JP2015130240A - insulated wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulated wire in which flexibility can be improved while inhibiting a plasticizer from blooming and from transferring to an insulator of another insulated wire.SOLUTION: An insulated wire 1 includes a conductor 2 and an insulator 3 covering an outer circumference of the conductor 2. The insulator 3 comprises a chlorine-containing resin and a polyurethane-based thermoplastic elastomer. As the polyurethane-based thermoplastic elastomer, there are used an ester group-containing polyurethane-based thermoplastic elastomer having an ester group in a soft segment in the molecule, an ether group-containing polyurethane-based thermoplastic elastomer having an ether group in a soft segment in the molecule, and their modified compounds.

Description

  The present invention relates to an insulated wire.

  Conventionally, an insulated wire having a conductor and an insulator covering the outer periphery of the conductor has been used in vehicles such as automobiles and electrical / electronic devices. In general, a vinyl chloride resin containing a plasticizer is often used as an insulator material.

  For example, Patent Document 1 discloses an insulated wire using a vinyl chloride resin, which contains a plasticizer, an inorganic filler, and an antioxidant, as an insulator.

JP 2011-209773 A

  However, the prior art has problems in the following points. That is, many conventional insulated wires having an insulator in which a plasticizer is blended with a vinyl chloride resin have a relatively small diameter. In recent years, a relatively large-diameter insulated wire such as a power cable is required. However, the conventional insulator has a problem that flexibility is insufficient when applied to a large-diameter insulated wire.

  In order to improve the flexibility of the conventional insulator, a method of increasing the blending amount of the plasticizer can be considered. However, the increased amount of plasticizer causes blooming of the plasticizer to the insulator surface. Moreover, when an insulated wire is used in a bundle as in the shape of a harness or the like, the plasticizer moves to an insulator included in the other insulated wires, and the characteristics of the other insulated wires are deteriorated.

  The present invention has been made in view of the above background, and is capable of improving flexibility while suppressing plasticizer blooming and migration of the plasticizer to an insulator of other insulated wires. Is to provide.

One embodiment of the present invention has a conductor and an insulator covering the outer periphery of the conductor,
The insulator is an insulated wire characterized by containing a chlorine-containing resin and a polyurethane-based thermoplastic elastomer.

  The insulated wire has an insulator containing a chlorine-containing resin and a polyurethane-based thermoplastic elastomer. That is, the insulated wire uses a polyurethane-based thermoplastic elastomer that is a flexible polymer compound having a higher molecular weight than that of a low-molecular weight plasticizer in order to make the insulator flexible. Therefore, the said insulated wire can improve a softness | flexibility, suppressing the blooming of a plasticizer and the transfer of the plasticizer to the insulator which another insulated wire has.

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

  In the above-described insulated wire, for example, a metal stranded wire formed by twisting a plurality of metal strands from the viewpoint of improving the flexibility of the insulated wire can be used as the conductor. A plurality of metal strands may be twisted together at one time, or may be twisted in a plurality of times. Specifically, the metal stranded wire can be configured such that a plurality of sub-metal stranded wires formed by twisting a plurality of metal strands are further twisted. In this case, even when the conductor cross-sectional area is relatively large, a lot of gaps are formed in the conductor, which is advantageous for improving the flexibility of the insulated wire. Examples of the metal (including alloy) constituting the conductor include copper, copper alloy, aluminum, aluminum alloy, and the like.

Conductor cross-sectional area of the conductor, from the viewpoint of sufficiently exhibiting the above action and effect, preferably ^{3mm 2 ~50mm} 2, more preferably be selected from the range of ^{5mm 2 ~50mm} 2.

  The insulator contains a chlorine-containing resin and a polyurethane-based thermoplastic elastomer.

  The said chlorine containing resin is resin which contains a chlorine atom in a molecule | numerator, Specifically, a vinyl chloride resin, chlorinated polyethylene, etc. can be illustrated. These can be used alone or in combination of two or more. Specific examples of the vinyl chloride resin include polyvinyl chloride, an ethylene-vinyl chloride copolymer, and a graft copolymer obtained by graft-polymerizing vinyl chloride on an ethylene-vinyl acetate copolymer. As a commercially available chlorine-containing resin, specifically, Leuron, TE-650, TE-800, TE-1050, TE-1300, TG-100, TH-500, TH-640, TH manufactured by Taiyo PVC Co., Ltd. -700, TH-800, TH-1000, TH-1300, TH-1700, TH-2500, TH-3800, Eraslen from Showa Denko KK, Shin-Etsu Chemical TK-500, TK-600, TK-700 TK-800, TK-1000, TK-1700E, TK-2000E, TK-2500LS, GR-800T, GR-1300T, GR-1300S, and the like.

  Examples of the polyurethane-based thermoplastic elastomer include an ester group-containing polyurethane-based thermoplastic elastomer containing an ester group in the soft segment in the molecule, an ether group-containing polyurethane-based thermoplastic elastomer containing an ether group in the soft segment in the molecule, and the like. Can be used. These can be used alone or in combination of two or more.

  Since the polyurethane-based thermoplastic elastomer has sufficient flexibility, it is suitable for improving the flexibility of an insulated wire by using it together with a chlorine-containing resin. In addition, since the polyurethane-based thermoplastic elastomer has a molecular weight larger than that of the plasticizer, it is difficult to bloom, and it does not shift to an insulator included in other insulated wires and deteriorate the wire characteristics.

  When modifying the polyurethane-based thermoplastic elastomer, as the modifier, for example, an unsaturated carboxylic acid, a derivative of an unsaturated carboxylic acid, or the like can be used. These can be used alone or in combination of two or more. Specific examples of the unsaturated carboxylic acid include maleic acid and fumaric acid. Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, maleic acid monoester, maleic acid diester, and the like. Among these, maleic acid, maleic anhydride, and the like are preferable from the viewpoints of improving adhesion with a conductor, improving adhesion with a filler such as an inorganic filler that can be added to an insulator, and improving dispersibility of the filler. Good.

  Examples of the modification method for the polyurethane thermoplastic elastomer include a graft method and a direct method. The amount of modification is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.2 to 5% by mass with respect to the elastomer before modification. .

  Specifically, as the polyurethane-based thermoplastic elastomer, one having a hard segment composed of diisocyanate and a short-chain diol and a soft segment composed of a long-chain diol can be suitably used.

  In this case, since the polyurethane-based thermoplastic elastomer does not easily take an excessive three-dimensional network structure, the polyurethane-based thermoplastic elastomer can sufficiently exhibit its function as a flexible component. Therefore, it is advantageous for improving the flexibility of the insulated wire. The short chain diol referred to above is a so-called chain extender.

  Specific examples of the long-chain diol include polycaprolactone glycol and polycarbonate diol. Specific examples of the short-chain diol include polytetramethylene glycol, polyethylene glycol, and polyethylene-propylene glycol. Specific examples of the diisocyanate include diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), toluene diisocyanate (TDI), xylylene diisocyanate (XDI), hydrogenated MDI, hexamethylene diisocyanate (HDI), and the like. Derivatives and the like.

  Specific examples of commercially available polyurethane-based thermoplastic elastomers include Elastollan C80A, C85A, C90A, S80A, S85A, and S90A (above, ester group-containing polyurethane-based thermoplastic elastomers) manufactured by BASF, 1180A, 1190ATR, 1195ATR, ET880, ET885, ET890 (above, ether group-containing polyurethane-based thermoplastic elastomer).

  In addition, the insulator may contain a polyolefin resin or the like. Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer (EEA).

  The said insulator WHEREIN: Content of a polyurethane-type thermoplastic elastomer is good to be in the range of 0.1 mass part-100 mass parts with respect to 100 mass parts of chlorine containing resin.

  In this case, the insulated wire can have appropriate flexibility and can exhibit excellent wear resistance.

  The content of the polyurethane-based thermoplastic elastomer is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.8 parts by mass, from the viewpoint of the balance between flexibility and wear resistance. Part or more, still more preferably 1 part by mass or more. Further, the content of the polyurethane-based thermoplastic elastomer is preferably 98 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 90 parts by mass or less, from the viewpoint of the balance between flexibility and wear resistance, and the like. More preferably, it can be 80 mass parts or less.

  If the said insulator is in the range which does not impair the effect mentioned above, 1 type (s) or 2 or more types of various additives, such as a filler, antioxidant, anti-aging agent, copper damage inhibitor, and a pigment, are added. May be.

  For example, when the insulator contains an appropriate amount of filler within a range that does not impair the above-described effects, it is advantageous for improving the wear resistance. In this case, the upper limit of the content of the polyurethane-based thermoplastic elastomer is 180 parts by mass or less, preferably 170 parts by mass or less, more preferably 160 parts by mass or less, and even more preferably 150 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. It can be expanded to a range of less than or equal to parts by mass. At this time, the content of the filler is specifically 1 to 30 parts by mass, preferably 3 to 20 parts per 100 parts by mass of the chlorine-containing resin, from the viewpoint of balance between improvement in flexibility and improvement in wear resistance. It can be in the range of 5 parts by mass, more preferably 5-15 parts by mass.

  Examples of the filler include calcium carbonate, magnesium oxide, and magnesium hydroxide. These can be used alone or in combination of two or more. In addition, the filler may be a homopolymer or copolymer of α-olefin such as 1-heptene, 1-octene, 1-nonene, 1-decene or a mixture thereof, or a surface treatment agent such as a silane coupling agent. It may be surface-treated.

  The average particle size of the filler is preferably 0.01 to 20 μm, more preferably 0.02 to 10 μm, and still more preferably 0.03 to 8 μm. By setting the average particle size of the filler to 0.01 μm or more, it becomes easy to suppress a decrease in mechanical properties due to secondary aggregation of the filler. Further, when the average particle size of the filler is 20 μm or less, it is difficult to cause an appearance defect of the insulator. The average particle diameter is the particle diameter (diameter) d50 when the volume-based cumulative frequency distribution measured by the laser diffraction / scattering method shows 50%.

  Specific examples of calcium carbonate include white gloss flower CC, white gloss flower CCR, white gloss flower DD, Vigot 10, Vigot 15, and white gloss flower U manufactured by Shiroishi Calcium. Specific examples of magnesium oxide include UC95S, UC95M, and UC95H manufactured by Ube Materials. Specific examples of magnesium hydroxide include UD-650-1 and UD-653 manufactured by Ube Materials.

  In the insulated wire, the thickness of the insulator is preferably from 0.1 mm to 3 mm, more preferably from 0.2 mm, from the viewpoint of the balance between improving the flexibility of the insulated wire and securing the wire characteristics such as wear resistance. It can be selected from the range of 2.5 mm.

  The said insulated wire can be used for vehicles, such as a motor vehicle, and an electronic / electrical apparatus. More specifically, the insulated wire can be suitably applied to a power cable or the like used for a hybrid vehicle or an electric vehicle.

  In addition, each structure mentioned above can be arbitrarily combined as needed, in order to acquire each effect etc. which were mentioned above.

  Hereinafter, the insulated wire of an Example is demonstrated using drawing.

Example 1
As shown in FIG. 1, the insulated wire 1 of this example includes a conductor 2 and an insulator 3 that covers the outer periphery of the conductor 2. The insulator 3 contains a chlorine-containing resin and a polyurethane-based thermoplastic elastomer.

  In this example, the conductor 2 is configured by further twisting a plurality of sub-metal strands 20 formed by twisting a plurality of metal strands (not shown). The metal strand is specifically an annealed copper wire. The chlorine-containing resin contained in the insulator 3 is specifically a vinyl chloride resin or chlorinated polyethylene. The polyurethane thermoplastic elastomer contained in the insulator 3 specifically has a hard segment composed of diisocyanate and a short-chain diol and a soft segment composed of a long-chain diol. The soft segment contains an ester group or an ether group.

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

(Experimental example)
-Preparation of materials-
The following materials were prepared as insulator materials.
-Chlorinated polyethylene (1) [Showa Denko Co., Ltd., "Elaslene 301A"]
-Chlorinated polyethylene (2) [Showa Denko Co., Ltd., "Elaslene 303B"]
・ Vinyl chloride resin (1) [manufactured by Taiyo PVC Co., Ltd., “Lyuron E-1700”]
・ Vinyl chloride resin (2) [manufactured by Taiyo PVC Co., Ltd., “Lyuron E-2200”]
-Polyurethane thermoplastic elastomer (1) (Ester group is contained in the soft segment in the molecule) ["Elastollan C90A" manufactured by BASF]
・ Polyurethane-based thermoplastic elastomer (2) (containing ether group in soft segment in molecule) [BASF, “Elastolan ET880”]
・ Polyurethane-based thermoplastic elastomer (3) (contains ether group in soft segment in molecule) [manufactured by BASF, "Elastollan 1195ATR"]
・ DINP (Diisononyl phthalate)
・ DOP (dioctyl phthalate)

―Production of insulated wire―
Each material was mixed at 200 ° C. using a biaxial kneader at a predetermined blending ratio shown in Table 1, and then formed into a pellet using a pelletizer. Then, the pellet-shaped molded product is extruded and coated on the outer periphery of a conductor formed by twisting 19 more annealed copper strands made of 9 annealed copper wires, thereby forming an insulator. did. The conductor diameter is 5.3 mm and the conductor cross-sectional area is 15 mm ² . The insulator has a thickness of 1.1 mm. Thereby, the insulated wires of Sample 1 to Sample 13 were produced.

-Flexibility-
A test wire having a length of 500 mm was taken from the insulated wire of each sample. Next, the test electric wires were fixed in a state of being bent in a lateral U shape between the plate jigs of the load cell to which the pair of plate jigs were attached. Specifically, each end of the curved test wire was fitted and fixed in each V-shaped groove formed on the surface of each plate-shaped jig. In addition, the distance between each plate-shaped jig | tool was 200 mm. Next, a load in the compression direction was applied to the test electric wire with the load cell, and the maximum load [N] when the load was applied until the distance between the plate-shaped jigs reached 100 mm was measured. The value of the maximum load indicates that the smaller the value, the better the flexibility of the insulated wire.

−Abrasion resistance−
When the flexibility of the insulator becomes excessive, it is considered that the insulator is worn and the wear resistance, which is one of the electric wire characteristics, is lowered. Accordingly, the wear resistance of the insulator was confirmed for the insulated wires of each sample.

  Specifically, the wear resistance of the insulator was evaluated by a blade reciprocation method in accordance with the Japan Automobile Engineers Association Standard “JASO D618”. That is, a test piece having a length of 750 mm was collected from the insulated wire of each sample. Next, the blade was reciprocated on the insulator surface of the test piece at a room temperature of 23 ± 5 ° C. at a length of 10 mm or more in the axial direction at a speed of 50 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. “A” indicates that the wear resistance is good when the number of reciprocations of the blade is 1500 times or more and less than 2000 times, and “A +” indicates that the number of reciprocations of the blade is 2000 times or more. It was.

  Table 1 summarizes the evaluation results of the composition (parts by mass), flexibility, and wear resistance of the insulators in the insulated wires of each sample.

  According to Table 1, the following can be understood. That is, each of the insulated wires of Sample 8 to Sample 13 has an insulator in which a chlorine-containing resin is mixed with a low molecular weight plasticizer. Among these, the insulated wires of Sample 8 to Sample 12 are blended with a plasticizer at the blending ratio shown in Table 1, but the maximum load in the flexibility test is as large as 38 [N] or more and is inferior in flexibility. You can see that Moreover, in order to improve the flexibility of the insulator, the insulated wire of Sample 13 in which the amount of the plasticizer was further increased exhibited blooming of the plasticizer on the surface of the insulator. From this result, it can be said that there is a limit in improving the flexibility of the insulator by increasing the amount of plasticizer. In addition, the insulated wires of Sample 8 to Sample 13 all contain a relatively large amount of low molecular weight plasticizer. Therefore, in the insulated wires of Sample 8 to Sample 13, when the insulated wires are used in bundles, the plasticizer easily migrates to the insulators of the other insulated wires, which may deteriorate the characteristics of the other insulated wires. Concerned.

  On the other hand, the insulated wires of Sample 1 to Sample 7 have an insulator containing a chlorine-containing resin and a polyurethane-based thermoplastic elastomer. That is, the insulated electric wires of Sample 1 to Sample 7 use a polyurethane-based thermoplastic elastomer that is a flexible high molecular compound and has a higher molecular weight than a low molecular weight plasticizer in order to make the insulator flexible. Therefore, the insulated wires of Sample 1 to Sample 7 have a smaller maximum load in the flexibility test and improved flexibility than the insulated wires of Sample 8 to Sample 13. In addition, since the insulated wires of Sample 1 to Sample 7 are not positively mixed with a plasticizer in order to improve flexibility, there is no blooming of the plasticizer, and the plasticizer to the insulators of other insulated wires has It can be said that the transition can also be suppressed.

  Furthermore, the insulated wires of Sample 1 to Sample 7 are compared. In the insulated wires of Samples 1 to 3 and Sample 6, the content of the polyurethane-based thermoplastic elastomer is in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. Therefore, it was confirmed that the insulated wires of Samples 1 to 3 and Sample 6 have moderate flexibility and excellent wear resistance.

  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.

1 Insulated wire 2 Conductor 3 Insulator

Claims (5)

A conductor and an insulator covering the outer periphery of the conductor;
The insulated wire contains a chlorine-containing resin and a polyurethane-based thermoplastic elastomer.   The polyurethane-based thermoplastic elastomer is an ester group-containing polyurethane-based thermoplastic elastomer containing an ester group in the soft segment in the molecule, an ether group-containing polyurethane-based thermoplastic elastomer containing an ether group in the soft segment in the molecule, and The insulated wire according to claim 1, wherein the insulated wire is at least one selected from the group consisting of these modified products.   The insulated wire according to claim 1 or 2, wherein the chlorine-containing resin is at least one selected from the group consisting of vinyl chloride resin and chlorinated polyethylene.   The polyurethane-based thermoplastic elastomer has a hard segment composed of diisocyanate and a short-chain diol and a soft segment composed of a long-chain diol. The insulated wire as described in the item.   The content of the polyurethane-based thermoplastic elastomer is in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. The insulated wire according to item 1.

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