JP2010123461A - Insulated cable, method of manufacturing same, and multilayer cable - Google Patents

Abstract

[PROBLEMS] To suppress the adhesion and blocking of electric wires and to prevent the occurrence of bleed-out and poor appearance during long-term storage while suppressing the adhesion of electric wires that tend to occur when used in a high-temperature atmosphere. Electric wire, method for manufacturing the same, and multilayer electric wire having a jacket on the outer periphery of the insulated wire, the force necessary for removing the jacket of the insulated wire is stable and easy, and poor appearance due to bleed-out A multilayer electric wire that does not have such a problem is provided.
An insulated wire having an insulating layer made of a resin covering a conductor and an outer periphery of the conductor, and a coating layer of an organic solvent swellable layered silicate formed on the surface of the insulating layer, A multilayer electric wire comprising: an insulated wire made of a resin that has been cross-linked by irradiation with ionizing radiation; a method for producing the same; and an insulated wire covering the outer periphery of the insulated wire and the insulated wire.
[Selection figure] None

Description

  The present invention relates to an insulated wire used in an electronic device or an automobile, a manufacturing method thereof, and a multilayered wire in which the insulated wire is covered with a jacket.

  Insulated wires used in electronic devices and automobiles are generally formed by covering the outer periphery of a central conductor with an insulating layer made of resin or the like. Such insulated wires are often shipped in the form of being wound on a reel. However, while the wires are in contact with each other and stored in the reel, the wires may be stuck or blocked. is there. The sticking or blocking of the electric wires may lead to marking peeling of the insulating layer or tearing of the insulating layer, which causes a complaint.

  Therefore, a method for preventing the wires from sticking and blocking is considered. For example, a method of adding an antiblocking agent or a lubricant to the resin constituting the insulating layer is known.

  For such an insulated wire, adhesion and fusion when used in a high temperature atmosphere may be a problem. For example, if the bound insulated wires are left in a high-temperature atmosphere, the wires may adhere to each other, peeling of the coating occurs when the binding is released (insulation layer peeling), and in serious cases, the conductor is exposed. In particular, when heated near the melting point of the insulating layer or above the melting point, the wires are fused, and this problem is remarkable.

  In order to prevent such adhesion and fusion between electric wires, a method of crosslinking the resin by irradiating the insulating coating with ionizing radiation is effective. In this case, oxygen in the air becomes a factor for inhibiting cross-linking. Therefore, a method for removing the release layer after coating a peelable resin on the insulated wire coating layer and irradiating with ionizing radiation has been proposed. (Patent Document 1). According to this method, the cross-linking efficiency of the insulating coating can be improved even by irradiation with ionizing radiation in the air, and adhesion of electric wires in a high-temperature atmosphere can be prevented. Further, there is no need to perform ionizing radiation irradiation in an inert gas atmosphere, and no significant facility modification is required.

  The insulated wire may be used as a multilayered wire (insulated wire having a multilayer coating layer of two or more layers) further provided with a shield layer or other jacket on the outermost periphery. In many cases, such multi-layer electric wires are used only when the outer sheath is removed and the inner insulated wires are used, but when the outer sheath and the inner insulated wires are fixed or fused, the outer sheath is removed. It becomes an obstacle.

Therefore, as a method of preventing adhesion and fusion between the outer sheath and the inner insulated wire, a method of applying silicone oil to the surface of the inner insulated wire (Patent Document 2) or talc powder before the outer sheath is formed. A method of attaching is known.
JP 2006-19147 A JP 2003-7143 A

  However, any of the above-described methods has the following problems, and a solution is desired.

  There is no anti-blocking agent that can be applied to all types of resin, and there is no anti-blocking agent that can be applied to all types of resin by adding an anti-blocking agent or lubricant to the resin that constitutes the insulation coating layer. It is necessary to use properly. In addition, there is a problem that the appearance of the insulated wire is poor, such as an anti-blocking agent bleed out and aggregates are deposited on the surface of the insulated wire, which may cause various complaints.

  Further, in order to suppress the adhesion of the electric wire when used in a high temperature atmosphere, a method in which a resin that can be peeled is further coated on the covering layer of the insulated electric wire and this layer is peeled after the electron beam irradiation ( The method described in Patent Document 1 is not easily performed because it requires extruding and removing the peelable resin layer, and the material loss is large.

  Furthermore, in order to prevent obstacles in the operation of removing the outer sheath of the multilayer electric wire, a certain amount of the method of applying silicone oil to the surface of the insulated wire (the method described in Patent Document 2) and the method of attaching talc powder However, it is difficult to stably reduce the force necessary for removing the outer cover. Further, when silicone oil is used, surface contamination due to bleed-out and short circuit due to generation of cyclic silicone are problematic.

  The present invention provides an insulated wire that prevents the occurrence of sticking and blocking between wires during storage, suppresses adhesion between wires in a high-temperature atmosphere, and does not easily cause bleed-out or poor appearance during long-term storage. The issue is to provide. It is another object of the present invention to provide a manufacturing method capable of easily manufacturing this insulated wire.

  Moreover, this invention makes it a subject to provide the insulated wire by which the adhesion | attachment of the wires in a high temperature atmosphere is suppressed more effectively as the further preferable aspect of the said invention.

  It is another object of the present invention to provide a multilayer electric wire that is stable and easy to remove and has no problems such as bleed out and poor appearance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has uniformly coated the surface of the insulating layer with an organic solvent-swellable layered silicate that swells with an organic solvent, thereby preventing the insulated wires from sticking to each other. I found out that I can do it.

  The invention according to claim 1 has been completed based on such knowledge, and is a conductor, an insulating layer covering the outer periphery thereof, and an organic solvent swellable layered silicate formed on the surface of the insulating layer. An insulated wire characterized by having a coating layer is provided.

  This insulated wire is characterized in that an organic solvent-swelling layered silicate coating layer is formed on the surface of the insulating layer, that is, on the outer periphery of the insulated wire. Therefore, the organic solvent-swelling layered silicate exists between the insulated wires that are in contact with each other, preventing direct contact between the insulating layers and preventing the insulated wires from sticking to each other. In addition, the organic solvent swellable layered silicate is coated on the surface of the insulating layer, but unless the thickness is too large, it does not impair the appearance of the electric wire, so there is no problem of poor appearance and long-term storage. There is no problem of bleeding out.

  Further, the melting point of the organic solvent swellable layered silicate is much higher than the temperature when the insulated wire is used. Although there exists a tendency for electric wires to adhere | attach easily in a high temperature atmosphere, adhesion | attachment of these electric wires is suppressed by interposing a high melting point organic-solvent swelling layered silicate between insulation layers.

  FIG. 1 is a diagram schematically showing a cross-sectional structure of an example of an insulated wire according to claim 1. As is apparent from FIG. 1, the insulated wire has a conductor 1 (conductor wire) disposed in the center, and the outer periphery of the conductor 1 is covered with an insulating layer 2 made of an insulating material (resin). The outer periphery of 2 is coated with an organic solvent swellable layered silicate 3. In the example of FIG. 1, the insulating layer 2 is one layer, but the case where the insulating layer is composed of two or more layers is also included in the insulated wire of the present invention.

  The organic solvent swellable layered silicate is a layered silicate that easily swells with an organic solvent, and in some cases, the layer is separated and dispersed in the organic solvent.

  The invention according to claim 2 is characterized in that the organic solvent-swellable layered silicate has an interlayer cation of a water-swellable layered silicate selected from smectite clay, vermiculite clay, halloysite, swellable mica, and a mixture thereof. 2. A layered silicate obtained by ion exchange with an organic cation selected from quaternary ammonium salts, quaternary phosphonium salts, quaternary sulfonium salts, and mixtures thereof. It is an insulated wire.

The organic solvent swellable layered silicate is usually obtained by treating a water-swellable layered silicate with an organic cation. Here, the water-swellable layered silicate is a layered silicate that easily swells with water, and the main components thereof are silicon, magnesium, and aluminum, and alkali metals and alkaline earth metals such as sodium, potassium, and lithium, It may contain a small amount of other metals. For example, the formula _{(Al 4-y Mg y)} (Si 8) O 20 (OH) ( wherein, X is a metal such as an alkali metal or alkaline earth metal.) 4 _{X z} those represented by Can be mentioned.

  More specifically, examples of the water-swellable layered silicate include smectite clay, vermiculite clay, halloysite, swellable mica, and the like. One of these may be used alone, or two selected from these. The above can be mixed and used. Commercially available products can be used as these water-swellable layered silicates.

  Examples of the smectite clay include natural or synthetic smectites such as montmorillonite (bentonite), beidellite, hectorite, saponite, stevensite, soconite, nontronite. Synthetic smectite can be produced, for example, by the method described in Japanese Examined Patent Publication No. 61-12848 or a similar method.

  As swelling mica, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., which are naturally or chemically synthesized and have Li ions or Na ions between the layers Mention may be made of sexual mica or a mixture thereof. Vermiculite, fluorine vermiculite, and the like can also be used.

  As a method for producing an organic solvent-swellable layered silicate by treating the water-swellable layered silicate with an organic cation, the water-swellable layered silicate is sufficiently peeled, dispersed, or dissolved in water, Alternatively, an organic cation dissolved in alcohol is added in an amount of 0.5 to 2.0 times the cation exchange capacity of the water-swellable layered silicate, and sodium ions adsorbed on the surface of the water-swellable layered silicate and Examples of the method include ion exchange of organic cation ions. The organic cation is adsorbed on the surface of the water-swellable layered silicate by ion exchange, and an organic solvent-swellable layered silicate having a hydrophobic crystal surface is generated.

  Examples of the organic cation used include organic cations composed of quaternary ammonium salts, quaternary phosphonium salts, quaternary sulfonium salts, and mixtures thereof.

  More specifically, quaternary ammonium salts include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, and trimethyl. Alkyltrimethylammonium ions such as dodecylammonium and trimethyloctadecylammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldioctadecylammonium and dimethyldioctadecylammonium, and trialkylmethylammonium such as trioctylmethylammonium and tridodecylmethylammonium Ions, may be mentioned benzethonium ion having two benzene rings.

  Examples of the quaternary phosphonium salt include quaternary phosphonium ions described in paragraph 0035 of JP-A-2006-52136.

  This organic solvent swellable layered silicate is easily swollen by various organic solvents, and in some cases, the layer is peeled and dispersed, so that a dispersion in the organic solvent can be easily produced, and the dispersion is insulated. By coating on the surface of the electric wire and drying, it is possible to uniformly coat the electric wire.

  The thickness of the organic solvent-swelling layered silicate coating layer may be about 0.03 μm to 10 μm. Even with such a thickness, the above-mentioned effect is sufficiently achieved. In addition, in the case where the irradiation cross-linking of ionizing radiation described later is performed after the coating of the organic solvent-swelling layered silicate, if the organic solvent-swelling layered silicate coating layer is thick, the cross-linking may be inhibited by the coating layer. However, if the thickness is within the above range, it cannot be a cause of inhibiting crosslinking.

  The invention according to claim 3 is the insulated wire according to claim 1 or 2, wherein the insulating layer is made of a resin crosslinked by irradiation with ionizing radiation. By providing a coating layer of organic solvent swellable layered silicate, the adhesion between wires due to use in a high temperature atmosphere is also suppressed, but when the atmosphere is at a temperature close to or above the melting point of the insulating layer In some cases, this means alone cannot sufficiently prevent adhesion in a high-temperature atmosphere. Furthermore, when the temperature is higher than the melting point, it is difficult to maintain the shape of the insulating layer itself. In particular, this problem is likely to occur when the melting point of the resin constituting the insulating layer is low.

  In such a case, if the resin constituting the insulating layer is cross-linked by irradiation with ionizing radiation, the adhesion (fusion) between the wires due to use in a high-temperature atmosphere is more effectively suppressed, and the shape of the insulating layer is also maintained. It is preferable because it is possible. That is, the insulated wire of the present invention, which is made of a resin in which the insulating layer is irradiated with ionizing radiation and cross-linked, can more effectively suppress adhesion between wires that is likely to occur in a high-temperature atmosphere.

  Examples of ionizing radiation used for cross-linking include high-energy electromagnetic waves such as gamma rays and X-rays, electron beams, etc., but the curing speed is high (productivity is high), and control and management are easy. And an electron beam is preferred. The electron beam irradiation can be performed using the same apparatus and method as in the case of the known electron beam irradiation performed for resin crosslinking. When the irradiation dose used for crosslinking is too small, crosslinking may be insufficient and the effect of crosslinking may not be sufficiently obtained. On the other hand, when the irradiation dose used for crosslinking is too large, the elongation of the coating is lost and discoloration may occur. Therefore, an optimal dose is selected in consideration of these points.

  The insulated wire of the present invention is formed by coating the conductor with a resin constituting the insulating layer by a known method to form a covered wire (a coated wire having an insulating layer made of a resin covering the conductor and its outer periphery) It can be produced by a method of coating the surface of the insulating layer with an organic solvent swellable layered silicate. The present invention as claimed in claim 4, further comprising the step of coating the surface of the covered electric wire having the manufacturing method, that is, the conductor and the insulating layer covering the outer periphery thereof with an organic solvent swellable layered silicate. An electric wire manufacturing method is also provided.

  The step of coating the surface of the covered electric wire (that is, the surface of the insulating layer) with an organic solvent swellable layered silicate is a dispersion obtained by dispersing an organic solvent swellable layered silicate in an organic solvent (hereinafter referred to as “organic solvent swelling”). This is carried out by passing the coated electric wire through the coated electric wire and attaching the organic solvent-swelling layered silicate dispersion to the surface of the electric wire, and then drying the dispersion. As described above, the organic solvent swellable layered silicate is easily dissolved or dispersed / peeled in the organic solvent. By this method, a uniform layer (thin film) of the organic solvent swellable layered silicate is formed on the insulating layer surface. It can be formed easily. Therefore, the insulated wire of the present invention can be easily manufactured by this manufacturing method.

  The invention according to claim 5 is characterized in that the coating step is performed by applying an organic solvent swellable layered silicate dispersion having a concentration of 10% by weight or less to the surface of the covered electric wire and drying. It is the manufacturing method of the insulated wire of Claim 4.

  The concentration of the organic solvent swellable layered silicate dispersion is preferably 10% by weight or less. When the concentration of the organic solvent swellable layered silicate dispersion exceeds 10% by weight, there may be problems such as poor application uniformity and poor appearance of the electric wire after drying. If the concentration is 10% by weight or less, uniform coating is possible, it is transparent even after drying, and the appearance of the wire is not deteriorated. Moreover, if it is 10 weight% or less, preparation of an organic solvent swelling layered silicate dispersion liquid is also easy. More preferably, the concentration is in the range of 0.1 to 10% by weight. When the concentration is less than 0.1% by weight, it may be difficult to obtain a layer (thin film) having a predetermined thickness.

  As a method of passing the covered electric wire through the organic solvent-swelling layered silicate dispersion liquid and drying the dispersion liquid adhering to the insulating layer surface, the electric wire pass line was filled with the organic solvent swelling layered silicate dispersion liquid. A method of installing a dispersion tank, allowing the coated electric wire to pass through the dispersion tank, and drying the dispersion adhering to the surface of the coated electric wire by natural drying or hot air drying until the reel is wound up. Can do.

  The preferred embodiment according to claim 3, that is, the insulating layer is made of a resin that has been cross-linked by being irradiated with ionizing radiation. The insulated wire according to claim 1 or 2, Furthermore, it can be manufactured by a method of irradiating ionizing radiation to crosslink the resin constituting the insulating layer. The meaning, method, conditions, etc. of the irradiation with ionizing radiation are the same as those described for the invention of claim 3.

Either the organic solvent-swellable layered silicate coating or the irradiation with ionizing radiation may be performed first. That is, after forming an insulating layer made of an insulating material on the conductor and coating the surface of the insulating layer with an organic solvent swellable layered silicate, irradiation with ionizing radiation may be performed,
After forming an insulating layer made of an insulating material on the conductor and irradiating the insulating layer with ionizing radiation, the organic solvent swellable layered silicate may be coated. In any case, the effects of the present invention are achieved.

  When irradiation with ionizing radiation is performed after coating, since the insulating layer is shielded from air, inhibition of crosslinking by oxygen can be prevented. Therefore, it is not necessary to provide facilities for irradiation under an inert gas atmosphere such as nitrogen, and a coating layer that is peeled off and discarded before commercialization as in the technique described in Patent Document 1 is further formed. In addition, there is no need for complicated processes such as peeling and disposal, and the insulated wire of the present invention can be easily and inexpensively manufactured.

  In addition, even when ionizing radiation such as electron beams is applied after coating, the affinity of the resin constituting the insulating layer and the organic solvent-swelling layered silicate is high, so the coating of the organic solvent-swelling layered silicate will peel off and drop off. There is nothing to do.

  A sixth aspect of the invention is a multilayer electric wire comprising the insulated wire according to any one of the first to third aspects and a jacket covering an outer periphery of the insulated wire.

  A multilayer electric wire is an electric wire, a cable, or the like in which a sheath covering an insulating layer is provided on the outer periphery of an insulated wire having a conductor and an insulating layer covering the outer periphery thereof. FIG. 2 is a diagram schematically showing a cross-sectional structure of an example of the multilayer electric wire according to claim 6. 2, 1, 2, and 3 are a conductor, an insulating layer, and an organic solvent-swellable layered silicate, respectively, and this portion is the same as the insulated wire in FIG.

  Two or more insulated wires may be included in the multilayer wire. That is, an electric wire, a cable, or the like in which the outer periphery of a twisted wire obtained by twisting two or more parallel insulated wires or two or more insulated wires with a jacket is also a multilayer electric wire.

  2 in FIG. 2 is a jacket. Examples of the material for the jacket include those generally used as an insulating material. For example, the same resin as described later as the resin constituting the insulating layer covering the conductor can be exemplified as the material of the jacket. The jacket may be composed of two or more layers. When the outer cover has two or more layers, the inner layer of the outer cover may be called an interposition.

  In such a multilayer electric wire, the outer sheath may be removed and only the internal insulated wire may be used for use. However, the outer sheath or the insulated electric wire is removed by pulling one from the other. Is called. In this case, when the insulating layer of the insulated wire and the outer cover are fixed and fused, it is difficult to remove the outer cover, and the workability (customer workability) at the time of use decreases. As is clear from FIG. 2, the multilayer electric wire of the present invention has an organic solvent-swelling layered silicate layer (3 in the figure) between the insulating layer 2 and the jacket 4, so that the insulating layer and Generation | occurrence | production of the adhesion | attachment between a jacket and a fusion | melting is prevented, the force (coating removal force) required for the removal of a jacket falls, and customer processability is improved. In addition, since the organic solvent swellable layered silicate can be uniformly and stably coated as described above, the outer coat removing power is stably reduced, and there is a problem when using conventional talc and silicone. Variations in the outer cover removal force are less likely to occur. That is, the multilayer electric wire of the present invention has an excellent feature that the outer wire removal of the insulated wire is stable and easy. Furthermore, since the multilayered electric wire of the present invention uses the insulated electric wire of the present invention, the insulated electric wire from which the outer sheath has been removed does not have a problem such as an appearance defect due to bleed-out.

  In the example of FIG. 2, the insulating layer 2 and the jacket 4 are each one layer, but both the insulating layer and the jacket may include two or more layers made of different types of materials. In this case, the organic solvent swellable layered silicate layer is provided between the outermost layer of the insulating layer and the innermost layer of the jacket.

  In the example of FIG. 2, the cross-sectional shape is a perfect circle, but the multi-layer electric wire of the present invention may have an elliptical shape, a flat angle, or other irregular shapes. Even if it is not a perfect circle, providing an organic solvent-swelling layered silicate layer between the insulating layer and the outer cover prevents adhesion and fusion between the insulating layer and the outer cover, and is necessary for removing the outer cover. Force (coating removal force) is stably reduced, and customer processability is improved.

  The multilayer electric wire of the present invention is an insulating electric wire having an insulating layer covering the conductor and its outer periphery by the above-described method, and the surface of the insulating layer is coated with an organic solvent swellable layered silicate. It can be easily manufactured by a method of covering the outer circumference of the insulated wire with a known method.

  The insulated wire of the present invention occurs when the wires are used in contact with each other in a reel or the like, which may occur when the wires are fixed, blocked, or bundled together in a high temperature atmosphere. Adhesion between easy electric wires is suppressed, and bleeding out and poor appearance during long-term storage are less likely to occur. These insulated wires can be easily manufactured by the method of the present invention.

  Next, a mode for carrying out the present invention, particularly the best mode will be described. However, the scope of the present invention is not limited to only this mode, and various modifications can be made without departing from the spirit of the present invention. It is possible to add.

  The material and form of the conductor constituting the insulated wire of the present invention are not particularly limited. It may be a single wire or a stranded wire. The cross-sectional shape may be a perfect circle or another shape. The thickness is not limited. Any material may be used as long as it is used for ordinary electric wires.

  The kind of the resin constituting the insulating layer covering the conductor is not particularly limited as long as it has insulating properties and can be extruded to cover the conductor. For example, polyethylene, polypropylene, ethylene binary and ternary copolymers, graft polymers of these polymers, thermoplastic elastomers, plant-derived resins, biodegradable resins, engineering plastics also have insulating layers. It can be used as a constituent resin. What blended two or more types of resin can also be used. As long as extrusion for forming the coating layer is possible, a flame retardant, a colorant, a crosslinking aid, an antioxidant, a metal deactivator, and the like may be added to the resin as necessary.

  Next, the manufacturing apparatus 11 for manufacturing suitably the insulated wire 10 of this invention is demonstrated based on FIG. As shown in FIG. 3, the production apparatus 11 includes a coating apparatus 12, a cooling water tank 13, an anti-sticking agent dispersion liquid tank 14 (a tank filled with an organic solvent swellable layered silicate, that is, an anti-sticking agent dispersion liquid), A dryer zone 15 and an electron beam irradiation device 16 are provided.

  The coating device 12 is provided with an extruder zone 23. The conductor 1 is wound around and stored in the unwinding portion 21, but is fed out from the unwinding portion 21 in the direction of the arrow in the drawing and passes through the extruder zone 23. By the extruder provided in the extruder zone 23, the resin constituting the insulating layer 2 is extruded onto the surface of the conductor 1, and the conductor 1 is covered with the resin to form the covered electric wire 5. As the extruder provided in the extruder zone 23, a known extruder such as a single screw extruder can be used.

  The covered electric wire 5 exiting the covering device 12 is cooled by passing through the cooling water tank 13, and the resin of the insulating layer is solidified. After that, the covered electric wire 5 passes through the anti-adhesive agent dispersion tank 14, and the adhering / fusing inhibitor dispersion liquid adheres to the outer periphery thereof. The time passing through the anti-sticking agent dispersion tank 14 may be as short as several seconds. Since it is not necessary to make the time passing through the anti-adhesion agent dispersion tank 14 long, the capacity of the anti-adhesion agent dispersion tank 14 can be reduced. The capacity of the anti-sticking agent dispersion tank 14 is appropriately selected in consideration of the drawing linear speed and the winding linear speed. Moreover, it is also possible to apply the anti-sticking agent dispersion liquid to the covered electric wire 5 by spraying, and the part of the anti-sticking agent dispersion liquid tank 14 can be used as a spray application tank.

  The anti-sticking agent dispersion tank 14 is filled with an organic solvent swellable layered silicate dispersion, and this dispersion is added with an organic solvent swellable layered silicate in an ordinary organic solvent and dispersed by stirring. Just adjust it. In order to further facilitate dispersion of the organic solvent swellable layered silicate into the organic solvent, ultrasonic waves or the like may be used, or a resin that is soluble in the organic solvent, for example, amorphous such as PMMA, polyester, or polyamide. A resin may be added to the dispersion. The addition of these improves the flexibility of the organic solvent-swellable layered silicate coating layer produced on the insulated wire and improves the adhesion to the insulating layer, which is preferable from the viewpoint of preventing peeling.

  Preferred organic solvents used to make organic solvent swellable layered silicate dispersions include xylene, benzene, hexane, heptane, styrene, ethyl acetate, MEK, acetone, toluene, methanol, ethanol, 2-propanol, Examples include ethylene glycol and DMF. Furthermore, dichloromethane, chloroform, tetrachloroethylene, and trichloroethylene can also be used when the use of halogen does not matter.

  The covered electric wire 5 having the adhesion / anti-fusing agent dispersion liquid adhered to the outer periphery thereof is sent to the dryer zone 15 and dried to form the insulated electric wire 10 of the present invention. Examples of the drying method include a method in which a drying furnace provided in the dryer zone 15 is set to about 50 to 80 ° C. and the electric wire is passed through in about 1 to 3 minutes. A method in which dryer hot air is applied to an electric wire passing through the dryer zone 15 for several tens of seconds may be used. Alternatively, even with natural drying, that is, a method in which the air-cooled section is passed through for several tens of seconds, it is possible to obtain adhesion that does not cause the organic solvent-swelling layered silicate coating layer to peel off or fall off from the insulating layer.

  The insulated wire 10 exiting the dryer zone 15 is sent to the electron beam irradiation device 16 where it is irradiated with the electron beam and the resin constituting the insulating layer is cross-linked. In the example of FIG. 3, the electron beam irradiation apparatus 16 is provided after the dryer zone 15, and bridge | crosslinking is performed after the coating of the organic solvent swelling layered silicate. However, it is also possible to employ a method in which the electron beam irradiation device 16 is provided in front of the anti-adhesion agent dispersion tank 14 and the organic solvent swellable layered silicate is coated after crosslinking. As the electron beam irradiation apparatus 16, the thing similar to the well-known electron beam irradiation apparatus used for bridge | crosslinking of the coating layer of an electric wire can be used.

  In addition, according to the manufacturing apparatus shown in FIG. 3, although each process of coating | covering an insulating layer, coating of an organic solvent swelling layered silicate, drying, and electron beam irradiation is performed continuously, each said process is performed. It is also possible to divide and perform. For example, after the coating of the insulating layer, the coating of the organic solvent swellable layered silicate, and the drying step, the electric wire may be temporarily wound, and the wound electric wire may be irradiated later with an electron beam.

  A reel 17 is installed behind the electron beam irradiation device 16, and the manufactured insulated wire is wound around the reel 17.

  Next, examples for more specifically explaining the present invention will be shown, but the examples do not limit the scope of the present invention.

Production Example 1 Production of Resin Composition for Forming Insulating Layer 100 parts by weight of ethylene-vinyl acetate copolymer, 100 parts by weight of magnesium hydroxide, antioxidant (pentaerythritol-tetrakis [3- (3,5-di-t- 1 part by weight of butyl-4-hydroxyphenyl) propionate], 3 parts by weight of a crosslinking aid (triethylene glycol dimethacrylate), twin-screw mixer (30 mmφ, L / D = 30, barrel temperature 140 ° C., screw rotation speed 100 rpm The resin composition for forming an insulating layer was obtained by using a strand cut pelletizer, and pellets of the resin composition for forming an insulating layer were prepared.

Production Examples 2 to 4 Production of Adhesion / Fixing Inhibitor Dispersion Solution The following adhesion / fusing inhibitor was dispersed in xylene to obtain the concentrations shown in Table 1 to obtain an adhesion / antifusion agent dispersion. . The dispersibility of these sticking / fusing inhibitors was visually observed, and the results are shown in Table 1 based on the following criteria.

[Standard of Dispersibility of Organic Solvent Swelling Layered Silicate Dispersion]
Good: No powder floating on the liquid surface or inside without being dispersed in an organic solvent.
Poor (NG): The state in which the agglomerated powder is not dispersed in the organic solvent and floats on the liquid surface or inside.

[Fixing / Fusing Agent]
Organic solvent swellable layered silicate A:
Fine powder type bentonite product (main component montmorillonite, interlayer distance about 1 nm. The viscosity of 7 wt% aqueous dispersion is about 2500 cps, and the cations between layers are exchanged by dimethyl distearyl ammonium. Loss on ignition at 800 ° C. 39%).
-Layered silicate B:
Talc mainly composed of magnesium silicate (particle diameter (D50) of laser diffraction method = 8.0 μm).

  As shown in Table 1, the layered silicate B had poor dispersibility (NG) even at a concentration of 1% by weight. On the other hand, the organic solvent swellable layered silicate A had good dispersibility even at a concentration of 5% by weight.

Example 1
Production example using a single-screw melt extruder (45 mmφ, L / D = 24) on the outer periphery of 50 twisted wires (diameter 3.8 mmφ) of 0.127 mmφ unplated copper wire The resin composition for forming an insulating layer obtained in 1 was extruded to produce a covered electric wire. After the coated electric wire extruded from the single-screw melt extruder is cooled by passing through a cooling water tank installed immediately after the extrusion part of the single-screw melt extruder, an anti-sticking agent dispersion liquid tank installed at the rear thereof, That is, it was passed through a tank (length: 50 cm) filled with the fixing / anti-fusing agent dispersion (1 wt% xylene dispersion of organic solvent swellable layered silicate A) produced in Production Example 2 for 2 seconds, and the organic solvent A coated electric wire having a swellable layered silicate xylene dispersion adhered to the outer surface was obtained.

  Thereafter, the insulated wire is passed through the dryer installation zone for 5 seconds, and the attached xylene dispersion is dried, whereby an insulated wire (referred to as insulated wire 1) coated with the organic solvent swellable layered silicate is obtained. This was obtained and wound on a reel. The thickness of the insulation coating was 0.75 mm, and the outer diameter of the insulated wire 1 was 5.3 mm (the same applies to Examples 2 to 4 below).

Example 2
An insulated wire coated with an organic solvent swellable layered silicate was produced under the same conditions as in Example 1. Thereafter, the produced insulated wire was irradiated with an accelerating electron beam having an acceleration voltage of 2000 kv in an air atmosphere and subjected to a crosslinking treatment, and then this insulated wire (referred to as insulated wire 2) was wound on a reel.

Example 3
Under the same conditions as in Example 1, the outer periphery of the stranded wire was coated with a resin composition for forming an insulating layer. The prepared coated electric wire was irradiated with an accelerating electron beam having an accelerating voltage of 2000 kv in an air atmosphere to perform a crosslinking treatment. Thereafter, the coated electric wire was passed through the dispersion tank filled with the fixing / fusing inhibitor dispersion (1 wt% xylene dispersion of organic solvent swellable layered silicate A) prepared in Production Example 2 for 2 seconds, Furthermore, drying was performed under the same conditions as in Example 1 to produce an insulated wire (insulated wire 3) coated with an organic solvent swellable layered silicate, and this was wound on a reel.

Example 4
Under the same conditions as in Example 1, the outer periphery of the stranded wire was coated with a resin composition for forming an insulating layer. The prepared coated electric wire was irradiated with an accelerating electron beam having an accelerating voltage of 2000 kv in an air atmosphere to perform a crosslinking treatment. After that, a suction type spray gun SSG that sprays the coated wire in 2 seconds and sprays the anti-adhesion / fusion preventing agent dispersion (1 wt% xylene dispersion of organic solvent swellable layered silicate A) produced in Production Example 2. It passed through the spray spray tank which installed 2-13 (made by Trusco Nakayama Co., Ltd.). Further, drying was performed under the same conditions as in Example 1 to produce an insulated wire (insulated wire 4) coated with an organic solvent swellable layered silicate, and this was wound on a reel.

Example 5
Instead of the fixing / fusing inhibitor dispersion prepared in Production Example 2, the fixing / fusing inhibitor dispersion (5% by weight xylene dispersion of organic solvent-swelling layered silicate A) prepared in Production Example 3 was used. An insulated wire (insulated wire 5) was prepared under the same conditions as in Example 3 except that it was used, and this was wound on a reel.

Comparative Example 1
An insulated wire (referred to as insulated wire 6) was prepared under the same conditions as in Example 2 except that the step of passing the dispersion tank filled with the fixing / fusing inhibitor dispersion was not performed, and this was wound on a reel. It was.

Comparative Example 2
Instead of the fixing / fusing inhibitor dispersion prepared in Production Example 2, the fixing / fusion preventing dispersion (1 wt% xylene dispersion of layered silicate B) prepared in Production Example 4 was used. An insulated wire (referred to as insulated wire 7) was produced under the same conditions as in Example 3 except that this was wound on a reel.

Comparative Example 3
Insulation under the same conditions as in Production Example 1 except that the resin composition for forming an insulating layer obtained by adding 1 part by weight of oleic acid amide (anti-blocking agent) at the stage of melt-kneading the resin composition was used. A resin composition for layer formation was obtained. Instead of using the resin composition for forming an insulating layer instead of the resin composition for forming an insulating layer obtained in Production Example 1, and not using the fixing / fusing inhibitor dispersion liquid, An insulated wire (referred to as insulated wire 8) was produced under the same conditions as in Example 1, and this was wound on a reel.

[Evaluation of insulated wires]
The following evaluation was performed about each of the insulated wire obtained in Examples 1-5 and Comparative Examples 1-3. The results are shown in Table 2.

(appearance)
The external appearance of the insulated wires 1-8 was confirmed. Compared with the insulated wire (Comparative Example 1) to which the fixing / fusing inhibitor was not applied, the one in which the aggregates could be visually confirmed was defined as NG, and the one in which the visual difference could not be distinguished was defined as good.

(Fixation)
After the insulated wires 1 to 8 wound on the reel were stored in a room at a temperature of 40 ° C. and a humidity of 50% for 1 day, the presence / absence of adhesion between the wires was confirmed. The case where the insulation wire was stuck with the lower insulation wire due to its own weight was defined as NG, and the case where there was no retention was determined as good.

(Fusion)
From each of the insulated wires 1 to 8, three wires having a length of 20 cm were cut out, and the three wires were bound at a position of 1 cm end using a binding band (made of 66 polyamide). After binding, it was left in a constant temperature bath at 150 ° C. for 1 hour. After leaving, it was taken out from the thermostat and cooled, and then the binding band was released, the wires were peeled off, and the presence or absence of fusion was confirmed. When the electric wire was peeled off, the insulation was whitened, broken, or torn, and it was assumed that it was fused, and was determined as NG. When the electric wire was peeled off, it could be easily peeled off, and the insulation was not whitened, broken or broken.

(Long-term storage: presence or absence of bleed)
After the insulated wires 1 to 8 were stored for one month, the presence or absence of white powder (bleed) on the surface of the wires was observed.

  Examples 1 to 4 are insulated electric wires coated with a xylene (organic solvent) dispersion of a layered silicate that easily swells with an organic solvent as an anti-adhesion / fusing agent, and agglomerates after drying are observed. The appearance was good, no sticking after winding was observed, and no bleed-out after long-term storage was observed. By comparison with this result and the result of the comparative example described later, the coating of the organic solvent swellable layered silicate on the outer periphery of the insulated wire can prevent sticking during winding and storage, and has a good appearance and bleed out. It is clear that neither occurs.

  In Example 2, electron beam irradiation was performed after coating the organic solvent swellable layered silicate, and in Example 3, the organic solvent swellable layered silicate was coated after the electron beam irradiation. It is a thing. Further, in Example 4, the coating of the organic solvent swellable layered silicate was carried out by spray coating instead of being immersed in the anti-sticking agent dispersion liquid tank. Even when stored in a bundled state in a high temperature (150 ° C.) atmosphere, no fusion of the insulated wires was observed. This result shows that it is possible to effectively suppress fusion of insulated wires in a bundled state in a high-temperature atmosphere by electron beam irradiation, and this effect is achieved by applying electron beam irradiation to an organic solvent swellable layered silicate. It is shown that it can be obtained in any case before or after. Further, as described above, appearance, adhesion, and bleed-out are not affected by electron beam irradiation.

  Example 5 is a case where a high concentration (5% by weight) is used as the xylene dispersion of the organic solvent swellable layered silicate, but a case where a low concentration (1% by weight) is used (implementation) The same effects (appearance, adhesion, bleed out, fusion) as in Example 3 etc. are obtained. From this result, it is shown that even if the concentration of the organic solvent swellable layered silicate organic solvent dispersion is increased, the effect (good appearance, etc.) of the present invention is not impaired if it is about 10% by weight or less. Yes.

  Comparative Example 1 is a case where no sticking / fusing prevention agent was used, but sticking occurred at the time of winding the reel, and even when the electron beam irradiation treatment was performed, in a high temperature (150 ° C.) atmosphere. Fusion was caused by binding.

  Comparative Example 2 is a case where a layered silicate that is difficult to disperse with an organic solvent is used as an adhesion / fusion prevention agent. However, since the adhesion / fusion prevention agent is not dispersed in an organic solvent, the surface is white. Aggregates adhered and the appearance was poor. Also, fusion occurred due to binding in a high temperature (150 ° C.) atmosphere.

  Comparative Example 3 is an example in which an insulated wire was prepared by adding oleic acid amide as an antiblocking agent when the insulating layer forming resin composition was prepared by melt kneading. Although the fixation at the time of winding the reel was improved, fusion occurred due to binding in a high temperature (150 ° C.) atmosphere. In addition, bleed-out occurred due to long-term storage, and white aggregates were observed on the insulated wire surface.

(Multi-layer wire (double-layer wire))
Example 6
Under the same conditions as in Example 3, the outer periphery of the base wire was coated with the insulating layer forming resin composition obtained in Production Example 1, and an accelerated electron beam with an acceleration voltage of 2000 kv was applied in an air atmosphere to the coated electric wire. Irradiated to give a crosslinking treatment. Thereafter, the covered electric wire was passed through the tank filled with the fixing / fusing inhibitor dispersion (1% by weight xylene dispersion of organic solvent-swelling layered silicate A) prepared in Production Example 2 in 2 seconds, and further Examples 3 was dried to obtain an insulated wire (outer diameter 5.3 mmφ) coated with the organic solvent swellable layered silicate A.

  A 60 mmφ single screw extruder (cylinder temperature average: about 150 ° C.) was used on the outer periphery of the insulated wire thus obtained, and an ethylene-vinyl acetate copolymer as a jacket material was 0.5 mm thick. Extrusion was performed so that the outer diameter was 6.3 mmφ, and a two-layer electric wire for evaluation was obtained.

Comparative Example 4
A two-layer electric wire for evaluation was obtained in the same manner as in Example 6 except that the step of passing the coated electric wire through a dispersion tank filled with the fixing / fusing inhibitor dispersion was not performed.

Comparative Example 5
Instead of passing the coated wire through a dispersion tank filled with the anti-adhesion and anti-fusing agent dispersion, the talc is spread on a plate that is vibrated so that the talc is easily attached to the wire. A two-layer electric wire for evaluation was obtained in the same manner as in Example 6 except that the step of attaching talc to the electric wire through the covered electric wire so as to touch the talc was performed.

[Evaluation of double-layer wire]
For each of the two-layer electric wires obtained in Example 6 and Comparative Examples 4 to 5, the jacket removal force was measured by the following method. The results are shown in Table 3. Table 3 also shows the evaluation results of the appearance of the insulated wires before the formation of the jacket (results evaluated by the same method and criteria as the above [Evaluation of insulated wires]).

(Coating removal force)
A two-layer electric wire for evaluation was cut to a length of 15 cm, and a 4 cm jacket was removed from each end to prepare a measurement sample. The portion of the insulated wire from which the jacket was removed was passed through a hole having the same size as the insulated wire, and the two-layered wire was fixed to a jig. Using a tensile tester (manufactured by Shimadzu Corporation: Autograph AGI), the insulated wire inside was pulled and pulled out from the jacket, and the pulling force was measured. The pulling force was defined as the jacket removing force. Three measurements were performed and the values are listed in Table 3.

  Example 6 is a two-layer electric wire produced by coating an insulated electric wire with an organic solvent-swelling layered silicate A (adhesion / fusing inhibitor) that easily swells with an organic solvent, and extruding the outer periphery thereof. is there. The jacket removal force is low and stable. This is presumably because the sticking / fusion preventing agent is evenly applied to the surface of the insulated wire and no sticking / fusion occurs.

  Comparative Example 4 was a case where no fixing / fusing inhibitor was used, and in this case, the outer cover removal force was too high, and it was difficult to remove the outer cover. This is probably because the adhesion between the jacket and the insulating layer of the insulated wire is too strong.

  Comparative Example 5 is a two-layer electric wire produced by applying talc powder to an insulated electric wire instead of coating an organic solvent-swellable layered silicate. From the results of Table 3, it is shown that, by coating with talc powder, the jacket removing power is reduced, but the jacket removing power is not stable, and varies, such as being too high or too low. It is considered that it is difficult to uniformly attach the talc powder to the surface of the insulated wire.

It is sectional drawing which shows the structure of the insulated wire of this invention typically. It is sectional drawing which shows the structure of the multilayer electric wire of this invention typically. It is a schematic diagram which shows typically an example of the manufacturing apparatus of the insulated wire of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, Conductor 2, Insulating layer 3, Organic solvent swelling layered silicate 4, Jacket | cover 5, Covered electric wire 10, Insulated electric wire 11, Manufacturing apparatus 12 for manufacturing an insulated electric wire, Coating apparatus 13, Cooling water tank 14, Adherence Inhibitor dispersion tank 15, dryer zone 16, electron beam irradiation device 17, reel 21, unwinding section 23, extruder zone

Claims (6)

  An insulated wire comprising a conductor, an insulating layer covering the outer periphery thereof, and a coating layer of an organic solvent-swelling layered silicate formed on the surface of the insulating layer.   The organic solvent swellable layered silicate is an interlayer cation of a water-swellable layered silicate selected from smectite clay, vermiculite clay, halloysite, swellable mica, and a mixture thereof. The insulated wire according to claim 1, which is a layered silicate obtained by ion exchange with an organic cation selected from a quaternary phosphonium salt, a quaternary sulfonium salt, and a mixture thereof.   The insulated wire according to claim 1 or 2, wherein the insulating layer is made of a resin crosslinked by irradiation with ionizing radiation.   The manufacturing method of the insulated wire characterized by having the process of coating the surface of the covered electric wire which has an insulating layer which coat | covers a conductor and its outer periphery with an organic solvent swelling layered silicate.   The coating step is a step of applying a dispersion liquid in which an organic solvent-swelling layered silicate having a concentration of 10% by weight or less is dispersed in an organic solvent to the surface of the covered electric wire and then drying. The manufacturing method of the insulated wire of Claim 4.   A multilayer electric wire comprising the insulated wire according to any one of claims 1 to 3 and a jacket for further covering the organic solvent-swellable layered silicate coating layer.

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