JPS63213206A - Self-fusing insulated wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a self-bonding insulated wire.

[Conventional technology and its problems]

Self-bonding insulation'r! In recent years, the use of single wire has been rapidly increasing due to the rationalization and labor saving of the coil processing process.
Also, its uses are being expanded. Conventionally, thermoplastic resins such as phenoxy resin, polyvinyl butyral resin, and polyamide resin have often been used as the fusion resin layer of this self-bonding insulated wire.

However, as the applications of these self-bonding insulated wires are rapidly expanding, attempts are being made to apply them not only to general-purpose applications but also to devices that are subject to vibration and are used at high temperatures, such as transformers and electric motors. . For such applications, if conventional thermoplastic resin is used for the adhesive layer, there are problems such as the coil coming apart due to vibration and high temperature.
In addition, there is a problem that the heat resistance of the entire device is reduced due to its inherently low heat resistance, and it also has poor refrigerant resistance when used in hermetic motors such as refrigerators, which is a major application field of enameled wire. The reality was that it could not be used. Many self-bonding insulated wires suitable for such uses have been studied, researched, and proposed. Among these proposals, the most commonly used method is to keep the curing of the fusion resin layer at the semi-cured so-called B stage and fuse and harden it by heating during coil molding.For example, phenoxy resin, phenol resin, melamine resin, etc. , and a titanium compound blended with polyhydroxypolyether resin have been proposed. However, this method of curing at the B stage has poor film flexibility and cannot be applied to modern high-speed automatic winding machines, and the shelf life of wire is very short, so it is practically impossible to apply it. Use is limited to large cloth.

[Means for solving problems]

The present invention was made as a result of intensive research to solve the above problems, and is a self-bonding insulated wire in which a fusion resin layer is provided on a conductor via another insulator. The layer is 100 parts by weight of low branched polyhydantoin resin, 4.4'
- Stabilized products of diphenylmethane diisocyanate 5 to 4
0 parts by weight, and 10 to 100 parts by weight of polyhydroxy polyether resin with a molecular weight of 10,000 or more dissolved in a solvent consisting of phenols or a mixture of phenols and aromatic hydrocarbons. 5
It is characterized by having a residual phenol-rich solvent of ~20% by weight.

First, the low-branched polyhydantoin used in the present invention is polyhydantoin acid in a solution state or partially ring-closed to form a polyhydantoin ring, and is usually obtained by reaction of glycine derivatives, isocyanates, amines, etc. It is something. Further, a detailed method for producing a polyhydantoin resin solution is described, for example, in Japanese Patent Publication No. 44-20115.

Further, in the case of the present invention, a lower degree of separation is preferable, and PH20, a product of Bayer AG, Germany, can be applied as a commercial product.

Next, the stabilized product of 4,4'-diphenylmethane diisocyanate used in the present invention is a product obtained by masking 4,4'-diphenylmethane diisocyanate with phenol, cresol, xylenol, etc., and has the following structural formula (1).

Note that a catalyst is used to stabilize this 4,4'-diphenylmethane diisocyanate, and zinc octylate or the like can be suitably used. Further, as a stabilized product, there is a product name MS-50 manufactured by Nippon Polyurethane Co., Ltd.

Next, the polyhydroxy polyether resin with a molecular weight of 10,000 or more used in the present invention has the following structural formula (2), (3)%
Formula % (n, m are positive integers, R represents an aliphatic or aromatic residue) The molecular weight of these polyhydroxy polyether resins needs to be 10,000 or more on average. This is because if it is less than 10,000, the resulting self-bonding insulated wire will lack flexibility. YP-50 (trade name manufactured by Tobu Kasei Co., Ltd.) is a commercially available polyhydroxy polyether resin.
, I (157, H353 (trade name, manufactured by Dainippon Ink Co., Ltd.).

In the present invention, the amount of the stabilizer of 4,4'-diphenylmethane diisocyanate was limited to 5 to 40 parts by weight per 100 parts by weight of the low-branched polyhydantoin resin. If the amount is less than 5 parts by weight, the effect of crosslinking and curing the low-branched polyhydantoin resin and polyhydroxy-excess ether resin will be poor, and the resulting film will lack heat resistance and refrigerant resistance. This is also because if the blending amount exceeds 40 parts by weight, flexibility will be insufficient. The reason why the amount of the polyhydroxy polyether resin is limited to 10 to 100 parts by weight per 100 parts by weight of the low-branched polyhydantoin resin is that if the amount of the resin is less than 10 parts by weight, the flexibility of the electric wire will be poor; This is also because the temperature required for adhesion becomes too high, which is not desirable in practice, and if the amount exceeds 100 parts by weight, the heat resistance of the entire film decreases, as well as the refrigerant resistance.

In addition to the above formulations, it is also possible to include small amounts of other components such as phenol resins, melamine resins, stabilized isocyanates, etc., to the extent that they do not impair the effects of the present invention, and these are also included in the invention. , their inclusion should be kept to a minimum.

In order to exhibit the characteristics of the self-bonding insulated wire obtained in the present invention, 5 to 20% by weight of a phenolic solvent such as phenol, cresol, xylenol, etc., used as a solvent must remain in the formed fusion resin layer. It is necessary to do so.

If the residual amount of solvent is less than 5% by weight, the fusion temperature will exceed 200°C and it cannot be used for practical purposes, and if it exceeds 20% by weight, the flexibility of the film will be poor and a large amount of solvent will remain even after fusion. This is not desirable because it means doing so.

[Example 1] The present invention will be described in detail below. Example 1 is a low-branched polyhydantoin resin solution (product name: PI42, manufactured by Bayer AG, Germany).
0, solid content 30%) 100 parts by weight, 15 parts by weight of a 30% cresol/naphtha solution of a stabilized product of 4゜4'-diphenylmethane diisocyanate (trade name MS50, manufactured by Nippon Polyurekun Kogyo Co., Ltd.), polyhydroxypolyether resin (
100 weight of a 30% cresol nonaphtha solution (trade name: YP50) manufactured by Tobu Kasei Co., Ltd. was charged into a flask and heated and stirred at 120°C for 3 hours to obtain a self-fusing paint. This self-adhesive paint is applied and baked onto an esterimide insulated copper wire with a diameter of 1.0 mm (furnace length: 3 m, furnace temperature: 300"C, line speed: 10 m/s).
) was repeated three times to obtain a self-bonding insulated wire of the present invention. The total solvent residual rate of phenols in the fused layer of the obtained insulated wire was measured using a pyrolysis gas chromatograph and found to be 12.5%.

Next, in order to examine the performance of this insulated wire, an adhesive strength test, a flexibility test, and a refrigerant extraction test were conducted and the results are also listed in Table 1.

For the adhesive strength test, a helical coil with a length of 80 am was created by tightly wrapping the sample around a round bar with a diameter of 6.5 mm, and this was heated at 150'Ct' for 1 hour to obtain a 7ASTM D-2 test.
The adhesive strength was measured at room temperature and at 120"C according to the standard No. 519. For the flexibility test, the sample was
The number of cracks in the film was examined by winding the film in turns. For the refrigerant extraction test, a sample was taken so that the total weight of the film layer was 2 g, washed with Freon R-113, and then heated at 150°C for 1 hour.
This was heated for an hour, then sealed in an autoclave with an internal volume of 450 cc along with 2200 g of Freon R-22, and heated to 120°C.
After heating for 72 hours, the autoclave was cooled to evaporate Freon, the weight of the extract was measured, and the extraction rate was calculated. However, [Examples 2 to 5] Self-bonding insulated wires were produced in the same manner as in Example 1 using the composition and manufacturing conditions shown in Table 1, and the same tests as in Example 1 were conducted. Also listed in the table.

[Comparative Examples 1 to 4] Self-bonding insulated wires were produced in the same manner as in Example 1 using the composition and manufacturing conditions shown in Table 1, and the same tests as in Example 1 were conducted, and the results are also listed in Table 1. did.

[Comparative Example 5] An esterimide insulated copper wire with a diameter of 1.0 m was tightly wound around a round bar with a diameter of 6.5 mm to create a helical coil with a length of 80 mm.
D, impregnated with George's product name PD923), 1
It was heat cured at 60"C for 3 hours.

Next, in order to examine the performance of this electric wire, an adhesive strength test and a refrigerant extraction test were conducted in the same manner as in Example 1, and the results are also listed in Table 1.

〔Effect of the invention〕

As is clear from Table 1 above, the self-bonding insulated wire of the present invention has excellent flexibility, heat resistance, and refrigerant resistance, so it can be used at high temperatures and subjected to vibrations from transformers, electric motors, etc. It can be applied to such devices.

Claims (1)

[Claims] In a self-bonding insulated wire in which a fusion resin layer is provided on a conductor via another insulator, the fusion resin layer is made of 100 parts by weight of a low-branched polyhydantoin resin and 4,4'-diphenylmethane diisocyanate. 5 to 40 parts by weight of stabilizer,
5-2 formed by applying a solution of 10 to 100 parts by weight of a polyhydroxy polyether resin having an average molecular weight of 10,000 or more dissolved in a solvent consisting of phenols or a mixture of phenols and aromatic hydrocarbons and baking the solution.
A self-bonding insulated wire having 0% by weight of residual phenolic solvent.