JP3737913B2 - Insulated wire - Google Patents

Description

【００３４】

【００３５】
表１及び表２の結果は、本発明の絶縁電線が、従来のポリエステル系絶縁電線の欠点を克服し、耐熱性、耐湿熱性及び半田剥離性を有していることを示している。
【００３６】
【発明の効果】
以上の本発明によれば、半田剥離性を有すると同時に耐熱性と耐湿熱性をも有する絶縁電線が提供される。本発明の絶縁電線は、近年の電気機器に用いるポリエステル系絶縁電線に対する要求特性に充分応えることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester-based insulated wire having heat resistance, wet heat resistance, and solder releasability.
[0002]
[Prior art]
In recent years, electric devices such as motors and transformers have been remarkably reduced in size, weight and performance.
In order to improve the reliability of electrical equipment, the heat resistance of insulated wires, which are the materials used, has progressed, and polyester-based insulated wires (PEW, EIW) and polyamide-imide insulated wires (AIW), etc. that are heat-resistant Class F or higher, have been developed. It has been put into practical use.
[0003]
In addition, with the sealing of electrical equipment, the operating temperature of the electrical equipment in an atmosphere where moisture is contained inside the electrical equipment often increases, and the insulation wire, which is the material used, is used to improve the reliability of the electrical equipment. It is also desired to have heat and moisture resistance.
On the other hand, electrical equipment manufacturers are rationalizing processes such as labor saving automation mainly for the purpose of cost reduction, and insulated wires require not only the heat resistance and heat and humidity resistance mentioned above, but also various characteristics that lead to labor saving automation. It has come to be.
[0004]
One of the various characteristics that leads to labor-saving automation is the line separation of insulated wire ends.
For the method of stripping the end of an insulated wire,
(1) machine peeling,
(2) Pyrolysis peeling
(3) chemical peeling,
(4) Although there is a method such as solder peeling, the method by (4) solder peeling is most preferable when considering the working time, making the conductor intact, continuous processing, and the like.
For this reason, an electric wire manufacturer is demanding an insulated wire having heat resistance, moisture and heat resistance, and solder releasability.
[0005]
[Problems to be solved by the invention]
Among the above insulated wires, polyester-based insulated wires that have productivity and economy in addition to various characteristics such as heat resistance are most widely used.
However, in polyester-based insulated wires that have been put to practical use, those that have heat resistance and moist heat resistance do not have solder releasability, and those that have heat resistance and solder releasability have insufficient moist heat resistance. There is a need for an insulated wire that satisfies both of these characteristics. Accordingly, an object of the present invention is to overcome the above-described drawbacks of the conventional polyester-based insulated wires, and to provide a polyester-based insulated wire having heat resistance, moisture and heat resistance, and solder releasability.
[0006]
As a result of intensive studies to achieve the above object, the present inventor has obtained a polyester-based resin obtained by using an acid component containing 10 equivalent% or more of 2,6-naphthalenedicarboxylic acid or a derivative thereof and an alcohol component as an insulating film forming resin. Polyester insulated wires formed by applying and baking an insulating coating on the conductor to overcome the disadvantages of conventional polyester insulated wires, have excellent heat resistance, moisture and heat resistance, and have solder releasability. As a result, the present invention has been completed.
[0007]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention is from 10 to 60 equivalent percent of 2,6-naphthalenedicarboxylic acid or its derivative (A) and 90 equivalents% less than 40 equivalent percent of trimellitic San及 beauty trimellitic anhydride 4,4 ' An alcohol component comprising an acid component comprising at least one (B) selected from diimidedicarboxylic acids comprising diaminodiphenylmethane and an alcohol component (C) which is at least one of aliphatic polyhydric alcohols having 2 to 8 carbon atoms An insulating coating obtained by dissolving a polyester resin obtained by reacting (C) in an amount that is equivalent to 1.2 to 2.0 times equivalent of the total acid component equivalent in an organic solvent is applied and baked on the conductor. This is a polyester-based insulated wire having solder releasability.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to embodiments of the invention.
Insulated wire of the present invention, 2,6-naphthalene dicarboxylic acid or its derivative (A) and anhydrous trimellitic acid, either or these diimide dicarboxylic acid consisting of trimellitic anhydride and 4,4'-diaminodiphenylmethane An insulating paint comprising, as an insulating film-forming resin, a polyester resin obtained by reacting an acid component comprising the mixture (B) and at least one of aliphatic polyhydric alcohols having 2 to 8 carbon atoms as the alcohol component (C) It is characterized by being baked on the conductor.
[0009]
In the above polyester-based resin, the use ratio of the component (A) in the acid component is 10 to 60 equivalent %, and the use ratio of the component (B) is less than 90 equivalent% to 40 equivalent% (however, the components (A) and ( B) is 100 equivalent%.) And the proportion of alcohol component (C) used is 1.2 to 2.0 times equivalent of the total acid component equivalent. Necessary for forming an insulating film having both excellent peelability.
When the ratio of the component (A) in the acid component is less than 10 equivalent%, not only the heat and moisture resistance of the resulting insulated wire is insufficient, but depending on the type of the component (B), the solder releasability itself may not be imparted. .
[0010]
From the viewpoint of the prior art, it is sufficient that the heat resistance and heat-and-moisture resistance of the resin can be improved by preparing a polyester resin using 2,6-naphthalenedicarboxylic acid or its derivative (A) as an acid component. It can be predicted that when the heat resistance is improved, it is easily predicted that the solder releasability, which is a characteristic contrary to the heat resistance, is inhibited.
However, by using 2,6-naphthalenedicarboxylic acid or a derivative thereof as an acid component in the above amount as described above, soldering to a polyester resin that is predicted not to impart solder releasability in addition to heat resistance and moist heat resistance. It was unexpected that the releasability was imparted and the solder releasability was imparted even though it was a polyester resin having heat resistance.
[0011]
As the acid component constituting the polyester resin used in the present invention, together with 2,6-naphthalene dicarboxylic acid or its derivative (A), anhydrous trimellitic acid, consisting of trimellitic anhydride and 4,4'-diaminodiphenylmethane Use of any one of diimide dicarboxylic acids or a mixture thereof (B) is necessary for imparting heat resistance to the obtained insulated wire, and use of an acid component other than the above is preferable because it impairs heat resistance. Absent.
Derivatives of 2,6-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid dimethyl ester le.
Diimide dicarboxylic acid composed of trimellitic anhydride and 4,4'-diaminodiphenylmethane is diimide dicarboxylic acid obtained by dehydrating 2 mol of trimellitic anhydride and 1 mol of 4,4'-diaminodiphenylmethane. is there.
[0012]
As the alcohol component (C) to be reacted with the acid component in the present invention, an aliphatic polyhydric alcohol having 2 to 8 carbon atoms is suitable. Aliphatic polyhydric alcohols having 9 or more carbon atoms are not preferred because they reduce heat resistance. Also, the use of polyhydric alcohols having an aromatic or heterocyclic ring is not preferable because it hinders solder releasability.
In order to obtain the polyester resin used in the present invention, the ratio of the alcohol component (C) to the acid components (A) and (B) is such that the alcohol component (C) is 1.2 to It is necessary to use it at an equivalent of 2.0 times, and if it is less than 1.2 times, it is easy to cause gelation during the synthesis reaction of the polyester resin, and it is difficult to put it to practical use. The polymerization degree of the resin is too low, and the film forming ability when baked as an insulating paint is not preferable.
[0013]
Examples of the aliphatic polyhydric alcohol having 2 to 8 carbon atoms include:
ethylene glycol,
Diethylene glycol,
1,3-propanediol,
1,4-butanediol,
1,5-pentanediol,
1,6-hexanediol,
1,2-propylene glycol,
1,3-butanediol and the like can be mentioned.
[0014]
The polyester resin used in the present invention is synthesized by a conventionally known method such as esterification reaction or transesterification reaction using the acid components (A) and (B) and the alcohol component (C) in the above amounts. The production method is not particularly limited. The synthesis reaction is usually performed in the presence of a solvent.
As an example of the solvent during the synthesis reaction and the solvent for dilution, for example,
Phenol,
Cresol,
Cresolic acid,
Xylenol,
Dimethylformamide,
Polar solvents such as N-methyl-2-pyrrolidone are used alone or in combination.
Moreover, as a cosolvent at the time of dilution, hydrocarbon solvents, such as toluene, xylene, solvent naphtha, methyl ethyl ketone, cyclohexanone, can be used, for example. Particularly useful are xylene and solvent naphtha, which are aromatic hydrocarbons, which can improve the workability when an insulated wire is manufactured by baking an insulating coating on a conductor.
[0015]
The insulating paint used in the present invention is produced by dissolving the polyester resin obtained as described above in a solvent. Usually, the solution after the synthetic reaction of the resin is used as it is or after being diluted.
In addition, when an insulated wire is manufactured by baking it on a conductor, adding a small amount of a metal desiccant or a titanic acid compound increases the production rate of the insulated wire and increases the insulation wire. Since surface smoothness is further improved, it is preferable.
Examples of the metal desiccant include zinc octenoate and lead naphthenate. The most useful are titanic acid compounds such as tetrabutyl titanate, tetraisopropyl titanate, etc., and the addition amount is 0.1 to 8.0 weight with respect to 100 parts by weight of the solid content of the insulating coating. Parts, preferably 1.0 to 6.0 parts by weight.
[0016]
In addition to the metal desiccant, the insulating paint used in the present invention is a heat-resistant material such as stabilized isocyanate, polyamide, polyester, polysulfone, etc., in which the isocyanate group of the polyisocyanate is blocked with phenol or the like, as long as the characteristics of the present invention are not impaired. Thermosetting resins such as plastic resins, melamine resins, and phenol resins, dyes, pigments, lubricants, other paint additives, and the like can be appropriately added.
[0017]
The insulated wire of the present invention is formed by adjusting the above-mentioned insulating paint to a viscosity suitable for work with an appropriate solvent, and then applying and baking on a conductor such as an annealed copper wire according to a conventionally known method to form an insulating layer (film). It is manufactured by doing.
Furthermore, the insulated wire of the present invention can be coated with a lubricant such as liquid paraffin or solid paraffin on the upper layer of the above insulating layer for winding properties, and generally has other characteristics. As is done, other insulating paints can be applied and baked to provide an insulating layer. For example, if further heat resistance is required, polyimide insulating coating or polyamideimide insulating coating is required, and if winding properties are required, polyamide coating such as 6,6 nylon, coil self-supporting is required. In such a case, a self-bonding paint such as polyvinyl butyral, phenoxy, polyester, polyamide, or polysulfone paint is used.
[0018]
【Example】
Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. The percentages in the text are based on weight.
[0019]
Reference production example 1
In a 5 liter flask equipped with a stirrer, nitrogen inlet tube, condenser and thermometer, 1,6-naphthalenedicarboxylic acid dimethyl ester 1,220 g (5 mol), ethylene glycol 233 g (3.75 mol), glycerin 233 g (2.5 mol) ), And while heating with nitrogen blowing, demethanol accompanying transesterification started at 160 ° C. After heating up to 240 degreeC over 10 hours, it was made to react at 240 degreeC for 3 hours, cresol 1,360g was prepared and reaction was stopped. Furthermore cresol 431 g, was diluted with xylene 185 g, at 100 ° C., mixed with tetrabutyl titanate 68 g, to obtain an insulating paint resin content of 40% Reference Example.
[0020]
Production Example 1
In the same manner as in Reference Production Example 1, 427 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 326 g (5.25 mol) of ethylene glycol, and 171 g (2.25 mol) of propylene glycol were charged in a flask. When heated while blowing nitrogen, demethanol accompanying transesterification started at 160 ° C. After setting to 200 ° C. over 8 hours, 760 g of cresol was added to temporarily stop the reaction. After this system was set to 120 ° C., 416 g (2.17 mol) of trimellitic anhydride was added and heated again, and dehydration accompanying the esterification reaction started at 180 ° C. After reacting while heating from 180 ° C. to 240 ° C. over 6 hours, 383 g of cresol was added to stop the reaction. Furthermore, after diluting with 363 g of cresol and 155 g of xylene, 57 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint- 1 having a resin content of 40%.
[0021]
Production Example 2
In the same manner as in Production Example 1 , 488 g (2 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 291 g (1.5 mol) of dimethyl terephthalate, 326 g (5.25 mol) of ethylene glycol, 140 g of glycerin ( 1.5 mol) was added to the reaction, 287 g of cresol was added to temporarily stop the reaction, 192 g (1 mol) of trimellitic anhydride was added to this system and reacted again, and 882 g of cresol was added to stop the reaction. I let you. Further, after dilution with 370 g of cresol and 159 g of xylene, 59 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint- 2 having a resin content of 40%.
[0022]
Production Example 3
In the same manner as in Production Example 1 , 366 g (1.5 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 485 g (2.5 mol) of dimethyl terephthalate, 279 g (4.5 mol) of ethylene glycol, 186 g of glycerin ( 2 mol) was charged into a flask and reacted, and then 263 g of cresol was added to temporarily stop the reaction. After cooling to 100 ° C. or lower and charging 384 g (2 mol) of trimellitic anhydride and 198 g (1 mol) of 4,4′-diaminodiphenylmethane to this system and heating again, an imidization reaction is carried out at 140 ° C. The accompanying dehydration then begins at 180 ° C. with the esterification reaction. From 140 ° C. to 210 ° C. over 6 hours and further reacted at 210 ° C. for 3 hours, 286 g of cresol was added to stop the reaction. Furthermore, after diluting with 494 g of cresol and 212 g of xylene, 79 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint- 3 having a resin content of 40%.
[0023]
Production Example 4
In the same manner as in Production Example 3 , 366 g (1.5 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 372 g (6 mol) of ethylene glycol and 93 g (1 mol) of glycerin were charged and reacted, and 644 g of cresol was added. The reaction was stopped once by addition. To this system, 704 g (3.67 mol) of trimellitic anhydride and 198 g (1 mol) of 4,4′-diaminodiphenylmethane were charged and reacted again, and then 860 g of cresol was added to stop the reaction. Furthermore, after diluting with 475 g of cresol and 203 g of xylene, 75 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating coating 4 having a resin content of 40%.
[0024]
Production Example 5
In the same manner as in Production Example 3 , the flask was charged with 732 g (3 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 233 g (3.75 mol) of ethylene glycol, and 233 g (2.5 mol) of glycerin and reacted. The reaction was stopped once by adding 1,655 g of cresol. To this system, 768 g (4 mol) of trimellitic anhydride and 396 g (2 mol) of 4,4′-diaminodiphenylmethane were charged and reacted again, and 368 g of cresol was added to stop the reaction. Further, after diluting with 638 g of cresol and 274 g of xylene, 101 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint- 5 having a resin content of 40%.
[0025]
Production Example 6
In the same manner as in Production Example 3 , 366 g (1.5 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 233 g (3.75 mol) of ethylene glycol, 114 g (1.5 mol) of propylene glycol, and 140 g of glycerin ( 1.5 mol) was added and reacted, and then 669 g of cresol was added to temporarily stop the reaction. In this system, 512 g (2.67 mol) of trimellitic anhydride and 198 g (1 mol) of 4,4′-diaminodiphenylmethane were charged and reacted again, and then 894 g of cresol was charged to stop the reaction. Furthermore, after diluting with 494 g of cresol and 212 g of xylene, 78 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint- 6 having a resin content of 40%.
[0026]
Production Example 7
In the same manner as in Reference Production Example 1, 970 g (5 mol) of dimethyl terephthalate, 233 g (3.75 mol) of ethylene glycol, and 233 g (2.5 mol) of glycerin were charged into a flask and reacted, and then cresol 1 , 108 g were charged to stop the reaction. Further, after dilution with 351 g of cresol and 151 g of xylene, 56 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 1 with a resin content of 40%.
[0027]
Production Example 8
In the same manner as in Reference Production Example 1, 61 g (0.25 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester, 922 g (4.75 mol) of dimethyl terephthalate, 233 g (3.75 mol) of ethylene glycol, After 233 g (2.5 mol) of glycerin was charged and reacted, 1,120 g of cresol was added to stop the reaction. Further, after dilution with 355 g of cresol and 152 g of xylene, 56 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 2 with a resin content of 40%.
[0028]
Production Example 9
In the same manner as in Production Example 1 , 679 g (3.5 mol) of terephthalic acid dimethyl ester, 372 g (6 mol) of ethylene glycol and 93 g (1 mol) of glycerin were charged and reacted, and 1,068 g of cresol was added. Once the reaction was stopped, 192 g (1 mol) of trimellitic anhydride was charged and reacted again, and 1,068 g of cresol was charged to stop the reaction. Further, after dilution with 339 g of cresol and 145 g of xylene, 54 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 3 with a resin content of 40%.
[0029]
Production Example 10
In the same manner as in Production Example 1 , 582 g (3 mol) of dimethyl terephthalate, 233 g (3.75 mol) of ethylene glycol and 233 g (2.5 mol) of glycerin were charged and reacted, and then 698 g of cresol was added. The reaction was stopped once. To this system, 768 g (4 mol) of trimellitic anhydride and 396 g (2 mol) of 4,4′-diaminodiphenylmethane were charged and reacted again, and then 341 g of cresol was added to stop the reaction. Furthermore, after diluting with 591 g of cresol and 253 g of xylene, 94 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 4 with a resin content of 40%.
[0030]
Production Example 11
In the same apparatus as in Reference Production Example 1, 1,280 g (6.67 mol) of trimellitic anhydride, 465 g (7.5 mol) of ethylene glycol, 495 g (2.5 mol) of 4,4′-diaminodiphenylmethane, After adding 634 g of cresol and reacting, 364 g of cresol was added to stop the reaction. Furthermore, after diluting with 630 g of cresol and 270 g of xylene, 100 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 5 with a resin content of 40%.
[0031]
Production Example 12
In the same apparatus as in Reference Production Example 1, 776 g (4 mol) of dimethyl terephthalate, 233 g (3.75 mol) of ethylene glycol, 653 g (2.5 mol) of tris (2-hydroxyethyl) isocyanurate, 384 g (2 mol) of merit acid, 198 g (1 mol) of 4,4′-diaminodiphenylmethane and 211 g of cresol were charged and reacted, and then 1,702 g of cresol was charged and the reaction was stopped. Further, after dilution with 603 g of cresol and 259 g of xylene, 96 g of tetrabutyl titanate was blended at 100 ° C. to obtain an insulating paint ratio of 6 with a resin content of 40%.
[0032]
Examples 1 6 and Comparative Examples 1 to 6
Each of the above-mentioned insulating paints was applied and baked on a copper wire having a conductor diameter of 0.32 mm in a horizontal baking furnace having a furnace length of 2.5 m under conditions of a furnace temperature of 500 ° C., six dies, and a take-up speed of 22 m / min. An insulated wire having a coating thickness of 0.018 mm was manufactured.
About the obtained insulated wire, the external appearance, adhesiveness, pinhole, flexibility, softening point, dielectric breakdown voltage, and solder peelability were tested according to JIS C 3003 (enamelled copper wire and enameled aluminum wire test method). The heat and humidity resistance is determined by enclosing two twisted samples in a dielectric breakdown voltage test of JIS C3003 together with 0.2 vol% of water in a 700 ml autoclave, leaving it in a constant temperature bath at 120 ° C. for 168 hours, and following the dielectric breakdown voltage test of JIS C3003. The retention rate relative to the initial value was measured. The above test results are shown in Tables 1 and 2.
[0033]

[0034]

[0035]
The results in Tables 1 and 2 show that the insulated wires of the present invention overcome the drawbacks of conventional polyester-based insulated wires and have heat resistance, moist heat resistance and solder peelability.
[0036]
【The invention's effect】
According to the present invention as described above, an insulated wire having both solder releasability and heat resistance and moist heat resistance is provided. The insulated wire of the present invention can sufficiently meet the required characteristics for polyester-based insulated wires used in recent electrical equipment.

Claims (1)

10-60 equivalent percent of 2,6-naphthalenedicarboxylic acid or its derivative (A) and 90 equivalent% less than 40 equivalent percent trimellitic San及 beauty of trimellitic anhydride and diimide consisting of 4,4'-diaminodiphenylmethane An acid component comprising at least one (B) selected from dicarboxylic acids and an alcohol component (C) which is at least one of aliphatic polyhydric alcohols having 2 to 8 carbon atoms, and the alcohol component (C) is a total acid. An insulating paint obtained by dissolving a polyester resin obtained by reacting in an amount equivalent to 1.2 to 2.0 times the component equivalent in an organic solvent is applied and baked on a conductor. Polyester insulated wire with solder releasability.