JP2943209B2 - Insulated wire - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an insulated wire having excellent solderability and good heat resistance.

(Prior art and its problems) Polyurethane insulated wires are widely used as windings for electronic devices because they can be soldered without stripping the insulating film.

In recent years, the miniaturization and high performance of equipment have been advanced, the operating temperature of equipment has risen, and the heat resistance of used parts has been required to be improved.

Accordingly, there have been applications in which conventional polyurethane insulated wires cannot satisfy the requirements for heat resistance, and polyester insulated wires and ester imide insulated wires have begun to be partially used.

When using the polyester and ester imide insulated wires described above, the heat resistance is satisfactory, but there is a problem that soldering is not possible, and the user has a choice between giving priority to heat resistance or giving priority to ease of terminal treatment. There is a strong demand for insulated wires having both heat resistance and solderability.

The present inventor has conducted intensive studies on the above problems,
By applying and baking an insulating paint made by mixing a suitable amount of a specific stabilized polyisocyanate with a polyamide-imide resin onto a conductor, it is possible to obtain an insulated wire that can be soldered while maintaining the excellent heat resistance of the polyamide-imide resin. Successful.

The present inventor studied the above technology in more detail, after applying and baking the above-mentioned insulating paint on the conductor,
Further, it was found that the effect was further increased by applying and baking a polyurethane insulating paint, and the present invention was reached.

(Constitution of the Invention) The present invention relates to a polyamideimide resin and 100 parts by weight of a stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate in an amount of 75 to 400 parts by weight. This is an insulated wire characterized by applying and baking insulated amount.

In the present invention, the polyamide imide resin has an amide bond and an imide bond in the molecule, and there are two specific examples of the production method.

One method involves reacting at least one tricarboxylic anhydride acid chloride with at least one diamine. Further, a part of the acid chloride of the above tricarboxylic anhydride may be at least one kind of dicarboxylic acid dichloride or at least one kind of tetracarboxylic dianhydride, or at least one kind of dicarboxylic acid dichloride and at least one kind of tetracarboxylic acid. It may be replaced with dianhydride.

A part of the diamine may be replaced by at least one kind of triamine, or at least one kind of tetramine, or at least one kind of triamine and at least one kind of tetramine.

Examples of acid chlorides of tricarboxylic anhydrides include:
And 4-acid chloride of trimellitic anhydride.

Examples of dicarboxylic acid dichloride include terephthalic acid dichloride, isophthalic acid dichloride, adipic acid dichloride and the like.

Examples of diamines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether m-phenylenediamine and the like. Examples of triamines are 3,
4,4'-triaminodiphenyl ether and the like. Examples of tetramine include 3,3 ', 4,4'-tetraaminodiphenyl ether.

Another example of a typical production method involves reacting at least one tricarboxylic anhydride with at least one diisocyanate. Also, a part of the tricarboxylic anhydride may be at least one dicarboxylic acid, or at least one tetracarboxylic dianhydride, or at least one dicarboxylic acid and at least one tetracarboxylic dianhydride. May be replaced.

In addition, at least a part of the above-mentioned diisocyanate is replaced by at least one kind of 3
Or higher polyisocyanate.

Examples of the tricarboxylic anhydride include trimellitic anhydride.

Examples of dicarboxylic acids include isophthalic acid, terephthalic acid, adipic acid and the like.

Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and the like. Examples of diisocyanates include diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.

Examples of the polyisocyanate include polymethylene polyphenylene polyisocyanate. Above all, when a polyamideimide resin obtained by the reaction of an aromatic tricarboxylic anhydride or a derivative thereof with an aromatic diisocyanate is used, the heat resistance characteristic of the polyamideimide resin can be further exhibited, which is not preferable.

Further, among polyamide-imide resins, the use of a polyamide-imide resin having a molecular weight of 0.2 to 0.5 in terms of reduced specific viscosity is preferable because the properties of the obtained insulated wire are good and the workability during the manufacture of the insulated wire is good.

The stabilized polyisocyanate obtained from diphenylmethane diisocyanate is diphenylmethane diisocyanate alone, or isocyanate group of polyisocyanate obtained by reacting diphenylmethane diisocyanate with polyol, polyamine, polycarboxylic acid, etc., to form phenols, alcohols, caprolactam. Any compound can be used as long as it is a compound blocked with a known blocking agent such as a compound.

Specific examples include Nippon Polyurethane Coroneo 2503 in which polyisocyanate obtained from diphenylmethane diisocyanate and polyol is blocked with phenols, Nippon Polyurethane Millionate MS-50 in which diphenylmethane diisocyanate is blocked with phenols, and the like. .

In the present invention, no effect is exhibited except for the stabilized polyisocyanate obtained from diphenylmethane diisocyanate.

For example, when a stabilized polyisocyanate obtained from a polyol and tolylene diisocyanate is used, the solderability is good, but only a poor flexibility of the insulating film can be obtained, and it is obtained from a trimer of tolylene diisocyanate. When a stabilized polyisocyanate containing an isocyanuric ring is used, the flexibility of the insulating film is good but soldering cannot be performed.

In the present invention, it is necessary to add 75 parts by weight to 400 parts by weight of the stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate to 100 parts by weight of the polyamideimide resin. If the amount is less than 75 parts by weight, the obtained insulated electrode cannot be soldered. If the amount is more than 400 parts by weight, the obtained insulated wire has little improvement in heat resistance and the flexibility of the insulating film is also reduced.

In addition, when the epoxy resin is blended with the insulating paint composed of the stabilized isocyanate compound obtained from the polyamideimide resin and diphenylmethane diisocyanate, the soldering property of the obtained insulating paint is not impaired, and the heat softening property and the crazing resistance are improved. preferable.

As the solvent used for the insulating paint obtained from the stabilized isocyanate compound obtained from the polyamideimide resin and diphenylmethane diisocyanate, used as the solvent for the polyamideimide resin, NM ₂ P, DMAC, DMF and other solvent naphtha, toluene A combination of diluents such as xylene is preferred, but phenol, cresols, cellosolve, phenyl cellosolve, methyl cellosolve, glycosolve, methyl glycosolve, phenyl glycosolve, phenyl glycosolve, and glycol ethers such as cellosolve acetate used in ordinary baking paints, Cyclohexanone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, nitrobenzene, dioxane, furfural, sulfolane, DM
SO, pyridine, aniline, diethyl carbonate, ethanol,
Methanol, butanol, cyclohexanol, or the like may be used or may be partially added.

The insulating paint of the present invention, if necessary, naphthenic acid,
Metal salts of octenoic acid and amines such as alkylamines and imidazoles can also be used as curing catalysts.

At the time of producing an insulated electrode, it is preferable to add an appropriate amount of the above-mentioned catalyst because it is easy to produce and a material having better heat resistance can be obtained.

Further, thermoplastic resins such as polyvinyl formal, polyamide, polyester, polyurethane, polyether, polysulfone, polyethersulfone, and polyetherimide, melamine resins, phenol resins, polyesters, polyurethanes, and polyesterimides to the extent that the features of the present invention are not impaired. , Thermosetting resins such as polyamide imide, polyester amide imide, polyimide, hydantoin,
It is also possible to add fillers, pigments, dyes, surfactants, lubricants, antioxidants, and the like.

In the present invention, the polyurethane insulating paint is prepared from a stabilized polyisocyanate and a compound having a hydroxyl group at a molecular terminal. Stabilized polyisocyanate is a polyisocyanate in which isocyanate groups are blocked with phenols, alcohols, lactams, and the like.Specific examples are Sumitomo Bayer Urethane Co., Ltd. Millionate Ms manufactured by Nippon Polyurethanes Co., Ltd., made from CT Stable, Diphenylmethane diisocyaneo
-50, Coronate 2503, Coronate 2515 manufactured by Nippon Polyurethane Co., Ltd. made from hexamethylene diisocyanate
Etc. The compound having a hydroxyl group at the molecular terminal is a compound having a molecular structure such as polyester, polyether, and polyesterimide, and having a hydroxyl group at the molecular terminal.As specific examples, desmophen 600,650,800, manufactured by Sumitomo Bayer Urethane Co., Ltd. There are 1200, 1600, F950, D70 and Nipporan 2006, 800, 1100, etc. manufactured by Nippon Polyurethane. These stabilized polyisocyanate and a compound having a hydroxyl group at a molecular terminal are blended in an appropriate paint and used.If necessary, a metal salt of naphthenic acid or octenoic acid, an alkylamine, or an imidazole amine is used. It can be used as a curing catalyst.

Commercially available examples of polyurethane insulating coatings include:
TPU-6500, TPU-7100, TPU-5100, TSF-1
00, TSF-135, TPU-F1, Hitachi Chemical WD-437, WD-430
6, Auto Chemical ATH-605, APU-21, Nitto Denko DU-
310, DU-331, DU-3056 and the like.

In the present invention, first, an insulating paint obtained by adding a stabilized isocyanate compound obtained from diphenylmethane diisocyanate to a polyamideimide resin is applied and baked, and then a polyurethane insulating paint is applied and baked. The two types of insulating paints may be applied and baked in the same baking furnace, or may be applied and baked in separate baking furnaces.

The thickness ratio of the film obtained by applying and baking the above two types of insulating dyes is not particularly limited, but the film obtained by applying and baking an insulating paint obtained by adding a stabilized isocyanate compound to a polyamideimide resin has a total film thickness. It is preferable that the content be 20% or more because the improvement in heat resistance is exhibited.

The contents of the present invention will be described in the following examples, but the present invention is not limited to these examples. The following reference examples show insulating paints used in comparative examples and examples.

Reference Example 1 (Polyamide imide insulating coating) 192.1 g (1.0 mol) of trimellitic anhydride and 250.3 g (1.0 mol) of diphenylmethane-4,4'-diisocyanate were added to 770 g of N-methyl-2-pyrrolidone and a solvent. In a mixed solvent with 330 g of naphtha (Swazol # 1000 manufactured by Maruzen Petrochemical), the mixture was reacted at 80 ° C. for 3 hours, heated to 140 ° C. in 4 hours, and reacted at this temperature for 2 hours to obtain a polyamideimide insulating paint. Was. The reduced specific viscosity of the resin was 0.38.

(Comparative Example 1) General-purpose polyurethane dye (TPU-5155 manufactured by Tokuto Seimitsu Co., Ltd.)
Was coated and baked on a 0.3 mmφ copper conductor so as to have a film thickness of 0.020 mm. Table 1 shows the results of measuring the properties of the obtained polyurethane insulated wires.

(Comparative Example 2) Heat-resistant polyurethane dye (ATH-605 manufactured by Auto Chemical Co., Ltd.)
In the same manner as in Comparative Example 1, a polyurethane insulated wire was produced and its characteristics were evaluated.

 Table 1 shows the results.

(Comparative Example 3) Coronate 2503 (hereinafter abbreviated as Coronate 2503) manufactured by Nippon Polyurethane Co., Ltd., which is a stabilized polyisocyanate obtained from polyol and diphenylmethane diisocyanate with respect to 100 parts by weight of the resin component of the polyamide-imide insulating paint prepared in Reference Example 1. ) Was added and 1 part by weight of dibutyltin laurate was added as a catalyst, and an insulated wire was prepared and evaluated in the same manner as in Comparative Example 1 using an insulating paint mixed and dissolved.

 The results are shown in Table 1.

(Example 1) The same insulating paint as in Comparative Example 3 was applied and baked on a 0.3 mmφ copper conductor to a film thickness of 0.010 mm, and then a polyurethane insulating paint TPU-5155 was applied to a film thickness of 0.010 mm. Applied and baked. Table 1 shows the characteristic evaluation results of the obtained insulated wires.

(Example 2) An insulated wire was obtained in the same manner as in Example 1 except that a heat-resistant polyurethane coating material ATH-605 was used instead of the polyurethane insulating coating material.

 Table 1 shows the characteristic evaluation results of the obtained insulated wires.

(Example 3) An insulated wire was obtained in the same manner as in Example 1 except that the coating thickness of the same insulating coating as that of Comparative Example 3 was 0.005 mm, and the coating thickness of the polyurethane coating TPU-5155 was 0.015 mm.

 Table 1 shows the characteristic evaluation results of the obtained insulated wires.

(Example 4) An insulated wire was obtained in the same manner as in Example 1, except that the coating thickness of the same insulating coating as that of Comparative Example 3 was 0.002 mm, and the coating thickness of the polyurethane coating TPU-5155 was 0.018 mm.

 Table 1 shows the characteristic evaluation results of the obtained insulated wires.

(Effects of the Invention) As described above, the insulated wire of the present invention has improved heat resistance and can be soldered as compared with the conventional polyurethane insulated wire.

Further, the solderability can be improved without greatly lowering the heat resistance than an insulated wire obtained by applying and baking an insulating paint obtained by adding a stabilized isocyanate compound obtained from diphenylmethane diisocyanate to a polyamideimide resin.

 Therefore, the industrial value of the present invention is great.

Continuation of the front page (56) References JP-A-2-197015 (JP, A) JP-A-2-304808 (JP, A) JP-A-2-87607 (JP, A) JP-A-62-108409 (JP) , A) JP-A-63-248867 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) H01B 7/34 H01B 3/30 H01B 7/02

Claims (2)

(57) [Claims] (1) 100 parts by weight of a polyamideimide resin,
An insulated wire characterized in that an insulating paint containing 75 to 400 parts by weight of a stabilized polyisocyanate compound obtained from diphenylmethane diisocyanate is applied and baked on a conductor, and then a polyurethane insulating paint is applied and baked. 2. Polyamideimide resin is a compound obtained by reacting aromatic tricarboxylic anhydride or its derivative with aromatic diisocyanate. The insulated wire according to claim 1.