JP2912196B2 - Insulated wire for soldering - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulated wire excellent in solderability and heat resistance suitable for windings of electronic equipment.

[0002]

2. Description of the Related Art Conventionally, as windings for electronic devices,
Polyurethane insulated wires are widely used. This is because the polyurethane insulating layer is melted and decomposed by heat, so that the insulating layer can be soldered without peeling. However, in recent years, the miniaturization and high performance of electronic devices have been progressing, and accompanying this, applications for functioning in a high-temperature atmosphere are also expanding. Although high heat resistance is required, there are many applications where conventional polyurethane insulated wires can no longer cope with the heat resistance.

Therefore, as an alternative to the polyurethane insulated wire, a modified polyester insulated wire and a modified polyesterimide insulated wire which can be soldered without peeling off the insulating layer have been developed and are already used for some applications. .

However, these modified polyester insulated wires and modified polyester imide insulated wires cannot sufficiently cope with the recent widespread use of electronic equipment in high-temperature applications, and have even higher heat resistance. Regarding the solderability, there is a strong demand for the development of an insulated wire in which the insulating layer is quickly decomposed and has good operability.

Accordingly, the present applicant has previously applied a polyamideimide paint obtained by reacting trimellitic anhydride and an aliphatic dicarboxylic acid with a diisocyanate compound.
A modified polyamide-imide insulated wire having a baked insulating layer has been developed and proposed as Japanese Patent Application No. 5-181725. This insulated wire has a very high heat resistance, the insulation layer is quickly decomposed during soldering, and the assembling operability is excellent, making it suitable for windings of electronic devices used at high temperatures in recent years. In addition, it has an excellent feature that both the heat resistance and the solderability can be adjusted according to the application, and has already been put to practical use.

[0006]

However, while the modified polyamide-imide insulated wire according to the above proposal has the above-mentioned excellent characteristics, the allowable range of manufacturing conditions such as the baking temperature is very narrow, so that the temperature at the time of baking is low. High quality products are difficult to obtain stably with difficulties in control, etc., especially when the heating furnace used for baking becomes large, it is difficult to maintain the distribution width and fluctuation width of the furnace temperature in an appropriate range, and mass production Had the drawback of causing problems.

[0007] A first object of the present invention is to provide, in view of the above-mentioned circumstances, both excellent heat resistance and solderability, such as the modified polyamide-imide insulated wire according to the above-mentioned proposal, and furthermore, manufacturing conditions such as a baking temperature. An object of the present invention is to provide an insulated wire for soldering having a wide allowable range and suitable for mass production. Also,
Another object of the present invention is to provide, in addition to the above-described excellent heat resistance, solderability, and mass productivity, various properties according to applications such as softening resistance, winding property (abrasion resistance), and self-fusing property. An object of the present invention is to provide an insulated wire for soldering .

[0008]

In the first object SUMMARY OF THE INVENTION, soldering insulated wire according to claim 1 of the present invention, three of trimellitic anhydride and lipid aliphatic dicarboxylic acid and an aromatic dicarboxylic acid Acid component, trimellitic anhydride /
When the molar ratio of all acid components is in the range of 0.2 to 0.7 and the fat is
Group dicarboxylic acid / total acid component molar ratio of 0.2 to 0.7
Based on the acid component in the range, the total number of moles of 0.9 to 1.1 times the moles of diisocyanate compounds such acid components by reacting polyamideimide paint which is obtained by coating, a structure having an insulating layer formed by baking It has been adopted.

[0009] In the second object, the insulated wire for soldering according to the second aspect of the present invention is the above-mentioned insulated wire according to the first aspect.
A configuration in which an insulating layer formed by applying and baking a polyimide-based insulating paint or a polyamide-imide-based insulating paint different from the base on an insulated electric wire for soldering is adopted.

[0010] For the same purpose, the solder according to claim 3 of the present invention.
Give for insulated wire, on an insulating wire according to the claim 1, in which the polyamide-based insulating paint application, adopts a configuration in which baking becomes an insulating layer is formed.

[0011] For the same purpose, the solder according to claim 4 of the present invention.
Give for insulated wire, on an insulating wire according to the claim 1, in which the self fusing insulating paint application, adopts the configuration baked comprising an insulating layer is formed.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The polyamide imide of the coating material for forming an insulating layer according to the present invention is different from a general polyamide imide using trimellitic anhydride and a diamine as reaction components, unlike trimellitic anhydride, dicarboxylic acid and diisocyanate. It is obtained by reacting with a compound,
The main chain has an imide bond due to a reaction between an acid anhydride structure of trimellitic anhydride and an isocyanate group, and an amide bond due to a reaction between a carboxyl group of trimellitic anhydride and dicarboxylic acid and an isocyanate group. Moreover, since an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid are used in combination as a dicarboxylic acid component, it has a structure in which an aromatic group and an aliphatic group are mixed in the main chain.

Thus, an insulated wire having an insulating layer obtained by applying and baking the above-mentioned polyamideimide paint has not only excellent heat resistance and solderability, but also has a wide allowable range of baking temperature of the paint. Therefore, even if a large heating furnace is used, temperature control is easy, and stable high-quality products can be mass-produced. It is not clear why such a feature is obtained, but when the trimellitic anhydride component is insufficient among the above-mentioned three acid components constituting the polyamideimide, the heat resistance is remarkably reduced, and the aliphatic dicarboxylic acid component is reduced. Insufficiency leads to a remarkable decrease in solderability, and insufficiency of the aromatic dicarboxylic acid component has been found to significantly reduce the allowable range of the baking temperature.In view of these points, polyimide based on trimellitic anhydride is While the structure is responsible for excellent heat resistance, the aliphatic dicarboxylic acid exhibits high thermal decomposability to ensure good solderability, and the aromatic dicarboxylic acid component has the above heat resistance and solderability. It is presumed that it has contributed to maintaining a wide balance of.

In order to prepare the above polyamideimide paint, three kinds of acid components, trimellitic anhydride, aliphatic dicarboxylic acid and aromatic dicarboxylic acid, and a diisocyanate compound are dissolved in a suitable solvent and heated. However, in order to synthesize a good polyamideimide, it is necessary to react the diisocyanate compound with the above-mentioned three kinds of acid components in an approximately equimolar amount. The molar ratio is in the range of 0.9 to 1.1 times the total number of moles of the acid component. That is, when the amount of the diisocyanate compound used is less than 0.9 mole, the appearance and flexibility of the formed insulating layer are deteriorated. become.

On the other hand, the use ratio of trimellitic anhydride is as follows:
Trimellitic anhydride / total acid component molar ratio of 0.2 to 0.2
The range of 0.7 is preferable. When the molar ratio is less than 0.2, the heat resistance is significantly reduced, and when the molar ratio exceeds 0.7, the solderability is significantly reduced.

The aliphatic dicarboxylic acid is used in a molar ratio of aliphatic dicarboxylic acid / total acid component of 0.2 to 0.2.
When the molar ratio is less than 0.2, the solderability becomes insufficient. Conversely, when the molar ratio is 0.7
If the temperature exceeds the above range, the allowable range of the baking temperature of the obtained polyamide-imide paint will be remarkably reduced, and the heat resistance will also be reduced.

The aliphatic dicarboxylic acid used in the synthesis of the polyamideimide is not particularly limited as long as it is a saturated dicarboxylic acid, but the carbon atom of the alkylene group such as succinic acid, adipic acid, alaisenic acid, sebacic acid and dodecane diacid is preferred. Those having a number of 2 or more are suitable, and these may be used in combination of two or more.

Similarly, as the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid and the like are preferable, but those having a plurality of aromatic rings can also be used.
These may be used in combination of two or more. Examples of the latter dicarboxylic acid having a plurality of aromatic rings include 4,4′-biphenyldicarboxylic acid, 3,3′-methylene dibenzoic acid,
4'-methylene dibenzoic acid, 4.4'-oxydibenzoic acid, 4.4'-thiodibenzoic acid, 4.4'-carbonyldibenzoic acid, 4.4'-sulfonyl dibenzoic acid, 1. 4
-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like.

Examples of the diisocyanate compound include toluene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, and 1,5-naphthalenediisocyanate. Can be used together.

In order to manufacture the insulated wire of the present invention, the above polyamideimide paint is adjusted in viscosity by adding a suitable diluting solvent, if necessary, and then applied and baked on a conductor such as a soft copper wire in a conventional manner. Then, an insulating layer may be formed. The thickness of the insulating layer varies depending on the diameter of the conductor.
The thickness is usually set to a necessary thickness by repeating the above-described coating and baking a plurality of times.

Further, the insulated wire of the present invention is characterized in that the insulating layer is formed by applying and baking another insulating paint on the insulating layer formed by applying and baking the above polyamideimide paint. Also included are those having two or more layers. In such an insulated wire having two or more insulating layers, for example,
In the case where there are various characteristics particularly required for applications such as softening resistance, winding property (abrasion resistance), self-fusing property, etc., these characteristics are imparted by the upper insulating layer and the lower layer described above. Solderability can be ensured by the polyamideimide insulating layer on the side.

That is, the insulating layer used on the upper layer side is originally poor in thermal decomposability. In the case of an insulated wire directly provided on a conductor, when the insulated wire is in contact with the solder, it is carbonized while adhering to the conductor. Even if it is a resin component that inhibits conduction, that is, a resin component that cannot be soldered, if the polyamide-imide insulating layer having good thermal decomposability is present in the lower layer, this lower layer is thermally decomposed and detaches from the conductor surface. As a result, the upper layer is also dissipated, so that sufficient solderability is obtained as a result. Of course, the same applies when the upper layer is two or more layers.

Although there is no particular limitation on the insulating paint used for forming the upper layer, for example, the following are suitable according to the required characteristics. That is, polyimide-based insulating coatings and polyamide-imide-based insulating coatings different from the lower layer are used for applications requiring heat resistance such as softening resistance, and 6,6-nylon is used for applications requiring winding property (abrasion resistance). Polyamide-based insulating paints such as (polyhexamethylene adipamide), and self-fusing insulating paints are used for self-holding the winding form as coils for motors and transformers.

As the polyamide-imide-based insulating coating different from the above-mentioned lower layer, a coating mainly composed of a general polyamide-imide obtained by reacting trimellitic anhydride with a diamine is preferable. Polyamideimide-based coatings comprising the following components can also be used. As the self-fusing insulating coating, any of those conventionally known for forming an insulating layer of a self-fusing insulated wire can be used.For example, polyvinyl butyral resin, epoxy resin, phenoxy resin, Polymerized polyamide resin,
Examples of the insulating paint include a polysulfone resin, a polyester resin, a polyesterimide resin, and a mixed resin of two or more of these resins.

[0025]

EXAMPLE 1 0.2 mol of trimellitic anhydride, 0.1 mol of terephthalic acid, 0.7 mol of adipic acid and 1.0 mol of 4.4'-diphenylmethane diisocyanate were added to N-methyl-2-methyl-2-diphenylmethane.
Pyrrolidone and added at 100 ° C. for 1 hour, then 1 hour
After reacting at 20 ° C. for 2 hours, the temperature was raised to 140 ° C. over 1 hour, and further reacted at this temperature for 1 hour.
After cooling, xylene was added and diluted to prepare a polyamide-imide paint. The paint was applied and baked a plurality of times on the surface of a 0.50 mm diameter soft copper wire to produce an insulated wire having an insulating layer having a thickness of 16 μm.

Example 2 0.4 mol of trimellitic anhydride and 0.1 mol of terephthalic acid.
An insulated wire was manufactured in the same manner as in Example 1 except that the amounts used were 3 mol and 0.3 mol of adipic acid, respectively.

Example 3 0.7 mol of trimellitic anhydride and 0.1 mol of terephthalic acid were used.
An insulated wire was manufactured in the same manner as in Example 1, except that the amounts used were 1 mol and 0.2 mol of adipic acid, respectively.

Example 4 An insulated wire was manufactured in the same manner as in Example 3, except that 0.1 mole of isophthalic acid was used instead of terephthalic acid, and 0.2 mole of alaisenic acid was used instead of adipic acid.

COMPARATIVE EXAMPLE 1 0.1 mol of trimellitic anhydride and 0.1 mol of terephthalic acid were used.
An insulated wire was manufactured in the same manner as in Example 1, except that the amounts used were 1 mol and 0.8 mol of adipic acid, respectively.

Comparative Example 2 0.8 mol of trimellitic anhydride and 0.1 mol of terephthalic acid were used.
An insulated wire was manufactured in the same manner as in Example 1, except that the amounts used were 1 mol and 0.1 mol of adipic acid, respectively.

Comparative Example 3 Insulation was performed in the same manner as in Example 1 except that terephthalic acid was not used, and that the amounts used were 0.5 mol for trimellitic anhydride and 0.5 mol for adipic acid, respectively. Electric wires were manufactured.

Comparative Example 4 An insulated wire having a 16 μm-thick insulating layer in the same manner as in Example 1 except that a modified polyesterimide paint (trade name: FS-2 manufactured by Dainichi Seika Co., Ltd.) was used instead of the polyamideimide paint. Was manufactured.

Comparative Example 5 An insulated wire was manufactured in the same manner as in Example 1 except that the amount of 4,4'-diphenylmethane diisocyanate was changed to 0.8 mol.

Comparative Example 6 The reaction was carried out in the same manner as in Example 1 except that the amount of 4,4′-diphenylmethane diisocyanate was changed to 1.2 mol. Could not be prepared.

Example 5 The polyamide-imide insulating paint used in Example 3 was used in an amount of 0.50.
Apply and bake multiple times on the surface of annealed copper wire
After forming an insulating layer having a thickness of 8 μm, a polyimide-based insulating coating (Pyre ML manufactured by EI DuPont) is applied and baked a plurality of times on the insulating layer.
Was formed, and an insulated wire having an insulating layer having a two-layer structure was manufactured.

Comparative Example 7 An insulated wire having a two-layered insulating layer was produced in the same manner as in Example 5, except that the modified polyesterimide paint used in Comparative Example 4 was used for forming a lower insulating layer.

Example 6 The polyamide-imide insulating paint used in Example 3 was used in an amount of 0.50.
Apply and bake multiple times on the surface of annealed copper wire
After forming an insulating layer having a thickness of μm, a polyamide-imide-based insulating paint (trade name: HI4 manufactured by Hitachi Chemical Co., Ltd.) is further formed on the insulating layer.
05) was applied and baked a plurality of times to form an insulation layer having a thickness of 8 μm, thereby producing an insulated wire having a two-layer insulation layer.

Comparative Example 8 An insulated wire having a two-layered insulating layer was produced in the same manner as in Example 6, except that the modified polyesterimide paint used in Comparative Example 4 was used for forming a lower insulating layer.

Example 7 The polyamide-imide insulating paint used in Example 3 was used in an amount of 0.50.
Apply and bake multiple times on the surface of a soft copper wire with a diameter of 1 mm to obtain a thickness of 1
After forming an insulating layer of 4 μm, a 6,6-nylon insulating coating (a solution of Amilan CM3001N (trade name, manufactured by Toray Co., Ltd.) in cresylic acid) is further applied and baked on this insulating layer to a thickness of 2 μm. Was formed, and an insulated wire having an insulating layer having a two-layer structure was manufactured.

Comparative Example 9 An insulated wire having a two-layered insulating layer was manufactured in the same manner as in Example 7, except that the modified polyesterimide paint used in Comparative Example 4 was used for forming a lower insulating layer.

Example 8 The polyamide-imide insulating paint used in Example 3 was used in an amount of 0.50.
Apply and bake multiple times on the surface of annealed copper wire
After forming an insulating layer having a thickness of 8 μm, an epoxy-based self-fusing insulating coating (Isopoxy 506, manufactured by Nippon Shokubai Co., Ltd.) is further applied and baked on the insulating layer several times.
To form a self-fusing insulated wire having a two-layer insulating layer.

Comparative Example 10 An insulated wire having a two-layered insulating layer was produced in the same manner as in Example 8, except that the modified polyesterimide paint used in Comparative Example 4 was used for forming a lower insulating layer.

Example 9 A two-layer structure was prepared in the same manner as in Example 8 except that a polyamide-based self-fusing insulating paint (trade name: PA-27 manufactured by Dainichi Seika Co., Ltd.) was used as the self-fusing insulating paint. A self-fusing insulated wire having an insulating layer was manufactured.

Comparative Example 11 An insulated wire having a two-layered insulating layer was manufactured in the same manner as in Example 9 except that the modified polyesterimide paint used in Comparative Example 4 was used for forming a lower insulating layer.

The appearance, flexibility, softening resistance, heat shock resistance, solderability, and proper baking temperature range (except for Examples 1 to 5) were obtained for each of the insulated wires (excluding Comparative Example 6) in the above Examples and Comparative Examples. Each test of Comparative Example 3), abrasion resistance (Example 7 and Comparative Example 9), and fusing property (Examples 8 and 9 and Comparative Examples 10 and 11) were performed. The results are shown in Tables 1 and 2 below. The test method for each item is as follows.

Appearance: JIS C 3003 4. Flexibility JIS C 3003 8.1 (2) Thermal shock JIS C 3003 13.1 (2) Softening JIS C 3003 12. (2) Solderability JIS C 3003 16. Abrasion resistance JIS C 3003 10. Fusing property JIS C 3003 17． Appropriate baking temperature range: A baking temperature range that satisfies the characteristics of softening temperature of 340 ° C or higher and solderability of 460 ° C for 6 seconds or less (linear speed is constant).

[0047]

[Table 1]

From the results shown in Table 1, the insulated wires of the present invention having a single insulating layer (Examples 1 to 4) had a higher heat resistance than the conventional solderable modified polyesterimide insulated wires (Comparative Example 4). Insulated wire having an insulating layer formed of a polyamideimide insulating paint obtained by reacting trimellitic anhydride and aliphatic dicarboxylic acid with a diisocyanate compound (comparative example) Compared to 3), it has the same solderability and the same or higher heat resistance, and the appropriate baking temperature range of the polyamide-imide insulating paint is about twice as high as 50 to 70 ° C, making it suitable for mass production. It is clear that the various performances required for the insulated wire can be satisfied.

From the comparison between Examples 1 to 4 and Comparative Examples 1 and 2, the molar ratio of trimellitic anhydride / total acid component, which is a component of the polyamide-imide paint used for forming the insulating layer, was 0.2 to 0. 0.7, and the molar ratio of aliphatic dicarboxylic acid / total acid component is in the range of 0.2 to 0.7.
An insulated wire that satisfies both heat resistance and solderability is obtained.
Further, from the comparison of Examples 1 to 3, it can be seen that by changing the ratio of the above constituent components within the above range, both characteristics of heat resistance and solderability can be freely controlled in a high range. As apparent from the characteristics of the insulated wire of Comparative Example 5, when the amount of the diisocyanate compound used in preparing the polyamide-imide insulating coating was too small relative to the acid component, the appearance and heat resistance of the formed insulating layer were reduced. The impact properties will deteriorate.

[0050]

[Table 2]

From the results in Table 2, it can be seen that in the case of an insulated wire having a two-layered insulating layer consisting of a lower layer of an insulating material which can be soldered and an upper layer of another insulating material, the specific lower layer is made of a specific polyamideimide. The insulated wire of the invention (Examples 5 to 9)
Compared with the conventional insulated wires in which the lower layer is a modified solderable polyesterimide which can be soldered (Comparative Examples 7 to 11), even if the upper layer is any of insulating layers of polyimide, polyamideimide, polyamide, and heat-fusible material, In addition, the heat resistance is greatly improved and the solderability is also improved, and other characteristics are as good as above. Particularly, the upper layer is made of polyamide (Example 7, Comparative Example 9).
In the case of, it can be seen that the abrasion resistance is also significantly improved.

[0052]

According to the first aspect of the present invention, it has high heat resistance and excellent solderability in a well-balanced manner, and can be sufficiently applied to windings of electronic devices used at recent high temperatures. In addition, there is provided a soldering insulated wire suitable for mass production, which has a wide allowable range of manufacturing conditions such as a baking temperature and can stably obtain a high-quality product.

According to the second aspect of the present invention, an insulated wire having extremely high heat resistance and capable of being soldered is provided.

According to the third aspect of the present invention, there is provided an insulated wire having particularly high abrasion resistance and excellent winding properties, and having both high heat resistance and excellent solderability.

According to the fourth aspect of the present invention, there is provided a self-fusing insulated wire having both high heat resistance and excellent solderability.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiro Goto 2-191-1, Inaji, Amagasaki-shi, Hyogo Pref. Ichigo Electric Engineering Co., Ltd. Daiichi Denko Corporation Engineering Department (72) Inventor Makoto Tai 2-9-1-1, Inaji, Amagasaki City, Hyogo Prefecture Daiichi Denko Corporation Engineering Department (56) References JP-A-55-139716 (JP, A) JP-A-6-103822 (JP, A) JP-A-58-28105 (JP, A) JP-A-60-223868 (JP, A) JP-B-46-22982 (JP, B1) (58) Fields investigated (Int) .Cl. ⁶ , DB name) H01B 7/02 C08G 73/16 C09D 179/08 H01B 3/30 H01B 7/34

Claims (4)

(57) [Claims] 1. A consists of three acid component trimellitic anhydride and lipid aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, anhydride
When the molar ratio of trimellitic acid / total acid component is 0.2 to 0.7
And the molar ratio of aliphatic dicarboxylic acid / total acid component is within
A polyamideimide paint obtained by reacting a diisocyanate compound having a mole ratio of 0.9 to 1.1 times the total number of moles of these acid components with an acid component in the range of 0.2 to 0.7 is applied and baked. An insulated wire for soldering having an insulating layer comprising: 2. The insulated wire according to claim 1,
Amide-based insulating paint or polyamideimide different from the base
Half with an insulating layer formed by applying and baking
Insulated wire for padding. 3. An insulated wire according to claim 1,
An insulating layer is formed by applying and baking a mid-based insulating paint.
Insulated wire for soldering . 4. A self-fusing wire on the insulated wire according to claim 1.
Insulating layer formed by applying and baking adhesive insulating paint
Insulated wire for soldering .