JPH05186683A - Solderable resin composition and insulated wire produced therewith - Google Patents

Abstract

PURPOSE:To provide a solderable resin composition giving excellent appearance even by increasing the coating film thickness, having excellent heat-resistance, especially softening resistance, and useful for the production of an insulated wire having excellent thermal shock resistance. CONSTITUTION:A resin composition containing a polyester resin having imide bond in the molecule, a stabilized isocyanate and a long-chain aminoamide salt of a polymeric acid polyester. An insulated wire produced by using the resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, and more specifically, a resin which produces a coating film which has a good appearance even if the coating film is thick and is excellent in solderability, heat resistance and thermal shock resistance. The present invention relates to a composition and an insulated wire.

[0002]

2. Description of the Related Art Conventionally, as an insulated wire having solderability, a polyurethane insulated wire is known, but its heat resistance classification is A to E class, and it is used for applications requiring heat resistance of B class or more. Had the drawback that it could not be used. Recently, in order to improve this defect, a resin composition containing a polyester resin having an imide group in the molecule and a stabilized isocyanate has been proposed and used for B-type insulation.
However, in this resin composition, although the heat resistance classification is improved to B type, when the coating is thickly baked, particles are formed in the coating,
There is a defect that foaming, rough skin, etc. occur and the appearance is inferior.
It is known to add polymer resins such as nylon resin, phenoxy resin, epoxy resin, polyester resin, etc. to improve the appearance of insulated wires. Has ineffectiveness or poor stickiness.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has an excellent appearance even if a coating is thickened and baked, and is capable of baking fine wires, and has solderability, (EN) Provided are a resin composition capable of obtaining an insulated electric wire excellent in heat resistance and thermal shock resistance, and an insulated electric wire using the same.

[0004]

Means for Solving the Problems By using a resin composition containing a polyester resin having an imide bond in the molecule, a stabilized isocyanate compound and a polymeric acid polyester long-chain aminoamide salt, The present invention has been completed by finding that the above object is achieved.
The present invention provides (a) a polyester resin containing an imide bond in the molecule, (b) a stabilized isocyanate, and (c).
A resin composition containing 0.01 to 1.0% by weight of a long-chain aminoamide salt of a high-molecular acid polyester based on the total amount of the polyester resin and the stabilized isocyanate, and the resin composition on a conductor. The present invention relates to an insulated electric wire coated and baked on.

The polyester resin (a) containing an imide bond in the molecule used in the present invention is obtained by the reaction between an acid component and an alcohol component. As a part of the component, the compound of the general formula (I)

[Chemical 1] An imidodicarboxylic acid represented by the formula (R in the formula means a divalent organic group) is used. The imidodicarboxylic acid represented by the general formula (I) is, for example, JP-B-51-40.
As disclosed in Japanese Patent No. 113, it is obtained by reacting 2 mol of trimellitic anhydride with 1 mol of diamine. Examples of the diamine include 4,4 ′
-Diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, 1,4-diaminonaphthalene, 4,4'-diaminodiphenyl ether, hexamethylenediamine, diaminodiphenylsulfone and the like. In the present invention, diisocyanates corresponding to the above diamines may be used instead of these diamines. From the viewpoint of solderability, heat resistance and thermal shock resistance of the final composition, the amount of the imidodicarboxylic acid represented by the general formula (I) is preferably 10 to 30 equivalent% based on the total acid components.

Examples of the acid component other than the imidodicarboxylic acid used in the polyester resin having an imide bond in the molecule include terephthalic acid or its lower alkyl ester such as dimethyl terephthalate, monomethyl terephthalate, and diester terephthalate. Be done. Also,
Compounds commonly used in polyester varnish for enameled wire,
For example, isophthalic acid, adipic acid, phthalic acid, sebacic acid, etc. can be used.

Examples of the alcohol component of the polyester resin having an imide bond in the molecule include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3 butanediol, neopentyl glycol 1,3. Diols such as butanediol and 1,4-butanediol, triols such as glycerin, trimethylolpropane, hexanetriol, and tris- (2-hydroxyethyl) isocyanurate are used. These acid components and alcohol components may be used alone or in combination of two or more. It is preferable to react all the alcohol components in excess with respect to the total acid components in an equivalent amount. This is because the hydroxyl group remains in the molecular chain of the polyester resin having an imide bond in the molecule, and this reacts with the stabilized isocyanate during baking to form a urethane bond. From the viewpoint of solderability and heat resistance, the equivalent ratio of total alcohol component / total acid component is 1.3 to
2.5 is preferable and 1.6 to 2.4 is more preferable.

The polyester resin (a) having an imide bond in the molecule is synthesized by mixing the above acid component and alcohol component in the presence of an esterification catalyst at 170 ° C. to 250 ° C.
It is carried out by heating at a temperature of ° C. Examples of the esterification catalyst used at this time include tetrabutyl titanate, lead acetate, dibutyltin laurate, zinc octenoate, zinc naphthenate and the like. The imidodicarboxylic acid may be a pre-synthesized one, and a component such as a diamine and trimellitic anhydride that becomes an imidic acid is mixed with another acid component and an alcohol component and heated at the same time for imidization and esterification. The conversion may be performed at the same time. The polyester resin having an imide bond in the molecule is preferably synthesized in the coexistence of a phenolic solvent such as phenol, cresol, xylenol or the like because the viscosity at the time of synthesis is high.

The stabilized isocyanate (b) used in the present invention is a compound obtained from 4,4'-diphenylmethane diisocyanate and xylenol (Millionate MS-50 manufactured by Nippon Polyurethane Industry Co., Ltd.), 4,
Compounds obtained from 4'-diphenylmethane diisocyanate, aliphatic polyols and phenols (Coronate 2503 manufactured by Nippon Polyurethane Industry Co., Ltd.), compounds obtained from tolylene diisocyanate, aliphatic polyols and phenols (Dismodule AP Stable manufactured by Bayer) Etc.

The mixing ratio of the polyester resin (a) having an imide bond in the molecule and the stabilizing isocyanate (b) is 100% from the viewpoint of solderability and heat resistance of the insulated wire. The amount of the stabilized isocyanate (b) is preferably 100 to 1000 parts by weight, more preferably 150 to 500 parts by weight, based on parts by weight.

The resin composition of the present invention comprises a long-chain aminoamide salt of a high-molecular acid polyester in an amount of 0. 0 relative to the total amount of the polyester resin (a) having an imide bond in the molecule and the stabilized isocyanate (b). It is obtained by blending in an amount of 01 to 1.0% by weight, more preferably 0.05 to 0.5% by weight. If the amount of the long-chain aminoamide salt of the high-molecular-weight polyester is more than 1.0% by weight, the appearance of the baked wire will be repelled, and if it is less than 0.01% by weight, the appearance of the baked wire will not be improved.

Examples of the long-chain amino amide salt of the high-molecular polyester include DISPARLON # 1860 (trade name of Kusumoto Kasei Co., Ltd.), BYK-405 (Tetsutani Co., Ltd.),
Product name) and the like.

The resin composition of the present invention may be added with an organometallic compound if necessary, dissolved in a solvent, and applied directly or together with another insulating coating on a conductor by a conventional method and baked to form an insulated wire. .. Examples of the organometallic compound include zinc, lead, manganese, and tin metal salts of an aliphatic carboxylic acid. These improve the linear velocity at the time of baking an insulated wire, shorten the curing time, lower the curing temperature, and Improves solderability. Further, as the solvent, for example, phenol, cresol, xylenol, cellosolves, cartols, xylene and the like are used.

[0014]

EXAMPLES Next, the present invention will be described in more detail by way of examples. In addition,% in the following examples means weight%. Example 1 In a four-necked flask equipped with a thermometer, a stirrer and a condenser,
4,4'-Diaminodiphenylmethane 99g (0.5 equivalent), trimellitic anhydride 192g (1.0 equivalent), dimethyl terephthalate 291g (3.0 equivalent), ethylene glycol 93g (3.0 equivalent), glycerin 92g
(3.0 equivalents), 217 g of cresol and 3.8 g of tetrabutyl titanate were added, and the temperature was raised to 170 ° C. in a nitrogen stream to react for 60 minutes. The resulting solution is then added to 2
The temperature was raised to 10 ° C. and the reaction was carried out for 3 hours. Further, 436 g of cresol was added to this solution to obtain a polyester resin solution having a nonvolatile content of 50% and having an imide bond in the molecule.
125 g of Coronate 2503 (stabilized isocyanate compound manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 g of a polyester resin solution having an imide bond in the obtained molecule.
Long-chain aminoamide salt of high-molecular acid polyester, Disparlon # 1860 (manufactured by Kusumoto Kasei Co., Ltd.) 0.0875 g
(0.05% by weight), cresol 210 g, xylene 5
5 g and 1.5 g of zinc naphthenate were added to obtain a resin composition of the present invention.

Example 2 100 g of a polyester resin solution having an imide bond in the molecule obtained in Example 1 was added to Coronate 2503 12
5 g, Disparlon # 1860 0.875 g (0.5
%), Cresol 210 g, xylene 55 g and zinc naphthenate 1.5 g were added to obtain a resin composition of the present invention.

Example 3 To 100 g of the resin solution having an imide bond in the molecule obtained in Example 1, 125 g of Coronate 2503, 1.75 g (1.0% by weight) of Disparlon # 1860, 210 g of cresol, 55 g of xylene and naphthene were added. 1.5 g of zinc acid was added to obtain a resin composition of the present invention.

Comparative Example 1 100 g of the polyester resin solution having an imide bond in the molecule obtained in Example 1 was added to Coronate 25031.
A resin composition was obtained by adding 25 g, 210 g of cresol, 50 g of xylene and 1.5 g of zinc naphthenate.

Comparative Example 2 A general-purpose polyurethane insulated wire varnish WD-437 (manufactured by Hitachi Chemical Co., Ltd.) is used as Comparative Example 2.

The following tests were conducted using the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

[Test example]

(1) Appearance Evaluation of Insulated Electric Wire A copper wire having a diameter of 0.07 mm was baked under the following conditions while changing the coating thickness, and the appearance was visually observed. The results are shown in Table 1. The baking conditions are as follows. Baking furnace: Horizontal furnace Furnace temperature: Inlet / outlet = 330 ° C / 380 ° C Linear velocity: 240m / min Coating method: Felt 7 times drawing

[0020]

[Table 1]

From the results shown in Table 1, it is shown that the resin composition of the present invention has a good appearance as compared with the resin composition of Comparative Example.

(2) Characteristic evaluation of insulated wire Various characteristics were evaluated by baking on a copper wire having a diameter of 0.4 mm under the same conditions as in (1). The results are shown in Table 2. The test items in the tests in Table 2 were measured according to JIS C3003 5-19. For the breakdown voltage after thermal deterioration, see J
Twisted electric wire manufactured according to IS C3003 20
After leaving it in a constant temperature bath of 0 ° C. for 168 hours, the dielectric breakdown voltage was measured.

[0023]

[Table 2]

From the results shown in Table 2, when the resin composition of the present invention is used, thermal shock resistance, retention of dielectric breakdown voltage after thermal deterioration and softening resistance are compared with those of conventional general-purpose polyurethane insulated wires. It is shown that the property is excellent, and the characteristics are not deteriorated as compared with the conventional heat-resistant urethane wire of Comparative Example 1.

[0025]

When the resin composition of the present invention is used, the appearance is good even if the film is thickened, the heat resistance, especially the softening resistance is excellent, and the solderability and the thermal shock resistance are also excellent. An insulated wire can be manufactured.

Claims (2)

[Claims] 1. 0.01 to 1.0 based on the total amount of (a) a polyester resin having an imide bond in the molecule, (b) a stabilized isocyanate, and (c) the polyester resin and a stabilized isocyanate. A resin composition comprising a long-chain amino amide salt of a high-molecular acid polyester in a weight percentage. 2. An insulated electric wire obtained by applying and baking the resin composition according to claim 1 on a conductor.