JP3504859B2 - Insulating paint - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating paint suitable for producing a polyesterimide insulated wire having excellent solder peeling property.

[0002]

2. Description of the Related Art In recent years, electric devices such as motors and transformers have been rapidly reduced in size and weight and have been improved in performance, and accordingly, the heat resistance of insulated wires, which is a material used for improving reliability of electric devices, has been improved. As a result, the heat resistance of polyester-imide insulated wires (EIW) of heat-resistant type F or higher using an insulating coating containing a polyesterimide resin and the polyamide-imide insulated electrical wire using an insulating coating containing a polyamide-imide resin (AI)
W) and the like have been developed and put into practical use.

On the other hand, electric equipment manufacturers are constantly trying to rationalize processes such as labor saving automation mainly for the purpose of cost reduction, and insulated wires have various characteristics that lead to labor saving automation as well as the heat resistance described above. Has come to be requested. One of the various characteristics that lead to labor automation, there is a line of terminal peeling of insulated wire (wire ends of the insulating skin covering delamination for soldering). There are methods such as (1) mechanical peeling, (2) thermal decomposition peeling, (3) chemical peeling, and (4) solder peeling as methods for peeling the insulated wire end, but the working time, the conductor being intact, and continuous. From the viewpoint of processing, etc.
It is said that the method (4) of peeling the solder is most preferable. For this reason, from the electrical equipment manufacturer, along with heat resistance,
There is a strong demand for insulated wires that can be stripped of solder at lower temperatures, and polyester-imide insulated wires that can be stripped of solder using an insulating coating containing a polyesterimide resin have been developed.
It has been put to practical use.

[0004]

SUMMARY OF THE INVENTION However, a polyesterimide insulated wire which has been put into practical use and which can be subjected to a solder peeling treatment using an insulating coating material containing a polyesterimide resin is required to be peeled by, for example, molten solder. When the temperature of the bath is 450 ° C., it takes 5 to 15 seconds, and a treatment time of several seconds is actually required. For that purpose, it is necessary to set the solder bath temperature to 480 ° C. or higher. However, at such a high temperature, oxidative deterioration of the solder, wire thinning due to dissolution of copper, which is an insulated wire conductor, into the solder, influence of other high temperature radiant heat during the solder stripping process on other members, and many When applying the solder peeling to the litz wire or the like in which the thin wires are joined together, there is a problem that the solder cannot be peeled sufficiently to the inner side, and the inner insulating film is carbonized and remains as scrap,
It cannot be said that the processability is always good, and there is a demand for an insulated wire having a molten solder bath temperature of 450 ° C. and a solder strippability up to a level of a peeling treatment time of 2 seconds or less.

As an insulated wire that can be soldered at the same time as solder peeling, there is a polyurethane insulated wire (UEW) using an insulating paint containing a polyureta resin, and the temperature of the molten solder bath is low at 340 to 400 ° C. Although it can be peeled off, its heat resistance is as low as Class E, and since it has a urethane group, its overcurrent characteristics are PEW (polyester insulated wire) and EI.
It has the drawback of being insufficient compared to W. Also U
A heat-resistant F-type polyesterimide urethane insulated wire using an insulating coating containing a polyesterimide urethane resin has been developed and put into practical use as a product for improving the heat resistance of EW, but because it has a urethane group like UEW, it has an overcurrent characteristic. Has a drawback that it is insufficient compared to PEW and EIW.

Therefore, an object of the present invention is to overcome the above-mentioned drawbacks of the conventional insulated wire (EIW) that can be subjected to the solder peeling treatment using the insulating coating material containing the polyesterimide resin when the solder is peeled off, and a large number of fine wires are offset. Even when the solder stripping is applied to the litz wires to be combined, the insulated wire is sufficiently solder stripped to the inside, specifically, the temperature of the molten solder bath is 45
An object of the present invention is to provide an insulating coating material capable of producing a polyesterimide insulated wire having a solder peeling time improved to a level of 2 seconds or less at 0 ° C.

[0007] The present inventor has intensely studied to achieve the above object, as an insulating skin layer forming component, a specific range of ratio of divalent carboxylic acids containing imide group of five-membered ring in the polycarboxylic acid component Is obtained by reacting these with a specific ratio of a primary aliphatic dihydric alcohol and an aliphatic dihydric alcohol having at least one secondary or higher alcohol group as alcohol components. Insulating paint containing polyesterimide resin was found to significantly improve the solder releasability of insulated wires using this,
The present invention has been completed based on this finding.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention is an insulating coating material obtained by dissolving a polyesterimide resin in an organic solvent,
The polyesterimide resin comprises (A) a divalent carboxylic acid containing a five-membered ring imide group or a derivative thereof or a mixture thereof, (B) a trivalent carboxylic acid or a derivative thereof or a mixture thereof, and (C) a second The amounts of the primary aliphatic dihydric alcohol or the mixture thereof and (D) the aliphatic dihydric alcohol having at least one secondary or higher alcohol group or the mixture thereof are expressed in equivalent amounts.
Of the total acid component [(A) + (B)] 100
Ratio of call component [(C) + (D)] of 130 to 230
At that time, the components in the total acid components [(A) + (B)]
The ratio of (A) is 10 to 35 equivalent%, the ratio of component (B)
, 90 to 65 equivalent%, all alcohol components [(C) +
The proportion of component (C) in (D)] is 25 to 85 equivalent%,
It is an insulating coating material obtained by reacting so that the proportion of the component (D) is 75 to 15 equivalent% .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the invention. The insulating paint of the present invention is an insulating material
Peel film forming component, using the above components (A) and component (B) as the acid component, using the above component (C) and component (D) as the alcohol component, the esterification of these according to a conventional method It is a feature that it is a polyesterimide resin obtained by the above.

When the above-mentioned polyesterimide resin is synthesized, the preferable proportion of the component used is such that, when the amount used is expressed as an equivalent amount, the total acid component [(A) + (B)] is 100 parts and the total alcohol component [( C) + (D)] is a ratio of 130 to 230. Percentage of the total alcohol component with difficulty at the time the polyester imide resin synthesis is less than 130, flexibility of the insulating skin layer exceeds 230 becomes insufficient. A more desirable ratio is 150 to 200.

The proportion of the component (A) in the total acid components [(A) + (B)] is preferably 10 to 35 equivalent%, and the proportion of the component (B) is preferably 90 to 65 equivalent%. Ratio is 10
Less than equivalent percent, becomes insufficient flexibility of the insulating skin layer proportion of the component (B) is more than 90 equivalent%, greater than 35 equivalent% proportion of the component (A), the proportion of component (B) is less than 65 equivalent percent become insufficient solder peeling of the insulating skin layer. A more desirable ratio of the component (A) is 15 to 30 equivalent%.

Further, all alcohol components [(C) +
The preferred ratio of the component (C) and the component (D) in (D)] is 25 to 85 equivalent% of the component (C) and 75 of the component (D).
~ 15 equivalent%. Ratio is less than 25 equivalent percent of component (C), becomes insufficient flexibility of the insulating skin layer proportion of the component (D) is more than 75 equivalent%, greater than 85 equivalent% proportion of the component (C), proportion of the component (D) becomes insufficient solder peeling the insulating skin film is less than 15 equivalent percent. A more desirable ratio of the component (C) is 30 to 80 equivalent%.

The (A) five-membered ring imide group-containing divalent carboxylic acid or derivative thereof used in the present invention is, for example, the following (a) by a conventionally known method.
And those obtained by reacting with (b) or (c). (A) a carboxylic acid anhydride containing at least one other reactive group in addition to the five-membered carboxylic acid anhydride group,
(B) A primary amine containing at least one other reactive group in addition to the primary amino group, and (c) a polyisocyanate.

Examples of (a) include tricarboxylic acid anhydrides such as trimellitic acid anhydride, hemimellitic acid anhydride, naphthalene tricarboxylic acid anhydride, diphenyl tricarboxylic acid anhydride and benzophenone tricarboxylic acid anhydride. . Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylmethanetetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride and the like.

Examples of (b) include aliphatic diamines such as ethylenediaminehexamethylenediamine, dimethylheptamethinediamine, dimethylhexamethylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, dimethylbisphenyldiamine, diamino. Examples thereof include aromatic diamines such as naphthalene, phenylenediamine, and xylylenediamine, amino alcohols such as monoethanolamine and dimethylethanolamine, and aminocarboxylic acids such as aminopropionic acid.

Examples of (c) include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate and xylene diisocyanate.

From the viewpoint of the heat resistance of the resulting insulated wire, the preferred (A) five-membered imide group-containing divalent carboxylic acid is obtained from 2 mol of trimellitic anhydride and 1 mol of aromatic diamine. It is a dicarboxylic acid. Economically, a divalent carboxylic acid obtained from 2 mol of trimellitic anhydride and 1 mol of diaminodiphenylmethane is preferable. The divalent carboxylic acid containing these five-membered imide groups is usually obtained by reacting (a) with (b) or (c) in a solvent.

Examples of the solvent include N-methyl-
2-pyrrolidone, dimethylformamide, phenol,
Examples include polar solvents such as cresol and xylenolic acid, and hydrocarbon solvents such as xylene, solvent naphtha, methyl ethyl ketone and ethyl acetate. These may be used alone or as a mixed solvent.

Examples of (B) trivalent carboxylic acid or its derivative include trimellitic acid, trimellitic anhydride, naphthalene tricarboxylic acid anhydride, diphenyl tricarboxylic acid anhydride and benzophenone tricarboxylic acid anhydride. To be Particularly useful is trimellitic anhydride. In addition, as long as the effect of the present invention is not impaired, a part of the trivalent carboxylic acid can be replaced with a divalent carboxylic acid or a derivative thereof. Examples of divalent carboxylic acids or their derivatives include terephthalic acid, dimethyl terephthalic acid, phthalic acid and adipic acid.

Examples of the primary aliphatic dihydric alcohol (C) include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexane. Examples include diol and the like.

Examples of (D) the aliphatic dihydric alcohol having at least one secondary or higher alcohol group include 1,2-propylene glycol, 1,3-butanediol, 1,2-butanediol, and 2 , 3-butylene glycol 2,5-hexanediol and the like.

In the present invention, the method for synthesizing the polyesterimide resin using these raw material compounds is not particularly limited, and the following known methods can be used. (1) After reacting (a) with (b) or (c) in a solvent to form the component (A), the component (B) is added to the system.
Add (C) and (D), and add 3-1 at 200-250 ° C.
A method of synthesizing by advancing the esterification reaction for 5 hours, (2) reacting (ii) with (ii) or (ii) in a solvent to form the component (A). Separately, a polyester intermediate comprising the components (B), (C) and (D) is formed. Then, a method of synthesizing the component (A) and this polyester intermediate by advancing an esterification reaction at 200 to 250 ° C. for 3 to 15 hours,

(3) A polyester intermediate consisting of the components (B), (C) and (D) is formed, and a solvent, (a) and (b) or (c) are added to this system. Ingredient (A)
Is formed, and then the esterification reaction is allowed to proceed at 200 to 250 ° C. for 3 to 15 hours to synthesize the compound.
(4) (a), (b) or (c), components (B), (C) and (D) are added all at once to the solvent and mixed, 12
A 5-membered ring imide is formed at 0 to 180 ° C., followed by 2
A method of synthesizing by advancing an esterification reaction at 00 to 250 ° C. for 3 to 15 hours.

The insulating coating material of the present invention can be obtained by adjusting the polyesterimide resin solution obtained by the above method or the like to an appropriate viscosity with a solvent. Examples of the solvent and the diluent solvent at the time of reaction include, for example, phenol, cresol, xylenol, dimethylformamide, N-
A polar solvent such as methyl-2-pyrrolidone can be used. Further, as the auxiliary solvent at the time of dilution, for example, a hydrocarbon solvent such as toluene, xylene, solvent naphtha, methyl ethyl ketone, cyclohexanone, etc. can be used. The most useful solvent for the insulating coating containing the polyesterimide resin of the present invention is cresylic acid. Cresolic acid is a mixed solvent containing phenol, cresol and xylenol and having a boiling range of 180 to 230 ° C. Further, the use of xylene and solvent naphtha, which are aromatic hydrocarbons, as the auxiliary solvent at the time of dilution is particularly effective in improving workability in producing an insulated wire by baking the insulating coating material of the present invention on a conductor. It is useful.

When the insulating coating material of the present invention thus obtained is coated and baked on a conductor to manufacture an insulated electric wire, the production speed of the insulated electric wire is increased and the surface smoothness of the insulated electric wire is increased. In order to improve the above, it is preferable to add a small amount of a metal desiccant or a compound of titanic acid. Examples of the metal desiccant include zinc octenoate and lead naphthenate, and examples of the compound of titanic acid include:
For example, tetrabutyl titanate, tetraisopropyl titanate, etc. may be mentioned, and the addition amount is usually about 0.1 to 8.0% by weight based on the solid content of the insulating coating.
It is preferably 1.0 to 5.0% by weight. The insulating paint of the present invention, to the extent that the effect of the present invention is not impaired,
Stabilized isocyanate or polyamide, polyester, polysulfone and other thermoplastic resins blocked with isocyanate groups of polyisocyanate with phenol, melamine resins, thermosetting resins such as phenol resins, dyes, pigments,
Lubricants and other additives for paints can also be added as appropriate.

An insulated wire using the insulating coating material of the present invention is prepared by adjusting the above coating material with a suitable solvent to a viscosity suitable for work,
It is manufactured by applying it on a conductor such as annealed copper wire according to a conventional method and baking it to form an insulating layer. In addition, in the insulated wire, in general, in order to improve the winding property, a lubricant such as liquid paraffin or solid paraffin can be applied onto an insulating layer formed by applying and baking the insulating paint of the present invention. It is also possible to further provide an insulating layer coated and baked with another insulating paint, as has been generally done conventionally in order to impart other various characteristics. As such an insulating paint, for example, a polyimide-based insulating paint or a polyamide-imide insulating paint is required when heat resistance is required, and a polyamide-based polyamide such as 6,6 nylon is used when winding property is required. If the coating requires coil self-supporting, self-fusing coating, for example,
Polyvinyl butyral, phenoxy, polyester, polyamide, polysulfone-based paints are used.

[0027]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 Trimellitic anhydride 48 was placed in a 5 liter flask equipped with a stirrer, a nitrogen inlet tube, a condenser and a thermometer.
0 g (7.5 equivalents), ethylene glycol 446 g (1
4.4 equivalents), 162 g of 1,3-butanediol (3.
(6 equivalents) was charged and heated while blowing nitrogen, and dehydration due to the esterification reaction started at 200 ° C.
After reacting at 200 ° C. for 5 hours and then at 220 ° C. for 3 hours, 701 g of cresol was charged to stop the reaction. After cooling to 100 ° C., 480 g (2.5 mol) of trimellitic anhydride and 248 g (1.25 mol) of 4,4′-diaminodiphenylmethane were charged into this system and heated again. It turned cloudy and dehydration started at 140 ° C. to start production of diimidodicarboxylic acid. After holding at 150 ° C for 5 hours, further heat to 20
After holding at 0 ° C. for 5 hours to carry out the esterification reaction,
Cresolic acid was diluted with 1,449 g and then with solvent naphtha 239 g to stop the reaction. After cooling to 100 ° C., 65 g of tetrabutyl titanate was further added to obtain a polyesterimide insulating paint having a resin content of 40% by weight.

Example 2 Trimellitic anhydride 48 was placed in a 5 liter flask equipped with a stirrer, a nitrogen inlet tube, a condenser and a thermometer.
0 g (2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 480 g (7.5 equivalent), ethylene glycol 446 g
(14.4 equivalents), 162 g of 1,3-butanediol
When (3.6 equivalents) and 701 g of cresol were charged and heated while blowing nitrogen, the system turned yellow at 120 ° C., and dehydration started at 140 ° C. to start production of diimidedicarboxylic acid. After holding at 150 ° C for 5 hours,
After further heating and holding at 200 ° C. for 7 hours to carry out the esterification reaction, 1,449 g of cresylic acid and then 239 g of solvent naphtha were added to dilute and stop the reaction. After cooling to 100 ° C., 65 g of tetrabutyl titanate was further added to obtain a polyesterimide insulating paint having a resin content of 40%.

Example 3 As in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenyl ether 250 g (1.25 mol), trimellitic anhydride 4
80 g (7.5 equivalents), ethylene glycol 446 g
(14.4 equivalents), 162 g of 1,3-butanediol
(3.6 equivalents) and 702 g of cresol were reacted, and then the reaction solution was diluted with 1,450 g of cresylic acid and 240 g of solvent naphtha and further mixed with 65 g of tetrabutyl titanate to prepare a polyester imide having a resin content of 40%. I got an insulating paint.

Example 4 As in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 391 g (1
2.6 equivalents), 1,2-propylene glycol 205 g
(5.4 equivalents) and 694 g of cresol were reacted, and then diluted with 1,440 g of cresylic acid and 237 g of solvent naphtha, and further blended with 65 g of tetrabutyl titanate to obtain a polyesterimide insulating paint having a resin content of 40%. Obtained.

Example 5 In the same manner as in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 167 g
(5.4 equivalents), 1,2-propylene glycol 479
g (12.6 equivalents) and 717 g of cresol, followed by diluting with 1,483 g of cresylic acid and 244 g of solvent naphtha, further blending with 67 g of tetrabutyl titanate, and a polyester imide insulating paint having a resin content of 40%. Got

Example 6 As in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), 1,6-hexanediol 731
g (12.6 equivalents), 1,2-propylene glycol 2
After reacting with 05 g (5.4 equivalents) and 842 g of cresol, 1,738 g of cresylic acid and 287 g of solvent naphtha were added for dilution, and 79 g of tetrabutyl titanate was further added to the polyester imide insulation of 40% resin content. Got the paint.

Example 7 480 g (2.5 mol) of trimellitic anhydride, 4,
248 g (1.25 mol) of 4'-diaminodiphenylmethane, 480 g (7.5 equivalents) of trimellitic anhydride,
Ethylene glycol 279 g (9.0 equivalents), 1,2-
Propylene glycol 171 g (4.5 equivalents), 1,3
203 g (4.5 equivalents) of butanediol and 720 g of cresol were reacted as in Example 2, then 1,490 g of crezoic acid and 245 of solvent naphtha.
Diluted with g, and further mixed with 67 g of tetrabutyl titanate to obtain a polyester imide insulating paint having a resin content of 40%.

Example 8 480 g (2.5 mol) of trimellitic anhydride, 4,
248 g (1.25 mol) of 4'-diaminodiphenylmethane, 480 g (7.5 equivalents) of trimellitic anhydride,
140 g (4.5 equivalents) of ethylene glycol, 1,6-
Hexanediol (266 g, 4.5 equivalents), 1,2-propylene glycol (342 g, 9.0 equivalents) and cresol (759 g) were reacted in the same manner as in Example 2, and then 1,568 g of cresolic acid and 259 g of solvent naphtha.
Was added to dilute, and 71 g of tetrabutyl titanate was further added to obtain a polyesterimide insulating coating material having a resin content of 40%.

Comparative Example 1 In the same manner as in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 558 g (1
8.0 eq.) And 680 g of cresol, followed by dilution with 1,404 g of cresylic acid and 232 g of solvent naphtha, and then tetrabutyl titanate 63.
g was blended to obtain a polyesterimide insulating paint having a resin content of 40%.

Comparative Example 2 In the same manner as in Example 2, 768 g of trimellitic anhydride
(4.0 mol), 397 g (2.0 mol) of 4,4'-diaminodiphenylmethane, trimellitic anhydride 384
g (6.0 equivalents), ethylene glycol 391 g (1
2.6 equivalents), 1,2-propylene glycol 205 g
(5.4 equivalents) and 1,286 g of cresol were reacted, and then diluted with 1,249 g of cresylic acid and 282 g of solvent naphtha to give tetrabutyl titanate 7
7 g was further compounded to obtain a polyesterimide insulating coating material having a resin content of 40%.

Comparative Example 3 In the same manner as in Example 2, 96 g of trimellitic anhydride
(0.5 mol), 4,4'-diaminodiphenylmethane 50 g (0.25 mol), trimellitic anhydride 608
g (9.5 equivalents), ethylene glycol 391 g (1
2.6 equivalents), 1,2-propylene glycol 205 g
After reacting with (5.4 equivalents) and 305 g of cresol, it was diluted with 1,204 g of clay acid and 269 g of solvent naphtha, and further tetrabutyl titanate 4 was added.
9 g was blended to obtain a polyesterimide insulating paint having a resin content of 40%.

Comparative Example 4 480 g (2.5 mol) of trimellitic anhydride, 4,
248 g of 4'-diaminodiphenylmethane (2.5 mol), 480 g of trimellitic anhydride (7.5 equivalents),
186 g (6.0 equivalents) of ethylene glycol, 1,3-
When 270 g of butanediol (6.0 equivalents) and 636 g of cresol were reacted in the same manner as in Example 2, the reaction system at 200 ° C. showed a gelation after a rapid thickening.

Comparative Example 5 In the same manner as in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 543 g (1
7.5 equivalents), 338 g of 1,3-butanediol (7.
5 equivalents) and 818 g of cresol, followed by 1,691 g of cresylic acid and solvent naphtha 2
Diluted with 79 g, and then 76 g of tetrabutyl titanate
Was blended to obtain a polyesterimide insulating paint having a resin content of 40%.

Comparative Example 6 In the same manner as in Example 2, 480 g of trimellitic anhydride
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 502 g (1
6.2 equivalents), 68 g of 1,2-propylene glycol
After reacting with (1.8 equivalents) and 685 g of cresol, 1,415 g of cresylic acid, diluted with 233 g of solvent naphtha, and further mixed with 64 g of tetrabutyl titanate, polyester imide insulating paint having a resin content of 40% Got

Comparative Example 7 In the same manner as in Example 2, 480 g of trimellitic anhydride.
(2.5 mol), 4,4'-diaminodiphenylmethane 248 g (1.25 mol), trimellitic anhydride 48
0 g (7.5 equivalents), ethylene glycol 84 g (2.
7 equivalents), 581 g of 1,2-propylene glycol (1
(5.3 equivalents) and 726 g of cresol, and then diluted with 1,499 g of cresylic acid and 247 g of solvent naphtha, and further mixed with 68 g of tetrabutyl titanate to obtain a polyesterimide insulating paint having a resin content of 40%. .

Evaluation of Insulating Paints The insulating paints of Examples and Comparative Examples were each prepared with a furnace length of 2.5.
In a horizontal baking furnace of m, a copper wire with a conductor diameter of 0.32 mm is coated and baked at a furnace temperature of 500 ° C., a die 6 times, and a take-up speed of 24 m / min, and an insulated electric wire with a film thickness of 0.018 mm is obtained. Manufactured. Regarding these electric wires, JIS C 30
In accordance with No. 03 (test method for enamel copper wire and enamel aluminum wire), the appearance, adhesion, flexibility, softening point, dielectric breakdown voltage and solder peeling property were evaluated. In addition, with respect to the insulating paint of Example 3, a polyamide-imide insulating paint, a polyamide insulating paint, and a self-fusing insulating paint were each applied as an overcoat insulating paint. The method of manufacturing these insulated wires is as follows. The above evaluation results are shown in Tables 1 to 3 together with the raw material composition at the time of synthesizing the polyesterimide resin.

Production of Insulated Electric Wire Using Overcoat Insulating Paint (Polyamideimide Insulating Paint) Polyamideimide insulating paint prepared by the following method was applied on the insulated wire using the insulating paint of Example 3 in a horizontal type with a furnace length of 2.5 m. at the baking furnace, furnace temperature 500 ° C., the die 2 times, was coated and baked at a take-up speed 24m / min conditions, to produce an insulated wire having an overcoat layer peel film of 0.006mm thickness. (Production of Polyamideimide Insulating Paint) 185 g (0.95 mol) of trimellitic anhydride and 250 g (1.0 mol) of diphenylmethane diisocyanate
810 g of N-methyl-2-pyrrolidone and xylene 90
It was added to the mixed solvent (g) at 100 ° C. for 5 hours, and the temperature was further raised to react at 140 ° C. for 3 hours to obtain an insulating coating material.

Production of Insulated Wire Using Overcoat Insulating Paint (Polyamide Insulating Paint) A polyamide insulating paint prepared by the following method was applied on an insulated wire using the insulating paint of Example 3 in a horizontal baking furnace having a furnace length of 2.5 m. at, furnace temperature 500 ° C., 1 times die, it was applied and baked at a take-up speed 24m / min conditions, to produce an insulated wire having an overcoat layer peel film of 0.0015mm thick. (Production of Polyamide Insulating Paint) A polyamide insulating paint was obtained by dissolving 150 g of 6,6-nylon resin in 850 g of cresol at 100 ° C.

Production of Insulated Wire Using Overcoat Insulating Paint (Self-Fusing Insulating Paint) On the insulated wire using the insulating coating of Example 3, the self-fusing insulating coating prepared by the following method,
In a horizontal baking furnace with a furnace length of 2.5 m, coating and baking were performed under the conditions of a furnace temperature of 350 ° C., a die 4 times, and a take-up speed of 25 m / min.
0.010mm to produce an insulated wire having a thickness of the overcoat layer peel film. (Production of Self-Fusing Insulating Paint) 166 g of Ultramid 1C (copolymerized polyamide resin manufactured by BASF), 580 g of cresol and 250 of xylene
dissolved in a mixed solvent of 100 g at 100 ° C.
10 g of a phenol resin solution manufactured by Hitachi Chemical Co., Ltd. was added and dissolved to obtain a self-fusing insulating coating material.

[0047]

[Table 1] Table 1 Resin raw material composition and insulated wire characteristics (Part 1)

[0048]

TABLE 2 tree AburaHara charge composition and an insulated wire characteristics (Part 2)

[0049]

[Table 3] Table 3 Resin raw material composition and insulated wire characteristics (Part 3)

The results of Tables 1 to 3 show that the insulated wire using the insulating coating material of the present invention has excellent solder peeling property overcoming the drawbacks of the conventional polyesterimide insulated wire. .

[0051]

INDUSTRIAL APPLICABILITY The insulating coating material containing the polyesterimide resin of the present invention has excellent solder releasability and is capable of sufficiently satisfying the characteristic requirements for the insulated wire used in recent electric equipment. Is possible.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Sunouchi 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (72) Inventor Setsuo Terada 1-7-chome Nihonbashi Bakuro-cho, Chuo-ku, Tokyo No. 6 in Dainichi Seika Kogyo Co., Ltd. (56) Reference JP-A-6-119819 (JP, A) JP-A-6-111627 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) H01B 3/30 C08L 79/08 C09D 5/25 C09D 179/08

Claims (5)

(57) [Claims] 1. An insulating coating obtained by dissolving a polyesterimide resin in an organic solvent, wherein the polyesterimide resin is (A) a divalent carboxylic acid having a five-membered ring imide group or a derivative thereof, or a mixture thereof. B) trivalent carboxylic acid or its derivative or a mixture thereof,
(C) a primary aliphatic dihydric alcohol or a mixture thereof, and (D) at least one secondary or higher alcohol group
When the amount of the aliphatic dihydric alcohol having one or a mixture thereof is expressed as an equivalent amount, the total acid component [(A) +
(B)] 100 to all alcohol components [(C) +
(D)] at a ratio of 130 to 230, in which case the total acid component
The ratio of the component (A) in [(A) + (B)] is 10 to 35.
% Equivalent, the proportion of component (B) is 90 to 65 equivalent%, total
Ratio of component (C) in rucor component [(C) + (D)]
Is 25 to 85 equivalent%, and the ratio of the component (D) is 75 to 15 equivalent.
An insulating paint, which is obtained by reacting so as to be a quantity% . Wherein the divalent carboxylic acids containing imide group of five-membered ring, insulating paint according to claim 1 is a diimide dicarboxylic acid consisting of trimellitic anhydride 2 mol and diaminodiphenylmethane 1 mol. Wherein the trivalent carboxylic acid, insulating paint according to claim 1 or 2 which is trimellitic anhydride. Wherein primary aliphatic dihydric alcohol is ethylene glycol and / or 1,6-hexanediol in a claim 1 to 3 of insulating paint according to any one. 5. The aliphatic dihydric alcohol having at least one secondary or more alcohol groups, 1,2-propylene glycol and / or 1,3-butanediol in which one of claims 1-4 1 Insulating paint according to paragraph.