WO2015115157A1

WO2015115157A1 - Insulated wire

Info

Publication number: WO2015115157A1
Application number: PCT/JP2015/050565
Authority: WO
Inventors: 豊貴古川; 諭村尾; 勇人大井
Original assignee: 株式会社オートネットワーク技術研究所; 住友電装株式会社; 住友電気工業株式会社
Priority date: 2014-01-29
Filing date: 2015-01-12
Publication date: 2015-08-06
Also published as: JP2015141820A

Abstract

An insulated wire (1) includes a conductor (2) and an insulator (3) that is extruded so as to cover the circumference of the conductor (2). The conductor (2) is Ni plated or Ni alloy plated. The insulator (3) is formed from a resin composition containing at least a sulfonyl-group-containing resin having sulfonyl groups in the repeating units. Preferably the sulfonyl group-containing-resin is at least one selected from the group consisting of polysulfone, polyether sulfone, and polyphenyl sulfone.

Description

Insulated wire

The present invention relates to an insulated wire, and more particularly, to an insulated wire that can be suitably used in a high-temperature oil under a vibrating environment.

Conventionally, as an insulated wire used in high-temperature oil, an insulated wire is known in which an outer periphery of a conductor is extrusion-coated with an insulator using fluorine rubber having excellent heat resistance and oil resistance (for example, (See Patent Document 1 and Patent Document 2). In general, the conductor is often subjected to Sn plating in order to prevent corrosion in high temperature oil.

Also, in an insulated wire used in a vibrating environment such as a vehicle, the insulator is likely to wear due to contact between the insulated wires, contact between the insulated wire and the protective material, contact between the insulated wire and the vehicle body, and the like. In recent years, an insulated wire used in an automobile or the like has been desired to be thinned by thinning in order to effectively use a limited space. Therefore, a technique has been proposed in which the insulator is thinned and the diameter is reduced by using polysulfone or polyethersulfone having excellent wear resistance (see, for example, Patent Document 3 and Patent Document 4).

JP-A-5-182543 JP-A-11-66960 JP-A-2-183907 JP-A-2-273411

However, the conventional insulated wire has the following problems. In other words, an insulated wire using fluororubber as an insulator has good high-temperature oil resistance of the insulator. Further, by using a conductor plated with Sn, the conductor is hardly corroded even in high temperature oil. However, an insulator made of fluororubber has low wear resistance. Therefore, it is difficult to reduce the thickness of the insulator, and there is a limit to reducing the diameter of the insulated wire.

On the other hand, an insulated wire using polysulfone or polyethersulfone as an insulator has good high-temperature oil resistance and wear resistance of the insulator. However, since the molding temperature during the extrusion coating of the insulator is high, the Sn plating of the conductor is melted by the high molding temperature. As a result, Sn plating is peeled off at the time of extrusion coating, and welding is likely to occur between the strands constituting the conductor. Furthermore, the portion where the Sn plating applied to the conductor is melted easily corrodes when exposed to high temperature oil. For this reason, an insulated wire using polysulfone or polyethersulfone as an insulator usually uses a conductor that is not plated.

The present invention has been made in view of the above-described background. The plating applied to the conductor during extrusion coating of the insulator is difficult to melt, the conductor is unlikely to corrode in high temperature oil, and the high temperature oil resistance and resistance of the insulator are reduced. An object of the present invention is to provide an insulated wire having good wear characteristics.

One aspect of the present invention is an insulated wire having a conductor and an insulator coated on the outer periphery of the conductor,
The conductor is subjected to Ni plating or Ni alloy plating,
The insulator is an insulated wire characterized in that it is composed of a resin composition containing at least a sulfonyl group-containing resin having a sulfonyl group in a repeating unit.

The above-mentioned insulated wire is composed of a resin composition in which an insulator coated on the outer periphery of a conductor contains at least a sulfonyl group-containing resin having a sulfonyl group in a repeating unit. The sulfonyl group-containing resin has good high-temperature oil resistance and wear resistance. Therefore, the said insulated wire becomes a thing with the high temperature oil resistance and abrasion resistance of an insulator favorable. The insulated wire uses a conductor plated with Ni or Ni alloy. Therefore, even if the molding temperature at the time of extrusion coating of the insulator composed of the resin composition is relatively high, the plating applied to the conductor due to the high molding temperature at that time is difficult to melt. Therefore, the insulated wire is unlikely to peel off the plating applied to the conductor during extrusion coating of the insulator or to cause welding between the strands constituting the conductor. Moreover, since the plating applied to the conductor is difficult to melt, the insulated wire is unlikely to corrode even when exposed to high temperature oil.

Therefore, according to the present invention, the plating applied to the conductor during extrusion coating of the insulator is difficult to melt, the conductor is unlikely to corrode in high-temperature oil, and the insulator has good high-temperature oil resistance and wear resistance. Can be provided.

1 is a cross-sectional view of an insulated wire of Example 1. FIG.

In the above insulated wire, the conductor can be composed of, for example, a strand (single wire), a stranded wire in which a plurality of strands are twisted together. The stranded wire may be compressed so that the conductor cross section becomes circular after a plurality of strands are twisted together. This is advantageous for reducing the diameter of the insulated wire. Moreover, as for a strand, the some strand which has the same diameter or an equivalent diameter may be twisted, and the some strand which has a different diameter may be twisted. Moreover, the strand may have a plurality of strands having the same, equivalent or similar cross-sectional shape twisted, or a plurality of strands having different cross-sectional shapes may be twisted together.

Specific examples of metals (including alloys, hereinafter omitted) that can constitute conductors include copper, copper alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, iron, and iron alloys. From the viewpoint of conductivity, copper or a copper alloy can be suitably used as the metal. Specific examples of the additive element that can be contained in the copper alloy include Fe, Ni, Mg, Si, and the like. Moreover, aluminum and an aluminum alloy can be used suitably from a viewpoint of electroconductivity and weight reduction. In addition, when a conductor consists of a strand wire, each strand which comprises a strand wire may be comprised from the same metal, and may be comprised from a different metal.

The conductor is plated with Ni or Ni alloy. Specifically, the Ni plating may be either electric Ni plating or electroless Ni plating. Similarly, the Ni alloy plating may be either electric Ni alloy plating or electroless Ni alloy plating. . Both the Ni plating and the Ni alloy plating may be composed of one layer, or may be composed of two or more layers. Moreover, the reflow process may be performed to Ni plating and Ni alloy plating.

When the conductor is made of a stranded wire, the stranded wire may be formed by twisting a plurality of strands that have been subjected to Ni plating or Ni alloy plating, or after the strands are twisted together, Ni plating or Ni alloy plating may be applied. In the former case, since the surface of each wire is plated with Ni or Ni alloy, there is an advantage that each wire inside the conductor is difficult to corrode in high temperature oil.

In the above insulated wire, the insulator is composed of a resin composition containing at least a sulfonyl group-containing resin having a sulfonyl group in the repeating unit. The resin composition can contain one or more sulfonyl group-containing resins.

Specific examples of the sulfonyl group-containing resin include polysulfone (PSU), polyethersulfone (PES), polyphenylsulfone (PPSU), and the like. These can be used alone or in combination of two or more. In the case where the sulfonyl group-containing resin is at least one selected from the group consisting of polysulfone, polyethersulfone, and polyphenylsulfone, the insulated wire has good high-temperature oil resistance and wear resistance of the insulator. Can be definitely obtained. The sulfonyl group-containing resin particularly preferably contains polyphenylsulfone. In this case, the high temperature oil resistance of the insulator can be further improved.

The resin composition can contain other resin components in addition to the sulfonyl group-containing resin. Specifically, the resin composition can further contain an aromatic polyester. In this case, it becomes easy to further improve the high temperature oil resistance and wear resistance of the insulator.

Specific examples of the aromatic polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) from the viewpoint of excellent compatibility with the sulfonyl group-containing resin and improvement of high-temperature oil resistance. ), Polybutylene naphthalate (PBN), and the like. These can be used alone or in combination of two or more. Among these, polyethylene naphthalate, polybutylene naphthalate having a naphthyl group in the repeating unit, a combination thereof, and the like are particularly preferable from the viewpoint of a large effect of improving oil resistance at high temperatures and compatibility.

The resin composition may further contain both an aromatic polyester and a polyester elastomer. When the polyester elastomer is blended alone in the resin composition, the polyester elastomer itself has a low compatibility with the sulfonyl group-containing resin, which may cause a decrease in physical properties of the insulator. However, as described above, when the polyester elastomer is blended with the aromatic polyester, the compatibility with the sulfonyl group-containing resin is improved, so that the elongation of the insulator is suppressed while suppressing the deterioration of the properties of the insulator. Can be improved.

Specific examples of polyester elastomers include block polymers having hard and soft segments in the molecule. Specific examples of the hard segment include aromatic polyesters such as polybutylene terephthalate (PBT) and polybutylene naphthalate, and aliphatic polyesters. Specific examples of the soft segment include aliphatic polyethers and aliphatic polyesters.

In the insulated wire, the sulfonyl group-containing resin is preferably contained in 100 parts by mass of the resin component in the resin composition, preferably in the range of 30 to 100 parts by mass. In this case, it is possible to reliably obtain an insulated wire having a good high temperature oil resistance and wear resistance of the insulator. The sulfonyl group-containing resin is more preferably 40 parts by mass or more, more preferably 100 parts by mass or more, more preferably in 100 parts by mass of the resin component in the resin composition from the viewpoint of easily improving the high temperature oil resistance and wear resistance of the insulator. 50 parts by mass or more, still more preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more. In addition, the sulfonyl group-containing resin contains other resin components, and from the viewpoint of easily improving the electric wire characteristics, in the resin component in 100 parts by mass in the resin composition, more preferably 95 parts by mass or less, more preferably It can be contained in an amount of 90 parts by mass or less, more preferably 85 parts by mass or less.

In the insulated wire, when the resin composition constituting the insulator further contains an aromatic polyester, the mass ratio of the sulfonyl group-containing resin and the aromatic polyester in 100 parts by mass of the resin component in the resin composition is 99. : 1 to 60:40. In this case, excellent high temperature oil resistance and wear resistance of the insulator are easily secured. The mass ratio is preferably in the range of 95: 5 to 70:30, more preferably in the range of 90:10 to 75:25, and still more preferably 85:15 from the viewpoint of easily obtaining the above effect. It can be in the range of up to 80:20.

In the insulated wire, when the resin composition constituting the insulator further contains both an aromatic polyester and a polyester elastomer, the content of the polyester elastomer in 100 parts by mass of the resin component in the resin composition is 50. It can be below mass parts. In this case, it is easy to ensure high temperature oil resistance and wear resistance of the insulator, and to improve the elongation of the insulator. From the viewpoint of easily obtaining the above effect, the content of the polyester-based elastomer is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. be able to. The content of the polyester elastomer is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more.

In the insulated wire, the resin composition constituting the insulator may contain, in addition to the resin component, one or more kinds of various additives generally used for the wire as needed. it can. Specific examples of the additive include fillers, antioxidants, anti-aging agents, lubricants, copper damage inhibitors, chain extenders, nucleating agents, and pigments.

In the above insulated wire, the thickness of the insulator is preferably 0.1 mm or more, more preferably 0.15 mm or more, and further preferably 0.18 mm or more from the viewpoint of ensuring high-temperature oil resistance and wear resistance. Can do. The thickness of the insulator is preferably 0.3 mm or less, more preferably 0.25 mm or less, and further preferably 0.22 mm or less, from the viewpoint of reducing the diameter of the insulated wire and reducing the weight of the insulated wire. Can do.

In the insulated wire, the insulator may be composed of a single layer or a plurality of layers. When the insulator is composed of a plurality of layers, at least one of the plurality of layers may be composed of the resin composition. Moreover, the said insulated wire may have an inclusion layer, a shield layer, etc. between a conductor and an insulator as needed.

The above-mentioned insulated wire is difficult to melt the plating applied to the conductor during extrusion coating of the insulator, hardly corrodes the conductor in high-temperature oil, and has good high-temperature oil resistance and wear resistance of the insulator. Therefore, for example, it can be suitably used in an environment in contact with high-temperature oil in an automobile, in a vibration environment, or in an environment in which these are combined. Moreover, since the said insulated wire has favorable abrasion resistance, there exists an advantage which is easy to aim at diameter reduction by thinning of an insulator. Moreover, since the plating applied to the conductor is Ni plating or Ni alloy plating, the insulated wire has an advantage that the flexibility of the wire can be relatively easily secured.

For example, the insulated wire is obtained by kneading a resin composition constituting an insulator using a kneader that is usually used such as an extruder (single or biaxial), a Banbury mixer, a pressure kneader, or a roll. It can be manufactured by extrusion-coating an insulator on the outer periphery of the conductor using a molding machine or the like.

In addition, each structure mentioned above can be arbitrarily combined as needed, in order to obtain each effect mentioned above.

Example 1
The insulated wire of Example 1 is demonstrated using FIG. As shown in FIG. 1, the insulated wire 1 of this example includes a conductor 2 and an electrically insulating insulator 3 that is extrusion-coated on the outer periphery of the conductor 2. The conductor 2 is subjected to Ni plating or Ni alloy plating.

In this example, specifically, the conductor 2 is composed of a stranded wire formed by twisting a plurality of strands 20 subjected to Ni plating. The strand 20 is an annealed copper wire. In addition, the strand wire has shown what was compressed so that the conductor cross section might become circular after the some strand 20 was twisted together.

In the insulated wire 1, the insulator 3 is composed of a resin composition containing at least a sulfonyl group-containing resin having a sulfonyl group in a repeating unit. In this example, the sulfonyl group-containing resin is at least one selected from the group consisting of polysulfone, polyethersulfone, and polyphenylsulfone.

Hereinafter, a plurality of insulated wire samples having different configurations were prepared and subjected to various evaluations. An experimental example will be described.

(Experimental example)
<Material preparation>
The following were prepared as materials for the resin composition constituting the insulator.
-Sulfonyl group-containing resin-
・ Polysulfone (PSU) (Solvay Specialty Polymers Japan, “Udel P-1700NT”)
・ Polyethersulfone (PES) (manufactured by Sumitomo Chemical Co., Ltd., “Sumika Excel 4100G”)
-Polyphenylsulfone (PPSU) (BASF, “Ultra Zone P3010”)
-Aromatic polyester-
・ Polybutylene terephthalate (PBT) (manufactured by Polyplastics, “Duranex 800FP”)
・ Polybutylene naphthalate (PBN) (manufactured by Teijin Chemicals Ltd., “TQB-OT”)
・ Polyethylene naphthalate (PEN) (manufactured by Teijin Chemicals Ltd., “Teonex TN-8065S”)
-Polyester elastomer-
・ Polyester elastomer (1) (manufactured by Toray DuPont, “Hytrel 5557”)
・ Polyester elastomer (2) (manufactured by Toray DuPont, “Hytrel 7277”)
・ Polyester elastomer (3) (Toyobo Co., Ltd., “Perprene EN-2034”)

<Production of insulated wires>
Each of the prepared materials was kneaded with a biaxial kneader at a predetermined blending ratio shown in each table described later to prepare each resin composition. At this time, kneading was performed so that the temperature of the resin composition in the vicinity of the head would be an optimum temperature for extrusion molding. In this example, the temperature during extrusion molding is about 270 ° C. to 320 ° C. Next, each kneaded resin composition was extrusion coated on the outer periphery of the conductor using an extruder to form each insulator. In the extrusion molding, a die having a diameter of 1.1 mm and a nipple having a diameter of 0.75 mm were used. The conductor is a twisted wire formed by twisting seven annealed copper wires subjected to predetermined plating shown in each table, or a twisted wire formed by twisting seven annealed copper wires that are not plated. Lines were used. The conductor cross-sectional area is 0.35 mm ² . The insulator has a thickness of 0.2 mm. Thereby, insulated wires of Samples 1 to 32 were produced.

<Conductor observation after extrusion coating>
The conductor was extracted from the insulator of the obtained insulated wire, and the appearance of the conductor after extrusion coating was observed. The case where peeling of the plating due to melting of the plating of the conductor due to the high molding temperature during the extrusion coating of the insulator or the welding between the strands was observed was regarded as “C”. The case where these phenomena were not observed was set as “A” as a pass.

<Observation of conductor after immersion in high temperature oil>
The conductor was extracted from the insulator of the obtained insulated wire. Next, the extracted conductor was immersed in ATF (Nissan genuine ATF: NS-3) at 120 ° C. for 1000 hours, and then the surface of the conductor was observed. A case where the conductor surface was significantly discolored due to corrosion was judged as “C” as a failure. The case where the conductor surface did not change color and did not corrode was evaluated as “A” as a pass.

<High temperature oil resistance>
The obtained insulated wire was immersed in ATF (Nissan genuine ATF: NS-3) at 120 ° C. for a predetermined time. Next, a withstand voltage test was performed in which the insulated wire was wound around a mandrel having the same diameter as the wire diameter, and 1 kV was applied to the insulated wire in that state for 1 minute. The case where the dielectric breakdown did not occur under the immersion conditions of 1000 hours or more and less than 2000 hours and could withstand the withstand voltage test was evaluated as “A”. The case where it was able to endure the withstand voltage test without causing dielectric breakdown under immersion conditions of 2000 hours or more was determined as “A +” as a pass. The case where the dielectric breakdown occurred under the immersion condition of less than 1000 hours and the withstand voltage test could not be endured was determined as “C”.

<Abrasion resistance>
In accordance with ISO6722, the abrasion resistance of the obtained insulated wire was evaluated by a blade reciprocation method. That is, a test piece having a length of 600 mm was collected from the insulated wire of each sample. Next, in a 23 ° C. environment, the blade was reciprocated on the insulator surface of the test piece at a length of 15 mm or more in the axial direction at a speed of 60 times per minute. At this time, the load applied to the blade was 7N. Then, the number of reciprocations until the blade contacted the conductor was measured. The number of tests per test piece is four. The case where the minimum value of the number of reciprocations of the blade measured at the number of tests of 4 was 200 or more and less than 500 was determined as “A” as a pass. The case where the minimum value was 500 times or more was determined as “A +”. The case where the above-mentioned minimum value was less than 200 times was judged as “C” as a failure.

Tables 1 to 4 collectively show the composition (parts by mass) of the resin composition used for the insulator of each insulated wire, the type of plating applied to the conductor, and the evaluation results.

According to Tables 1 to 4, the following can be understood. That is, as for the insulated wire of the sample 30, the plating type of the conductor is electric Sn plating. For this reason, the Sn plating of the conductor was melted by the high molding temperature during the extrusion coating of the insulator, and as a result, peeling of the plating and welding between the strands occurred.

The insulated wire of the sample 31 has a conductive plating type of electroless Sn plating. Therefore, the result was similar to that of the sample 30.

The insulated wire of the sample 32 is not plated on the conductor. For this reason, the corrosion resistance of the conductor was lowered, the surface of the conductor was discolored in high temperature oil, and corrosion occurred.

On the other hand, the insulated wires of Sample 1 to Sample 29 are composed of a resin composition in which the insulator extruded on the outer periphery of the conductor contains at least a sulfonyl group-containing resin having a sulfonyl group in a repeating unit. . The sulfonyl group-containing resin has good high-temperature oil resistance and wear resistance. Therefore, the insulated wires of Sample 1 to Sample 29 had good high temperature oil resistance and wear resistance of the insulator.

In particular, it can be seen that when the sulfonyl group-containing resin contains polyphenylsulfone, the high-temperature oil resistance of the insulator can be further improved. It can also be seen that when the resin composition further contains an aromatic polyester, the high-temperature oil resistance and wear resistance of the insulator can be further improved. Moreover, when the polyester-type elastomer was mix | blended with aromatic polyester in the resin composition, the elongation of the insulator was able to be improved, suppressing the physical property fall of an insulator. This is because the compatibility between the sulfonyl group-containing resin and the polyester elastomer is improved.

In addition, among the insulated wires of Sample 1 to Sample 29, the mass ratio of the sulfonyl group-containing resin and the aromatic polyester in 100 parts by mass of the resin component in the resin composition is in the range of 99: 1 to 60:40. It was confirmed that the high-temperature oil resistance and wear resistance of the insulator were easily secured.

Of the insulated wires of Sample 1 to Sample 29, the resin composition further contains both an aromatic polyester and a polyester elastomer, and the polyester elastomer is contained in 100 parts by mass of the resin component in the resin composition. It was confirmed that those having an amount of 50 parts by mass or less are likely to ensure high-temperature oil resistance and wear resistance of the insulator. It was also possible to improve the elongation of the insulator.

In addition, the insulated wires of Sample 1 to Sample 29 are made of Ni-plated conductors. Therefore, even if the molding temperature at the time of insulation extrusion coating is relatively high, the plating applied to the conductor is difficult to melt due to the high molding temperature at that time, and peeling of the plating and welding between the strands hardly occur. . In addition, in the insulated wires of Sample 1 to Sample 29, the Ni plating applied to the conductor was difficult to melt, so that the conductor was difficult to corrode even when exposed to high temperature oil.

As mentioned above, although the Example of this invention was described in detail, this invention is not limited to the said Example, A various change is possible within the range which does not impair the meaning of this invention.

Claims

An insulated wire having a conductor and an insulator coated on the outer periphery of the conductor,
The conductor is subjected to Ni plating or Ni alloy plating,
The insulated wire is composed of a resin composition containing at least a sulfonyl group-containing resin having a sulfonyl group in a repeating unit.
The insulated wire according to claim 1, wherein the sulfonyl group-containing resin is at least one selected from the group consisting of polysulfone, polyethersulfone, and polyphenylsulfone.
3. The insulated wire according to claim 1, wherein the resin composition further contains an aromatic polyester and a polyester-based elastomer, or an aromatic polyester.
The mass ratio of the sulfonyl group-containing resin and the aromatic polyester in 100 parts by mass of the resin component in the resin composition is in the range of 99: 1 to 60:40. 3. The insulated wire according to 3.
The insulated wire according to claim 3 or 4, wherein the content of the polyester elastomer in 100 parts by mass of the resin component in the resin composition is 50 parts by mass or less.