KR102487667B1 - Manufacturing method of high flame retardant thermoplastic elastomer compound and electric cable for vessels operating in ice-covered waters having flexibility, cold resistance, oil resistance and ice accretion resistance - Google Patents

Abstract

The present invention relates to a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance, and a method for manufacturing a polar navigation ship cable coated therewith, and more particularly, to a thermoplastic elastomer selected from ethylene terpolymers by weight of 10,000 15,000 to 50,000 parts by weight of a flame retardant and surface-treated flame retardant, 500 to 2,000 parts by weight of a self-lubricant selected from polysiloxane copolymers, 200 to 1,000 parts by weight of an auxiliary flame retardant selected from modified silicone oil, 100 to 600 parts by weight of an antioxidant, 100 to 400 parts by weight of a stabilizer selected from thiophenol compounds, 500 to 3,000 parts by weight of a sunscreen pigment, and 5,000 to 16,000 parts by weight of a compatibilizer selected from an ethylene copolymer are sequentially put into a kneader mixer at a temperature of 140 to 170 ° C. After melting and kneading for 10 to 60 minutes, and after the melting and kneading step, 2 to 8 parts by weight of the masterbatch and 6,000 to 12,000 parts by weight of polyethylene resin are sequentially added to the mixing mixer at a temperature of 140 to 170 ° C. A loaf of melt-mixed dough for 30 minutes is transferred to a single screw or twin screw extruder to produce composition pellets with a size of 2 to 5 mm through extrusion molding, dried in an oven at 60 to 80 ° C, and subjected to a particle size selection process to form a thermoplastic elastomer composition. It is characterized by a thermoplastic elastomer composition for producing and a method for producing a polar navigation ship cable coated therewith.
Therefore, the present invention provides flexibility, cold resistance, oil resistance, flame retardancy and resistance compared to the insulation coating composition of conventional polar navigation ship cables by adjusting the type of resin used in the insulation coating composition of each configuration, additives and fillers and their amount. By improving ice icing properties, when applied to ships operating in polar regions, electrical, mechanical, and chemical properties as well as workability and productivity can be improved.

Description

High flame retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance, polar navigation ship cable coated therewith, and manufacturing method thereof flexibility, cold resistance, oil resistance and ice accretion resistance}

The present invention relates to a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance, and a method for manufacturing a polar navigation ship cable coated therewith, and more particularly, to the types of resins used in each component of the insulation coating composition. , Additives and fillers, and adjusting their amount, improve flexibility, cold resistance, oil resistance, flame retardancy and ice icing resistance compared to the conventional insulation coating composition of polar navigation ship cables, and electrical, mechanical, and chemical properties when applied to polar navigation ships In addition to properties, it relates to a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance, and ice icing resistance that can improve workability and productivity, a polar navigation ship cable coated therewith, and a manufacturing method thereof.

According to the National Snow and Ice Data Center, as of August 15, 2018, the Arctic sea ice area was about 5.7 million square kilometers, larger than in 2012, but the average from 1981 to 2010 The overall trend of sea ice extent is declining, with 1.58 million square kilometers less than sea ice extent.

As such, the decrease in the Arctic sea ice area has a considerable impact on the global environmental system, but in terms of the shipbuilding/marine industry, the opening of the Arctic route in summer can lead to demand for new ice-sea vessels or polar offshore plants, providing new opportunities. .

In particular, as the Polar Code took effect in January 2017, all newly built ships are subject to the Polar Code, and interest in the safety of ships operating in the polar region is also increasing. winterization) is also a trend that is considered very important from the point of view of ship design and operation.

Accordingly, the demand for cables that can withstand extreme temperatures is increasing, and the level of technical requirements is also increasing.

Cables are used to transmit communication signals and electricity to equipment/equipment in polar icebreakers and drilling facilities, and must transmit current stably even in cryogenic conditions of minus 70℃, and must not be cracked even in external shocks and bending.

Therefore, the cable sheath material market for special ships is progressing according to the expansion of high value-added special purpose ships worldwide. Cables used for ships equipped with crude oil and gas production facilities or special ships for polar regions maintain cold flexibility even in extreme maritime environments such as polar regions, and have strong resistance to heat, oil vapor, and ozone generated from the lower deck of the ship. material is required

In addition, as a fire on board is directly related to large-scale human resources, ship materials have particularly strict requirements for fire safety. In case of fire, smoke generation should be minimized, and halogen or corrosive gases that cause great damage to machinery and people should not be generated.

In addition, in the case of ships operating in polar waters, an ice accretion or icing phenomenon occurs in upper structures or various devices. This icing phenomenon is caused by moisture in the air, snow, rain, fog, and sea water spray blowing from the sea during ship operation. is considered

This icing problem impairs the stability of the ship, interferes with the operation of various equipment, and deteriorates the work and safety of the crew, so it does not satisfy the International Convention for the Safety of Life at Sea (SOLAS) or various regulations, ultimately leading to safe navigation of the ship. Since this makes it impossible, technologies to prevent or mitigate this icing phenomenon are required in ship design.

However, most of these technologies have technological competitiveness overseas and preoccupy related markets, so the barriers to market entry that domestic shipyards and equipment companies experience are relatively high, so it is urgent to develop core technologies in related fields in Korea as well.

In addition, since wire manufacturers have been improving productivity by increasing the extrusion speed of cables as high as possible, the insulation coating material for cables must satisfy the extrusion processability as well as the above physical properties.

Accordingly, there is an urgent need to develop a cable insulation coating composition having excellent flexibility, cold resistance, oil resistance, ice accretion resistance, and flame retardancy, and a cable for polar navigation vessels using the composition.

In order to improve these characteristics, prior art and patent documents that have been developed and applied for patents are as follows.

Patent Registration No. 10-1336290 includes preparing a core wire containing tin-plated copper; stacking a plurality of insulating layers including Teflon on the core wire; stacking a plurality of polymer semiconductor layers including Teflon on the insulating layer by taping; laminating a plurality of polymer layers containing polystyrene on the polymer semiconductor layer by taping; laminating a first braided wire layer containing glass fibers on the polymer layer; It relates to a method for manufacturing a cable for cryogenic use, including laminating a second braided wire layer containing SUS on the first braided wire layer by taping, and the physical properties and use of the cable even in a cryogenic state such as a cargo hold of an LNG carrier It has an effect that allows the characteristic to be maintained. Patent Registration No. 10-1716231 discloses a polyketone solution prepared from a copolymer of carbon monoxide, ethylene and propylene, polyketone fibers having excellent strength from the polyketone solution, and a polyketone cryogenic insulation material manufacturing method including the same. Regarding Patent No. 10-1792609, the inner sheath and outer sheath are composed of Low Smoke Zero Halogen (LSHZ), so that the physical properties and usage characteristics of the cable are continuously maintained even in cryogenic conditions of about -65℃ or less. Disclosed is a method of manufacturing a power cable for marine vessels. Publication No. 10-2015-0090358 discloses a composition consisting of 150 to 200 parts by weight of an inorganic flame retardant, 5 to 10 parts by weight of a flame retardant aid, 20 to 30 parts by weight of a plasticizer, and 5 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of a base resin. A peroxide for cryogenic use that can be crosslinked to a conductor or insulator through a crosslinking method to be used up to -60℃, so it can be used in polar regions, and is manufactured through a crosslinking method to simplify the manufacturing process and reduce manufacturing costs. Bridged solar cables are provided. Patent Publication No. 10-2019-0141387 has cold resistance of -40 ° C, and at the same time, oil resistance and chemical resistance, which are in a trade off, are not deteriorated, mechanical properties are excellent, and even though a non-halogen flame retardant is used, Nevertheless, a non-halogen-based sheath composition having excellent flame retardancy, being environmentally friendly, and having excellent processability as well as cold resistance and oil resistance, and a cable including a sheath layer formed therefrom are provided. Patent Publication No. 10-2019-0055932 relates to an insulating composition having excellent cold resistance and flexibility and a cable including an insulating layer formed therefrom. In addition, it is possible to easily manufacture a cable including an insulation composition that is environmentally friendly and has excellent processability and an insulation layer formed therefrom. Patent Registration No. 10-0644490 discloses 100 parts by weight of a base resin including 5 to 80 parts by weight of chlorosulfonated polyethylene and 30 to 90 parts by weight of an ethylene vinyl acetate copolymer having a content of 28 to 80% by weight of vinyl acetate; As a flame retardant, 30 to 150 parts by weight of a metal hydroxide; 1 to 30 parts by weight of a cold-resistant plasticizer; 0.5 to 10 parts by weight of a silane-based coupling agent; 0.5 to 8 parts by weight of a crosslinking aid; And 3 to 20 parts by weight of a crosslinking agent; relates to a flame retardant wire covering material composition comprising a flame retardant wire covering material composition and a marine cable using the same, wherein the flame retardant wire covering material composition has excellent oil resistance to oil components without deterioration in mechanical properties , It has the advantage of providing excellent durability, such as having cold resistance that can withstand even at -40 ° C, minimizing the emission of toxic gases in the event of a fire and providing excellent flame retardancy and a marine cable using the same. Registration Patent No. 10-0745170 is made of non-asbestos as a composite insulation fiber by mixing para-aramid fiber, silica fiber, and fluorine fiber, Teflon fiber, and maintains the properties of the fiber for a long time even at high and low temperatures, and has fire resistance and composite fibers using heat-resistant and cold-resistant composite fibers having excellent non-adhesiveness, low friction coefficient, oiliness, electrical properties, and chemical resistance as well as good insulation properties, and a method for manufacturing the same, tape-type, tube-type (loop-type) Heat-resistant and cold-resistant composite insulation fibers composed of fabrics in the form of fabrics, etc., do not change their properties even after a long period of time at temperatures of over 1,000℃ and low temperatures of minus 270℃, so heat and cold resistance are required. It has characteristics that can be used for the purpose of. Patent Registration No. 10-1457612 provides a non-halogen-based polymer resin composition and a polymer resin material manufactured using the composition, particularly cables for ships or drillships. The polymeric resin material prepared using the composition according to the present invention maintains flexibility even at a low temperature of -40 ° C, has flame retardancy and satisfies the standard characteristics of general ship cables, and has oil resistance inside offshore structures such as oil rigs and oil drilling structures, or satisfies the standard characteristics for use in drillships. Registered Patent No. 10-1535079 uses magnesium hydroxide instead of environmentally harmful substances such as antimony, bromine, and chlorine, which are previously used as flame retardants, so it is environmentally friendly and has excellent flame retardant properties, and uses polypropylene and high-density polyethylene to increase tensile strength. and mechanical strength are improved, and mechanical properties such as durability and abrasion resistance are improved, cross-linking between molecules is strong, and at the same time, resistance to vibration is strong, destruction and thermal deformation due to temperature can be prevented, and intermolecular cross-linking is realized. It is resistant to scratches and resistant to vibration at the same time by realizing cross-linking, and can prevent destruction and thermal deformation according to temperature, so it can be applied to insulation materials required for manufacturing wires, power lines, communication lines and cables, and at the same time, in extreme and high-temperature environments. It can be used as wire material for automobiles, interior materials for automobiles such as artificial leather and filler, and wire material for ships requiring vibration and durability. PO (Poly Olefin), TPE (Thermo Plastic Elastomer), To provide a TOE flame retardant resin composition capable of securing flame retardancy by being used as a flame retardant material for TPR (Thermo Plastic Rubber), TPO (Thermo Plastic Olefin) and TPEE (Thermoplastic Polyether Ester Elastomer) and a manufacturing method thereof. Patent Registration No. 10-0874990 relates to a composite resin composition for cable coating that is resistant to solvents contained in paint and has excellent cold resistance, oil resistance, abrasion resistance, and tear resistance, and specifically, polyvinyl chloride (PVC) and Thermoplastic polyurethane elastomer (TPU) with excellent compatibility and excellent chemical resistance is alloyed with polyvinyl chloride (PVC), and more preferably maleic anhydride-modified ethylene-vinyl acetate (EVA-g-MAH) as a compatibilizer ), by containing a surface-modified inorganic flame retardant or a mixture thereof, it completely improves the phenomenon of rapid drop in elongation retention after aging due to degradation of polymer molecular chains by paint or solvent, and has cold resistance, oil resistance, abrasion resistance, and tear resistance. Provided is an excellent composite resin composition for coating a cable whose resistance properties are comparable to those of crosslinked rubber. Publication No. 10-2019-0022909 relates to a crosslinkable polymer composition for use as a sheath layer of a cable and a cable comprising a crosslinked layer obtained from the composition, wherein the crosslinkable polymer composition is an ethylene vinyl acetate copolymer and an ethylene methyl acrylate copolymer, a flame retardant filler and a crosslinking agent.

The technical problem to be achieved by the present invention has been devised to solve the above-mentioned needs, and the manufacture of a highly retardant thermoplastic elastomer composition having good constructor convenience and excellent flexibility, cold resistance, oil resistance, and ice icing resistance, and a polar navigation ship cable coated therewith It is an object of the present invention to provide a method.

The present invention for achieving the above object is a red master batch (master batch) manufacturing step and; A fatty acid surface treatment step of preparing a flame retardant surface-treated with a fatty acid; A silane surface treatment step of preparing a flame retardant surface-treated with silane; a step of preparing a cross-linked insulating composition; preparing a cross-linked semiconducting composition; 10,000 parts by weight of thermoplastic elastomer selected from ethylene terpolymer and 15,000 to 50,000 parts by weight of surface-treated flame retardant, 500 to 2,000 parts by weight of self-lubricant selected from polysiloxane copolymer, 200 to 200 parts by weight of auxiliary flame retardant selected from modified silicone oil 1,000 parts by weight, 100 to 600 parts by weight of antioxidant, 100 to 400 parts by weight of stabilizer selected from thiophenol compounds, 500 to 3,000 parts by weight of sunscreen pigment, 5,000 to 16,000 parts by weight of compatibilizer selected from ethylene copolymer sequentially put into a kneader mixer and melt-kneaded at a temperature of 140-170 ° C. for 10-60 minutes, and after the melt-kneading step, 2-8 parts by weight of the masterbatch and 6,000-12,000 parts by weight of polyethylene resin in the mixing mixer are sequentially added. , and melt-mixed for 1 to 30 minutes at a temperature of 140 to 170 ° C. The dough is transferred to a single screw or twin screw extruder to produce composition pellets with a size of 2 to 5 mm through extrusion molding, and then to an oven at 60 to 80 ° C. A step of preparing a thermoplastic elastomer composition by drying in a step of particle size selection and preparing a thermoplastic elastomer composition; An insulated wire manufacturing step in which a first semiconducting layer, an insulating layer, and a second semiconducting layer are formed on the outer periphery of a conductor made of a metal wire, a metal plated wire, or a metal alloy wire; ; a shielding layer forming step of forming a shielding layer on an outer periphery of the insulated wire on which the semiconducting layer is formed; A taping step of taping with a binder tape while passing an insulated wire formed with a plurality of combined shielding layers and a filler together with a taping column of a cable taping machine; an inner coating layer forming step of molding an inner coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition production step on the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed; An external reinforcing layer forming step of forming a reinforcing layer by single or two or more plying and braiding of metal wire, inorganic fiber yarn, aramid fiber yarn, etc. on the outer periphery of the insulated wire on which the inner coating layer is formed in the inner coating layer forming step; Through an outer coating layer forming step of forming an outer coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition production step on the outer periphery of the insulated wire on which the reinforcing layer produced in the external reinforcing layer forming step is formed; A highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance and a polar navigation ship cable coated therewith can be easily manufactured.

The present invention for achieving the above object, the red master batch (master batch) manufacturing step and; A fatty acid surface treatment step of preparing a flame retardant surface-treated with a fatty acid; A silane surface treatment step of preparing a flame retardant surface-treated with silane; a step of preparing a cross-linked insulating composition; preparing a cross-linked semiconducting composition; 10,000 parts by weight of thermoplastic elastomer selected from ethylene terpolymer and 15,000 to 50,000 parts by weight of surface-treated flame retardant, 500 to 2,000 parts by weight of self-lubricant selected from polysiloxane copolymer, 200 to 200 parts by weight of auxiliary flame retardant selected from modified silicone oil 1,000 parts by weight, 100 to 600 parts by weight of antioxidant, 100 to 400 parts by weight of stabilizer selected from thiophenol compounds, 500 to 3,000 parts by weight of sunscreen pigment, 5,000 to 16,000 parts by weight of compatibilizer selected from ethylene copolymer sequentially into a kneader mixer and melt-kneaded at a temperature of 140-170 ° C. for 10-60 minutes, and after the melt-kneading step, 2-8 parts by weight of the masterbatch and 6,000-12,000 parts by weight of the polyethylene resin are added to the mixing mixer. After sequentially introducing and transferring the melt-mixed loaf dough at a temperature of 140 ~ 170 ℃ for 1 ~ 30 minutes to a single screw or twin screw extruder to produce composition pellets with a size of 2 ~ 5 mm through extrusion molding, A step of preparing a thermoplastic elastomer composition by drying in an oven and undergoing a particle size selection process to prepare a thermoplastic elastomer composition; An insulated wire manufacturing step in which a first semiconducting layer, an insulating layer, and a second semiconducting layer are formed on the outer periphery of a conductor made of a metal wire, a metal plated wire, or a metal alloy wire; ; a shielding layer forming step of forming a shielding layer outside the insulated wire on which the semiconducting layer is formed and manufactured in the insulated wire manufacturing step on which the semiconducting layer is formed; A taping step of taping with a binder tape while passing an insulated wire formed with a plurality of combined shielding layers and a filler together with a taping column of a cable taping machine; an inner coating layer forming step of molding an inner coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition production step on the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed; An external reinforcing layer forming step of forming a reinforcing layer by plying and braiding single or two or more types of metal wire, inorganic fiber yarn, or aramid fiber yarn on the outer circumference of the insulated wire on which the inner coating layer is formed in the inner coating layer forming step; Through an outer coating layer forming step of forming an outer coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition production step on the outer periphery of the insulated wire on which the reinforcing layer produced in the external reinforcing layer forming step is formed; It is possible to easily manufacture a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance, and ice icing resistance, and a polar navigation ship cable coated therewith.

1 is a process flow diagram illustrating a method of practicing the present invention;

An embodiment of the present invention, which can meet the above objectives and characteristics in the best form, will be described in detail based on FIG. 1 as follows.

According to the process flow diagram of Figure 1

After maintaining the feeder temperature of the twin extruder at 40 to 60 ° C and raising the internal temperature of the screw-equipped extruder to 80 to 160 ° C, 10,000 weight of ethylene copolymer or polyethylene resin is first added to the feeder After melting by adding 100 to 500 parts by weight of a lubricant selected from calcium stearate, zinc stearate, and barium stearate, and 4,000 to 8,000 parts by weight of red phosphorus, A red master batch manufacturing step of kneading for 60 minutes and then cutting through a melt extrusion process to make polymer pellets having a size of about 2 to 5 mm;

Magnesium hydroxide phosphate having an average particle diameter of 0.1 to 20 μm, calcium hydroxide, aluminum hydroxide or magnesium hydroxide alone or in combination with metal hydrates 10,000 parts by weight of a flame retardant selected from more than one species and 7,500 to 15,000 parts by weight of an organic solvent selected from ethanol, isopropyl alcohol, chloroform, and dimethylsulfoxide, pentadecanoic 2,500 to 5,000 parts by weight of a fatty acid selected from pentadecanoic acid, hexadecanoic acid, octadecanoic acid, and dodecanoic acid in an aeration blender A fatty acid surface treatment step of the flame retardant to prepare a flame retardant surface-treated with fatty acid by continuously supplying to a through-flow blender, kneading and filtering, and drying at 60 to 120 ° C;

In a reactor equipped with an agitator, 9,500 parts by weight of alcohol such as methanol or ethanol, 500 parts by weight of distilled water, vinyl silane, tris (methoxyethoxy) vinylsilane [tris (methoxyethoxy) )vinyl silane], triisopropoxy-vinylsilane, trimethoxy(vinyl)silane, tetraethoxy silane, methyltriethoxysilane , methyltrimethoxysilane, methyltri(2-methoxyethoxy)silane, 3-methacryloyloxypropyl-trimethoxysilane, 3-mercaptopropyl-tri Add 1,000 to 5,000 parts by weight of a reactive silane selected from methoxysilane (3-mercaptopropyl-trimethoxysilane) and 3-aminopropyl-trimethoxysilane (3-aminopropyl-trimethoxysilane) alone or two or more, and add hydrochloric acid or acetic acid 19,000 to 45,000 parts by weight of a flame retardant having an average particle diameter of 0.01 to 20 μm was added to a solution stirred at a speed of 50 to 300 RPM for 20 to 60 minutes while maintaining pH 3 to 5 by adding 500 to 2,000 parts by weight of an acid catalyst, followed by adding 20 to 45,000 parts by weight of a flame retardant at a speed of 50 to 300 RPM. A silane surface treatment step of the flame retardant to prepare a flame retardant surface-treated with silane by stirring for ~120 minutes, filtering, and drying at 60 ~ 120 ° C;

An ethylene polymer selected from polyethylene, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer in a mixing mixer in Kneader, Henschel or Banbury ) or ethylene copolymer (ethylene copolymer) 10,000 parts by weight, 6,000 to 10,000 parts by weight of the surface-treated flame retardant produced in the fatty acid surface treatment step of the flame retardant or the silane surface treatment step of the flame retardant, silica or carbon black ), magnesium carbonate, aluminum silicate, magnesium silicate, 10 to 1,200 parts by weight of a reinforcing agent selected from diatomaceous earth, 1 to 600 parts by weight of zinc oxide, thiodiethylene bis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate] [thiodiethylene bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or thiodipropionic acid dioctadecyl ester (thiodipropionic acid dioctadecylester), distearyl thiodipropionate, 5 to 20 parts by weight of an antioxidant used alone or in combination of two or more among sulfur compounds in 3-mercaptopropionic acid, 10 to 120 parts by weight of fatty acid or fatty acid metal salt lubricant is sequentially administered and kneaded at a temperature of 80 to 130 ° C for 5 to 60 minutes. Insulation composition pellets having a size of ~ 5 mm are prepared. 100 to 500 parts by weight of organic peroxide is added to 16,025 to 21,340 parts by weight of the insulation composition pellets in a separate kneader, Henschel, or a mixing mixer in Banbury, and at a temperature of 60 to 100 ° C. Kneading for 60 minutes to form a cross-linked insulating composition A step of preparing a cross-linked insulating composition to produce pellets;

10,000 parts by weight of polymeric elastomer and electro-conductive carbon black, carbon nanotube, graphite, or graphene in a mixing mixer in Kneader, Henschel, or Banbury ), 500 to 2,000 parts by weight of an electrically conductive filler selected from among, 43 to 64 parts by weight of an antioxidant, and 25 to 40 parts by weight of a fatty acid or fatty acid metal salt lubricant are sequentially added to 100 to 2,000 parts by weight. The kneaded dough at a temperature of 140 ° C for 10 to 60 minutes is transferred to a single-screw or twin-screw extruder to produce semiconductive elastomer pellets having a surface resistance of 10 ⁵ to 10 ⁸ Ω and a size of 3 to 5 mm through extrusion molding. 10,568 to 12,104 parts by weight of the semiconducting elastomer pellets and 95 to 150 parts by weight of the organic peroxide are administered to a separate kneader, Henschel, or mixing mixer in Banbury, and kneaded at a temperature of 60 to 100 ° C. for 10 to 60 minutes to obtain a cross-linked semiconducting composition pellet a step of preparing a cross-linked semiconducting composition;

Ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1,6-octadiene, ethylene-propylene-1 ,9-decadiene (ethylene-propylene-1,9-decadiene), ethylene-propylene-5-methyl-1,4-hexadiene (ethylene-propylene-5-methyl-1,4-hexadiene), ethylene-propylene -3,7-dimethyl-1,6-octadiene, ethylene-propylene-dicyclopentadiene, ethylene-propylene-1,3-cyclopentadiene ), ethylene-propylene-1,4-cyclohexadiene, ethylene-propylene-1,5-cyclooctadiene, Ethylene-propylene-1,5-cyclododecadiene, ethylene-propylene-tetrahydroindene, ethylene-propylene-methyltetrahydroindene -propylene-methyl tetrahydroindene), ethylene-propylene-5-propenyl-2-norbornene, ethylene-propylene-5-isopropylidene-2-norbornene propylene-5-isopropylidene-2-nor bornene), ethylene-propylene-5-(4-cyclopentenyl)-2-norbornene, ethylene-propylene-5-(4-cyclopentenyl)-2-norbornene 5-cyclohexylidene-2-norbornene (ethylene-propylene-5-cyclohexylidene-2-norbo rnene), ethylene-propylene-5-vinyl-2-norbornene, ethylene-propylene-5-ethylidene-2-norbornene -2-norbornene), ethylene-propylene-5-vinylidene-2-norbornene, ethylene-propylene-5-methylene-2-norbornene 5-methylene-2-norbornene) 10,000 parts by weight of a thermoplastic elastomer selected from ethylene terpolymers and 15,000 to 50,000 parts by weight of a surface-treated flame retardant selected from a flame retardant fatty acid surface treatment step or a flame retardant silane surface treatment step, poly( poly(dimethylsiloxane)-poly(ethylene oxide) copolymer, poly(dimethylsiloxane)-poly(propylene oxide) copolymer ], poly(dimethylsiloxane)-poly(butylene oxide) copolymer [poly(dimethylsiloxane)-poly(butylene oxide) copolymer], poly(dimethylsiloxane)-poly(phenylene oxide) copolymer [poly(dimethylsiloxane)- poly(phenylene oxide) copolymer] 500 to 2,000 parts by weight of a self-lubricant selected from the polysiloxane copolymer in the copolymer, poly(methoxymethyl)-co-poly(methylhydro)siloxane [poly(methoxymethyl)-co-poly( methylhydro)siloxane], poly(ethoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane [poly(ethoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane], poly (Methoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane [Poly(methox ymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane], polymethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methylhydro)siloxane [Poly(methylperfluorobutylethyl) -co-poly(methylethoxy)-co-poly(methylhydro)siloxane], poly(ethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methylhydro)siloxane[poly(ethylperfluorobutylethyl)-co 200 to 1,000 parts by weight of an auxiliary flame retardant selected from modified silicone oil in -poly(methylethoxy)-co-poly(methylhydro)siloxane, tetrakis[methylene-3(3',5'-di-tert -Butyl-4'-hydroxyphenyl) propionate] methanetetrakis [methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] methane or butylhydroxytoluene , Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate)][octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)- propionate)], poly(1,2-dihydro-2,2,4-trimethylquinoline) [poly(1,2-dihydro-2,2,4-trimethyl quinoline)], 2,6-di-tert- Butyl-4-methylphenol (2,6-di-tert-butyl-4-methyl phenol), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) methane [tetrakis [methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane], tris(2,4-di-tert-butyl-phenyl) phosphite [tris(2,4-di-tert- butyl-phenyl) phosphite], tris(2,4-ditert-butylphenyl) phosphite) [tris(2,4-ditert-butylph 100 to 600 parts by weight of an antioxidant selected from enyl) phosphite], 4,4'thiobis (2-tert-butyl-5-methylphenol) [4,4'thiobis (2-t-butyl-5-methylphenol) )] B, 2,5-dimethyl-4-(4-butylbenzylthio)phenol [2,5-dimethyl-4-(4-butylbenzylthio)phenol], 2-dimethylbenzyl-4,4(hexylthio)phenol [2-dimethylbenzyl-4,4(hexylthio)phenol], 2,4-dibutyl-6-(butylthio)phenol [2,4-dibutyl-6-(butylthio)phenol],2,6-bis(1 Selected from thiophenol compounds among ,1-dimethylbutyl)-4-(1,1-dimethylbutylthio)phenol [2,6-bis(1,1-dimethylbutyl)-4-(1,1-dimethylbutylthio)phenol] 100 to 400 parts by weight of the stabilizer, selected from titanium dioxide, carbon black, zinc oxide, tungsten oxide, or cesium oxide alone or two or more 500 to 3,000 parts by weight of UV-blocking pigment, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer ( ethylene-acrylic acid copolymer), ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-butyl methacrylate copolymer butyl methacrylate copolymer) 5,000 to 16,000 parts by weight of a compatibilizer selected from ethylene copolymers sequentially with a kneader mixer or It is put into a mixing mixer made of a Banbury mixer, melt-kneaded at a temperature of 140-170 ° C. for 10-60 minutes, and after the melt-kneading step is finished, red phosphorus master prepared in the master batch manufacturing step in the mixing mixer Batch 200 ~ 800 parts by weight and polyethylene resin selected from high density polyethylene, medium density polyethylene, linear low density polyethylene, and low density polyethylene 6,000 ~ 12,000 By sequentially introducing parts by weight, the melt-mixed lump dough is transferred to a single screw or twin screw extruder at a temperature of 140 to 170 ° C. for 1 to 30 minutes to prepare composition pellets having a size of 2 to 5 mm through extrusion molding, and then 60 to 80 A step of preparing a thermoplastic elastomer composition by drying in an oven at ° C. and preparing a thermoplastic elastomer composition through a particle size selection process;

The semiconducting elastomer pellets prepared in the step of preparing the crosslinked semiconductive composition were placed in a first hopper, the pellets of the crosslinked insulating composition prepared in the step of preparing the crosslinked insulating composition were placed in a second hopper, and the crosslinked semiconducting After the semiconductive elastomer pellets prepared in the composition manufacturing step are injected into the third hopper, a metal wire or metal plated wire is placed on the head of the extruder to which the co-extrusion die is attached. wire) and alloy wire (metal alloy wire) while passing through the conductor, the temperature conditions are 100 ~ 120 ℃ for cylinder 1 and cylinder 2, 105 ~ 125 ℃ for cylinder 3, extrusion head 110 ~ 130 ℃, the extrusion die (extrusion die) is extruded at a speed of 10 ~ 40kg / hour at a temperature condition of 110 ~ 130 ℃, a continuous vulcanization pipe maintained at 80 ~ 120 ℃ and 10 ~ 20 atmospheric pressure an insulated wire manufacturing step having a semiconducting layer formed thereon through an extrusion vulcanization step at a speed of 20 to 50 m/min to produce an insulated wire having a semiconducting layer;

The outer periphery of the insulated wire having the semiconducting layer manufactured in the manufacturing step of the insulated wire having the semiconducting layer is taped with a metal tape or a metal coating film or braided with a metal wire among metal wires, metal plating wires, or alloy wires to form a shielding layer. Constituting a shielding layer forming step;

A taping column of a cable taping machine passes an insulated wire formed with a plurality of combined shielding layers and a filler together, while polyester, polyketone, or polyimide A taping step of taping with a binder tape selected from polyimide and polysulfone tapes;

Cylinder 1 and Cylinder 2: 100 ~ 180 ℃, Cylinder 3: 120 ~ 200 ℃, Die: 120 ~ an inner coating layer forming step of forming an inner coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition preparation step at a temperature of 200 ° C. at a rate of 5 to 50 kg / hour;

Metal wires such as copper wire, metal-coated copper wire, iron wire, nickel wire, glass fiber yarn, basalt fiber yarn, elvan fiber yarn, ceramic fiber yarn, carbon fiber yarn on the outer periphery of the insulated wire on which the inner coating layer is formed in the inner coating layer forming step An external reinforcing layer forming step of forming a reinforcing layer by plying and braiding single or two or more of the same inorganic fiber yarn or aramid fiber yarn;

Cylinder 1 and Cylinder 2: 100 ~ 180 ℃, Cylinder 3: 120 ~ 200 ℃, Die: Through an outer coating layer forming step of forming an outer coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition preparation step under a temperature condition of 120 to 200 ° C. at a rate of 5 to 50 kg / hour;

A highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance and a polar navigation ship cable coated therewith can be easily manufactured.

Ethylene terpolymers in the melt-kneading step are thermoplastic elastomers, ethylene-propylene-1,4-hexadienna, ethylene-propylene-1,6-octadiene, ethylene-propylene-1,9-decadiene, ethylene-propylene -5-methyl-1,4-hexadiene, ethylene-propylene-dicyclopentadiene, ethylene-propylene-1,3-cyclopentadiene, ethylene-propylene-1,4-cyclohexadiene, ethylene-propylene- 1,5-cyclooctadiene, ethylene-propylene-1,5-cyclododecadiene (ethylene-propylene-tetrahydroindene, ethylene-propylene-tetrahydroindene, ethylene-propylene-methyltetrahydroindene, Ethylene-propylene-5-propenyl-2-norbornene, ethylene-propylene-5-isopropylidene-2-norbornene, ethylene-propylene-5-(4-cyclopentyl)-2-norbornene, ethylene-propylene -5-cyclohexylidene-2-norbornene, ethylene-propylene-5-vinyl-2-norbornene, ethylene-propylene-5-ethylidene-2-norbornene, ethylene-propylene-5-vinylidene-2 It is selected from norbornene and ethylene-propylene-5-methylene-2-norbornene, and 100 parts by weight is used.

The surface-treated flame retardant selected in the flame retardant fatty acid surface treatment step or the flame retardant silane surface treatment step of the melt-kneading step is used in an amount of 150 to 500 parts by weight as a main flame retardant for imparting flame retardancy to the composition.

At this time, when the surface-treated flame retardant is less than 150 parts by weight, the flame retardancy of the composition is lowered, and when it is 500 parts by weight or more, mechanical properties are lowered.

The self-lubricating agent in the melt-kneading step imparts ice resistance to the surface of the cable after being extruded as a coating, and poly(dimethylsiloxane)-poly(ethylene oxide) copolymer, poly(dimethylsiloxane)-poly(propylene oxide) copolymer, poly 5 to 20 parts by weight of (dimethylsiloxane)-poly(butylene oxide) copolymer and poly(dimethylsiloxane)-poly(phenylene oxide) copolymer are used.

At this time, if the self-lubricant is less than 5 parts by weight, the ice icing resistance is poor, and if it is more than 20 parts by weight, the compatibility with the outside is poor.

The auxiliary flame retardant of the melt-kneading step imparts flame retardancy to the composition, and poly(methoxymethyl)-co-poly(methylhydro)siloxane], poly(ethoxymethyl)-co-poly(dimethyl)-co-poly(methyl) Hydro)siloxane, poly(methoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane, polymethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methyl 2 to 10 parts by weight of hydro)siloxane, polyethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methylhydro)siloxane is used.

At this time, when the auxiliary flame retardant is less than 2 parts by weight, the flame retardancy of the composition is lowered, and when it is 10 parts by weight or more, the kneading property is lowered.

The antioxidant in the melt-kneading step provides thermal oxidation occurring during kneading and long-term thermal stability of the composition, and tetrakis[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, butylhydroxytoluene, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate), poly(1,2-dihydro-2 ,2,4-trimethylquinoline), 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)methane, 1 to 6 parts by weight of tris(2,4-di-tert-butyl-phenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite) is used,

At this time, when the antioxidant is less than 1 part by weight, the heat resistance stability of the composition is poor, and when it is 6 parts by weight or more, it migrates to the outside.

The stabilizer in the melt-kneading step imparts light and thermal stability to the composition and is 4,4'thiobis(2-tert-butyl-5-methylphenol) or 2,5-dimethyl-4-(4-butylbenzylthio )phenol, 2-dimethylbenzyl-4,4(hexylthio)phenol, 2,4-dibutyl-6-(butylthio)phenol,2,6-bis(1,1-dimethylbutyl)-4-(1 , 1-4 parts by weight of 1-dimethylbutylthio) phenol is used.

At this time, when the stabilizer is less than 1 part by weight, the light stability of the composition is lowered, and when it is 4 parts by weight or more, it migrates to the outside.

The sunscreen pigment in the melt-kneading step imparts color to the composition and is selected from among titanium dioxide, carbon black, zinc oxide, tungsten oxide, and cesium dioxide in an amount of 5 to 30 parts by weight, but the present invention is limited thereto not.

At this time, when the amount of the sunscreen pigment is less than 5 parts by weight, the light stability of the composition is deteriorated, and when it is greater than 30 parts by weight, the compoundability is deteriorated.

In addition, pigments may be blended to impart color to the composition. Table 1 summarizes the pigments and colors.

color classification Corresponding pigment White titanium oxide Red iron oxide White calcium carbonate green chromium oxide black carbon black

In the step of manufacturing the insulated wire in which the semiconducting layer is formed, the conductor is a component for transmitting signals or power, and it is preferable to use a copper wire having high electrical conductivity, a tin-plated copper wire, or a nickel-plated copper wire, but it is not limited to the present invention.

As the conductor, it is preferable to use a plurality of metal aggregate wires in addition to a single metal wire.

The filler in the taping step maintains the concentricity of the insulated wire, serves as waterproof, and is preferably non-hygroscopic inorganic fiber yarn or polymer fiber yarn, but is not limited to the present invention.

The binder tape of the taping step combines the filler and the insulated wire to maintain a concentric circle, and it is preferable to use a polyester, polykapton, polyimide, or polysulfone tape, but it is not limited to the present invention.

The external reinforcing layer forming step and the external reinforcing layer are metal wires such as copper wire, metal-plated copper wire, iron wire, nickel wire, glass fiber yarn, basalt fiber yarn, or elvan fiber to protect insulation from external impact and prevent gnawing by rodents. It is selected from yarn, ceramic fiber yarn, inorganic fiber yarn such as carbon fiber yarn, and aramid fiber yarn, and is formed by plying and braiding single or two or more kinds.

A method for manufacturing a highly retardant composition for cable insulation coating having flexibility, oil resistance and heat resistance according to the present invention will be examined in more detail, and examples thereof will be described as follows.

The present invention will be described in more detail through the following examples.

However, the scope of the present invention is not limited only to the illustrated examples.

Example 1

After maintaining the feeder temperature of the twin-screw extruder at 55 ° C and raising the internal temperature of the extruder to 135 ° C, 10,000 g of ethylene vinyl acetate copolymer was first added to the feeder to melt, and then 200 g of calcium stearate and 7,000 g of red phosphorus were added to the feeder. After kneading for 20 minutes, it was cut through a melt extrusion molding process to prepare a red master batch having a size of about 3 to 5 mm.

10,000 parts by weight of magnesium hydroxide having an average particle diameter of 10 μm, 12,000 parts by weight of ethanol, and 4,000 parts by weight of octadecanoic acid are continuously supplied to an aeration blender, kneaded and filtered, and dried at 80 ° C to obtain octadecanoic acid A surface-treated magnesium hydroxide was prepared.

10,000 g of ethylene-propylene copolymer, 8,000 g of magnesium hydroxide surface-treated with octadecanoic acid, 1,200 g of diatomaceous earth, 600 g of zinc oxide, thiodiethylene bis[3-(3,5-di-tert-butyl -4-hydroxyphenyl) propionate] 15 g, thiodipropionic acid dioctadecyl ester 2 g, and octadecanoic acid 110 g were sequentially administered to a Benbury mixer and kneaded at 80 ° C for 20 minutes, and then 420 parts by weight of dicumyl oxide was additionally added thereto and kneaded at a temperature of 60° C. for 10 minutes to prepare ethylene-propylene copolymer pellets.

10,000g of ethylene propylene copolymer, 1,400g of electrically conductive carbon black, 52g of tris(2,4-ditert-butylphenyl)phosphite, and 30g of zinc stearate were sequentially added to a 20L kneader and kneaded at 100℃ for 20 minutes. The lump dough was transferred to a twin-screw extruder and extruded to prepare semi-conductive ethylene-propylene copolymer pellets having a surface resistance of 10 ⁶ Ω and a size of 3 to 5 mm. In a separate 20L Henschel mixer, the prepared semiconducting ethylenepropylene copolymer pellets and 120 g of dicumyl peroxide were administered and kneaded at 80° C. for 20 minutes to prepare crosslinked semiconducting ethylenepropylene copolymer pellets.

10,000 g of ethylene-propylene-1,4-hexadiene, 25,000 g of magnesium hydroxide surface-treated with octadecanoic acid, 1,100 parts by weight of poly(dimethylsiloxane)-poly(ethylene oxide) copolymer, poly(methoxy Methyl)-co-poly(methylhydro)siloxane 500g, tetrakis[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane 300g, 4,4' 200 g of thiobis (2-tert-butyl-5-methylphenol), 1,500 g of carbon black, and 1,000 g of ethylene-vinyl acetate copolymer were put into a kneader mixer and melt-kneaded for 30 minutes at a temperature of 150 to 155 ° C. 400 g of the masterbatch and 8,000 g of linear low-density polyethylene were added, melted and mixed at a temperature of 150 to 165 ° C for 10 minutes, and the dough was transferred to a twin-screw extruder to produce composition pellets having a size of 3 to 5 mm through extrusion molding. After drying in an oven at 80° C. and undergoing a particle size screening process, a thermoplastic elastomer composition was prepared.

The cross-linked semi-conductive ethylene-propylene copolymer pellets were injected into the first hopper, the ethylene-propylene copolymer pellets into the second hopper, and the cross-linked semi-conductive ethylene-propylene copolymer pellets into the third hopper. Cylinder 1 is 105°C, cylinder 2 is 110°C, cylinder 3 is 115°C, extrusion head is 115°C, and extrusion die is 120°C while passing a tinned wire with a diameter of 23Φmm through the head of an extruder to which a 32Φmm coextrusion die is attached. While extruding at a speed of 22 kg/hour under a temperature condition of 110℃ and passing a curing tube maintained at 15 atm at a speed of 30 m/min, an insulated wire having a semi-conductive layer is manufactured, and then braided with tin-plated wire to shield A single-screw extruder with a 78mm extrusion die attached after forming a layer and taping it with polyester tape while passing the insulated wire and the polypropylene yarn filler together with the shielding layer formed by combining three strands with the taping column of the cable taping machine. (Cylinder 1: 160°C, Cylinder 2: 170°C, Cylinder 3: 180°C, Die: 175°C) A thermoplastic elastomer composition is injected into a hopper and extruded to a thickness of 2 mm at a rate of 20 kg/hour to form an inner coating layer. and braided with iron wire to form a reinforcing layer, and a hopper of a single screw extruder (cylinder 1: 160 ° C, cylinder 2: 170 ° C, cylinder 3: 180 ° C, die: 175 ° C) to which an 84 mm die for extrusion is attached A highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and icing resistance by extruding to a thickness of 2.6 mm at a rate of 20 kg/hour to form an outer coating layer and a polar navigation ship cable coated with the thermoplastic elastomer composition Manufacturing is complete.

Example 2

After maintaining the feeder temperature of the twin-screw extruder at 55 ° C and raising the internal temperature of the extruder to 135 ° C, 10,000 g of ethylene vinyl acetate copolymer was first added to the feeder to melt, and then 200 g of calcium stearate and 7,000 g of red phosphorus were added to the feeder. After kneading for 20 minutes, it was cut through a melt extrusion molding process to prepare a red master batch having a size of about 3 to 5 mm.

9,500 g of ethanol, 500 g of distilled water, 1,000 g of 3-methacryloyloxypropyl-trimethoxysilane, and 600 g of acetic acid were added to a 20L reactor equipped with a temperature controller and a stirrer, followed by stirring at a speed of 100 RPM for 30 minutes. 30,000 g of magnesium hydroxide having an average particle diameter of 10 μm was administered, stirred at a speed of 200 RPM for 60 minutes, filtered, and dried at a temperature of 80 ° C. The surface was treated with 3-methacryloyloxypropyl-trimethoxysilane. Magnesium hydroxide was prepared.

10,000 g of ethylene-propylene copolymer, 8,000 g of magnesium hydroxide surface-treated with 3-methacryloyloxypropyl-trimethoxysilane, 1,200 g of diatomaceous earth, 600 g of zinc oxide, thiodiethylene bis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] 15 g, thiodipropionic acid dioctadecyl ester 2 g, and octadecanoic acid 110 g were sequentially administered to a Benbury mixer to reach 80 After kneading at ° C. for 20 minutes, 420 parts by weight of dicumyl oxide was additionally added thereto, and kneading was performed at a temperature of 60 ° C. for 10 minutes to prepare ethylene-propylene copolymer pellets.

10,000g of ethylene propylene copolymer, 1,400g of electrically conductive carbon black, 52g of tris(2,4-ditert-butylphenyl)phosphite, and 30g of zinc stearate were sequentially added to a 20L kneader and kneaded at 100℃ for 20 minutes. The lump dough was transferred to a twin screw extruder and extruded to prepare semi-conductive ethylene propylene copolymer pellets having a surface resistance of 10 ⁶ Ω and a size of 3 to 5 mm. In a separate 20L Henschel mixer, the prepared semiconducting ethylenepropylene copolymer pellets and 120 g of dicumyl peroxide were administered and kneaded at 80° C. for 20 minutes to prepare crosslinked semiconducting ethylenepropylene copolymer pellets.

10,000 g of ethylene-propylene-1,4-hexadiene, 25,000 g of magnesium hydroxide surface-treated with 3-methacryloyloxypropyl-trimethoxysilane, and 3-methacryloyloxypropyl-trimethoxysilane Surface-treated magnesium hydroxide, poly(dimethylsiloxane)-poly(ethylene oxide) copolymer 1,100 parts by weight, poly(methoxymethyl)-co-poly(methylhydro)siloxane 500g, tetrakis[methylene-3(3') ,5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane 300g, 4,4'thiobis(2-tert-butyl-5-methylphenol) 200g, carbon black 1,500g, ethylene -Introduce 1,000g of vinyl acetate copolymer into a kneader mixer and melt-knead it for 30 minutes at a temperature of 150 ~ 155℃, add 400g of the masterbatch and 8,000g of linear low-density polyethylene and mix it at a temperature of 150 ~ 165℃ for 10 minutes. The melt-mixed loaf dough was transferred to a twin-screw extruder to produce composition pellets having a size of 3 to 5 mm through extrusion molding, dried in an oven at 80 ° C., and subjected to particle size selection to prepare a thermoplastic elastomer composition.

The cross-linked semi-conductive ethylene-propylene copolymer pellets were injected into the first hopper, the ethylene-propylene copolymer pellets into the second hopper, and the cross-linked semi-conductive ethylene-propylene copolymer pellets into the third hopper. Cylinder 1 is 105°C, cylinder 2 is 110°C, cylinder 3 is 115°C, extrusion head is 115°C, and extrusion die is 120°C while passing a tinned wire with a diameter of 23Φmm through the head of an extruder to which a 32Φmm coextrusion die is attached. While extruding at a speed of 22 kg / hour under the temperature condition of 110 ° C. and passing through a curing tube maintained at 15 atm at a speed of 30 m / min, an insulated wire having a semi-conductive layer is manufactured, and then taped with copper tape to form a shielding layer. Constructed, and taped with polyketone tape while passing the insulated wire formed with a shielding layer combined with three strands and the polypropylene yarn filler together with the taping column of the cable taping machine, and then a single screw extruder with a 78mm extrusion die attached ( Cylinder 1: 160° C., Cylinder 2: 170° C., Cylinder 3: 180° C., Die: 175° C.) The thermoplastic elastomer composition was injected into a hopper and extruded to a thickness of 2 mm at a rate of 20 kg/hour to form an inner coating layer, , Braided with iron wire to form a reinforcing layer, and in the hopper of a single screw extruder (cylinder 1: 160 ° C, cylinder 2: 170 ° C, cylinder 3: 180 ° C, die: 175 ° C) to which an 84 mm die for extrusion is attached Preparation of a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance by extruding the thermoplastic elastomer composition to a thickness of 2.6 mm at a rate of 20 kg/hour to form an outer coating layer and a polar navigation ship cable coated therewith has been completed.

Example 3

After maintaining the feeder temperature of the twin-screw extruder at 55 ° C and raising the internal temperature of the extruder to 135 ° C, 10,000 g of ethylene vinyl acetate copolymer was first added to the feeder to melt, and then 200 g of calcium stearate and 7,000 g of red phosphorus were added to the feeder. After kneading for 20 minutes, it was cut through a melt extrusion process to prepare a red master batch having a size of about 3 to 5 mm.

9,500 g of ethanol, 500 g of distilled water, 1,000 g of tris(methoxyethoxy)vinyl silane, and 600 g of acetic acid were added to a 20L reactor equipped with a temperature controller and stirrer, and stirred at a speed of 100 RPM for 30 minutes. After administering 30,000 g of magnesium hydroxide and stirring at a speed of 200 RPM for 60 minutes, filtering and drying at a temperature of 80 ° C., magnesium hydroxide surface-treated with 3-methacryloyloxypropyl-trimethoxysilane manufactured.

10,000 g of ethylene-propylene copolymer, 8,000 g of magnesium hydroxide surface-treated with tris (methoxyethoxy) vinyl silane, 1,200 g of diatomaceous earth, 600 g of zinc oxide, thiodiethylene bis[3-(3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate] 15 g, thiodipropionic acid dioctadecyl ester 2 g, and octadecanoic acid 110 g were sequentially administered to a Benbury mixer and kneaded at 80 ° C for 20 minutes. Then, 420 parts by weight of dicumyloxide was additionally added thereto, and kneading was performed at a temperature of 60° C. for 10 minutes to prepare ethylene-propylene copolymer pellets.

10,000g of ethylene propylene copolymer, 1,400g of electrically conductive carbon black, 52g of tris(2,4-ditert-butylphenyl)phosphite, and 30g of zinc stearate were sequentially added to a 20L kneader and kneaded at 100℃ for 20 minutes. The lump dough was transferred to a twin-screw extruder and extruded to prepare semi-conductive ethylene-propylene copolymer pellets having a surface resistance of 10 ⁶ Ω and a size of 3 to 5 mm. In a separate 20L Henschel mixer, the prepared semiconducting ethylenepropylene copolymer pellets and 120 g of dicumyl peroxide were administered and kneaded at 80° C. for 20 minutes to prepare crosslinked semiconducting ethylenepropylene copolymer pellets.

10,000 g of ethylene-propylene-tetrahydroindene, 25,000 g of magnesium hydroxide surface-treated with tris(methoxyethoxy)vinyl silane, 1,100 parts by weight of poly(dimethylsiloxane)-poly(ethylene oxide) copolymer, poly(methoxymethyl )-co-poly(methylhydro)siloxane 500g, tetrakis[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane 300g, 4,4'thio 200 g of bis(2-tert-butyl-5-methylphenol), 1,500 g of carbon black, and 1,000 g of ethylene-ethyl acrylate copolymer were put into a kneader mixer and melt-kneaded for 30 minutes at a temperature of 150 to 155 ° C. 400 g of the masterbatch and 8,000 g of linear low-density polyethylene were added, melted and mixed at a temperature of 150 to 165 ° C for 10 minutes, and the dough was transferred to a twin-screw extruder to produce composition pellets having a size of 3 to 5 mm through extrusion molding. After drying in an oven at 80° C. and undergoing a particle size screening process, a thermoplastic elastomer composition was prepared.

The cross-linked semi-conductive ethylene-propylene copolymer pellets were injected into the first hopper, the ethylene-propylene copolymer pellets into the second hopper, and the cross-linked semi-conductive ethylene-propylene copolymer pellets into the third hopper. Cylinder 1 is 105°C, cylinder 2 is 110°C, cylinder 3 is 115°C, extrusion head is 115°C, and extrusion die is 120°C while passing a tinned wire with a diameter of 23Φmm through the head of an extruder to which a 32Φmm coextrusion die is attached. While extruding at a speed of 22 kg/hour under a temperature condition of Polyimide tape is formed by taping or forming a braided layer with metal wires, metal plating wires, and metal wires among alloy wires, and insulated wires formed with a plurality of combined shielding layers with a taping column of a cable taping machine and Kevlar filler while passing them together After taping, the thermoplastic elastomer composition is injected into the hopper of a single-screw extruder (cylinder 1: 160 ° C, cylinder 2: 170 ° C, cylinder 3: 180 ° C, die: 175 ° C) to which a 78 mm die for extrusion is attached, and Extruded to a thickness of 2 mm at a rate of kg / hour to form an inner coating layer, braided with carbon fiber yarn / Kevlar yarn (50:50 mixed yarn) to form a reinforcing layer, and a single screw extruder (cylinder 1) with an 84 mm die for extrusion molding attached : 160°C, Cylinder 2: 170°C, Cylinder 3: 180°C, Die: 175°C) The thermoplastic elastomer composition was injected into a hopper and extruded to a thickness of 2.6 mm at a speed of 20 kg/hour to form an outer coating layer to achieve flexibility. , the production of a highly retardant thermoplastic elastomer composition having cold resistance, oil resistance and ice icing resistance and a polar navigation ship cable coated therewith was completed.

Example 4

In the preparation of the thermoplastic elastomer composition of Example 3, flexibility and cold resistance were obtained in the same manner as in Example 3, except that ethylene-propylene-5-cyclohexylidene-2-norbornene was used instead of ethylene-propylene-tetrahydroindene. , The production of a highly retardant thermoplastic elastomer composition having oil resistance and ice icing resistance and a polar navigation ship cable coated therewith was completed.

Example 5

In the preparation of the thermoplastic elastomer composition of Example 3, flexibility, cold resistance, oil resistance, The production of a highly retardant thermoplastic elastomer composition having ice icing resistance and a polar navigation ship cable coated therewith was completed.

Comparative Example 1 (Physical properties of other examples are inferior)

A highly flexible thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and icing resistance in the same manner as in Example 1, except that ethylene-propylene-1,4-hexadiene was not used in the preparation of the thermoplastic elastomer composition of Example 1, and The production of the coated ship cable for polar navigation was completed.

Comparative Example 2

In the preparation of the thermoplastic elastomer composition of Example 2, the poly(dimethylsiloxane)-poly(ethylene oxide) copolymer and poly(methoxymethyl)-co-poly(methylhydro)siloxane are not used, but the same as in Example 2. In this way, the manufacture of a highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance and a polar navigation ship cable coated therewith was completed.

For the thermoplastic elastomer composition thus prepared, specimens having a thickness of 1.5 mm were prepared at 170° C. using a hot-press, and oxygen index, tensile strength, elongation, icing resistance, and oil resistance were measured. The cable was subjected to a cold bend test, and the results are shown in Table 2, showing the measurement results of each experiment according to the embodiment.

Test Items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Cold bend (-70℃) pass pass pass pass fail fail Oxygen index (%) 35 35 35 35 35 28 icing resistance Good Good Good Good Good icing tensile properties Strength (MPa) 14.5 14.2 14.8 14.9 13.8 13.9 Elongation (%) 530 510 505 512 470 485 Oil resistance (70℃, after aging for 4 hours, ±40%) Strength residual rate (%) 94 92 90 92 80 82 Kidney residual rate (%) 81 80 82 83 72 75

As shown in Table 2, it can be seen that the cold bend, oxygen index, tensile strength, elongation, icing resistance, and oil resistance of the examples according to the present invention are superior to those of the comparative examples.

The highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance of the present invention and the manufacturing method of a polar navigation ship cable coated therewith are the types of resins, additives and fillers used in each component of the insulation coating composition, and their By adjusting the amount used, flexibility, cold resistance, oil resistance, flame retardancy and ice icing resistance can be improved compared to the insulation coating composition of conventional polar navigation ship cables, and when applied to polar navigation ships, in addition to electrical, mechanical and chemical properties, workability and It has the effect of improving and improving productivity, so the value of industrial use will be great.

Claims (3)

Ethylene copolymer or polyethylene melted by maintaining the feeder temperature of the twin extruder at 40 to 60 ° C, raising the internal temperature of the screw-equipped extruder to 80 to 160 ° C, and then introducing it into the feeder 100 to 500 parts by weight of a lubricant selected from among calcium stearate, zinc stearate, and barium stearate, and 4,000 to 8,000 parts by weight of red phosphorus are added to 10,000 parts by weight of resin, and 10 to 60 parts by weight are added. After kneading for minutes, cutting through a melt extrusion molding process to make a polymer pellet having a size of about 2 to 5 mm (master batch) manufacturing step;
Magnesium hydroxide phosphate having an average particle diameter of 0.1 to 20 μm, calcium hydroxide, aluminum hydroxide or magnesium hydroxide alone or in combination with metal hydrates 7,500 to 15,000 parts by weight of an organic solvent selected from ethanol, isopropyl alcohol, chloroform, and dimethylsulfoxide, pentadecano Aeration of 2,500 to 5,000 parts by weight of a fatty acid selected from pentadecanoic acid, hexadecanoic acid, octadecanoic acid, and dodecanoic acid A fatty acid surface treatment step of a flame retardant for preparing a flame retardant surface-treated with a fatty acid by continuously supplying it to a blender (through-flow blender), kneading and filtering, and drying at 60 to 120 ° C;
In a reactor equipped with an agitator, 9,500 parts by weight of alcohol (methanol or ethanol), 500 parts by weight of distilled water, vinyl silane, tris (methoxyethoxy) vinyl silane [tris (methoxyethoxy) )vinyl silane], triisopropoxy-vinylsilane, trimethoxy(vinyl)silane, tetraethoxy silane, methyltriethoxysilane , methyltrimethoxysilane, methyltri(2-methoxyethoxy)silane, 3-methacryloyloxypropyl-trimethoxysilane, 3-mercaptopropyl-tri Add 1,000 to 5,000 parts by weight of a reactive silane selected from methoxysilane (3-mercaptopropyl-trimethoxysilane) and 3-aminopropyl-trimethoxysilane (3-aminopropyl-trimethoxysilane), and hydrochloric acid or acetic acid as an acid catalyst 19,000 to 45,000 parts by weight of a flame retardant having an average particle diameter of 0.01 to 20 μm was added to a solution stirred at a speed of 50 to 300 RPM for 20 to 60 minutes while maintaining pH 3 to 5 by adding 500 to 2,000 parts by weight of 20 to 45,000 parts by weight at a speed of 50 to 300 RPM. A silane surface treatment step of the flame retardant to prepare a flame retardant surface-treated with silane by stirring for 120 minutes, filtering, and drying at 60 to 120 ° C;
An ethylene polymer selected from polyethylene, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer in a mixing mixer in Kneader, Henschel, or Banbury ) or ethylene copolymer (ethylene copolymer) 10,000 parts by weight, 6,000 to 10,000 parts by weight of the surface-treated flame retardant produced in the fatty acid surface treatment step of the flame retardant or the silane surface treatment step of the flame retardant, silica or carbon black ), magnesium carbonate, aluminum silicate, magnesium silicate, 10 to 1,200 parts by weight of a reinforcing agent selected from diatomaceous earth, 1 to 600 parts by weight of zinc oxide, thiodiethylene bis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate] [thiodiethylene bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or thiodipropionic acid dioctadecyl ester (thiodipropionic acid dioctadecylester), distearyl thiodipropionate, 5 to 20 parts by weight of an antioxidant used alone or in combination of two or more among sulfur compounds in 3-mercaptopropionic acid, 10 to 120 parts by weight of fatty acid or fatty acid metal salt lubricant is sequentially administered and kneaded at 80 to 130 ° C for 5 to 60 minutes. After preparing the insulation composition pellets with a size of ~ 5 mm, the insulation composition is mixed in a separate kneader, Henschel or Banbury mixing mixer A step of preparing a cross-linked insulating composition by adding 100 to 500 parts by weight of an organic peroxide to 16,025 to 21,340 parts by weight of pellets and kneading at a temperature of 60 to 100 ° C. for 10 to 60 minutes to prepare cross-linked insulating composition pellets;
In a mixing mixer in Kneader, Henschel, or Banbury, 10,000 parts by weight of polymer elastomer, electro-conductive carbon black, carbon nanotube, graphite, graphene ( 500 to 2,000 parts by weight of an electrically conductive filler selected from graphene), 43 to 64 parts by weight of an antioxidant, and 25 to 40 parts by weight of a fatty acid or fatty acid metal salt lubricant are sequentially added to 100 The kneaded dough at a temperature of ~140 ° C for 10 to 60 minutes is transferred to a single screw or twin screw extruder to produce semiconductive elastomer pellets with a surface resistance of 10 ⁵ to 10 ⁸ Ω and a size of 3 to 5 mm through extrusion molding. , 10,568 to 12,104 parts by weight of the semiconducting elastomer pellets and 95 to 150 parts by weight of the organic peroxide were added to a separate kneader, Henschel, or a mixing mixer in Banbury, and kneaded at a temperature of 60 to 100 ° C. for 10 to 60 minutes to obtain a cross-linked semiconducting composition a step of preparing a cross-linked semiconducting composition to produce pellets;
Ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1,6-octadiene, ethylene-propylene-1 ,9-decadiene (ethylene-propylene-1,9-decadiene), ethylene-propylene-5-methyl-1,4-hexadiene (ethylene-propylene-5-methyl-1,4-hexadiene), ethylene-propylene -3,7-dimethyl-1,6-octadiene, ethylene-propylene-dicyclopentadiene, ethylene-propylene-1,3-cyclopentadiene ), ethylene-propylene-1,4-cyclohexadiene, ethylene-propylene-1,5-cyclooctadiene, Ethylene-propylene-1,5-cyclododecadiene, ethylene-propylene-tetrahydroindene, ethylene-propylene-methyltetrahydroindene -propylene-methyl tetrahydroindene), ethylene-propylene-5-propenyl-2-norbornene, ethylene-propylene-5-isopropylidene-2-norbornene propylene-5-isopropylidene-2-nor bornene), ethylene-propylene-5-(4-cyclopentenyl)-2-norbornene, ethylene-propylene-5-(4-cyclopentenyl)-2-norbornene 5-cyclohexylidene-2-norbornene (ethylene-propylene-5-cyclohexylidene-2-norbo rnene), ethylene-propylene-5-vinyl-2-norbornene, ethylene-propylene-5-ethylidene-2-norbornene -2-norbornene), ethylene-propylene-5-vinylidene-2-norbornene, ethylene-propylene-5-methylene-2-norbornene 5-methylene-2-norbornene), 15,000 to 50,000 parts by weight of a surface-treated flame retardant selected from a flame retardant fatty acid surface treatment step or a flame retardant silane surface treatment step, 10,000 parts by weight of a thermoplastic elastomer selected from ethylene terpolymers, poly (dimethylsiloxane)-poly(ethylene oxide) copolymer [poly(dimethylsiloxane)-poly(ethylene oxide) copolymer], poly(dimethylsiloxane)-poly(propylene oxide) copolymer [poly(dimethylsiloxane)-poly(propylene oxide) copolymer], poly(dimethylsiloxane)-poly(butylene oxide) copolymer [poly(dimethylsiloxane)-poly(butylene oxide) copolymer], poly(dimethylsiloxane)-poly(phenylene oxide) copolymer [poly(dimethylsiloxane) -poly(phenylene oxide) copolymer] 500 to 2,000 parts by weight of a self-lubricant selected from the polysiloxane copolymer in the copolymer, poly(methoxymethyl)-co-poly(methylhydro)siloxane [poly(methoxymethyl)-co-poly (methylhydro)siloxane], poly(ethoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane], Poly(methoxymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane [Poly(metho xymethyl)-co-poly(dimethyl)-co-poly(methylhydro)siloxane], polymethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methylhydro)siloxane [Poly(methylperfluorobutylethyl) -co-poly(methylethoxy)-co-poly(methylhydro)siloxane], poly(ethylperfluorobutylethyl)-co-poly(methylethoxy)-co-poly(methylhydro)siloxane[poly(ethylperfluorobutylethyl)-co 200 to 1,000 parts by weight of an auxiliary flame retardant selected from modified silicone oil in -poly(methylethoxy)-co-poly(methylhydro)siloxane, tetrakis[methylene-3(3',5'-di-tert -Butyl-4'-hydroxyphenyl) propionate] methanetetrakis [methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] methane or butylhydroxytoluene , Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate)][octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)- propionate)], poly(1,2-dihydro-2,2,4-trimethylquinoline) [poly(1,2-dihydro-2,2,4-trimethyl quinoline)], 2,6-di-tert- Butyl-4-methylphenol (2,6-di-tert-butyl-4-methyl phenol), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) methane [tetrakis [methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane], tris(2,4-di-tert-butyl-phenyl) phosphite [tris(2,4-di-tert- butyl-phenyl) phosphite], tris(2,4-ditert-butylphenyl) phosphite) [tris(2,4-ditert-butylp henyl) phosphite] antioxidant selected from 100 to 600 parts by weight, 4,4'thiobis (2-tert-butyl-5-methylphenol) [4,4'thiobis (2-t-butyl-5-methylphenol )] or 2,5-dimethyl-4-(4-butylbenzylthio)phenol [2,5-dimethyl-4-(4-butylbenzylthio)phenol], 2-dimethylbenzyl-4,4(hexylthio)phenol [2-dimethylbenzyl-4,4(hexylthio)phenol], 2,4-dibutyl-6-(butylthio)phenol [2,4-dibutyl-6-(butylthio)phenol],2,6-bis(1 Selected from thiophenol compounds among ,1-dimethylbutyl)-4-(1,1-dimethylbutylthio)phenol [2,6-bis(1,1-dimethylbutyl)-4-(1,1-dimethylbutylthio)phenol] 100 to 400 parts by weight of the stabilizer, selected from titanium dioxide, carbon black, zinc oxide, tungsten oxide, or cesium oxide alone or two or more 500 to 3,000 parts by weight of UV-blocking pigment, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer ( ethylene-acrylic acid copolymer), ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-butyl methacrylate copolymer butyl methacrylate copolymer) 5,000 to 16,000 parts by weight of a compatibilizer selected from ethylene copolymers sequentially in a kneader mixer ) or Banbury mixer, and melt-kneaded at a temperature of 140-170 ° C. for 10-60 minutes, and after the melt-kneading step, prepared in the master batch manufacturing step written in the mixing mixer 200 to 800 parts by weight of red-green masterbatch and polyethylene resin selected from among high density polyethylene, medium density polyethylene, linear low density polyethylene, and low density polyethylene 6,000 ~12,000 parts by weight are sequentially added, and the melt-mixed dough is transferred to a single screw or twin screw extruder at a temperature of 140 to 170 ° C. for 1 to 30 minutes to prepare composition pellets having a size of 2 to 5 mm through extrusion molding. A step of preparing a thermoplastic elastomer composition by drying in an oven at ~80° C. and undergoing a particle size selection process to prepare a thermoplastic elastomer composition;
The semiconducting elastomer pellets prepared in the step of preparing the crosslinked semiconductive composition were placed in a first hopper, the pellets of the crosslinked insulating composition prepared in the step of preparing the crosslinked insulating composition were placed in a second hopper, and the crosslinked semiconducting After the semiconductive elastomer pellets prepared in the composition manufacturing step are injected into the third hopper, a metal wire or metal plated wire is placed on the head of the extruder to which the co-extrusion die is attached. wire) and alloy wire (metal alloy wire), the temperature conditions are 100 ~ 120 ℃ for cylinder 1, 100 ~ 120 ℃ for cylinder 2, 105 ~ 125 ℃ for cylinder 3, extrusion Head (extrusion head) 110 ~ 130 ℃, extrusion die (extrusion die) curing tube maintained at 80 ~ 120 ℃ and 10 ~ 20 atmospheric pressure by extruding at a speed of 10 ~ 40 kg / hour at a temperature condition of 110 ~ 130 ℃ (continuous vulcanization pipe) at a speed of 20 ~ 50 m / min through the extrusion vulcanization step to produce an insulated wire formed with a semi-conductive layer formed insulated wire manufacturing step;
The outer periphery of the insulated wire having the semiconducting layer manufactured in the manufacturing step of the insulated wire having the semiconducting layer is taped with a metal tape or a metal coating film or braided with a metal wire among metal wires, metal plating wires, or alloy wires to form a shielding layer. Constituting a shielding layer forming step;
A taping column of a cable taping machine passes an insulated wire formed with a plurality of combined shielding layers and a filler together, while polyester, polyketone, or polyimide A taping step of taping with a binder tape selected from polyimide and polysulfone tapes;
Cylinder 1: 100 to 180 ° C, Cylinder 2: 100 to 180 ° C, Cylinder 3: 120 to 200 ° C , Die: forming an inner coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition preparation step at a temperature of 120 to 200 ° C. at a rate of 5 to 50 kg / hour to form an inner coating layer;
Metal wire, which is one of copper wire, metal-coated copper wire, iron wire, and nickel wire, glass fiber yarn, basalt fiber yarn, elvan fiber yarn, ceramic fiber yarn, carbon An external reinforcing layer forming step of forming a reinforcing layer by plying and braiding single or two or more of inorganic fiber yarns and aramid fiber yarns, which are fiber yarns;
Cylinder 1: 100 ~ 180 ℃, Cylinder 2: 100 ~ 180 ℃, Cylinder 3: 120 ~ 200 ° C, die: temperature conditions of 120 ~ 200 ° C. Through the outer coating layer forming step of molding the outer coating layer by extruding the thermoplastic elastomer composition prepared in the thermoplastic elastomer composition manufacturing step at a rate of 5 ~ 50 kg / hour under temperature conditions A highly retardant thermoplastic elastomer composition having flexibility, cold resistance, oil resistance and ice icing resistance, characterized in that it is produced, and a method for producing a polar navigation ship cable coated therewith. 10,000 parts by weight of ethylene polymer or ethylene copolymer, 6,000 to 10,000 parts by weight of flame retardant, 10 to 1,200 parts by weight of reinforcing agent, 5 to 20 parts by weight of antioxidant, 10 to 120 parts by weight of lubricant A cross-linked insulating composition obtained by kneading 100 to 500 parts by weight of an organic peroxide with 16,025 to 21,340 parts by weight of the kneaded insulating composition pellets having a size of 3 to 5 mm;
10,000 parts by weight of polymeric elastomer, 500 to 2,000 parts by weight of electrically conductive filler, 43 to 64 parts by weight of antioxidant, and 25 to 40 parts by weight of lubricant are sequentially added at a temperature of 100 to 140 ° C. A cross-linking semiconductive composition obtained by kneading 10,568 to 12,104 parts by weight of an organic peroxide with 10,568 to 12,104 parts by weight of semiconducting elastomer pellets having a surface resistance of 10 5 to 10 8 Ω and having a surface resistance of 10 ⁵ to 10 ⁸ Ω kneaded for 10 to 60 minutes;
10,000 parts by weight of thermoplastic elastomer, 15,000 to 50,000 parts by weight of a flame retardant surface-treated with fatty acid or a flame retardant surface-treated with silane, 500-2,000 parts by weight of self-lubricating agent, 200-1,000 parts by weight of auxiliary flame retardant, 100-600 parts by weight of antioxidant, 500 to 3,000 parts by weight of sunscreen pigment and 5,000 to 16,000 parts by weight of compatibilizer are sequentially mixed and melt-kneaded, and 200 to 800 parts by weight of red masterbatch, which is a polymer pellet, and 6,000 to 12,000 parts by weight of polyethylene resin are sequentially added. A highly flexible thermoplastic elastomer composition having flexibility, cold resistance, oil resistance, and ice icing resistance, characterized in that it is made of a thermoplastic elastomer composition obtained by delete

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