JPH1060276A - Extrusion coated insulated electric wire and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject electric wire, excellent in direct soldering characteristics when processing terminals and capable of manifesting excellent effects when used especially for miniaturized and higher-performance electric and electronic machinery and apparatus, etc., and satisfying heat resistance class B by providing a specific extrusion coated insulating layer on the outside of a conductor. SOLUTION: This extrusion coated insulated electric wire is obtained by providing an extrusion coated insulating layer comprising a resin composition consisting essentially of a resin mixture prepared by blending 100 pts.wt. polyether imide resin represented by formula I [R1 is phenylene, methylphenylene, diphenyl, dimethyldipheyl, etc.; R2 is phenylene, methylphenylene, diphenyl, diphenyl ether, etc.; (m) is a positive integer] with 10-70 pts.wt. polycarbonate resin represented by formula II [R3 is phenylene, methylphenylene, diphenyl, naphthalene, etc.; (n) is a positive integer] directly or through another layer on a conductor or on the outside of a conductor core or a multi-core stranded wire obtained by stranding plural insulated cores.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant insulated wire having an extruded insulation layer having excellent solderability. More specifically, it is a heat-resistant insulated wire in which an insulating layer can be formed by an extrusion coating method, and despite having high heat resistance,
When the insulating layer is immersed in a solder bath, it is removed in a short time and the solder can be attached to the conductor, so it has excellent solderability, and it is excellent especially when used in miniaturized and high-performance electrical and electronic equipment. The present invention relates to an extruded insulated wire that exhibits an effect.

[0002]

2. Description of the Related Art In recent years, with the miniaturization and high performance of electronic equipment and the like, the atmosphere and operating conditions of parts and coils used in such electronic equipment have become increasingly severe. Along with this, it has become an extremely important issue to impart high performance and high reliability to insulated wires used for the above-mentioned components or coils.

[0003] In addition, in order to obtain such an insulated wire, it is necessary to have a high-performance insulating layer, and improvements have been made exclusively by substituting a high heat-resistant material.

However, an insulated wire provided with an insulating layer made of a high heat-resistant material has a problem that when the insulating layer is peeled off to perform terminal connection, the insulating layer becomes extremely difficult to peel off. This reduces the solderability at the end of the insulated wire, which has been a great obstacle to the development of high reliability of the insulated wire.
That is, when the insulating layer is peeled off by a chemical or a machine, if a high heat-resistant material is used as the material of the insulating layer, the peeling conditions become severe, and the residual due to the chemical or the damage due to the mechanical peeling increases, which adversely affects the terminal connection. . On the other hand, if this problem is avoided to improve the reliability of terminal connection, the improvement in heat resistance as an insulated wire is largely prevented.

[0005] Further, as the diameter of the insulated wire becomes smaller, performing the conventional method as a method of peeling the insulating layer makes the work more and more difficult and loses the reliability as the insulated wire. Met.

On the other hand, as a method for forming an insulating layer of a heat-resistant resin on a conductor, there are three methods: a method in which a varnish in which a resin is dissolved in an organic solvent is applied and dried on the conductor, a method by powder coating, and a method by extrusion coating. In order to solve the above-mentioned problem, any of the conventional methods has been applied. However, the varnish coating method has a problem in pollution treatment because an organic solvent is used, and the latter two methods are preferred methods in that respect. In particular, the extrusion coating method is a preferable method because it is inexpensive in terms of equipment, easy to stabilize production conditions, and excellent in high-speed productivity as compared with powder coating. However, unlike the varnish coating method, the powder coating method and the extrusion coating method largely depend on the characteristics of the applied resin, such as the melt viscoelasticity, so it is particularly suitable for applications that require thin coating such as insulated wires. Is generally limited to a resin to be applied. At present, this tendency is particularly strong when high heat resistant resins are applied.For high heat resistant resins excluding specific resins such as polyetheretherketone and polyarylate, coating on the conductor by the varnish coating method is not possible. Have been tried. In addition, in addition to the above, the powder coating method is not very practical as a manufacturing method for increasing the heat resistance of the insulated wire because pinholes in the obtained insulated wire are inevitable.

Incidentally, polycyclohexanedimethane terephthalate (P) is a heat-resistant insulating material which can be extrusion-coated and has the property of being directly solderable from immersion in a solder bath.
CT) and a combination of a heat-resistant polyamide have been proposed (JP-A-06-223634).
The heat resistance evaluated according to the regulations of Publication 172 was at most Class B (130 ° C.), which was not a satisfactory heat resistance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide an insulating layer formed by extrusion coating, which has excellent direct solderability and at least heat resistance of IE.
An object of the present invention is to provide an extruded insulated wire having a heat resistance class B or more specified in C standard 172.

[0009]

Means for Solving the Problems In order to achieve the above-mentioned object, as a result of diligent studies on various heat-resistant resins alone and their mixtures, extrusion molding has been extremely difficult, and solderability is essential. Based on a polyetherimide resin which is considered to be defective, a composition obtained by blending a polycarbonate resin with this resin is surprisingly found to be capable of thin extrusion and exhibiting good solderability, The present invention has been reached. That is, in the present invention, the extrusion coating insulation layer provided with an extrusion coating layer directly or through another layer on the conductor, or on the outside of a multi-core stranded wire obtained by twisting a plurality of conductor cores or insulation cores. In the electric wire, the extrusion-coated insulating layer has a general formula (1):

Embedded image [Wherein R ₁ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, a naphthalene group, and R ₂ is a phenylene group, a methylphenylene group, Diphenyl group, dimethyldiphenyl group, diphenyl ether group, diphenylmethane group, 2,
2-diphenylpropane group, selected from naphthalene group,
m is a positive integer]
General formula (2):

Embedded image [Wherein R ₃ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, and a naphthalene group, and n is a positive integer]. An extruded insulated wire characterized by comprising a resin composition containing as a main component a resin blend containing 10 to 70 parts by weight of a polycarbonate resin.

In the present invention, a resin admixture obtained by mixing 10 to 70 parts by weight of a polycarbonate resin represented by the general formula (2) with 100 parts by weight of the polyetherimide resin represented by the general formula (1) is used as a main component. The resin composition to be,
A conductor, or a multi-core stranded wire obtained by twisting a plurality of conductor cores or insulated cores, is preheated to a temperature of 140 ° C. or less, or is extruded on the outside of the conductor or the multi-core stranded wire without preheating. A method for manufacturing an insulated wire is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The resin admixture of the present invention contains a polyetherimide resin and a polycarbonate resin described below as essential components.

Among them, as the polyetherimide resin represented by the general formula (1), those produced by a known method using aromatic bis (ether anhydride) and an organic diamino compound as raw materials can be used. Examples of the aromatic bis (ether acid anhydride) include 1,3-bis (2,3-dicarboxyphenoxy) benzenediacid anhydride and 4,4′-bis (3,
4-dicarboxyphenoxy) diphenyl ether dianhydride, bis [4- (3,4-dicarboxyphenoxy) -phenyl] methane dianhydride, 2,2′-bis [4- (3,4-dicarboxyphenoxy) ) -Phenyl] propanedioic anhydride, 1,5-bis (3,4-dicarboxyphenoxy) naphthalene, and the like. Examples of the organic diamino compound include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane,
1,5-diaminonaphthalene and the like can be mentioned. As an example, 2,2'-bis [4- (3,4-dicarboxyphenoxy) -phenyl] propanedioic anhydride and 4,4'-
It is synthesized by solution polycondensation of diaminodiphenylmethane with ortho-dichlorobenzene as a solvent. Commercially available resins include ULTEM (trade name of Japan GE Plastics).

In the present invention, a polyetherimide resin synthesized by any combination of the aromatic bis (ether anhydride) and the organic diamino compound can be used.
In particular, 2,2'-bis [4- (3,4-dicarboxyphenoxy) -phenyl] propanedioic anhydride and 4,4'-
It is preferable to use a resin synthesized from diaminodiphenylmethane.

The other components of the resin admixture of the present invention include:
It is a polycarbonate resin represented by the general formula (2), and a resin produced by a known method using dihydric phenols and phosgene as raw materials can be used. Examples of the dihydric phenol include 1,4-dihydroxybenzene,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylpropane, 1,5-dihydroxynaphthalene and the like. Commercially available resins include Lexan (trade name of Japan GE Plastics), Iupilon (trade name of Mitsubishi Gas Chemical Company), NOVAREX (trade name of Mitsubishi Chemical Corporation), and the like.

In the present invention, any of the above-mentioned dihydric phenols as a raw material can be used, but in particular, a polycarbonate resin synthesized from 4,4'-dihydroxydiphenylpropane and phosgene is preferably used. Is preferred.

In the resin mixture according to the present invention, the mixing ratio of the polyetherimide resin and the polycarbonate resin is 100 parts by weight of the former and 10 to 7 parts by weight of the latter.
It is set in the range of 0 parts by weight. When the amount of the latter is less than 10 parts by weight, the heat resistance of the formed insulating layer is increased and there is no problem, but the direct solderability as an insulated wire is significantly reduced. In particular, only the former shows no solderability. When the compounding amount is more than 70 parts by weight, the direct solderability as an insulated wire is good, but the former excellent heat resistance is reduced, and the heat resistance of the formed insulating layer is remarkably reduced. A problem arises and it becomes impossible to achieve both heat resistance and solderability. In particular, the latter alone not only has poor heat resistance, but also has a solderability far from a practical level. A particularly preferable mixing ratio of the two is 20 to 50 parts by weight with respect to 100 parts by weight of the former.

In the present invention, as described above, by using an extruded coating insulating layer containing, as an essential component, a resin admixture in which both a polyetherimide resin and a polycarbonate resin are blended in a specific ratio, the mechanism of developing characteristics is as follows. Although it is not clear, it is possible to obtain a practical level insulated wire having high heat resistance and excellent direct solderability.

The resin admixture can be melt-blended using a conventional kneader such as a twin screw extruder, a kneader or a co-kneader. It has been found that the kneading temperature of the compounded resin directly affects the solderability, and that the better the direct solderability is, the higher the temperature setting of the kneader during mixing is set. A temperature setting of 320 ° C. or higher, particularly 360 ° C. or higher is preferable.

Other heat resistant resins can be added to the resin mixture as long as the solderability and heat resistance are not impaired. The heat-resistant resin which can be added preferably has good solderability itself. Examples thereof include thermoplastic polyester resins such as modified polycyclohexanedimethane terephthalate resin and heat-resistant resins such as 4,6-nylon and 6,6-nylon. And a plastic polyamide resin.

Additives, inorganic fillers, processing aids, coloring agents, etc., which are usually used, are added to the resin admixture as long as the solderability and heat resistance are not impaired. It can be a composition.

As the conductor used in the present invention, a bare conductor, an insulated conductor in which a thin insulating layer is provided on a bare conductor, a multi-core stranded wire obtained by twisting conductor wires, or a thin insulated wire core is stranded. Multicore strands can be used. The number of stranded wires of these stranded wires can be arbitrarily selected depending on the application. However, the thin insulating material must be a resin having good solderability by itself such as an ester imide-modified urethane resin and a urea-modified polyurethane resin.
TPU-7000 or the like made by Toku Paint Co., Ltd. can be used.

The extrusion-coated insulated electric wire of the present invention is formed by extrusion-coating a resin composition containing a resin mixture of the polyetherimide resin and the polycarbonate resin as a main component on the outside of the conductor to form an insulation layer having a desired thickness. It is manufactured by forming. When forming an extruded coating insulating layer on a conductor, usually, the conductor is often preheated to a temperature higher than the melting point or softening point of the extruded material by induction heating or the like. By not performing preheating exceeding 140 ° C., extremely good solderability can be obtained. As the conductor preheating temperature is set lower, the solderability tends to be better, and the best solderability is obtained when no preheating is performed. Unless the conductor is pre-heated, the adhesion between the conductor and the coating resin deteriorates, and the residual stress of the resin increases, so that the insulation layer shrinks when the wire is cut and the conductor is exposed. However, in the present invention, the adhesion between the insulating layer and the conductor is appropriately good, and the above phenomenon does not occur under the conditions of use as an insulated wire, but when immersing in a solder bath and soldering. For the first time, heat shrinkage of about 10 to 30% occurs in the insulating layer, and the solderability is improved.

[0023]

【Example】

Examples 1 to 9 and Comparative Examples 1 to 3 Each component shown in Table 1 was kneaded at the indicated ratio (parts by weight) to prepare a resin composition for each extrusion coating layer. A stranded wire is prepared by twisting seven insulated cores obtained by coating an insulated varnish made by Hitachi Chemical Co., Ltd. on a soft copper wire having a wire diameter of 0.4 mm and a soft copper wire having a wire diameter of 0.15 mm and coated with an insulating varnish WD-4305 manufactured by Hitachi Chemical Co., Ltd. The resin composition was extrusion-coated so that the coating thickness became the thickness shown in Table 1 and at a preheating temperature of 200 ° C., 140 ° C. or no preheating of the conductor, thereby producing an insulated wire. In addition, at the time of compounding the resin composition for extrusion coating, the kneading temperature was set to two points of 320 ° C. and 360 ° C.

With respect to the above 12 kinds of extruded insulated wires, various characteristics were evaluated according to the following specifications.

Solderability: about 4 ends of extruded insulated wire
Time (sec) until the 0 mm part is immersed in molten solder at a temperature of 450 ° C. and the solder adheres to the immersed 30 mm part
Was measured. The shorter this time, the better the solderability. The value shown is the average of three measurements.

Heat resistance: Extruded insulated wire and bare copper wire
Two pieces were twisted in accordance with SC3003, and in that state, a heat treatment was performed at a temperature of 220 ° C. for 7 days, and then the dielectric breakdown voltage was measured. The larger the value is, the more excellent the heat resistance is, and the ratio of the dielectric breakdown voltage after the deterioration to the dielectric breakdown voltage in the normal state before the deterioration, that is, the residual ratio (%) of the dielectric breakdown voltage after deterioration is 30. % Or more, it is determined that the heat resistance class B of the IEC standard is satisfied.

Table 1 summarizes the above results.

[0028]

[Table 1]

Example 1 is an example in which a resin composition in which 20 parts by weight of a polycarbonate resin is blended with respect to 100 parts by weight of a polyetherimide resin in an insulating layer on a conductor is used. I understand. Example 2
Is an example in which a resin composition in which 65 parts by weight of a polycarbonate resin is blended with respect to 100 parts by weight of a polyetherimide resin in an insulating layer is used, and it can be seen that both properties are excellent. In addition, in the said Example, at the time of extrusion coating of each resin composition, the preheating of the conductor was performed at 200 degreeC.

Examples 3, 4 and 5 are examples in which a resin composition in which 40 parts by weight of a polycarbonate resin is blended with respect to 100 parts by weight of a polyetherimide resin in an insulating layer on a conductor is used. It can be seen that all the characteristics are excellent. Example 3 and Example 4 are examples in which the conductor was preheated at 200 ° C. and 140 ° C., respectively, during extrusion coating of the resin composition, and Example 5 was an example in which preheating was not performed. Comparing the above three examples, when the preheating temperature is set to 140 ° C. or less including the case where the conductor is not preheated,
It can be seen that the solderability is considerably improved.

Example 6 is the same as Example 5 except that the conductor was replaced with a stranded wire and the thickness of the extruded insulation layer was changed from 100 μm to 50 μm. I understand.

Example 7 is the same as Example 3 except that the kneading temperature of the resin composition for extrusion coating was changed from 360 ° C. to 320 ° C., and all the characteristic values were excellent.
It can be seen that the solderability is higher in Example 3 where the kneading temperature is higher.

Examples 8 and 9 are the same as Example 3 except that modified polycyclohexanedimethane terephthalate resin (PCT resin) and 4,6-nylon resin were added as components of the resin composition for extrusion coating. It can be seen that all the characteristics are excellent.

Comparative Example 1 is an example in which a polyetherimide resin was used alone for the insulating layer on the conductor, and shows that although it has high heat resistance, it does not show any solderability.

Comparative Example 2 is an example in which a resin composition in which 100 parts by weight of a polyetherimide resin was blended with 100 parts by weight of a polyetherimide resin in an insulating layer on a conductor was used. There is, but heat resistance IE
It turns out that it does not pass the heat-resistant class B prescribed | regulated to C standard. This is an example in which the heat resistance is reduced due to an excessive amount of the polycarbonate resin.

Comparative Example 3 is an example in which polyethylene, which has been widely used as an insulating material, is used for the insulating layer on the conductor.

[0037]

As is apparent from the above description, the extruded insulated wire according to the present invention has excellent direct soldering characteristics at the time of terminal processing, and also has characteristics satisfying the heat resistance class B specified in IEC standard 172. It also has. Furthermore, the extrusion-coated insulated wire of the present invention has a very high productivity at the time of manufacture because the insulating layer is formed by extrusion coating.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 69:00)

Claims (2)

[Claims] 1. Directly or via another layer on a conductor,
Alternatively, in an extruded coated insulated wire having an extruded coated insulating layer provided on the outside of a multi-core stranded wire in which a plurality of conductor cores or insulated cores are stranded, the extruded coated insulating layer has a general formula (1): 1) [Wherein R ₁ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, a naphthalene group, and R ₂ is a phenylene group, a methylphenylene group, Diphenyl group, dimethyldiphenyl group, diphenyl ether group, diphenylmethane group, 2,
2-diphenylpropane group, selected from naphthalene group,
m is a positive integer]
The formula (2) is based on 00 parts by weight: [Wherein R ₃ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, and a naphthalene group, and n is a positive integer]. An extruded insulated wire comprising a resin composition containing a resin mixture containing 10 to 70 parts by weight of a polycarbonate resin as a main component. 2. General formula (1): [Wherein R ₁ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, a naphthalene group, and R ₂ is a phenylene group, a methylphenylene group, Diphenyl group, dimethyldiphenyl group, diphenyl ether group, diphenylmethane group, 2,
2-diphenylpropane group, selected from naphthalene group,
m is a positive integer]
The formula (2) is based on 00 parts by weight: [Wherein R ₃ is selected from a phenylene group, a methylphenylene group, a diphenyl group, a dimethyldiphenyl group, a diphenylether group, a diphenylmethane group, a 2,2-diphenylpropane group, and a naphthalene group, and n is a positive integer]. A resin composition containing as a main component a resin admixture containing 10 to 70 parts by weight of a polycarbonate resin, a conductor, or a multi-core stranded wire obtained by twisting a plurality of conductor cores or insulated cores to a temperature of 140 ° C. or less. A method for manufacturing an extruded insulated wire, comprising preheating or extruding the conductor or the multi-strand wire outside without preheating.