JP2015201362A - Insulation wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulation wire capable of improving flexibility while suppressing blooming of a plasticizer and transition of the plasticizer to an insulator which other insulation wire has, and having good heat resistance.SOLUTION: An insulation wire 1 has a conductor 2 and an insulation body 3 coating circumference of the conductor 2. The insulation body 3 is constituted by a water crosslinked body of a composition containing a chlorine-containing resin and a silane graftmer by grafting an unsaturated alkoxysilane compound to a chlorine-containing main polymer. The silane graftmer has the graft amount of the unsaturated alkoxysilane compound of 1 mass% or more based on the chlorine-containing main chain polymer.

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 includes a conductor and an insulator that covers the outer periphery of the conductor.
The insulator is
A water-crosslinked product of a composition comprising a chlorine-containing resin and a silane grafter obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer,
The silane grafter is an insulated wire characterized in that a graft amount of the unsaturated alkoxysilane compound to the chlorine-containing main chain polymer is 1% by mass or more.

  In the insulated wire, the insulator is composed of a water-crosslinked product of a composition containing a chlorine-containing resin and a silane grafter obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer. That is, the insulated wire uses the silane grafter, which is a flexible polymer compound having a higher molecular weight than 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. Moreover, since the said silane grafter uses the chlorine containing main chain polymer, its compatibility with chlorine containing resin is good. Therefore, the insulated wire is advantageous for improving flexibility. 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.

  Moreover, the said insulated wire contains the silane grafter whose grafting amount of the unsaturated alkoxysilane compound with respect to a chlorine containing main chain polymer is 1 mass% or more in the said composition. Therefore, the insulator comprised from the water crosslinked body of the said composition can improve the crosslinking degree by silane grafter. 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 is composed of a water-crosslinked product of a composition containing a chlorine-containing resin and a silane grafter.

  A chlorine-containing resin is a resin containing a chlorine atom in the molecule. Specific examples of the chlorine-containing resin include vinyl chloride resin and chlorinated polyethylene. 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.

  The silane grafter is obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer. The silane grafter can be used alone or in combination of two or more.

  The chlorine-containing main chain polymer in the silane grafter contains a chlorine atom in the molecule. Specific examples of the chlorine-containing main chain polymer include chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated butyl rubber, epichlorohydrin rubber, and chloroprene rubber. These can be used alone or in combination of two or more. Further, the chlorine-containing main chain polymer may be either a random copolymer or a block copolymer. When these chlorine-containing main chain polymers are used, the flexibility of the insulator can be reliably improved. Moreover, since it is easy to increase the molecular weight of the silane grafter, it is easy to suppress the blooming of the silane grafter and the migration of the silane grafter to the insulator of other insulated wires.

  The chlorosulfonated polyethylene can be used alone or in combination of two or more. In the chlorosulfonated polyethylene, for example, a part of hydrogen atoms in the polyethylene main chain may be substituted with an alkyl group. Specific examples of commercially available chlorosulfonated polyethylene include TOSO-CSM TS-430, TS-530, TS-830, TS-930, TS-320, extos ET-8010, and ET-8510 manufactured by Tosoh Corporation. And so on.

  The chlorinated polyethylene can be used alone or in combination of two or more. Specific examples of commercially available chlorinated polyethylene include Eraslen 301MA, 301A, 351A, 401A, 303A, 252B, 303B, and 104B manufactured by Showa Denko KK.

  The chlorinated butyl rubber can be used alone or in combination of two or more. Specific examples of commercially available chlorinated butyl rubbers include JSR CHLOROBUTYL 1066 and JSR CHLOROBUTYL 1068 manufactured by JSR.

  Epichlorohydrin rubber can be used alone or in combination of two or more. The epichlorohydrin rubber may be a homopolymer or a multi-component copolymer such as a binary copolymer or a ternary copolymer. The epichlorohydrin rubber may be modified. Specific examples of the epichlorohydrin rubber include epichlorohydrin homopolymer, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide. -An allyl glycidyl ether copolymer, an allyl glycidyl ether modified epichlorohydrin-ethylene oxide copolymer, etc. can be mentioned. Specific examples of commercially available epichlorohydrin rubber include Epichromer H, Epichromer H50, Epichromer C, Epichromer C55, Epichromer D, Epichromer CG, Epichromer CG102, Hydrin H75, Hydrin H1100, and Hydrin C2000 manufactured by Nippon Zeon. , Hydrin T3100, and the like.

  The chloroprene rubber can be used alone or in combination of two or more. The chloroprene rubber may be a homopolymer or a multi-component copolymer such as a binary copolymer or a ternary copolymer. The chloroprene rubber may be modified with, for example, a mercaptan compound, xanthogen oxide, sulfur or the like. Specific examples of commercially available chloroprene rubbers include Skyspuren B-30, B-31, B-5, B-10, TSR-41, TSR-42, E-20, and E-33 manufactured by Tosoh Corporation. , R-22, R-10, Denkachloroprene M-30, M-31, S-40, EM-40, ES-40, DCR-30, manufactured by Denki Kagaku Kogyo, Showrene GS, W manufactured by Showa Denko KK , WXJ, WB, WK, TW, and the like.

  The unsaturated alkoxysilane compound grafted to the chlorine-containing main chain polymer of the silane grafter may be any of an unsaturated monoalkoxysilane compound, an unsaturated dialkoxysilane compound, and an unsaturated trialkoxysilane compound. These may be used alone or in combination of two or more. More specific examples of the unsaturated alkoxysilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and allyltributoxysilane. These can be used alone or in combination of two or more. Moreover, these are comparatively easy to acquire and are easy to carry out the water bridge | crosslinking of the silane grafters in presence of a silanol condensation catalyst. Therefore, when these are used, there exists an advantage which becomes easy to obtain the water crosslinked body of the said composition.

Here, the amount of the unsaturated alkoxysilane compound grafted to the chlorine-containing main chain polymer in the silane grafter is 1% by mass or more. When the graft amount is less than 1% by mass, the silane grafters are not sufficiently cross-linked at the time of water cross-linking of the composition, the degree of cross-linking cannot be improved, and an insulated wire having good heat resistance is obtained. It becomes impossible. The amount of grafting is preferably 1.3% by mass or more, from the viewpoint that it is easy to ensure good heat resistance, and that it is easy to suppress blooming and migration to other materials due to crosslinking between silane grafters. Preferably, it is 1.4 mass% or more, More preferably, it can be 1.5 mass% or more. On the other hand, when the graft amount is excessively large, there is a high possibility that adjacent graft side chains in the same silane grafter are water-crosslinked, and the significance of grafting the unsaturated alkoxysilane compound is reduced. In addition, useless unsaturated alkoxysilane compounds are also required, which leads to an increase in the cost of electric wire production. Therefore, the graft amount is preferably 15% by mass or less from the viewpoint of efficiently forming a crosslinking site that contributes to the heat resistance of the insulator during water crosslinking of the insulator. The graft amount is more preferably 13% by mass or less, further preferably 12% by mass or less, still more preferably 11% by mass or less, and still more preferably 10% by mass or less. The graft amount can be measured by ¹ H-NMR method.

  The silane grafter is obtained, for example, by heating a mixture of a chlorine-containing main chain polymer, an unsaturated alkoxysilane compound, and an organic peroxide at a temperature of about 150 ° C. to 160 ° C. for about 5 minutes to 10 minutes. be able to.

  In this case, specific examples of the organic peroxide include di-t-hexyl peroxide, dicumyl peroxide, n-butyl 4,4-di (t-butylperoxy) valerate, di-t-butyl. Examples thereof include peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like. These can be used alone or in combination of two or more. Specific examples of commercially available organic peroxides include Perhexyl D, Park Mill D, Perhexa V, Perbutyl D, Perbutyl C, and Perhexa 25B manufactured by NOF Corporation.

  In the insulated wire, the composition may contain a silanol condensation catalyst. In this case, when the composition and moisture are brought into contact with each other and water crosslinking is performed, the silane grafters can be efficiently crosslinked to improve the degree of crosslinking. Therefore, in this case, it becomes easy to obtain an insulated wire having good heat resistance. Specific examples of the silanol condensation catalyst include dibutyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, tetrabutyl ester titanate, and lead stearate. And organometallic compounds such as zinc stearate, cadmium stearate, barium stearate and calcium stearate. These can be used alone or in combination of two or more.

  The said insulated wire WHEREIN: The said composition can contain 1-100 mass parts of silane grafters with respect to 100 mass parts of chlorine containing resins. In this case, the insulator has an appropriate flexibility and can exhibit excellent wear resistance.

  The content of the silane grafter in the composition is preferably 0.3 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, from the viewpoint of balance between flexibility and wear resistance. Even more preferably, it can be 7 parts by mass or more, still more preferably 10 parts by mass or more. The content of the silane grafter in the composition 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. It can be.

  In the insulated wire, the composition 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, if the said composition is in the range which does not impair the effect mentioned above, 1 type, or 2 or more types of various additives, such as a filler, antioxidant, anti-aging agent, copper damage inhibitor, and a pigment, will be added. May be.

  In the insulated wire, for example, when the composition contains an appropriate amount of filler within a range not impairing the above-described effects, it is advantageous for improving the wear resistance. In this case, the upper limit of the content of the silane grafter in the composition is 180 parts by mass or less, preferably 170 parts by mass or less, more preferably 160 parts by mass or less, even more preferably 100 parts by mass of the chlorine-containing resin. It can be expanded to a range of 150 parts by mass or less, even more preferably 140 parts by mass or less. At this time, the content of the filler in the composition is specifically 1 to 30 parts by mass with respect to 100 parts by mass of the chlorine-containing resin, preferably from the viewpoint of balance between improvement in flexibility and improvement in wear resistance. Can be within a range of 3 to 20 parts by mass, more preferably 5 to 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 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.

(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 is composed of a water-crosslinked product of a composition containing a chlorine-containing resin and a silane grafter obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer. In the silane grafter, the amount of the unsaturated alkoxysilane compound grafted to the chlorine-containing main chain polymer is 1% by mass or more.

  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). Specifically, the metal strand is an annealed copper wire. The chlorine-containing main chain polymer is at least one selected from the group consisting of chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated butyl rubber, epichlorohydrin rubber, and chloroprene rubber.

  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.
・ 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"]
・ Silane grafter (1)
100 parts by mass of chlorosulfonated polyethylene [manufactured by Tosoh Corporation, “TS-830”], 3 parts by mass of vinyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-1003”], and organic peroxide [manufactured by NOF Corporation] “Park Mill D”] was sufficiently kneaded with 0.2 parts by mass using a Banbury mixer, and then heated at 150 ° C. for 10 minutes. As a result, a silane grafter (1) obtained by grafting vinyltrimethoxysilane onto chlorosulfonated polyethylene was obtained. In the silane grafter (1), the graft amount of vinyltrimethoxysilane to chlorosulfonated polyethylene measured by ¹ H-NMR method was 1.2% by mass.
・ Silane grafter (2)
100 parts by mass of chlorinated polyethylene [manufactured by Showa Denko KK, “Elaslene 301MA”], 3 parts by mass of allyltrimethoxysilane [manufactured by Toray Dow Corning Silicone, “Z6825”], organic peroxide [manufactured by NOF Corporation, “Park mill D”] 0.5 parts by mass was sufficiently kneaded using a Banbury mixer, and then heated at 150 ° C. for 10 minutes. As a result, a silane graft polymer (2) obtained by grafting allyltrimethoxysilane onto chlorinated polyethylene was obtained. In the silane grafter (2), the graft amount of allyltrimethoxysilane with respect to chlorinated polyethylene measured by ¹ H-NMR method was 1.5% by mass.
・ Silane grafter (3)
100 parts by mass of chlorinated butyl rubber [manufactured by JSR, “JSR CHLOROBUTYL1068”], 5 parts by mass of vinyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBE-1003”], organic peroxide [manufactured by NOF Corporation, Park Mill D "] 0.5 parts by mass was sufficiently kneaded using a Banbury mixer, and then heated at 150 ° C for 10 minutes. As a result, a silane grafter (3) obtained by grafting vinyltriethoxysilane to chlorinated butyl rubber was obtained. In the silane grafter (3), the graft amount of vinyltriethoxysilane to the chlorinated butyl rubber measured by ¹ H-NMR method was 3.6% by mass.
・ Silane grafter (4)
100 parts by mass of epichlorohydrin rubber [Daiso, “Epichromer C”], 8 parts by mass of vinyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBE-1003”], organic peroxide [manufactured by NOF Corporation, “Park mill D”] 1 part by mass was sufficiently kneaded using a Banbury mixer, and then heated at 150 ° C. for 10 minutes. As a result, a silane graft polymer (4) obtained by grafting vinyltriethoxysilane to epichlorohydrin rubber was obtained. In the silane grafter (4), the graft amount of vinyltriethoxysilane with respect to epichlorohydrin rubber measured by ¹ H-NMR method was 4% by mass.
・ Silane grafter (5)
100 parts by mass of chlorosulfonated polyethylene [manufactured by Tosoh Corporation, “TS-320”], 10 parts by mass of vinyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-1003”], and organic peroxide [manufactured by NOF Corporation] “Park Mill D”] was sufficiently kneaded with 2 parts by mass using a Banbury mixer, and then heated at 150 ° C. for 10 minutes. As a result, a silane graft polymer (5) obtained by grafting vinyltrimethoxysilane onto chlorosulfonated polyethylene was obtained. In the silane grafter (5), the graft amount of vinyltrimethoxysilane to chlorosulfonated polyethylene measured by ¹ H-NMR method was 6.2% by mass.
・ Silane grafter (6)
100 parts by mass of chloroprene rubber [manufactured by Denki Kagaku Kogyo, “DCR-30”], 15 parts by mass of allyltrimethoxysilane [manufactured by Toray Dow Corning Silicone, “Z6825”], and organic peroxide [manufactured by NOF Corporation] , “Perhexyl D”] was sufficiently kneaded with a Banbury mixer and then heated at 150 ° C. for 10 minutes. As a result, a silane graft polymer (6) obtained by grafting allyltrimethoxysilane onto chloroprene rubber was obtained. In the silane grafter (6), the graft amount of allyltrimethoxysilane to the chloroprene rubber measured by ¹ H-NMR method was 9% by mass.
・ Silane grafter (7)
100 parts by mass of chloroprene rubber [manufactured by Denki Kagaku Kogyo, “DCR-30”], 1 part by mass of allyltrimethoxysilane [manufactured by Toray Dow Corning Silicone, “Z6825”], and organic peroxide [manufactured by NOF Corporation] , “Perhexyl D”] was sufficiently kneaded with a Banbury mixer and then heated at 150 ° C. for 10 minutes. As a result, a silane grafter (7) obtained by grafting allyltrimethoxysilane onto chloroprene rubber was obtained. In the silane grafter (7), the graft amount of allyltrimethoxysilane to chloroprene rubber measured by ¹ H-NMR method was 0.3% by mass.
・ Silane grafter (8)
100 parts by mass of epichlorohydrin rubber [manufactured by Daiso Corporation, “Epichromer C”], 1.5 parts by mass of vinyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBE-1003”], and organic peroxide [NOF Corporation] [Perhexa V]] 0.2 parts by mass was sufficiently kneaded using a Banbury mixer, and then heated at 150 ° C. for 10 minutes. As a result, a silane graft polymer (8) obtained by grafting vinyltriethoxysilane on epichlorohydrin rubber was obtained. In the silane grafter (8), the graft amount of vinyltriethoxysilane to the epichlorohydrin rubber measured by ¹ H-NMR method was 0.6% by mass.
・ Silane grafter (9)
100 parts by mass of chlorosulfonated polyethylene [manufactured by Tosoh Corporation, “TS-830”], 1.5 parts by mass of vinyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-1003”], organic peroxide [NOF After being sufficiently kneaded with 0.3 parts by mass of “Perbutyl D”] manufactured by the company using a Banbury mixer, it was heated at 150 ° C. for 10 minutes. As a result, a silane grafter (9) obtained by grafting vinyltrimethoxysilane onto chlorosulfonated polyethylene was obtained. In the silane grafter (9), the graft amount of vinyltrimethoxysilane to chlorosulfonated polyethylene measured by ¹ H-NMR method was 0.8% by mass.
Inorganic filler (1) (magnesium oxide) [manufactured by Ube Materials, “UC95S”]
Inorganic filler (2) (magnesium hydroxide) [manufactured by Ube Materials, “UD-653”]
Silanol condensation catalyst (dibutyltin dilaurate)
・ DINP (Diisononyl phthalate)
・ DOP (dioctyl phthalate)

―Production of insulated wire―
A conductor was prepared by twisting 19 more annealed copper strands made of 9 annealed copper wires. The conductor diameter is 5.3 mm, and the conductor cross-sectional area is 15 mm ² .

  Next, after excluding the silanol condensation catalyst, each material was mixed at 200 ° C. using a biaxial kneader so as to have a predetermined blending ratio shown in Tables 1 and 2, and then formed into pellets using a pelletizer. . Next, using an extrusion molding machine, a predetermined amount of silanol condensation catalyst shown in Tables 1 and 2 was mixed with each composition, and each composition was extruded and coated on the outer periphery of the conductor with a thickness of 1.1 mm. . Subsequently, this was placed in a wet heat environment of 60 ° C. × 95% RH for 12 hours to hydrocrosslink the silane grafters to form an insulator composed of the water cross-linked body of the above composition. This produced the insulated wire of samples 1-24.

  Moreover, after mixing each material at 200 degreeC using a biaxial kneader so that it may become the predetermined | prescribed mixture ratio shown in Table 3, each composition was obtained by shape | molding into a pellet form using a pelletizer. . Next, an insulator composed of the above composition was formed by extruding and coating each composition at a thickness of 1.1 mm on the outer periphery of the conductor using an extrusion molding machine. This produced the insulated wire of samples 25-30.

-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.

-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. The heat resistance test was performed on samples 1 to 24.

−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.

  Tables 1 to 3 summarize the evaluation results of the composition (parts by mass) of each composition used for forming the insulator in the insulated wire of each sample, the flexibility, heat resistance, and wear resistance of the insulator. .

  According to Tables 1 to 3, the following can be understood. That is, as shown in Table 3, all of the insulated wires of Samples 25 to 30 are composed of a composition in which an insulator is blended with a low molecular weight plasticizer in a chlorine-containing resin. Among these, the insulated wires of Sample 25 to Sample 29 are blended with a plasticizer at the blending ratio shown in Table 3, but the maximum load in the flexibility test is as large as 39 [N] or more, and the flexibility is poor. You can see that Moreover, in order to improve the flexibility of the insulator, in the insulated wire of Sample 30 in which the amount of the plasticizer was further increased, the blooming of the plasticizer occurred 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 25 to Sample 30 all contain a relatively large amount of low molecular weight plasticizer. Therefore, in the insulated wires of Sample 25 to Sample 30, when the insulated wires are used in bundles, the plasticizer easily moves 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 Samples 1 to 16 are water-crosslinked compositions in which the insulator includes a chlorine-containing resin and a silane grafter obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer. It consists of a body. In other words, the insulated wires of Samples 1 to 16 have the molecular weight larger than that of the low molecular weight plasticizer and the flexible silane grafter, which is a flexible polymer compound, in order to make the insulator flexible. Used. Therefore, the insulated wires of Sample 1 to Sample 16 have a smaller maximum load in the flexibility test and improved flexibility than the insulated wires of Sample 25 to Sample 29. In addition, since the insulated wires of Sample 1 to Sample 16 are not positively mixed with a plasticizer for improving flexibility, there is no blooming of the plasticizer, and the plasticizer to the insulators 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 16, no silane grafter blooming was observed. This is because the free movement of the silane grafter in the insulator is effectively suppressed by the large molecular weight of the silane grafter and the water crosslinking between the silane grafters.

  Next, as shown in Table 2, the insulated wires of Sample 17 to Sample 24 contain a silane grafter in the composition, similarly to the insulated wires of Sample 1 to Sample 16. However, in the insulated wires of Samples 17 to 24, the graft amount of the unsaturated alkoxysilane compound to the chlorine-containing main chain polymer in the silane grafter is less than 1% by mass. Therefore, the insulated wires of Sample 17 to Sample 24 were inferior in heat resistance of the insulator. This is because the silane grafters were not sufficiently cross-linked during the water cross-linking of the composition, and the degree of cross-linking could not be improved.

  Next, the insulated wires of Sample 1 to Sample 16 are compared. In the insulated wires of Sample 1 to Sample 10, the content of the silane grafter in the composition is within the range of 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 10 have excellent wear resistance while ensuring good flexibility and heat resistance. In particular, according to the results of Sample 7, Sample 8, and Sample 10, the type of the main chain polymer in the silane grafter and the adjustment of the graft amount within the range of 1 to 10% by mass are optimally performed. It can be seen that excellent wear resistance can be exhibited while ensuring good flexibility and excellent heat resistance without using a filler.

  In addition, the insulated wires of Samples 11 to 14 have a silane grafter content in the composition of 100 parts by mass or more. Therefore, the insulated wires of Samples 11 to 14 tended to have lower wear resistance than the insulated wires of Samples 1 to 10. On the other hand, in the insulated wires of Sample 15 and Sample 16, an appropriate amount of inorganic filler is blended in the above composition within a range that does not impair flexibility. Therefore, the insulated wires of Sample 15 and Sample 16 were able to ensure excellent wear resistance as compared with the insulated wires of Sample 11 to Sample 14. From this result, even when the content of the silane grafter in the composition is 100 parts by mass or more, by using an appropriate amount of filler, excellent flexibility and excellent heat resistance can be ensured. It can be seen that it is possible to exhibit wear.

  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 (6)

A conductor and an insulator covering the outer periphery of the conductor;
The insulator is
A water-crosslinked product of a composition comprising a chlorine-containing resin and a silane grafter obtained by grafting an unsaturated alkoxysilane compound to a chlorine-containing main chain polymer,
The insulated wire according to claim 1, wherein the amount of the unsaturated alkoxysilane compound grafted onto the chlorine-containing main chain polymer is 1% by mass or more.   2. The chlorine-containing main chain polymer is at least one selected from the group consisting of chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated butyl rubber, epichlorohydrin rubber, and chloroprene rubber. The insulated wire as described in 1.   The insulated wire according to claim 1 or 2, wherein the chlorine-containing resin is a vinyl chloride resin and / or chlorinated polyethylene.   The unsaturated alkoxysilane compound is at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and allyltributoxysilane. The insulated wire according to any one of claims 1 to 3, wherein the insulated wire is provided.   The insulated wire according to any one of claims 1 to 4, wherein the composition contains 1 part by mass to 100 parts by mass of the silane grafter with respect to 100 parts by mass of the chlorine-containing resin.   5. The composition according to claim 1, wherein the composition contains a filler and contains 1 part by mass to 180 parts by mass of the silane grafter with respect to 100 parts by mass of the chlorine-containing resin. The insulated wire of Claim 1.

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