JPH0770256B2 - Lubricated insulated wire with excellent heat resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lubricated insulated wire having excellent surface lubricity and heat resistance.

[Conventional technology]

Insulated wires coated with polyurethane paint, polyester paint, etc. on a conductor and baked are widely used as coils for electric and electronic equipment, but prevent deterioration of processing during coil winding and wire breakage during wire feeding, It is necessary to lubricate the surface of the insulating film or to improve the mechanical strength of the film to increase the wear resistance in order to improve the wear resistance. For this reason,
Conventionally, a method of applying a lubricant such as liquid paraffin or refrigerating machine oil to the surface of the insulating film, nylon (6
-Nylon, 6-6 nylon, etc.) is applied to the outer periphery of the insulating film, and a lubricant is further applied, or a method of adding a lubricant to the insulating paint has been used.

[Problems to be Solved by the Invention]

However, as electric and electronic devices have become smaller and higher in performance in recent years, attention has been paid to organic gas generated from insulating materials as a cause of malfunction of the device, and it is desirable to reduce the generation of such organic gas as much as possible. It is rare. For example, in a relay circuit, liquid paraffin applied as a lubricant on the surface of the insulation film is decomposed by the arc generated when the relay contact opens and closes and adheres to the contact as carbon, increasing contact resistance and consuming the contact. There was a problem of hurrying. In addition, there is a problem that it is difficult to apply the lubricant evenly on the surface of the electric wire when the lubricant is applied, and stable surface lubricity cannot be obtained. Further, although the wear resistance of the coating can be improved by coating the outer periphery of the insulating coating with nylon, there is a problem that the heat resistance is lowered due to the characteristics of the nylon resin.

In addition, since an additive type lubricant such as a higher fatty acid ester is added to the insulating paint, the boiling point of the higher fatty acid ester, which is a lubricant, is close to that of cresol, which is a solvent of the insulating paint. It volatilizes and rarely remains in the film, so it tends to lose the lubricity effect, and the lubricant has poor compatibility or dispersibility with the paint due to the difference in chemical structure, and the addition amount is limited. There was a problem. In addition, in order to solve these above problems, a lubricating nylon paint prepared by adding a lubricant to nylon and dissolving it in an organic solvent is applied to the outer periphery of the insulating film and baked,
Measures have been taken to improve the wear resistance and surface lubricity of insulated wires. However, there has been a problem that the heat resistance of the insulating film is lowered and the reliability of the insulated wire is significantly impaired.

The present invention has been made to solve the problems of these conventional techniques and has uniform surface lubricity.
It is an object of the present invention to provide a lubricated insulated electric wire having good winding property and excellent heat resistance.

[Means for Solving the Problems]

In order to achieve the above object, the present invention relates to 100 parts by weight of a polyetherimide resin, a reactive silicone having an amino group at a terminal and a molecular weight of 1,000 to 10,000, and an epoxy equivalent of 4
The silicone-modified epoxy resin obtained by pre-reacting 50-4,000 bisphenol A type epoxy resin is 0.1-2.
Heat resistance characterized by adding 0 parts by weight, preferably 5 to 15 parts by weight, and dispersing and dissolving this in an organic solvent to apply or bake a lubricating insulating paint directly on the conductor or through an insulating film Excellent in lubricity insulated wire.

The polyetherimide resin used as the main component of the lubricating insulating paint of the present invention is an amorphous thermoplastic polymer and is represented by the following general formula.

This polyetherimide resin has heat resistance, mechanical properties,
It has excellent electrical characteristics. Generally, 6-nylon, 6-6
In the case of a crystalline resin such as nylon, the physical property values tend to change rapidly as the temperature rises. On the other hand, the polyether imide resin is an amorphous resin in terms of its molecular structure, and therefore has very little change in physical properties due to temperature rise, and has toughness and high strength in a wide temperature range.

As a specific example of the polyetherimide resin, Ultem 10
00 (engineering plastics company trade name) can be mentioned.

The silicone-modified epoxy resin used as the second component of the lubricating insulating paint has a molecular weight having an amino group at the terminal.
It is obtained by reacting 1,000 to 10,000 reactive silicone (hereinafter abbreviated as reactive silicone) with bisphenol A type epoxy resin (hereinafter abbreviated as epoxy resin) having an epoxy equivalent of 450 to 4,000. It is used for the purpose of imparting lubricity to the surface of the insulated wire and improving the winding property by adding it to the polyetherimide resin. Moreover, this silicone-modified epoxy resin is also excellent in electrical insulation and weather resistance. The reactive silicone is used as a component that imparts lubricity, but when it is directly added to a polyetherimide resin and dispersed or dissolved in an organic solvent, the stability of the coating composition is poor and the coating composition separates when left for a long time. Further, the reactive silicone has an amino group, but since the polyetherimide resin has no reactive group, a chemical reaction does not occur during baking of the paint, and the reactive silicone is almost volatilized, which is good. Surface lubricity cannot be obtained. Therefore, a silicone-modified epoxy resin obtained by previously reacting a reactive silicone with an epoxy resin is used as a lubricity imparting component. The reactive silicone is represented by the following general formula.

As a specific example, silaplane FM3311, same FM3321, same FM
3325 (trade name of Chisso Corporation) can be mentioned.

The reason why the molecular weight of the reactive silicone is limited to 1,000 to 10,000 is that when the molecular weight is less than 1,000, the effect as a lubricity-imparting component is small, and when the molecular weight exceeds 10,000, the stability of the coating is lacking. The epoxy resin is used for the purpose of reacting with the reactive silicone to improve paint stability and thermal stability of the lubricant during baking. As a specific example, Epicoat 1001,
Examples thereof include 1004, 1007, 1009 (trade name of Yuka Shell Epoxy Co., Ltd.), Epotote YD-011, YD-014, and YD-017 (trade name of Toto Kasei Co., Ltd.). The reason for limiting the epoxy equivalent of the epoxy resin to 450 to 4,000 is that when the epoxy equivalent is less than 450, it is difficult to control the reaction with the reactive silicone due to the high reactivity of the epoxy resin, and when the epoxy equivalent exceeds 4,000. This is because the content of silicone in the reaction product is reduced and good surface lubricity cannot be obtained.

The reason why the addition amount of the silicone-modified epoxy resin is limited to 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyetherimide resin is that good surface lubricity cannot be obtained when the addition amount is less than 0.1 parts by weight. If the amount exceeds 20 parts by weight, the properties of the polyetherimide resin are impaired. That is, when the added amount is large, the plasticizing effect of the silicone-modified epoxy resin appears, and the thermal softening temperature of the film is lowered.

[Work]

The lubricated insulated wire of the present invention is obtained by coating and baking a lubricative insulating coating obtained by dispersing and dissolving a polyetherimide resin and a silicone-modified epoxy resin in an organic solvent, either directly on the conductor or through an insulating film. can get. Therefore,
The insulated wire has excellent heat resistance due to the polyetherimide resin and excellent surface lubricity due to the silicone-modified epoxy resin.

Since the silicone-modified epoxy resin has a benzene ring in the resin skeleton, it has good dispersibility in a lubricating coating containing a polyetherimide resin as a main component, and improves the stability of the coating. Even after baking, since it is uniformly dispersed in the polyetherimide resin as the main component, it is possible to impart uniform and stable lubricity to the coating surface.

〔Example〕

The contents of the present invention will be described below with reference to examples and comparative examples.

Example 1 In a 2,000 ml separable round-bottomed flask equipped with a stirrer, a thermometer and a cooling tube, 100 g of silaplane FM3321 as reactive silicone and Epicoat 1 as epoxy resin were placed.
100 g of 007 and 1,133 g of m-cresol as a solvent are added and gradually heated with stirring. When the internal temperature reaches 180 ℃, continue heating and stirring at that temperature for 3 hours,
The reactive silicone was reacted with the epoxy resin. After the reaction, the reaction mixture was cooled to room temperature to obtain a cresol dispersion liquid of a silicone-modified epoxy resin having a concentration of 15% (hereinafter abbreviated as silicone-modified epoxy resin dispersion liquid A). In addition, polyether imide resin Ultem 1000 is m-cresol / xylol =
It was dissolved in a 6/4 (weight ratio) solvent to obtain a 15% concentration polyetherimide resin solution (hereinafter abbreviated as PEI solution).

The above silicone-modified epoxy resin dispersion A (47.6 g) was added to a PEI solution (952.4 g) and sufficiently stirred to prepare a lubricating insulating paint.

Next, in a enamel wire baking furnace (horizontal length of 2.5 m), a 0.20 mm copper wire was coated with a B class polyurethane insulating paint WD4305 (Hitachi Chemical Co., Ltd. product name) at a concentration of 35%. After applying and baking 7 times at a temperature of 60 ° C / min), a lubricating insulating coating was applied and baked 4 times under the same baking conditions to produce a lubricating insulated wire.

Example 2 Silicone-modified epoxy resin dispersion liquid obtained in Example 1
A lubricous insulated electric wire was produced in the same manner as in Example 1 except that A91.0 g was added to PEI solution 909.0 g and sufficiently stirred to prepare a lubricative insulating paint.

Example 3 Silicone-modified epoxy resin dispersion obtained in Example 1
A lubricous insulated wire was produced in the same manner as in Example 1 except that 130.4 g of A13 was added to 869.6 g of PEI solution and sufficiently stirred to prepare a lubricative insulating coating material.

Example 4 In a 2,000 ml separable round bottom flask similar to that of Example 1, 50 silaplane FM3321 was added as a reactive silicone.
g, 100 g of Epicoat 1007 as an epoxy resin, and 850 g of m-cresol as a solvent were added, and a cresol dispersion of a silicone-modified epoxy resin having a concentration of 15% was prepared in the same manner as in Example 1 (hereinafter referred to as Silicone-modified epoxy resin dispersion B). Abbreviated). Also, a PEI solution was obtained in the same manner as in Example 1.

The above silicone-modified epoxy resin dispersion B (47.6 g) was added to PEI solution (952.4 g) and sufficiently stirred to prepare a lubricating insulating coating material. Next, a lubricated insulated wire was manufactured in the same manner as in Example 1.

Example 5 Silicone-modified epoxy resin dispersion obtained in Example 4
Lubricated insulated electric wires were produced in the same manner as in Example 4 except that B9 (1.0 g) was added to the PEI solution (909.0 g) and the mixture was sufficiently stirred to prepare a lubricating insulating paint.

Example 6 Silicone-modified epoxy resin dispersion obtained in Example 4
Lubricated insulated electric wires were produced in the same manner as in Example 1 except that 130.4 g of B13 was added to 869.6 g of PEI solution, and the mixture was sufficiently stirred to prepare a lubricating insulating coating material.

Comparative Example 1 In the enameled wire baking furnace of Example 1, the concentration of the class B polyurethane insulating paint WD4305 (trade name of Hitachi Chemical Co., Ltd.) on the copper wire of 0.20 mm
35% was applied 10 times under the same baking conditions as in Example 1 and baked, and then liquid polyurethane paraffin was applied to the surface of the film to produce a polyurethane insulated electric wire.

Comparative Example 2 120 g of polyamide resin CM3001N (trade name of Toray Industries, Inc.) was dissolved in 880 g of m-cresol / xylol = 6/4 (weight ratio) to obtain a nylon coating having a concentration of 12%. Next, in a enamel wire baking furnace of Example 1, a B type polyurethane paint WD4305 (Hitachi Chemical Co., Ltd. trade name) concentration of 35% was applied on a 0.20 mm copper wire, and Example 1 was used.
After applying and baking 7 times under the same baking conditions, the nylon paint of this comparative example is applied and baked 4 times under the same baking conditions,
Furthermore, a polyurethane nylon insulated wire in which liquid paraffin was applied to the surface of the film was manufactured.

Characteristic test 1 The general characteristics of the lubricated insulated wire of the present invention and the insulated wire of the comparative example were tested, and the results are shown in Table 1.

Characteristic test 2 (heat resistance test) In accordance with JIS C 3003 "Testing method for enamel copper wire and enamel aluminum wire", using the insulated wires of Examples 1 to 6 and Comparative Examples 1 and 2, two An individual twist sample was prepared. This sample was left in a constant temperature bath kept at 220 ° C. for 168 hours and then taken out, and the dielectric breakdown voltage was measured at room temperature. The residual ratio with respect to the initial value was calculated from the dielectric breakdown voltage after heat treatment and is shown in Table 2.

[Effects of the Invention] The lubrication-insulated electric wire of the present invention has a film having a very excellent surface lubricity with a surface friction coefficient μ of 0.10 to 0.11 as shown in the examples of Table 1, so that Very good winding property. That is, when the coil is wound, the electric wire is easily paid out from the bobbin so that there is no breakage and the wire can be wound with a stable tension, so that there is little deterioration of the electric wire, and high-speed winding is possible. Furthermore, since liquid paraffin that generates an organic gas that causes malfunction of the electric / electronic device, refrigerating machine oil, etc. are not applied to the surface of the film, the reliability of the electric / electronic device is significantly improved. In addition, as shown in the examples of Table 2, the heat resistance is extremely excellent, so that it can withstand use at high temperatures. Therefore, the lubricating insulated electric wire of the present invention is useful as a highly reliable insulated electric wire suitable for the application in the severer use environment due to miniaturization and higher performance of electric and electronic equipment.

Continuation of the front page (56) References JP-A-63-29411 (JP, A) JP-A-63-29412 (JP, A) JP-A-62-17048 (JP, A)

Claims (1)

[Claims] 1. Obtained by previously reacting 100 parts by weight of a polyetherimide resin with a reactive silicone having an amino group at a terminal and having a molecular weight of 1,000 to 10,000 and a bisphenol A type epoxy resin having an epoxy equivalent of 450 to 4,000. Heat resistance characterized by adding 0.1 to 20 parts by weight of silicone-modified epoxy resin, dispersing and dissolving this in an organic solvent, and applying and baking a lubricating insulating paint directly or through an insulating film on the conductor Lubricating insulated wire with excellent properties.