JP2015225837A - Insulated wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulated wire which enables improvement of flexibility while suppressing blooming of a plasticizer and transfer of a plasticizer to insulators of other insulated wires and has good heat resistance.SOLUTION: An insulated wire 1 includes a conductor 2 and an insulator 3 covering the outer periphery of the conductor 2. The insulator 3 contains a chlorinated vinyl chloride type resin and a vinyl chloride-based thermoplastic elastomer. The content of the vinyl chloride-based thermoplastic elastomer is preferably 0.1-100 pts. mass to 100 pts. mass of the chlorinated vinyl chloride type resin.

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 insulator in the conventional insulated wire, 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.

  Insulated electric wires applied to automobiles and the like are often used under various thermal environments, and are desired to have good heat resistance.

  The present invention has been made in view of the above background, and it is possible to improve flexibility while suppressing plasticizer blooming and migration of the plasticizer to the insulator of other insulated wires, And it aims at providing the insulated wire which has favorable heat resistance.

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 chlorinated vinyl chloride resin and a vinyl chloride thermoplastic elastomer.

  The insulated wire has an insulator containing a chlorinated vinyl chloride resin and a vinyl chloride thermoplastic elastomer. That is, the insulated wire uses a vinyl chloride thermoplastic elastomer, which 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. In addition, the said insulated wire does not have a possibility that the abrasion resistance of the insulator which is one of the electric wire characteristics may be significantly reduced by improving the flexibility of the insulator.

  The insulated wire contains a chlorinated vinyl chloride resin in the insulator. Chlorinated vinyl chloride resins have higher heat resistance than non-chlorinated vinyl chloride resins. Therefore, the heat resistance of the insulator is improved. Therefore, the insulated wire can exhibit good heat resistance.

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

  In the above 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 may have a configuration in which a plurality of sub-metal stranded wires obtained 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.

  In the above insulated wire, the insulator contains a chlorinated vinyl chloride resin and a vinyl chloride thermoplastic elastomer.

  One or more chlorinated vinyl chloride resins can be used in combination. From the viewpoint of improving the heat resistance of the insulator, the chlorinated vinyl chloride resin preferably has a chlorine content of 60% by mass or more, more preferably 61% by mass or more, and still more preferably 62% by mass or more. Even more preferably, the content is 63% by mass or more. The chlorine content is preferably 80% by mass or less from the viewpoint of easily securing a chlorination reaction during production of the chlorinated vinyl chloride resin and improving the yield of the chlorinated vinyl chloride resin. be able to. The chlorine content can be measured by ICP mass spectrometry.

  Specific examples of commercially available chlorinated vinyl chloride resins include PVC-HA series HA-05H, HA-05K, HA-15F, HA-24F, HA-22H, HA-22F, HA, manufactured by Sekisui Chemical Co., Ltd. -24K, HA-24L, HA-31K, HA-53K, HA-17F, HA-27F, CPVC series manufactured by Kaneka H305, H438, H536, H516A, H447, H547, H638, H727, H829, H716S, H816S And so on.

  One or two or more vinyl chloride thermoplastic elastomers can be used in combination. Further, the vinyl chloride thermoplastic elastomer may be modified.

  When the vinyl chloride thermoplastic elastomer is modified, examples of the modifying agent include unsaturated carboxylic acid and unsaturated carboxylic acid derivatives. 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 of the vinyl chloride 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. .

  Specific examples of commercially available vinyl chloride thermoplastic elastomers include Sunplane FA55JB, FA60GA, FA65KC, FA65DZ, FA70HH, FE60JB, FE60AD, FE65HB, FE70DH, FG40EA, FG60FA, FF40FB, FF55JC, manufactured by Mitsubishi Chemical Corporation. FF65EC, FF70GA, Sun Frost KB75GA, KD55JB, KD60HA, KD70QA, KD80MA, KD90EA, KF65GA, AFKJ600, ATKK600, AFCL600, AFKS600, ATKT600, AFKU600, EF-ET, 000-000, EH-ET , EK-000, EW-000, EU-000, FK-5500, IF-000, IH-000, IT-000 Such as IK-000, IW-000 can be mentioned.

  In the above insulated wire, the content of the vinyl chloride thermoplastic elastomer in the insulator is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin.

  In this case, it is possible to obtain an insulated wire having excellent wear resistance while ensuring good flexibility and excellent heat resistance.

  The content of the vinyl chloride thermoplastic elastomer is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.000 parts by mass from the viewpoint of balance between flexibility and wear resistance. The amount can be 8 parts by mass or more, and more preferably 1 part by mass or more. The content of the vinyl chloride thermoplastic elastomer is preferably 98 parts by mass or less, more preferably 95 parts by mass or less, and still more preferably 90 parts by mass or less, from the viewpoint of balance between flexibility and wear resistance. can do.

    In the insulated wire, 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). Moreover, as long as the insulator does not impair the above-described effects, one or more various additives such as fillers, antioxidants, anti-aging agents, copper damage inhibitors, and pigments are added. It may be.

  In the insulated wire, 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 in improving wear resistance. In this case, the upper limit of the content of the vinyl chloride thermoplastic elastomer in the insulator is 180 parts by mass or less, preferably 170 parts by mass or less, more preferably 160 parts by mass or less, with respect to 100 parts by mass of the chlorinated vinyl chloride resin. Even more preferably, it can be expanded to a range of 150 parts by mass or less. At this time, the content of the filler in the insulator is specifically 1 to 30 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin from the viewpoint of balance between improvement in flexibility and improvement in wear resistance. , Preferably 3-20 mass parts, More preferably, it can be in the range of 5-15 mass parts.

  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 commercially available calcium carbonate include white gloss flower CC, white gloss flower CCR, white gloss flower DD, Vigot10, Vigot15, and white gloss flower U manufactured by Shiraishi Calcium. Specific examples of commercially available magnesium oxide include UC95S, UC95M, and UC95H manufactured by Ube Materials. Specific examples of commercially available 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 chlorinated vinyl chloride resin and a vinyl chloride 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.

  Hereinafter, a plurality of insulated wire samples having different insulator configurations 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 vinyl chloride resin (1) (chlorine content: 67 mass%) [manufactured by Sekisui Chemical Co., Ltd., "HA-05K"]
・ Chlorinated vinyl chloride resin (2) (chlorine content: 65% by mass) [manufactured by Sekisui Chemical Co., Ltd., “HA-15F”]
・ Chlorinated vinyl chloride resin (3) (chlorine content: 63% by mass) [manufactured by Kaneka Corporation, "H305"]
-Chlorinated vinyl chloride resin (4) (chlorine content 64.5% by mass) [manufactured by Kaneka Corporation, "H536"]
・ Vinyl chloride thermoplastic elastomer (1) [Mitsubishi Chemical Corporation, "Sunplane FA60GA"]
・ Vinyl chloride thermoplastic elastomer (2) [manufactured by Sun Arrow Kasei Co., Ltd., “ATKK600”]
・ Vinyl chloride thermoplastic elastomer (3) [manufactured by Sun Arrow Kasei Co., Ltd., “EH-000”]
・ Vinyl chloride resin (1) [Shin-Etsu Chemical Co., Ltd. “TK-1000”]
-Vinyl chloride resin (2) [Shin-Etsu Chemical Co., Ltd., "TK-1700E"]
-Vinyl chloride resin (3) [manufactured by Taiyo PVC Co., Ltd., "TE-1050"]
-Vinyl chloride resin (4) [manufactured by Taiyo PVC Co., "TH-1700"]
・ Inorganic filler (calcium carbonate) [manufactured by Shiraishi Calcium Co., Ltd. “Vigot15”]
・ 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 Tables 1 and 2, 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 14 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.

-Heat resistance-
The conductor was extracted from the insulated wire of each sample, and the obtained insulator was used as a test piece. Then, each test piece was taken out in a thermostat at 150 ° C. for 10 days. Thereafter, using a tensile tester, a tensile test is performed on the test piece before being put in the thermostatic bath and the test piece after being put in the thermostatic bath under the conditions of the distance between marked lines: 20 mm and the tensile speed: 50 mm / min. The elongation of each test piece was measured. When the initial elongation before entering the thermostatic bath is 100%, when the elongation after entering the thermostatic bath is 70% or more, “A +” is defined as having excellent heat resistance, and the elongation is 50%. The case of less than 70% was designated as “A” as having good heat resistance, and the case of less than 50% as “C” as being inferior in heat resistance.

  Tables 1 and 2 summarize the evaluation results of the composition (parts by mass) of the insulators in the insulated wires of each sample, the flexibility, wear resistance, and heat resistance of the insulators.

  According to Tables 1 and 2, the following can be understood. That is, as shown in Table 2, each of the insulated wires of Samples 9 to 14 has an insulator in which a low molecular weight plasticizer is blended with a normal vinyl chloride resin that is not chlorinated. ing. Among these, the insulated wires of Sample 9 to Sample 13 are blended with a plasticizer at the blending ratio shown in Table 2, but the maximum load in the flexibility test is as large as 39 [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 14 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 9 to Sample 14 all contain a relatively large amount of low molecular weight plasticizer. Therefore, in the insulated wires of Sample 9 to Sample 14, 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 8 have an insulator containing a chlorinated vinyl chloride resin and a vinyl chloride thermoplastic elastomer. That is, the insulated wires of Sample 1 to Sample 8 use a vinyl chloride thermoplastic elastomer, which 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 8 have a smaller maximum load in the flexibility test and improved flexibility than the insulated wires of Sample 9 to Sample 14. In addition, since the insulated wires of Sample 1 to Sample 8 are not positively mixed with a plasticizer in order to improve flexibility, there is no blooming of the plasticizer, and the plasticizer to the insulator of other insulated wires It can be said that the transition can also be suppressed. In addition, in the insulated wires of Samples 1 to 8, blooming of the vinyl chloride thermoplastic elastomer was not recognized.

  Furthermore, the insulated wires of Sample 1 to Sample 8 are compared. In the insulated wires of Samples 1 to 4 and Sample 6, the content of the vinyl chloride thermoplastic elastomer in the insulator is 0.1 to 100 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin. It is within the range. Therefore, it was confirmed that the insulated wires of Samples 1 to 4 and Sample 6 have excellent wear resistance while ensuring good flexibility and heat resistance. In particular, according to the results of Sample 4 and Sample 8, it can be seen that excellent wear resistance can be exhibited while ensuring good flexibility and excellent heat resistance without using a filler. .

  In the insulated wire of sample 8, the content of the vinyl chloride thermoplastic elastomer in the insulator is over 100 parts by mass. However, in the insulated wire of Sample 8, an appropriate amount of inorganic filler is blended within a range that does not impair flexibility. Therefore, the insulated wire of sample 8 was able to ensure excellent wear resistance as compared with the insulated wire of sample 7. From this result, even when the content of the vinyl chloride thermoplastic elastomer in the insulator is 100 parts by mass, by using an appropriate amount of filler, it is excellent while ensuring good flexibility and excellent heat resistance. It can be seen that the wear resistance can be exhibited.

  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 (3)

A conductor and an insulator covering the outer periphery of the conductor;
The insulated wire contains a chlorinated vinyl chloride resin and a vinyl chloride thermoplastic elastomer.   The content of the vinyl chloride thermoplastic elastomer is in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin. Insulated wire as described. The insulator contains a filler,
The content of the vinyl chloride thermoplastic elastomer is in the range of 0.1 to 180 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin. Insulated wire as described.

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