JP5313505B2 - Electric wire and electric wire manufacturing method - Google Patents

Abstract

An electrical wire and a method of making an electrical wire are disclosed. The electrical wire comprises a conductor and a covering. The covering comprises a thermoplastic composition comprising a poly(arylene ether), a polyolefin and a polymeric compatibilizer. The thermoplastic composition may further comprise a flame retardant.

Description

  The present invention relates to an electric wire and an electric wire manufacturing method.

  Electric wires have been used for a wide variety of applications. In many applications, the core is surrounded by a thermoplastic coating for electrical insulation. Many of the requirements for insulating thermoplastic coatings vary depending on how and where the wires are used, but for most applications (especially high voltage applications such as under-hood applications in automobiles), insulating thermoplastic coatings It is required not to show a spark leak. Spark leaks are caused by defects (eg, pinholes) in the insulation coating that surrounds the wire. When manufacturing electric wires for automotive applications, the electric wires are tested for spark leaks, and if a spark leak is found, the wire is cut and the section containing the spark leak is discarded. If there is a spark leak during production, the continuity of the wire is interrupted and the productivity is reduced. The wires are cut to remove the section containing the spark leak, resulting in multiple lengths of wires. Typically, these lengths are summed to form an overall length that is packaged and sold.

  Wires are typically sold in the form of spools or containers that include the total wire length determined in part by the cross-sectional area of the core. The electric wire is taken out from the spool or container and used in various articles such as an automobile wiring harness. For example, for wires having a cross-sectional area of 0.14-1.00 square millimeters, the total length of wires on the spool can be 13500-15500 meters and the number of individual wires on the spool can be 1-6. . In this case, the minimum length of each electric wire is 150 meters. Spools or containers containing a greater number of individual wires or shorter lengths often result in low productivity and high yield loss when manufacturing articles from the wires.

  Conventionally, an automobile electric wire disposed under a hood in an engine room is insulated by a single heat-resistant insulating material layer disposed over an uncoated copper core wire. Thermoplastic polyesters, cross-linked polyethylene and halogenated resins (eg, fluoropolymers and polyvinyl chloride) have long been required for heat-resistant insulation, chemical resistance, and flame resistance in such harsh environments. And has met the need for flexibility.

  Thermoplastic polyester insulation layers with outstanding resistance to gases and oils are mechanically tough and resistant to copper-catalyzed degradation, but break early due to hydrolysis There is. Insulating layers in thermoplastic polyester insulated wires have also been found to crack when exposed to hot salt water and to break when exposed to wet temperature cycles.

  Due to the negative impact on the environment, there is a growing demand to reduce or eliminate the use of halogenated resins in the insulating layer. In fact, many countries are beginning to mandate a reduction in the use of halogenated materials. However, since many of the wire coating extruders are made based on the specifications of halogenated resins such as polyvinyl chloride, any alternative material must be able to be handled in the same way as polyvinyl chloride.

  Although cross-linked polyethylene has been very successful in providing heat resistant insulation, this success can be difficult to maintain as the requirements for automotive wires evolve. The amount of wiring in an automobile is increasing exponentially as more and more electronic devices are being used in modern vehicles. Due to the dramatic increase in wiring, automobile manufacturers are trying to reduce the overall wire diameter by defining a reduced insulation layer thickness and a smaller core size. For example, ISO 6722 specifies that for core wires having a cross-sectional area of 2.5 square millimeters, the thickness of the thin insulation material is 0.35 millimeters and the thickness of the ultra-thin insulation material is 0.25 millimeters. doing.

  The reduction in insulation wall thickness presents difficulties when using cross-linked polyethylene. For cross-linked polyethylene, the thin insulating layer thickness provides a short thermal life when aged at 150-180 ° C. oven temperature. This limits its thermal rating. For example, an electric wire having an adjacent cross-linked polyethylene insulating layer with a thickness of 0.75 mm along with a copper core wire is flexible, and the insulating layer does not crack even if it is bent around a mandrel after being exposed to 150 ° C. for 3000 hours. . However, similar wires with a cross-linked polyethylene insulation layer having a wall thickness of 0.25 millimeters become brittle after exposure to 150 ° C. for 3000 hours. The deleterious effects created by these extremely thin wall thickness requirements are attributed to copper catalyzed degradation, which is widely recognized as a problem in the industry.

Accordingly, there is a need for an electric wire that is suitable for use in an automotive environment and that does not contain a halogenated resin, and a method for manufacturing such an electric wire.
International Publication No. 2003/025064 International Publication No. 2000/015680 International Publication No. 2001/092410 Specification International Publication No. 97/01600 Specification International Publication No. 89/00756 Specification European Patent No. 0467113 European Patent No. 0413972 European Patent No. 0379286 European Patent No. 0369814 European Patent No. 0329423 EP 0639620 Specification US Patent Application Publication No. 2002/035206 US Patent Application Publication No. 2003/181484 US Patent Application Publication No. 2004/0016503 U.S. Pat. No. 2,933,480 US Pat. No. 3,093,621 U.S. Pat. No. 3,211,709 US Pat. No. 3,646,168 US Pat. No. 3,790,519 U.S. Pat. No. 3,884,993 US Pat. No. 3,894,999 U.S. Pat. No. 4,059,654 U.S. Pat. No. 4,166,055 U.S. Pat. No. 4,239,673 U.S. Pat. No. 4,383,082 US Pat. No. 4,584,334 U.S. Pat. No. 4,760,118 US Pat. No. 4,990,558 US Pat. No. 5,166,264 US Pat. No. 5,258,455 US Pat. No. 5,262,480 US Pat. No. 5,294,655 US Pat. No. 5,364,898 US Pat. No. 5,398,822 US Pat. No. 5,455,292 US Pat. No. 6,306,978 US Pat. No. 6,610,422 US Pat. No. 5,612,624 US Pat. No. 5,132,629 US Pat. No. 6,184,691 US Pat. No. 5,302,904 US Pat. No. 5,416,419 US Pat. No. 6,646,205 US Pat. No. 6,627,701 US Pat. No. 6,495,630 JP 09-241446 A JP 09-048883 A Japanese Patent Laid-Open No. 07-166026 Japanese Patent Laid-Open No. 06-057130 JP 2003-261760 A JP-A-11-209534 Japanese Patent Laid-Open No. 11-185532 JP 07-224193 A JP-A-06-009828 Japanese Patent Laid-Open No. 02-133462 Japanese Patent Laid-Open No. 03-220231 Japanese Patent Laid-Open No. 03-267146 Japanese Patent Laid-Open No. 03-418209 Japanese Patent Laid-Open No. 03-447042 JP 2003-253066 A Japanese Patent Laid-Open No. 03-226792 JP 09-048883 A Carroll, David “How to choose the best tester for your application: AC vs. DC” Clinton Instrument Company, 2 pages. “High Voltage Pinhole Detection Technology”, Clinton Instrument Company, 2 pages. Clinton, Henry “Grounding of conductors theuring test,” Clinton Instrument Company, 2 pages. “Digital High Frequency Sine Wave Spark Tester”, Clinton Instrument Company, 2 pages. “Seven Steps to a Good Spark Test”, Spark Test News, January 2002, Clinton Instrument Company, 2 pages.

The above-mentioned needs are electric wires comprising a core wire and a coating disposed over the core wire,
The coating is (i) poly (arylene ether);
(Ii) a polyolefin, and (iii) a thermoplastic resin composition containing a polymer compatibilizer,
The core has a cross-sectional area of 0.15-1.00 square millimeters, and the coating has a thickness of 0.15-0.25 millimeters;
Furthermore, about 13500-15500 meters of electric wires, there are electric wires with an individual length of 6 or less, and each electric wire with an individual length is filled with an electric wire having a length of 150 meters or more. The thermoplastic resin composition may further contain a flame retardant.

In another embodiment, a core wire;
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
A sheath is placed over the core,
A sheath is placed over the core,
Furthermore, an electric wire having a spark leak of 5 or less for an electric wire of 2500 to 15500 meters is provided.

In another embodiment, a method of manufacturing an electric wire comprising:
Melt mixing poly (arylene ether), polyolefin and polymer compatibilizer to form a first mixture;
Melt filtering the first mixture through a first filter having a pore size of 20-150 micrometers to form a first filtered mixture;
Melt filtering the first filtration mixture through a second filter having a pore size of 20 to 150 micrometers to form a second filtration mixture, and applying the second filtration mixture to the core wire A method is provided.

In another embodiment, a method of manufacturing an electric wire comprising:
A step of melt-filtering a composition comprising poly (arylene ether), a polyolefin and a polymer compatibilizer to form a filtration composition, and a step of applying the filtration composition to a core wire to form an electric wire, Has a step of having a spark leak of 3 or less for a 2500 to 15500 meter wire.

In another embodiment, a coating comprising a thermoplastic resin composition comprising:
The thermoplastic resin composition is (i) poly (arylene ether);
(Ii) a polyolefin, and (iii) a polymer compatibilizer,
Further, a coating having a spark leak of 5 or less is provided for an electric wire having 2500 to 15500 meters of the electric wire including the coating disposed over the core wire. The thermoplastic resin composition may further contain a flame retardant.

In another embodiment, a coating comprising a thermoplastic resin composition comprising:
The thermoplastic resin composition is (i) poly (arylene ether);
(Ii) a polyolefin, and (iii) a polymer compatibilizer,
A coating is provided in which the thermoplastic resin composition is substantially free of visible particulate impurities. The thermoplastic resin composition may further contain a flame retardant.

In another embodiment,
There is provided a coating comprising a thermoplastic resin composition produced by a process comprising melt mixing poly (arylene ether), polyolefin and polymer compatibilizer to form a mixture, and melt filtering the mixture through a filter. The

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of a cross section of an electric wire.

  2 and 3 are perspective views of an electric wire having a plurality of layers.

  A number of terms are used throughout the specification and claims, which are defined to have the following meanings:

  Even in the singular form, it includes plural cases unless it is clear from the context.

  The term “optional” or “optionally” means that the event or situation described following the term may or may not occur, and such description may or may not occur. Includes no case.

  All range endpoints describing the same property are independently combinable and include the endpoints described. Values indicated as "greater than ..." or "less than ..." include the stated endpoints. For example, “greater than 3.5” includes a value of 3.5.

  ISO 6722 referred to herein is the December 15, 2002 version of this standard.

  Poly (arylene ether) / polyolefin blends are not well selected as polymer coatings for electrical wires for several reasons. These types of compositions have been used extensively in applications that require rigidity, but are generally considered unsuitable for applications that require flexibility (eg, electrical wires). In addition, poly (arylene ether) / polyolefin blends as described herein include poly (arylene ether) dispersed in a polyolefin matrix. Given the known problems of metal catalyzed degradation in polyolefins, it is unlikely that a composition having a polyolefin matrix could be used successfully in an environment where metal catalyzed degradation can occur. It seems to be. Furthermore, poly (arylene ether) has a tendency to form microparticles and gels when exposed to temperatures above its glass transition temperature (Tg), which can cause defects in the polymer coating that create spark leaks. Increase sex.

  A method for producing coated cores (eg, electrical wires) with little or no spark leak is typically used in a melt blending device, such as a compounding extruder or Banbury mixer, to form a thermoplastic coating. Including melt mixing (compounding) the components of the product. In one embodiment, the poly (arylene ether), the polymer compatibilizer and the polyolefin are melt mixed at the same time. In another embodiment, the first molten mixture is formed by melt mixing poly (arylene ether), a polymer compatibilizer, and optionally a portion of the polyolefin. The polyolefin or the remainder of the polyolefin is then further melt mixed with the first melt mixture to form a second melt mixture. Alternatively, a portion of the poly (arylene ether) and polymer compatibilizer is melt mixed to form a first melt mixture, and then the remainder of the polyolefin and polymer compatibilizer is further melt mixed with the first melt mixture. Thus, a second molten mixture can be formed.

  The melt mixing method described above can be performed without isolating the first melt mixture, or can be performed by isolating the first melt mixture. In these methods, one or more melt mixing devices including one or more melt mixing devices can be used. In one embodiment, some of the components of the thermoplastic resin composition that forms the coating can be introduced and melt mixed into the extruder used to coat the core.

  When the polymer compatibilizer comprises two block copolymers (ie, those having an arylalkylene content of 50% by weight or more and a second having an arylalkylene content of less than 50% by weight), the poly ( An arylene ether) and a block copolymer having an arylalkylene content of 50% by weight or more are melt-mixed to form a first melt mixture, and then a polyolefin and a block copolymer having an arylalkylene content of 50% by weight or less are first mixed. The second molten mixture can be formed by melt mixing with the molten mixture.

  The addition method and location of the optional flame retardant is typically determined by the type of flame retardant and the physical properties (eg, solid or liquid), as is well known in the general art of polymer alloys and their production. . In one embodiment, the flame retardant is combined with one component of the thermoplastic resin composition (eg, a portion of the polyolefin) to form a concentrate, which is then melt mixed with the remaining components.

  The poly (arylene ether), polymer compatibilizer, polyolefin and optional flame retardant are melt mixed at a temperature above the glass transition temperature of the poly (arylene ether) but below the decomposition temperature of the polyolefin. For example, poly (arylene ether), polymer compatibilizer, polyolefin, and optional flame retardant can be melt mixed at an extruder temperature of 240-320 ° C., however, there may be a short period of time exceeding this range during melt mixing. . Within this range, the temperature may be 250 ° C. or higher, more specifically 260 ° C. or higher. Again within this range, the temperature can be 310 ° C. or less, more specifically 300 ° C. or less.

  After some or all of the components are melt mixed, the molten mixture can be melt filtered through one or more filters having a pore size of 20 to 150 micrometers. Within this range, the pore size can be 130 micrometers or less, more particularly 110 micrometers or less. Again within this range, the pore size can be 30 micrometers or more, more specifically 40 micrometers or more.

  Any suitable melt filtration system or apparatus that can remove particulate impurities from the molten mixture can be used. In one embodiment, the melt is filtered with a single melt filtration system. Multiple melt filtration systems are also envisioned.

  Suitable melt filtration systems include filters made of various materials including, but not limited to, sintered metal, metal mesh or screen, fiber metal felt, ceramic, combinations of the above materials, and the like. Particularly useful filters are described in Pall Corporation and Martin Kurz & Company, Inc. It is a sintered metal filter showing a high degree of bend, such as a sintered wire mesh filter manufactured in the above.

  Melt filters of any geometric shape including but not limited to cone shape, pleated shape, candle shape, stack shape, flat shape, wraparound shape, screen, cartridge, pack disc, and combinations of the above. Can be used. The choice of geometry can vary depending on various parameters such as the size of the extruder and the desired throughput and the desired degree of particle filtration. Exemplary structural materials include stainless steel, titanium, nickel, and other metals and alloys. Various weave wire meshes can be used including plain weave, Dutch weave, scare weave, twill weave and combinations of these weaves. Particularly useful are filters designed to minimize internal volume and low flow areas and to withstand repeated cleaning cycles.

  The melt filtration system can include periodic or continuous screen exchange filters or batch filters. For example, a continuous screen exchange filter includes a screen filter ribbon that slowly moves into the melt flow path in the extruder. The molten mixture passes through the filter and the filter collects particulate impurities in the melt. As the filter ribbon is periodically or continuously replaced with new parts of the ribbon, these impurities are carried out of the extruder along with the filter ribbon.

  In one embodiment, the filter has a maximum pore size that is less than or equal to 1/2 the thickness of the coating applied to the core. For example, if the coated wire has a coating thickness of 200 micrometers, the filter has a maximum pore size of 100 micrometers or less.

  The minimum pore size of the filter depends on several variables. As the filter pore size decreases, a higher pressure may be generated upstream of the filter. Therefore, the filter pore size and operating method must be selected to prevent dangerous upstream pressure. In addition, the use of a filter with a pore size of less than 20 micrometers can cause poor flow both upstream and downstream of the filter. Poor flow can increase the residence time for some portion of the molten mixture. Long residence times can result in the generation or expansion of particulates in the composition and can cause spark leaks when such compositions are applied to the core.

  In one embodiment, the melt filtration mixture is passed through a die head and pelletized by strand pelletization or underwater pelletization. The pelletized material can be packaged, stored and transported. In one embodiment, the pellets are packaged in a metal foil lined plastic bag (eg, a polypropylene bag) or a metal foil lined paper bag. Virtually all air can be evacuated from the bag filled with pellets.

  In one embodiment, the thermoplastic resin composition is substantially free of visible particulate impurities. Visible particulates or “black spots” are dark or colored particulates that are generally visible to the human eye without magnification and have an average diameter of 40 micrometers or greater. Some people can visually perceive particles with an average diameter of less than 30 micrometers without magnification, while others can only recognize particles with an average diameter greater than 40 micrometers, as specified herein. The terms “visible particles”, “visible particles” and “black spots” used without reference to average diameter mean particles having an average diameter of 40 micrometers or more. As used herein, the term “substantially free of visible particulate impurities”, when applied to a thermoplastic resin composition, is injection molded to a size of 75 millimeters × 50 millimeters and 3 millimeters. When five plaques having a thickness of 5 are formed and all the surfaces of the plaque are visually inspected for the presence or absence of black spots, the total number of black spots on all five plaques is 100 or less, more specifically 70 or less. More specifically, it means 50 or less.

  In one embodiment, the wires are formed by melting the pellets and applying the composition to the core wire by a suitable method such as extrusion coating. For example, a coating extruder equipped with a screw, crosshead, breaker plate, distributor, nipple and die can be used. The molten thermoplastic resin composition forms a coating disposed around the core wire. For extrusion coating, a single taper die, a double taper die, or other suitable die or combination of dies can be used to center the core and avoid die lip build-up.

  In one embodiment, the composition is applied to the core to form a coating disposed over the core. Additional layers can also be applied to the coating.

  In one embodiment, a coating disposed over the core wire is formed by applying a coating material to the core wire having one or more intervening layers between the core wire and the coating. For example, an arbitrary adhesion improver can be disposed between the core wire and the coating. In another example, the core can be coated with a metal deactivator prior to application of the coating. In another example, the intervening layer comprises a thermoplastic resin or thermosetting resin composition, which is optionally foamed.

  The core can consist of a single strand or multiple strands. In some cases, the core wire can be formed by bundling, twisting, or knitting a plurality of strands. Furthermore, the core wire can have various shapes such as circular or elliptical. The core wire can be any type of core wire used to transmit signals. Exemplary signals include optical, electrical and electromagnetic. Glass fiber is an example of an optical core. Suitable electrical core wires include, but are not limited to, copper, aluminum, lead, and alloys containing one or more of the aforementioned metals. The core wire can also be a conductive ink or paste.

  The cross-sectional area of the core and the thickness of the coating can vary, but are usually determined by the end use of the wire. The electric wire can be used as an electric wire without particular limitation including, for example, a harness wire for an automobile, an electric wire for home appliances, an electric wire, an instrument wire, an information communication wire, an electric vehicle, a ship or an airplane wire. In one embodiment, the coated core is an optical cable and can be used in indoor applications (inside buildings), outdoor applications (outside buildings), or indoor / outdoor applications. Exemplary applications include data transmission networks and voice transmission networks such as local area networks (LANs) and telephone networks.

  In some embodiments, it may be useful to dry the thermoplastic resin composition prior to extrusion coating. Exemplary drying conditions are 60-90 ° C. for 2-20 hours. Further, in one embodiment, the thermoplastic resin composition is melt filtered through one or more filters having a pore size of 20 to 150 micrometers prior to formation of the coating during extrusion coating. Within this range, the pore size can be 30 micrometers or more, more specifically 40 micrometers or more. Again within this range, the pore size can be 130 micrometers or less, more specifically 110 micrometers or less. The coated extruder can include one or more of the filters as described above.

  In one embodiment, prior to forming the coating during extrusion coating, the thermoplastic resin composition is melt filtered through one or more filters having a maximum pore size of 1/2 or less of the thickness of the coating applied to the core. For example, if the wire has a coating that is 200 micrometers thick, the filter has a maximum pore size of 100 micrometers or less.

  In another embodiment, the melt filtered mixture obtained by melt mixing is not pelletized. Instead, using a coating extruder in series with a melt mixing device (typically a compounding extruder), the melt filtration mixture is formed directly into the coating for the core wire. The coated extruder can include one or more of the filters as described above.

  Color concentrates or masterbatches can be added to the composition before or during extrusion coating. When a color concentrate is used, it is typically present in an amount of 3% or less by weight based on the total weight of the composition. In one embodiment, the dyes and / or pigments used in the color concentrate do not contain chlorine, bromine and fluorine. As will be appreciated by those skilled in the art, the color of the composition prior to the addition of color concentrate may affect the final color obtained, and in some cases it may be advantageous to use bleach and / or color stabilizers. Sometimes it is. Bleaching agents and color stabilizers are known in the art and are commercially available.

  The extruder temperature during extrusion coating is generally 320 ° C. or lower, more specifically 310 ° C. or lower, and more specifically 290 ° C. or lower. Further, the processing temperature is adjusted to provide a melt composition that is fluid enough to coat the core. For example, the processing temperature is higher than the melting point of the thermoplastic resin composition, more specifically, 10 ° C. or more higher than the melting point of the thermoplastic resin composition.

  After extrusion coating, the wire is typically cooled using a water bath, water spray, air jet, or a combination comprising one or more of the cooling methods described above. An exemplary water bath temperature is 20-85 ° C. The water can be deionized water and can be filtered to remove impurities. As described above, the wire is inspected for spark leaks using an in-line method. An exemplary spark leak test method involves using the core of the wire as a ground electrode and passing the wire in the vicinity of or through the charging electrode such that the wire contacts the charging electrode. If the polymer coating on the wire contains defects such as pinholes or cracks, an arc is generated between the charged electrode and the core of the wire and is detected. Exemplary charging electrodes include bead chains and brushes. The electrode may be charged using alternating current or direct current as indicated by the end use of the wire and any relevant industry standard for the wire. The voltage can be determined by one skilled in the art of spark leak testing. The frequency used depends on the load capacitance, but can still be determined by one skilled in the art of spark leak testing. Spark test equipment is commercially available from, for example, The Clinton Instrument Company, Beta LaserMike, and Zumbach.

  When a spark leak is detected, the portion having the spark leak is removed by cutting the electric wire. Thus, each spark leak produces a new length line. After inspection of the spark leak, the wire can be wound on a spool or similar device. An exemplary winding speed is 50-1500 meters / minute (m / minute). The wires can be housed in a container with or without a spool or similar device. Multiple lengths of lines may be combined to obtain the total length of the lines stored in the container or on a spool or similar device. The total length of a line stored in a container or on a spool or similar device usually depends on the cross-sectional area of the core and the thickness of the coating.

  The length of the wire between the spark leaks is important. If the wire container includes a wire section having a length of less than 150 meters, the wire usage efficiency may be poor. This is because electric wires are used in a continuous manner to manufacture various articles (for example, wire harnesses). The work flow must be interrupted and a new wire section must be started. Furthermore, if there are more than 7 individual wire sections per container, the use of wires is still inefficient. Thus, the amount and frequency of spark leaks is important.

  Thus, it is clear that the thermoplastic resin composition should be applicable to the wire in a robust state such that spark leaks are minimized or absent at all. That is, when a wire is tested using a spark leak test method suitable for the type of wire, the minimum length of a wire that does not show a spark leak is 150 meters, more specifically 250 meters, and even more particularly 500 meters. Don't be. Spark leaks can be caused by defects in the coating such as gaps (eg, pinholes), particulate matter, etc. in the wire coating.

  Such defects may be introduced by the coating process or may be derived from the thermoplastic resin composition. Defects introduced by the coating process can occur when the coating extruder is insufficiently cleaned or when the thermoplastic resin composition forms gels or black spots due to the operation of the coating extruder being stopped for a long time. Can occur. Residual material from previous coatings can form particulates, which can lead to defects and spark leaks. Defects introduced into the thermoplastic resin composition can be reduced or eliminated by thorough cleaning of the coating extruder (particularly the section after the filter) and melt filtration of the thermoplastic resin composition.

  Similarly, cleaning of melt mixing equipment (particularly the section after the filter) can also reduce or eliminate particulate matter and gels derived from residual material from previous use of the compounding extruder.

  A cross section of an exemplary wire is shown in FIG. FIG. 1 shows a coating 4 disposed over a core wire 2. In one embodiment, the coating 4 comprises a foamed thermoplastic resin composition. A perspective view of an exemplary wire is shown in FIGS. FIG. 2 shows a coating 4 disposed over a core wire 2 comprising a plurality of strands and an optional additional layer 6 disposed over the coating 4 and the core wire 2. In one embodiment, the coating 4 comprises a foamed thermoplastic resin composition. The core 2 may consist of a single core. FIG. 3 shows a coating 4 and an intervening layer 6 disposed over a single core wire 2. In one embodiment, the intervening layer 6 comprises a foam composition. The core 2 may be composed of a plurality of strands.

In one embodiment, the electric wire has a coating of core wire and thickness 0.15 to 0.25 mm in cross-sectional area from 0.15 to 1.10 mm2 (mm ²⁾ (mm). For electric wires with a total length of 13500-15500 meters, there are individual lengths of 6 or less, more specifically 4 or less, and more specifically 3 or less, and each individual length is 150 meters or more, more specifically 250 meters or more, and further Specifically, it is 500 meters or more. As used herein, individual length refers to a single length line having two ends.

In another embodiment, the wire has a core wire with a cross-sectional area of 0.30 to 1.30 mm ² and a coating with a thickness of 0.19 to 0.31 mm. For electric wires with a total length of 8500 to 14000 meters, there are individual lengths of 6 or less, more specifically 4 or less, and more specifically 3 or less. Each individual length is 150 meters or more, more specifically 250 meters or more, and further. Specifically, it is 500 meters or more.

In another embodiment, the wire has a core wire with a cross-sectional area of 1.20-2.10 mm ² and a coating with a thickness of 0.29-0.36 mm. For electric wires having a total length of 5000 to 7100 meters, there are individual lengths of 6 or less, more specifically 4 or less, and more specifically 3 or less. Each individual length is 150 meters or more, more specifically 250 meters or more, and further. Specifically, it is 500 meters or more.

In another embodiment, the wire has a core wire with a cross-sectional area of 2.90 to 4.50 mm ² and a coating with a thickness of 0.3 to 0.8 mm. For electric wires with a total length of 2500 to 5000 meters, there are individual lengths of 6 or less, more specifically 4 or less, and more specifically 3 or less, and each individual length is 150 meters or more, more specifically 250 meters or more, and further. Specifically, it is 500 meters or more.

  The thermoplastic resin compositions described herein include at least two phases, a polyolefin phase and a poly (arylene ether) phase. The polyolefin phase is a continuous phase. In some embodiments, the poly (arylene ether) phase is dispersed in the polyolefin phase. Good compatibilization between the two phases can result in improved physical properties, including high impact strength at low temperatures and room temperature, good heat aging, good flame retardancy, and high tensile elongation. In general, it is recognized that the morphology of a composition represents the degree or quality of compatibilization. The uniform distribution of small and relatively uniform sized poly (arylene ether) particles throughout the region of the composition represents good compatibilization.

  The thermoplastic resin compositions described herein are substantially free of alkenyl aromatic resins such as polystyrene or rubber modified polystyrene (also known as high impact polystyrene or HIPS). Substantially free means less than 10 wt% (wt%), more specifically less than 7 wt%, more specifically less than 5 wt%, and even more based on the total weight of poly (arylene ether), polyolefin and block copolymer. Specifically, it is defined as containing less than 3 wt% alkenyl aromatic resin. In one embodiment, the composition is completely free of alkenyl aromatic resins. Surprisingly, the presence of an alkenyl aromatic resin can negatively affect the compatibilization of the poly (arylene ether) phase and the polyolefin phase.

In one embodiment, the composition has a flexural modulus of 8000 kg / cm (kg / cm ²⁾ to less than 18000kg / cm ² (800 MPa (from MPa) to less than 1800 MPa). Within this range, the flexural modulus can be 10000 kg / cm ² (1000 MPa) or more, more specifically 12000 kg / cm ² (1200 MPa) or more. Also within this range, the flexural modulus can be 17000 kg / cm ² (1700 MPa) or less, more specifically 16000 kg / cm ² (1600 MPa) or less. The flexural modulus described herein is measured using ASTM D790-03 and a speed of 1.27 millimeters / minute. The flexural modulus value is the average of three samples. Samples for flexural modulus are available from Toyo Machine & Metal Co. Formed on Plastar Ti-80G ₂ obtained from LTD, using an injection pressure of 600-700 kilogram weight / square centimeter and a dwell time of 15-20 seconds. The remaining molding conditions are shown in Table 1.

一実施形態では、電線はＩＳＯ６７２２の要件（詳しくは、耐摩耗性に関する要件、クラスＡ、Ｂ、Ｃの熱老化性に関する要件、耐薬品性に関する要件、及び環境サイクリングに関する要件）を満たし又は超える。

In one embodiment, the wire meets or exceeds the requirements of ISO 6722 (specifically, requirements for wear resistance, requirements for class A, B, C thermal aging, requirements for chemical resistance, and requirements for environmental cycling).

  As used herein, “poly (arylene ether)” includes a plurality of structural units having the following formula (I):

式中、各構造単位について、Ｑ^１及びＱ^２は各々独立に水素、ハロゲン、第一若しくは第二低級アルキル（例えば、１〜７の炭素原子を含むアルキル）、フェニル、ハロアルキル、アミノアルキル、アルケニルアルキル、アルキニルアルキル、炭化水素オキシ、アリール、又はハロゲン原子と酸素原子とを２以上の炭素原子が隔てているハロ炭化水素オキシである。若干の実施形態では、各Ｑ^１は独立にアルキル又はフェニル（例えば、Ｃ_１−４アルキル）であり、各Ｑ^２は独立に水素又はメチルである。ポリ（アリーレンエーテル）は、通例はヒドロキシ基に対してオルト位に位置するアミノアルキル含有末端基を有する分子を含み得る。また、通例はテトラメチルジフェニルキノン副生物が存在する反応混合物から得られるテトラメチルジフェニルキノン（ＴＭＤＱ）末端基が存在することも多い。

In the formula, for each structural unit, Q ¹ and Q ² are each independently hydrogen, halogen, primary or secondary lower alkyl (eg, alkyl containing 1 to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, alkenyl. Alkyl, alkynylalkyl, hydrocarbonoxy, aryl, or halohydrocarbonoxy in which two or more carbon atoms are separated from a halogen atom and an oxygen atom. In some embodiments, each Q ¹ is independently alkyl or phenyl (eg, C _1-4 alkyl) and each Q ² is independently hydrogen or methyl. The poly (arylene ether) can comprise a molecule having an aminoalkyl-containing end group, typically located ortho to the hydroxy group. Also, there are often tetramethyldiphenylquinone (TMDQ) end groups typically obtained from reaction mixtures in which tetramethyldiphenylquinone by-product is present.

  The poly (arylene ether) may have the form of a homopolymer, copolymer, graft copolymer, ionomer or block copolymer, as well as combinations including one or more of the foregoing. Poly (arylene ether) includes polyphenylene ether containing 2,6-dimethyl-1,4-phenylene ether units optionally with 2,3,6-trimethyl-1,4-phenylene ether units.

  Poly (arylene ethers) are oxidative cups of monohydroxy aromatic compounds such as 2,6-xylenol, 2,3,6-trimethylphenol, and combinations of 2,6-xylenol and 2,3,6-trimethylphenol. Can be manufactured with a ring. A catalyst system is generally used for such coupling. The catalyst system includes a heavy metal compound, such as a compound of copper, manganese or cobalt, usually with various other materials (eg, secondary amines, tertiary amines, halides, or combinations of two or more of the foregoing). obtain.

  In one embodiment, the poly (arylene ether) comprises a capped poly (arylene ether). The terminal hydroxy group can be blocked with a blocking agent by, for example, an acylation reaction. The sequestering agent preferably is one that reduces or prevents cross-linking of the polymer chains and formation of gels or black spots during processing at high temperatures by producing a less reactive poly (arylene ether). Suitable blocking agents include, for example, salicylic acid, anthranilic acid or esters of substituted derivatives thereof, and esters of salicylic acid, particularly salicyl carbonate and linear polysalicylate are preferred. As used herein, the term “ester of salicylic acid” includes compounds in which a carboxy group, a hydroxy group, or both are esterified. Suitable salicylates include, for example, aryl salicylates such as phenyl salicylate, acetylsalicylic acid, salicyl carbonate and polysalicylate (including both linear polysalicylate and cyclic compounds such as disalicylide and trisalicylide). In one embodiment, the sequestering agent is selected from salicyl carbonate and polysalicylate (particularly linear polysalicylate), and combinations comprising one or more of the foregoing. Exemplary capped poly (arylene ethers) and their preparation are described in US Pat. Nos. 4,760,118 (White et al.) And 6,306,978 (Braat et al.).

  The capping of poly (arylene ether) with polysalicylate is also believed to reduce the amount of aminoalkyl end groups present in the poly (arylene ether) chain. The aminoalkyl group is the result of an oxidative coupling reaction that uses an amine during the process of producing the poly (arylene ether). Aminoalkyl groups that are ortho to the terminal hydroxy group of poly (arylene ether) are susceptible to degradation at high temperatures. Such degradation is believed to result in the regeneration of primary or secondary amines and the generation of quinone methide end groups, which may generate 2,6-dialkyl-1-hydroxyphenyl end groups. If a poly (arylene ether) containing an aminoalkyl group is capped with a polysalicylate, the amino group is removed to form a blocked terminal hydroxy group of the polymer chain, thereby producing 2-hydroxy-N, N-alkylbenzamine (salicylimide). It is thought to bring about. Removal of the amino group and blocking provides a poly (arylene ether) that is more stable to high temperatures, thereby reducing the degradation products produced during processing of the poly (arylene ether).

  Poly (arylene ether) is 3000 to 40000 grams / mole as measured by gel permeation chromatography using a monodisperse polystyrene standard (40 ° C. styrene-divinylbenzene gel) and a sample having a concentration of 1 milligram per milliliter of chloroform. It may have a number average molecular weight of (g / mol) and a weight average molecular weight of 5000 to 80000 g / mol. The poly (arylene ether) or combination of poly (arylene ethers) can have an initial intrinsic viscosity of about 0.25 dl / g or greater as measured in chloroform at 25 ° C. The initial intrinsic viscosity is defined as the intrinsic viscosity of the poly (arylene ether) before melt mixing with the other components of the composition, and the final intrinsic viscosity is the poly (arylene ether) after melt mixing with the other components of the composition. ). As will be appreciated by those skilled in the art, the viscosity of poly (arylene ether) can be as high as 30% after melt mixing. The percent increase can be calculated by ((final intrinsic viscosity) − (initial intrinsic viscosity)) / (initial intrinsic viscosity). When two initial intrinsic viscosities are used, the determination of the exact ratio depends somewhat on the exact intrinsic viscosity of the poly (arylene ether) used and the desired final physical properties.

The poly (arylene ether) used to produce the thermoplastic resin composition can be substantially free of visible particulate impurities. In one embodiment, the poly (arylene ether) is substantially free of particulate impurities having a diameter greater than 15 micrometers. As used herein, the term “substantially free of visible particulate impurities” as applied to poly (arylene ether) is 10 grams of poly (dissolved in 50 milliliters of chloroform (CHCl ₃ ). Arylene ether) means that the sample shows less than 5 visible spots when observed with the naked eye in a light box. Particles visible to the naked eye are typically those with a diameter greater than 40 micrometers. As used herein, the term “substantially free of particulate impurities greater than about 15 micrometers” is used by Pacific Instruments for a 40 gram poly (arylene ether) sample dissolved in 400 milliliters of CHCl ₃ . When measured with an ABS2 analyzer, five samples of 20 milliliters of dissolved polymer material each having a particle size of 15 micrometers flow through the analyzer at a flow rate of 1 milliliter / minute (± 5%). Means less than 50 based on the average.

  The thermoplastic resin composition comprises poly (arylene ether) in an amount of 30 to 65 wt% (wt%) based on the total weight of the composition. Within this range, the amount of poly (arylene ether) can be 40 wt% or more, more specifically 45 wt% or more. Again within this range, the amount of poly (arylene ether) can be 55 wt% or less.

Polyolefins have the general structure C _n H _2n and include polyethylene, polypropylene and polyisobutylene. Exemplary homopolymers include polyethylene, LLDPE (linear low density polyethylene), HDPE (high density polyethylene), MDPE (medium density polyethylene) and isotactic polypropylene. Polyolefin resins having such a general structure and methods for producing the same are known in the art. For example, U.S. Pat. Nos. 2,933,480, 3,093,621, 3,211,709, 3,646,168, 3,790,519, No. 3,884,993, No. 3,894,999, No. 4,059,654, No. 4,166,055 and No. 4,584,334.

Copolymers of polyolefins such as copolymers of ethylene and α-olefins (eg, propylene, octene and 4-methylpentene-1) and copolymers of ethylene and one or more rubbers and copolymers of propylene and one or more rubbers Can also be used. (Herein referred to as EPDM copolymers) of ethylene and _C 3 _{-C 10} Copolymers of monoolefins and non-conjugated diene are also suitable. Examples of suitable _C 3 _{-C 10} monoolefins for EPDM copolymers, some propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 3-hexene. Suitable dienes include 1,4-hexadiene and monocyclic and polycyclic dienes. Mole ratios of ethylene to other _C 3 _{-C 10} monoolefin monomers 95: 5 to 5: is with get in the range of 95, the diene units can be present in an amount of from 0.1 to 10 mol%. EPDM copolymers can be functionalized with acyl groups or electrophilic groups for grafting onto polyphenylene ether as disclosed in US Pat. No. 5,258,455.

  The thermoplastic resin composition may comprise a single homopolymer, a combination of homopolymers, a single copolymer, a combination of copolymers, or a combination of homopolymers and copolymers.

  In one embodiment, the polyolefin is selected from the group consisting of polypropylene, high density polyethylene, and a combination of polypropylene and high density polyethylene. The polypropylene can be a homopolypropylene or a polypropylene copolymer. Copolymers of polypropylene and rubber or block copolymers are sometimes referred to as impact modified polypropylene. Such copolymers are typically heterophasic and have each component section long enough to have both an amorphous phase and a crystalline phase. Further, the polypropylene can consist of a combination of homopolymer and copolymer, a combination of homopolymers having different melting temperatures, or a combination of homopolymers having different melt flow rates.

  In one embodiment, the polypropylene comprises a crystalline polypropylene such as isotactic polypropylene. Crystalline polypropylene is defined as a polypropylene having a degree of crystallinity of 20% or more, more specifically 25% or more, and more specifically 30% or more. Crystallinity can be measured by differential scanning calorimetry (DSC).

  In some embodiments, the polypropylene has a melting temperature of 134 ° C. or higher, more specifically 140 ° C. or higher, and more specifically 145 ° C. or higher.

  Polypropylene has a melt flow rate (MFR) of greater than 0.4 grams / 10 minutes and no greater than 15 grams / 10 minutes (g / 10 minutes). Within this range, the melt flow rate can be 0.6 g / 10 min or more. Again within this range, the melt flow rate can be 10 g / 10 min or less, more specifically 6 g / 10 min or less, and even more specifically 5 g / 10 min or less. Melt flow rate can be measured according to ASTM D1238 using powdered or pelletized polypropylene, a load of 2.16 kilograms, and a temperature of 230 ° C.

The high density polyethylene can be a homopolyethylene or a polyethylene copolymer. Further, the high density polyethylene may consist of a combination of homopolymer and copolymer, a combination of homopolymers having different melting temperatures, or a combination of homopolymers having different melt flow rates, and generally 0.941 to 0.965 g / cm ^3. Can have a density of

  In some embodiments, the high density polyethylene has a melting temperature of 124 ° C. or higher, more specifically 126 ° C. or higher, and more specifically 128 ° C. or higher.

  High density polyethylene has a melt flow rate (MFR) of 0.10 grams / 10 minutes or more and 15 grams / 10 minutes or less (g / 10 minutes). Within this range, the melt flow rate can be 1.0 g / 10 min or more. Again within this range, the melt flow rate can be 10 g / 10 min or less, more specifically 6 g / 10 min or less, and even more specifically 5 g / 10 min or less. Melt flow rate can be measured according to ASTM D1238 using powdered or pelletized polyethylene, a load of 2.16 kilograms, and a temperature of 190 ° C.

  The composition may comprise a polyolefin in an amount of 15-35 wt% (wt%) relative to the total weight of the composition. Within this range, the amount of polyolefin may be 17 wt% or more, more specifically 20 wt% or more. Again within this range, the amount of polyolefin can be 33 wt% or less, more specifically 30 wt% or less.

  In one embodiment, the polyolefin comprises high density polyethylene (HDPE) and polypropylene, wherein the amount by weight of HDPE is less than the amount by weight of polypropylene.

  In one embodiment, the polyolefin is present in an amount by weight that is less than the amount by weight of poly (arylene ether).

  Polymer compatibilizers are resins and additives that improve the compatibility between the polyolefin phase and the poly (arylene ether) phase. Polymer compatibilizers include block copolymers, polypropylene-polystyrene graft copolymers, and combinations of block copolymers and polypropylene-polystyrene graft copolymers as described below.

  As used herein, “block copolymer” refers to only one block copolymer or combination of block copolymers. The block copolymer includes one or more blocks (A) composed of repeating aryl alkylene units and one or more blocks (B) composed of repeating alkylene units. The arrangement of the blocks (A) and (B) can be a so-called radial teleblock structure having a linear structure or a branched chain. The ABA triblock copolymer contains two blocks A consisting of repeating arylalkylene units. The pendant aryl portion of the aryl alkylene unit can be monocyclic or polycyclic and can have a substituent at any available position on the cyclic portion. Suitable substituents include alkyl groups having 1 to 4 carbon atoms. An exemplary arylalkylene unit is phenylethylene as shown below in Formula II.

ブロックＡはさらに、アリールアルキレン単位の量がアルキレン単位の量を超える限り、炭素原子数２〜１５のアルキレン単位を含み得る。

Block A may further comprise alkylene units of 2 to 15 carbon atoms so long as the amount of aryl alkylene units exceeds the amount of alkylene units.

  Block B consists of repeating alkylene units of 2 to 15 carbon atoms such as ethylene, propylene, butylene or combinations of two or more of the foregoing. Block B may further comprise aryl alkylene units as long as the amount of alkylene units exceeds the amount of aryl alkylene units.

  Each block A may have the same or different molecular weight as the other blocks A. Similarly, each block B may have the same or different molecular weight as the other blocks B. Block copolymers can be functionalized by reaction with α, β-unsaturated carboxylic acids.

  In one embodiment, the B block consists of a copolymer of aryl alkylene units and alkylene units of 2 to 15 carbon atoms (eg, ethylene, propylene, butylene, or combinations of two or more of the foregoing). The B block may further contain some unsaturated non-aromatic carbon-carbon bonds.

  The B block can be a controlled distribution copolymer. As used herein, “controlled distribution” is defined to refer to a molecular structure that lacks a distinct block of any monomer. That is, as shown by the presence of only one glass transition temperature (Tg) in the middle of the Tg of each homopolymer, or as shown by proton nuclear magnetic resonance methods, "Has an average maximum number of 20 units. When the B block consists of a controlled distribution copolymer, each A block can have an average molecular weight of 3000 to 60000 g / mol as measured by light scattering techniques, while each B block has an average molecular weight of 30000 to 300000 g / mol. obtain. When the B block is a controlled distribution copolymer, each B block includes one or more terminal regions rich in alkylene units adjacent to the A block and regions rich in aryl alkylene units that are not adjacent to the A block. The total amount of aryl alkylene units is 15 to 75% by weight, based on the total weight of the block copolymer. The weight ratio of alkylene units to arylalkylene units in the B block can be 5: 1 to 1: 2. Exemplary block copolymers are further disclosed in US Patent Application Publication No. 2003/181854 and are commercially available from Kraton Polymers under the KRATON trademark. Exemplary grades are A-RP6936 and A-RP6935.

  Repeated arylalkylene units are obtained by polymerization of arylalkylene monomers such as styrene. Repeated alkylene units are obtained by hydrogenation of repeating unsaturated units derived from dienes such as butadiene. Butadiene can consist of 1,4-butadiene and / or 1,2-butadiene. The B block may further contain some unsaturated non-aromatic carbon-carbon bonds.

  Exemplary block copolymers include polyphenylethylene-poly (ethylene / propylene) -polyphenylethylene (sometimes referred to as polystyrene-poly (ethylene / propylene) -polystyrene) and polyphenylethylene-poly (ethylene / butylene) -poly. There is phenylethylene (sometimes referred to as polystyrene-poly (ethylene / butylene) -polystyrene).

  In one embodiment, the polymer compatibilizer consists of two block copolymers. The first block copolymer has an arylalkylene content of 50% by weight or more based on the total weight of the first block copolymer. The second block copolymer has an arylalkylene content of 50 wt% or less, based on the total weight of the second block copolymer. An exemplary combination of block copolymers includes a first polyphenylethylene-poly (ethylene / butylene) -polyphenylethylene having a phenylethylene content of 15-40% by weight, based on the total weight of the block copolymer, and A second polyphenylethylene-poly (ethylene / butylene) -polyphenylethylene having a phenylethylene content of 55 to 70% by weight, based on the total weight of the block copolymer, can be used. Exemplary block copolymers having an arylalkylene content greater than 50% by weight include those having a grade name such as H1043, commercially available under the trade name TUFTEC from Asahi, and the product SEPTON from Kuraray. There are some grades available by name. Exemplary block copolymers having an arylalkylene content of less than 50% by weight include G-1701, G-1702, G-1730, G-1641, G-commercially available under the KRATON trademark from Kraton Polymers. There are grade names such as -1650, G-1651, G-1652, G-1657, A-RP6936 and A-RP6935.

  In one embodiment, the polymer compatibilizer comprises a diblock copolymer and a triblock copolymer.

  In some embodiments, the block copolymer has a number average molecular weight of 5,000 to 1,000,000 grams / mole (g / mol) as measured by gel permeation chromatography (GPC) using polystyrene standards. Within this range, the number average molecular weight can be 10000 g / mol or more, more specifically 30000 g / mol or more, and even more specifically 45000 g / mol or more. Again within this range, the number average molecular weight may preferably be 800,000 g / mol or less, more specifically 700,000 g / mol or less, and even more specifically 650000 g / mol or less.

  As used herein, a polypropylene-polystyrene graft copolymer is defined as a graft copolymer having a propylene polymer backbone and one or more styrene polymer grafts.

The propylene polymer material forming the main chain or backbone of the polypropylene-polystyrene graft copolymer is (a) a homopolymer of propylene, (b) propylene and an olefin selected from the group consisting of ethylene and C _{4 to} C ₁₀ olefins. Random copolymers (provided that if the olefin is ethylene, the polymerized ethylene content is up to about 10% by weight, preferably up to about 4% by weight, and if the olefin is a C _{4 to} C ₁₀ olefin, the polymerized C _{4 to} C ₁₀ olefin content is up to about 20% by weight, preferably up to about 16% by weight.) (C) 2 selected from the group consisting of propylene, ethylene and C _{4 to} C ₁₀ α-olefins random terpolymers of species or more olefins (provided that the polymerization _C 4 _{-C 10} alpha-olefin The content is up to about 20% by weight, preferably up to about 16% by weight, and when ethylene is one of the olefins, the polymerized ethylene content is up to about 5% by weight, preferably up to about 4% by weight. ), Or (d) a homopolymer or random copolymer of propylene modified in impact resistance with ethylene-propylene monomer rubber in a reactor or by physical blending, wherein the improved polymer has an ethylene-propylene monomer rubber content. From about 5 to about 30% by weight and the rubber has an ethylene content of from about 7 to about 70% by weight, preferably from about 10 to about 40% by weight. Examples of C _{4 to} C ₁₀ olefins include 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 3,4-dimethyl-1-butene, 1 - heptene, 1-octene, 3-methyl - there are linear and branched _C 4 _{-C 10} alpha-olefins such as hexene. Propylene homopolymer and impact modified propylene homopolymer are preferred propylene polymer materials. Although not preferred, propylene homopolymers and random copolymers improved in impact with an ethylene-propylene-diene monomer rubber having a diene content of about 2 to about 8% by weight can also be used as the propylene polymer material. Suitable dienes include dicyclopentadiene, 1,6-hexadiene, ethylidene norbornene and the like.

The term “styrene polymer” as used in reference to a grafted polymer present on the backbone of a propylene polymer material in a polypropylene-polystyrene graft copolymer is (a) a homopolymer of styrene or one or more C ₁ -C ₄ linear. Or a homopolymer of alkyl styrene (particularly p-alkyl styrene) having a branched alkyl endocyclic substituent, (b) (a) a copolymer in any ratio of monomers, and (c) one or more (a) A copolymer of a monomer and its α-methyl derivative (eg, α-methylstyrene) is meant that the α-methyl derivative accounts for about 1 to about 40% of the weight of the copolymer.

  The polypropylene-polystyrene graft copolymer may comprise from about 10 to about 90% by weight propylene polymer backbone and from about 90 to about 10% by weight styrene polymer graft. Within this range, the propylene polymer backbone can occupy about 20% or more of the total graft copolymer, and the propylene polymer backbone can occupy about 40% or less of the total graft copolymer. Again within this range, the styrene polymer graft may comprise about 50% or more by weight of the total graft copolymer, more specifically about 60% or more.

  A process for producing a polypropylene-polystyrene graft copolymer is described, for example, in US Pat. No. 4,990,558 (DeNicola, Jr. et al.). Suitable polypropylene-polystyrene graft copolymers are also commercially available from, for example, Basel as P1045H1 and P1085H1.

  The polymer compatibilizer is present in an amount of 2-30% by weight relative to the total weight of the composition. Within this range, the polymer compatibilizer may be present in an amount of 4 wt% or more, more specifically 6 wt% or more, based on the total weight of the composition. Also within this range, the polymer compatibilizer may be present in an amount of 18 wt% or less, more specifically 16 wt% or less, even more specifically 14 wt% or less, based on the total weight of the composition.

  Exemplary flame retardants include melamine (CAS No. 108-78-1), melamine cyanurate (CAS No. 37640-57-6), melamine phosphate (CAS No. 20208-95-1), melamine pyrophosphate. (CAS No. 15541-60-3), melamine polyphosphate (CAS No. 218768-84-4), melam, melem, melon, zinc borate (CAS No. 1332-07-6), boron phosphate, red Phosphorus (CAS No. 7723-14-0), organophosphate ester, monoammonium phosphate (CAS No. 7722-76-1), diammonium phosphate (CAS No. 7783-28-0), alkylphosphonate ( CAS No. 78-38-6 and 78-40-0), metal dialkylphosphine Sulfonate, ammonium polyphosphate (CAS No.68333-79-9), low melting point glass, as well as combinations of two or more of the flame retardants mentioned above.

  Exemplary organophosphate flame retardants include, but are not limited to, phenyl groups, substituted phenyl groups, or phosphate esters containing a combination of phenyl and substituted phenyl groups, resorcinol-based bis-aryl phosphate esters (e.g., Resorcinol bis-diphenyl phosphate) as well as those based on bisphenol (eg, bisphenol A bis-diphenyl phosphate). In one embodiment, the organophosphate ester is a tris (alkylphenyl) phosphate (eg, CAS No. 89492-23-9 or CAS No. 78-33-1), resorcinol bis-diphenyl phosphate (eg, CAS No. 57583-54-7), bisphenol A bis-diphenyl phosphate (e.g., CAS No. 181028-79-5), triphenyl phosphate (e.g., CAS No. 115-86-6), tris (isopropylphenyl) phosphate ( For example, it is selected from a mixture of two or more of CAS No. 68937-41-7) and the above-mentioned organophosphate.

  In one embodiment, the organophosphate ester consists of a bis-aryl phosphate having the following formula III:

式中、Ｒ、Ｒ^５及びＲ^６は各々独立に炭素原子数１〜５のアルキル基であり、Ｒ^１〜Ｒ^４は独立に炭素原子数１〜１０のアルキル基、アリール基、アリールアルキル基又はアルキルアリール基であり、ｎは１〜２５に等しい整数であり、ｓ１及びｓ２は独立に０〜２に等しい整数である。若干の実施形態では、ＯＲ^１、ＯＲ^２、ＯＲ^３及びＯＲ^４は独立にフェノール、モノアルキルフェノール、ジアルキルフェノール又はトリアルキルフェノールから導かれる。

In the formula, R, R ⁵ and R ⁶ are each independently an alkyl group having 1 to 5 carbon atoms, and R ^{1 to} R ⁴ are independently an alkyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms. Or an alkylaryl group, n is an integer equal to 1-25, and s1 and s2 are independently integers equal to 0-2. In some embodiments, OR ¹ , OR ² , OR ³ and OR ⁴ are independently derived from phenol, monoalkylphenol, dialkylphenol or trialkylphenol.

  As will be readily appreciated by those skilled in the art, bis-aryl phosphates are derived from bisphenols. Exemplary bisphenols include 2,2-bis (4-hydroxyphenyl) propane (so-called bis A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane , Bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane. In one embodiment, the bisphenol comprises bisphenol A.

  Since organophosphates can have different molecular weights, it is difficult to determine the amount of various organophosphates used in the thermoplastic resin composition. In one embodiment, the amount of phosphorus resulting from the organophosphate is 0.8-1.2% by weight relative to the total weight of the composition.

  When present in the thermoplastic composition, the amount of flame retardant is sufficient for the wire to have a quenching time of 70 seconds or less as measured according to the flame propagation method included in ISO 6722.

  In one embodiment, the flame retardant comprises an organophosphate ester present in an amount of 5 to 18 wt% (wt%) relative to the total weight of the composition. Within this range, the amount of organophosphate can be 7 wt% or more, more specifically 9 wt% or more. Again within this range, the amount of organophosphate may be 16 wt% or less, more specifically 14 wt% or less.

In addition, the composition comprises antioxidants, fillers and reinforcements having an average particle size of 10 micrometers or less (eg, silicates, TiO ₂ , fibers, glass fibers, glass spheres, calcium carbonate, talc and mica). , Mold release agents, UV absorbers, stabilizers (eg, light stabilizers), lubricants, plasticizers, pigments, dyes, colorants, antistatic agents, foaming agents, foaming agents, metal deactivators, and Various additives may optionally be included such as combinations including one or more of the above-described additives.

  The composition and wire are further illustrated in the following non-limiting examples.

  The following examples were prepared using the materials shown in Table 2.

熱可塑性樹脂組成物は、二軸押出機で成分を溶融混合することで製造した。ＰＰＥ及びブロックコポリマーは供給スロートで添加し、ＰＰは押出機の第二の開口を通して下流で添加した。有機リン酸エステルは、押出機の第二半部において液体インゼクターで添加した。組成物は、フィルター（メッシュ）を用いずに製造するか、或いは表４及び５に示すように孔径の異なる１以上のフィルターを用いて溶融濾過しながら製造した。ストランドペレット化の使用により、材料を押出機の端部でペレット化した。組成物を表３に示す。

The thermoplastic resin composition was produced by melting and mixing the components with a twin screw extruder. PPE and block copolymer were added at the feed throat and PP was added downstream through the second opening of the extruder. The organophosphate was added with a liquid injector in the second half of the extruder. The composition was manufactured without using a filter (mesh), or manufactured by melt filtration using one or more filters having different pore sizes as shown in Tables 4 and 5. The material was pelletized at the end of the extruder by the use of strand pelletization. The composition is shown in Table 3.

The thermoplastic resin composition was dried at 80 ° C. for 3 to 4 hours, and then extruded with a core wire to form an electric wire. The core wire was a copper wire having a core wire size of 0.2 square millimeters (mm ² ). The wire was manufactured at a line speed of 250 meters / minute. Preheat the thermoplastic resin composition to 100 ° C. and extrude it onto the core wire at 275 ° C. without using a filter (mesh), or use a filter having a pore size (micrometer unit) as shown in Tables 4 and 5 And extruded while melting and filtering. The coating had a thickness of 0.2 millimeters (Table 4) and 0.15 millimeters (Table 5). Using a high frequency AC spark tester (Model No. HF-ISA / BD-12) available from The Clinton Instrument Company (Clinton, Connecticut, USA), the spark of the wire at 5 kilovolts (KV) over a length of 1250 meters A test was conducted. Tables 4 and 5 show the number of spark leaks for each set of manufacturing conditions.

表４及び５からわかる通り、溶融混合中、押出被覆中、又は溶融混合及び押出被覆中に濾過することは、特に被覆の厚さが減少した場合、火花リークがほとんど又は全くない電線を製造するために不可欠である。

As can be seen from Tables 4 and 5, filtering during melt mixing, extrusion coating, or melt mixing and extrusion coating produces wires with little or no spark leakage, especially when the coating thickness is reduced. Indispensable for.

  Although the present invention has been described with respect to some embodiments, those skilled in the art will appreciate that various changes and equivalent replacements can be made without departing from the scope of the present invention. Like. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, the present invention is not limited to the specific embodiment disclosed as the best mode envisaged for carrying out the invention, but includes all embodiments included in the scope of the claims.

  The disclosures of all cited patents, patent applications, and other references are incorporated herein by reference.

1 is a schematic diagram of a cross section of an electric wire. It is a perspective view of an electric wire which has a plurality of layers. It is a perspective view of an electric wire which has a plurality of layers.

Explanation of symbols

2 Core wire 4 Coating 6 Intervening layer

Claims (17)

With the heart
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
The thermoplastic resin composition comprises 20-35% by weight of polyolefin, based on the total weight of the composition;
A sheath is placed over the core,
The core has a cross-sectional area of 0.15-1.00 square millimeters, and the coating has a thickness of 0.15-0.25 millimeters;
About the electric wire of 13500-15500 meters, the electric wire of 6 or less individual length exists, and the electric wire of each individual length has a length of 150 meters or more. With the heart
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
The thermoplastic resin composition comprises 20-35% by weight of polyolefin, based on the total weight of the composition;
A sheath is placed over the core,
The core has a cross-sectional area of 0.30 to 1.30 square millimeters and the coating has a thickness of 0.15 to 0.35 millimeters;
About the electric wire of 8500-14500 meters, the electric wire of 6 or less individual length exists, and the electric wire of each individual length has a length of 150 meters or more. With the heart
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
The thermoplastic resin composition comprises 20-35% by weight of polyolefin, based on the total weight of the composition;
A sheath is placed over the core,
The core has a cross-sectional area of 1.20 to 2.10 square millimeters and the coating has a thickness of 0.29 to 0.36 millimeters;
An electric wire having an individual length of 6 or less and an electric wire having an individual length of 150 meters or more for an electric wire of 5000 to 7100 meters. With the heart
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
The thermoplastic resin composition comprises 20-35% by weight of polyolefin, based on the total weight of the composition;
A sheath is placed over the core,
The core has a cross-sectional area of 2.90 to 4.50 square millimeters and the coating has a thickness of 0.3 to 0.8 millimeters;
An electric wire having an individual length of 6 or less and an electric wire having an individual length of 150 meters or more for an electric wire of 2500 to 5000 meters. With the heart
(I) poly (arylene ether),
An electric wire comprising (ii) a polyolefin, and (iii) a coating made of a thermoplastic resin composition containing a polymer compatibilizer,
The thermoplastic resin composition comprises 20-35% by weight of polyolefin, based on the total weight of the composition;
A sheath is placed over the core,
An electric wire having a spark leak of 5 or less for an electric wire of 2500 to 15500 meters. A method for producing a coating for an electric wire or a core wire,
Melt mixing poly (arylene ether), polyolefin, and polymer compatibilizer to form a first mixture, wherein the first mixture comprises 20-35 wt% polyolefin based on the total weight of the mixture. Including,
Melt filtering the first mixture through a first filter having a pore size of 20-150 micrometers to form a first filtered mixture;
Melt filtering the first filtration mixture through a second filter having a pore size of 20 to 150 micrometers to form a second filtration mixture, and applying the second filtration mixture to the core wire How to be. A method of manufacturing an electric wire,
Melting and filtering a composition comprising poly (arylene ether), a polyolefin, and a polymer compatibilizer comprising 20 to 35% by weight of polyolefin relative to the total weight of the composition to form a filtered composition And the method of forming a wire by applying the filtration composition to the core wire, the wire having a spark leak of 5 or less for a 2500 to 15500 meter wire. An electric wire or coating produced by the method according to claim 6 or 7. The electric wire or coating according to claim 8, wherein the coating has a thickness and the second filter has a maximum pore diameter of ½ or less of the coating thickness. The electric wire or covering according to any one of claims 1 to 5, 8, and 9, wherein the core wire is composed of a single strand or a plurality of strands. The electric wire or coating according to any one of claims 1 to 5 and 8 to 10, wherein the polyolefin is selected from the group consisting of polypropylene, high-density polyethylene, and a combination of polypropylene and high-density polyethylene. The electric wire or coating according to any one of claims 1 to 5 and 8 to 11, wherein the polymer compatibilizer comprises a block copolymer having a block which is a controlled distribution copolymer. The polymer compatibilizer is 50 wt% based on the total weight of the first block copolymer and the second copolymer having an arylalkylene content of 50 wt% or more based on the total weight of the first block copolymer The electric wire or coating according to any one of claims 1 to 5 and 8 to 12, comprising a second block copolymer having the following arylalkylene content. The electric wire or coating according to any one of claims 1 to 5 and 8 to 13, wherein the polymer compatibilizer comprises a diblock copolymer and a triblock copolymer. The electric wire or coating according to any one of claims 1 to 5 and 8 to 14, wherein the polymer compatibilizer comprises a polypropylene-polystyrene graft copolymer. The electric wire or coating according to any one of claims 1 to 5 and 8 to 15, wherein the thermoplastic resin composition further contains a flame retardant. The thermoplastic resin composition comprises the polyolefin in a weight-based amount that is less than the weight-based amount of the poly (arylene ether) based on the total weight of the polyolefin and poly (arylene ether). The electric wire or coating | cover in any one of 16.

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