JP3298768B2 - Insulated wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an insulated wire having excellent solderability and heat resistance.

[0002]

Conventionally, as an insulated wire which can be directly soldered without peeling off an insulating film,
Polyurethane insulated wires are widely used. However, in recent years, with the miniaturization and high performance of electric equipment, the operating temperature of the equipment often rises,
Insulated wires, which are used materials for electrical equipment, are required to have higher heat resistance. Therefore, the use of the conventional polyurethane insulated wires that cannot satisfy the heat resistance requirement has appeared. On the other hand, an insulated wire that can be soldered without peeling off an insulating film, similarly to a polyurethane insulated wire, is desired because of the simplicity of terminal treatment of the insulated wire.

As a substitute for the above-mentioned polyurethane insulated wires, similarly, polyesterimide insulated wires and polyesterimide urethane insulated wires which can be soldered without peeling off the insulating film have been developed and used for some applications. Although imide insulated wires have sufficient heat resistance, solderability is significantly inferior to polyurethane insulated wires.
Although the solderability of polyester insulated urethane insulated wires can be almost satisfied, the requirements for heat resistance are not sufficiently satisfied. Therefore, development of an insulated wire having both solderability and heat resistance is strongly demanded.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a urethane bond in a molecule obtained by reacting a polyhydric alcohol with a polycarboxylic acid or a derivative thereof and a polyisocyanate has Amide bond and imine
The present inventors have found that, when an insulating paint containing a stabilized polyisocyanate compound added to a resin having a metal bond and applied and baked on a conductor, an insulated wire having both solderability and heat resistance can be obtained. Was achieved.

[0005] By using an insulating paint containing a specific resin, an insulated wire having both excellent solderability and heat resistance is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the present invention. The insulating paint used in the present invention has a polyhydric alcohol content of 5 to 45 mol% and a polycarboxylic acid or a derivative thereof of 45 to 5 mol%, and a ratio of 0.8 to 1.10. It is preferable to use an insulating coating obtained by adding 75 parts by weight to 200 parts by weight of a stabilized polyisocyanate compound to 100 parts by weight of a resin obtained by reacting with a mol% of a polyisocyanate. The ethylene glycol as a polyhydric alcohol, diphenylmethane the polycarboxylic acid or trimellitic anhydride and / or pyromellitic anhydride benefits acid as its derivatives, polyisocyanate diphenylmethane diisocyanate, and as a stabilizing polyisocyanate compound Preferred are stabilized polyisocyanate compounds obtained from diisocyanates.

[0007] More specifically, the resin which is a component of the paint used in the present invention are those obtained by reacting a diphenylmethane diisocyanate and ethylene glycol and trimellitic acid and / or pyromellitic anhydride benefits anhydride, A urethane bond is formed between the isocyanate group and the alcohol group, an imide bond is formed between the isocyanate group and the acid anhydride structure of trimellitic anhydride and / or pyrrolitic anhydride, and further, an isocyanate group and trimellitic anhydride and / or considered to have an amide bond between the carboxyl group of pyromellitic anhydride benefits acid.

An insulated wire having an insulating layer formed by applying and baking an insulating paint containing a stabilized polyisocyanate compound obtained from such a resin and diphenylmethane diisocyanate on a conductor is excellent in the presence of a urethane bond. The presence of imide and amide bonds,
It is considered that it shows excellent heat resistance. To prepare the aforementioned insulating coating material, first, in a suitable solvent, after the reaction of diphenylmethane diisocyanate with ethylene glycol at room temperature, the addition of trimellitic anhydride and / or pyromellitic anhydride benefits acid heated After reacting to obtain the resin,
What is necessary is just to mix the stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate.

[0009] As another method for obtaining a resin, diphenylmethane diisocyanate and ethylene glycol, and after batch mixing trimellitic anhydride and / or pyromellitic anhydride benefits acid at room temperature, may be heated and reacted. Diphenylmethane diisocyanate and trimellitic anhydride and / or
Or after heating the reaction of pyromellitic anhydride benefits acids, it is also possible to react the ethylene glycol.

A part of ethylene glycol can be replaced by another polyol, for example, glycerin, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate (THEIC), etc., within a range not to impair the object of the present invention. It is.

A part of trimellitic anhydride may be replaced with another polycarboxylic acid, for example, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic anhydride, as long as the object of the present invention is not impaired. It is possible.

The stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate includes diphenylmethane diisocyanate or a polyisocyanate obtained by reacting diphenylmethane diisocyanate with a polyol, polyamine, polycarboxylic acid or the like to form a phenol, alcohol, caprolactam or isocyanate group. Specific examples are Millionate MS-50 manufactured by Nippon Polyurethane Co., Ltd. in which diphenylmethane diisocyanate is masked with phenols, and Coronate 2503 manufactured by Nippon Polyurethane Co., Ltd. in which polyisocyanate composed of diphenylmethane diisocyanate and polyol is masked with phenols. Etc.

The solvent used in the insulating coating of the present invention is preferably a combination of diluents such as xylene and solvent naphtha with NMP, DMAC, DMF, etc., which are solvents, but phenol, cresols, glycol ethers, alcohols Or a solvent such as ketones used in ordinary baking paints may be used or may be partially added.

The insulating paint of the present invention may optionally contain a catalyst such as a metal salt of naphthenic acid or octenoic acid, an amine such as an alkylamine or imidazole, or an organic tin compound. At the time of manufacturing the insulated wire, it is preferable to add an appropriate amount of these catalysts because workability such as improvement of the baking width is improved.

The insulating coating of the present invention includes thermoplastic resins such as polyamides, polyesters, polysulfones, polyvinylformals and epoxies, polyesters, polyesterimides, polyurethanes, polyamideimides, melamines and the like as long as the characteristics of the present invention are not impaired. Resins, thermosetting resins such as phenolic resins, dyes, pigments, lubricants, and other paint additives can also be added.

In order to manufacture the insulated wire of the present invention, the above resin coating is adjusted to a viscosity suitable for work with an appropriate solvent,
An insulating layer is formed by coating and baking on a conductor such as an annealed copper wire in a conventional manner.

Further, the insulated wire according to the present invention may be provided with another insulating paint as generally used for imparting various other properties to an upper layer of the insulating layer to which the above resin paint is applied and baked. It is also possible to provide a coated and baked insulating layer. For example, when heat resistance is further required, polyimide-based insulating paint or polyamide-imide-based paint, when winding property is required, polyamide-based paint such as 6,6-nylon, coil shape self-holding Is required, there are self-fusing paints such as polyvinyl butyral, epoxy, phenoxy, polyester, polyamide and polysulfone paints.

[0018]

EXAMPLES The present invention will be described in the following examples, but the present invention is not limited to these examples. Example 1 1.0 mol of ethylene glycol and 4.0 mol of trimellitic anhydride were combined with N-methyl-2-pyrrolidone (hereinafter referred to as NMP).
) At room temperature for 0.5 hour,
Resin 100 obtained by adding 4.9 mol of diphenylmethane diisocyanate, heating and reacting at 120 ° C. for 3 hours.
To 100 parts by weight of a coronate 2503 manufactured by Nippon Polyurethane Co., Ltd., which is a stabilized polyisocyanate obtained from diphenylmethane diisocyanate, and 1 part by weight of dibutyltin laurate as a catalyst, dissolved and mixed, was used as an insulating coating. Coating thickness 0.015 on 0.2mm soft copper wire
mm to obtain an insulated wire.

Example 2 An insulated wire was obtained in the same manner as in Example 1, except that the coronate 2503 was changed to 150 parts by weight.

Example 3 After reacting 2.5 mol of ethylene glycol and 2.5 mol of trimellitic anhydride in NMP at room temperature for 0.5 hour, 4.6 mol of diphenylmethane diisocyanate was added and the mixture was heated to 120 mol. 100 parts by weight of Coronate 2503 to 100 parts by weight of the resin obtained by reacting at
An insulating paint obtained by adding 1 part by weight of dibutyltin laurate as a catalyst and dissolving and mixing was baked in the same manner as in Example 1 to obtain an insulated wire.

Example 4 After reacting 4.0 mol of ethylene glycol and 1.0 mol of trimellitic anhydride in NMP at room temperature for 0.5 hour, 4.8 mol of diphenylmethane diisocyanate was added thereto, followed by heating. 100 parts by weight of Coronate 2503 to 100 parts by weight of the resin obtained by reacting at
An insulating coating obtained by adding 1 part by weight of dibutyltin laurate as a catalyst and dissolving and mixing was baked in the same manner as in Example 1 to obtain an insulated wire.

Example 5 An insulated wire was obtained in the same manner as in Example 4, except that the coronate 2503 was changed to 150 parts by weight.

Comparative Example 1 An insulated wire was obtained in the same manner as in Example 1 by using a solderable polyesterimide paint (trade name: FS-2 manufactured by our company).

Comparative Example 2 Polyester imide urethane paint (trade name FS-
141), an insulated wire was obtained in the same manner as in Example 1.

With respect to the insulated wires of the above Examples and Comparative Examples, the results of each test of appearance, flexibility, stretch pinhole property, softening point, dielectric breakdown voltage, thermal shock resistance, and solderability are described below. The results are shown in Table 1. The test method is JIS C
Measured according to 3003.

Table 1 Note 1) Dielectric breakdown voltage residual ratio The residual ratio to the initial value of the dielectric breakdown voltage after deterioration at 220 ° C for 7 days. Note 2) Thermal shock resistance 20% elongation at 220 ° C for 1 hour. Note 3) Solderability. Comparative Example 1 is 460 ° C.

From the results shown in Table 1, the insulated wire of the present invention shows much better solderability than the conventional polyesterimide insulated wire which can be soldered. Further, the polyesterimide urethane insulated wire shows excellent heat resistance despite the same solderability.

[0028]

The insulated wire according to the present invention has both excellent solderability and high heat resistance, and can sufficiently respond to the characteristic requirements for the insulated wire used in recent electronic devices.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Setsuo Terada 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-8-188713 (JP, A) Japanese Unexamined Patent Publication (Kokai) No. 7-166054 (JP, A) JP-A-8-134215 (JP, A) JP-A-60-89904 (JP, A) JP-A-6-145503 (JP, A) JP-A-3-233811 ( JP, A) JP-A-7-216058 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01B 3/16-3/56 H01B ^7/ 00-7/02

Claims (5)

(57) [Claims] 1. A urethane bond, an amide bond and an imide bond in a molecule obtained by reacting a polyhydric alcohol with a polycarboxylic acid or a derivative thereof and a polyisocyanate.
An insulated electric wire having an insulating layer formed by applying and baking an insulating paint obtained by adding a stabilized polyisocyanate compound to a resin having the above-mentioned properties on a conductor. 2. An insulating coating composition comprising: a polyhydric alcohol, 5 to 45 mol%, a polycarboxylic acid or a derivative thereof, 45 to 5 mol%,
And 0.8 to 1.10.
The insulating paint according to claim 1, wherein a stabilized polyisocyanate compound is added in an amount of 75 parts by weight to 200 parts by weight with respect to 100 parts by weight of a resin obtained by reacting with a mol% of polyisocyanate having a ratio of: Electrical wire. Wherein the polyhydric alcohol is ethylene glycol, a polycarboxylic acid or derivative thereof trimellitic acid and / or pyromellitic anhydride benefits anhydride, polyisocyanate is diphenylmethane diisocyanate,
The insulated wire according to claim 1, wherein the stabilized polyisocyanate compound is a stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate. 4. The insulated wire according to claim 3, wherein a part of ethylene glycol is substituted with trimethylolpropane, glycerin or tris (2-hydroxyethyl) isocyanurate. 5. The insulated wire according to claim 3, wherein a part of trimellitic anhydride is substituted with an aromatic dicarboxylic acid.