminophenoxy) benzene and a polyamide-imide resin substantially free of an adhesion improver, wherein the adhesion strength of the insulating layer to the conductor is 50 g / mm or more.   The polyamide-imide resin is composed of at least a diamine component, a diisocyanate component, and an acid component, and the proportion of the 1,3-bis (4-aminophenoxy) benzene is 30 mol% or more and 100 mol% or less in the diamine component. The insulating paint according to claim 6, which is contained in

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