KR100288182B1 - Black polyethylene composition for coating electric wire - Google Patents

Abstract

PURPOSE: Provided is a black polyethylene composition for coating the electric wire which has excellent mechanical property, resistance to environment and stress cracking, and extruding processability at high temperature. Unlike using the conventional ethylene vinylacetate copolymer, this composition uses low crystallinity and very low density polyethylene(VLDPE) of low pressure method together with polyethylene as a base resin, anti-oxidant, carbon black and lubricant. CONSTITUTION: The composition comprises: 77-95wt.%(based on the whole composition) of the base polyethylene(PE) with 0.910-0.970g/cm¬3 density and 0.1-3.0g/10min melt index; 3-20wt.%(based on 100 wt.% of the base resin) of VLDPE with 0.880-0.910g/cm¬3 density and 0.1-100g/10min melt index, made by polymerization of ethylene with α-olefin with more than C4, as an improver for anti environment stress cracks; 2-5wt.%(based on 100wt.% of the base PE) of carbon black with the particle size of not more than 20nm, pH 3.0-8.0, surface area of 80-150m¬2/g and DBP absorbance of 100-200cc/100g; 0.05-2.0wt.%(base on 100wt.% of base PE) of an antioxidant; and 0.5-8wt.%(based on 100wt.% of the carbon black) of one lubricant selected from metal stearate, aluminum monoalkoxy compound, low mol.wt. polyethylene wax and low mol.wt. polypropylene wax, saturated or unsaturated fatty acid and their derivatives.

Description

[Name of invention]

Black polyethylene resin composition for electric wire coating

Detailed description of the invention

The present invention relates to a black polyethylene-based resin composition for outermost layer coating of various communication cables and power cables. More specifically, the present invention relates to an antioxidant, carbon black, lubricant, and environmental stress cracking modifier using polyethylene resin as a base resin. The black polyethylene-based resin composition for wire coating containing, wherein the environmental stress cracking modifier among the additives has excellent effect of modifying the environmental stress cracking resistance and compatibility with the polyethylene resin, ethylene and excellent high temperature stability of the resin itself Compound manufactured using low-crystalline low-pressure ultra low density polyethylene (VLDPE) polymerized from α-olefins containing 4 or more carbon atoms. When applied to outermost sheath of communication cable and power cable, mechanical strength and environmental stress crack resistance Communication cable and electric wire to obtain coating material with excellent high temperature extrusion processability It relates to a black resin composition for power cable coating.

The sheath of the cable can be divided into insulation and sheath (aka jacket). The insulator is sheathed on the conductor for protection and electrical insulation of the conductor, and the sheath body is sheathed on the outermost layer of the cable to protect the insulation and other cable components. do.

Communication cables are generally manufactured by coating polyethylene or foamed polyethylene on the core wire to make primary insulated telephone wires, wrapping these telephone wires with steel or aluminum, and then covering the sheathed black polyethylene composition on the core wires. It is prepared by coating polyolefin or crosslinkable polyolefin to make primary insulated wire, wrapping these insulated wires with binder tape, and then coating the black polyvinyl chloride resin composition or black polyolefin composition for coating thereon.

Cable sheathing is generally required for long term durability over 30 years, and to satisfy this endurance, it is a protective coating for physical and chemical action that is primarily encountered from the external environment when the cable is laid on the ground or underground. The black coating forming the outermost layer of the cable shall have safety. Therefore, the outermost sheath of the cable requires at least 30 years of durability against external environmental stress in the place where it is constructed. Therefore, the mechanical, ultraviolet, low temperature, and thermal oxidation stability should be excellent. Because of its cylindrical shape, the stress resistance against residual stress and physicochemical stress from the external environment during extrusion or cable construction should be excellent in environmental stress cracking resistance. Therefore, the development process of cable sheathing products with long-term stability against physical and chemical stresses that can be subjected to cable is as follows.

Polyethylene, like other polyethylene resins, is easily photolyzed by ultraviolet rays when exposed to the outdoors. Carbon black is used as an additive in materials requiring weather resistance such as cable sheaths because of its excellent role in preventing aging caused by ultraviolet rays. The UV blocking effect of carbon black varies greatly depending on the particle size of the carbon black, and the use of carbon black having a small particle size at the same content greatly improves weather resistance. In addition, weather resistance varies greatly depending on the dispersion state in the base resin. Cable coverings using a compound having a poor dispersion state of carbon black do not effectively block ultraviolet rays, thereby reducing the cable life.

The degradation of the cable covering polyethylene by ultraviolet rays could be solved by the addition of carbon black, but the polyethylene itself itself is not susceptible to the extremely high level of environmental stress cracking required by the cable covering. Therefore, in the 1960s, the polyethylene molecular weight was increased to improve the molecular weight, that is, the melt index (MI) was lowered to 2.0 level, but it was insufficient as the base resin of the black compound for cable coating.

The coating compound manufactured using only the high molecular weight polyethylene as the base resin does not satisfy the environmental stress cracking resistance when applied as a cable sheath, and in the 1970s, rubber-based elastomers and ethylene copolymers were used. That is, by mixing the ethylene vinyl acetate (EVA) copolymer was able to greatly improve the environmental stress cracking resistance.

The most effective and widely used environmental stress cracking modifier used in cable sheathing compound is ethylene vinyl acetate copolymer. Currently, the black coating compound commercialized worldwide has a melt index of 0.1-1.0g / 10min. It is a form in which ethylene vinyl acetate copolymer is mixed with the high molecular weight polyethylene which is a range.

The functions of the above-mentioned additives have satisfied the properties required for long-term stability of the cable sheathing compound.

On the other hand, the carbon black used as the UV stabilizer, as mentioned earlier, the smaller the particles and the better the dispersion state, the better the UV blocking effect, but the carbon black itself has a high water absorption rate is difficult to store long-term and carbon black The smaller the particle size, the more difficult to disperse the carbon black. It is rare to directly mix the carbon black with the resin, and after producing the MASTER BATCH, it is allowed to let-down with the base resin and carbon black to the final desired content. A method of dispersing and dispersing is generally used.

In this case, the dispersibility of the carbon black is improved to some extent. However, if the carbon black absorbs moisture in its own characteristics and storage, there is a limit of dispersion even if the carbon black is dispersed in the base resin according to the above procedure. There is a problem that the carbon compound dispersion of the black compound becomes bad.

In addition, the ethylene vinyl acetate copolymer used as an environmental stress cracking modifier in the composition of the black polyethylene compound for cable coating has a poor compatibility with polyethylene. On the other hand, the compatibility with polyethylene is worse, which lowers the mechanical properties of the polyethylene / ethylenevinylacetate mixture. This results in a phase separation phenomenon when processing speed is increased in terms of workability, resulting in poor appearance of the coating formed during cable extrusion coating.

Therefore, in order to improve the mechanical properties, the improvement of carbon black dispersibility, and the extrusion processability mentioned above, Korean Patent Application No. 89-4203 discloses a titanium or zirconium monoalkoxy compound as a surface treatment agent and a lubricant. When manufacturing black master batch, carbon black is surface treated to form a thin film of organic layer on the surface of carbon black to increase the dispersion and dispersibility of carbon black in base resin, making the carbon black dispersion extremely excellent, and It has been described that the affinity between ethylene vinyl acetate copolymers acting as environmental stress modifiers has been obtained to improve the mechanical properties of the coating when the cable is coated and to improve the extrusion processability.

However, the present inventors have found the following problem as a result of earnestly examining the above application contents.

First, the conventional black compound for cable coating uses ethylene vinyl acetate copolymer as an environmental stress cracking modifier, and the ethylene vinyl acetate copolymer has a low molecular weight and a high content of vinyl acetate, which is a polar substance. Although it is known that the modification effect of the resin is excellent, this property is excellent in the modification effect of environmental stress cracking resistance when the non-polar polyethylene is used as the base resin, but the final extrusion molded product has no compatibility due to the mixing between the polar material and the nonpolar material. It causes a decrease in the mechanical properties of the cable coating, and also has a problem of causing a poor appearance of the final cable coating by phase separation during high-speed extrusion processing.

As a method for enhancing the affinity between the polyethylene and ethylene vinyl acetate mixture, Patent Application No. 89-4203 discloses a carbon black master batch using a titanium or zirconium monoalkoxy compound (aka titanium or zirconium-based coupling agent). When carbon black is used as a surface treatment, it is described as one of the effects that the affinity between the polyethylene of the base resin and the ethylene vinyl acetate copolymer can be enhanced to improve the mechanical strength of the final extruded cable coating.

However, the monoalkoxy compound is known to enhance the affinity of the organic material and the inorganic material rather than the affinity between the organic material and the organic structure, and from this point of view, the role of the monoalkoxy compound in the conventional black polyethylene compound is a base resin. Rather than improving the affinity between phosphorus polyethylene and ethylene vinyl acetate, an environmental stress cracking modifier, the mechanical strength was improved by the action of carbon black, which is an inorganic material, that is, by increasing the affinity between polyethylene or ethylene vinyl acetate and carbon black. Can be.

Second, conventional cable coating black compounds containing an ethylene vinyl acetate copolymer as an environmental stress cracking modifier are required to be processed at high temperatures, especially when using medium density polyethylene or high density polyethylene with high crystallinity as the base resin. The ethylene vinyl acetate copolymer is a low crystalline resin, which contains vinyl acetate having a low heat resistance temperature and a low thermal initiation temperature, which is very vulnerable in terms of thermal stability. This results in poor appearance of the sheathed cable during final cable extrusion.

Accordingly, the present inventors have made diligent efforts on the above-mentioned problems in manufacturing the conventional black polyethylene compound for cable coating. As a result, the present invention has excellent compatibility with polyethylene, which is a base resin, as a non-polar material, and has an excellent effect of modifying environmental stress crack resistance. Conventional ethylene vinyl by using low crystalline low pressure method ultra low density polyethylene polymerized from ethylene having excellent heat stability due to its high heat resistance temperature and α-olefin having 4 or more carbon atoms as an environmental stress cracking modifier of black compound for cable coating In the black compound using the acetate copolymer as an environmental stress cracking modifier, it is possible to prevent a decrease in mechanical strength due to incompatibility between the base resin polyethylene and the environmental stress cracking modifier ethylene vinyl acetate copolymer. Vinyl acetate Due to the poor thermal stability of the polymer, it improves the problem of the appearance defect of the final extruded cable coating by pyrolysis during high temperature processing, and has excellent mechanical properties, environmental stress cracking resistance, and extrusion process at high temperature. Polyolefin compound compositions have been invented.

Hereinafter, the present invention will be described in more detail.

In the present invention, the material which can be used as the base resin of the black resin composition for cable coating is polyethylene resin, which has a density of 0.910-0.970 g / cm 3, a melt index of 0.1-3.0 g / 10 min, low density polyethylene, medium density polyethylene, high density polyethylene or Mixtures of polymers can be used, and the amount is appropriately 77-95wt% based on the total composition weight of the black coating compound. If the melt index of the above-mentioned polyolefin resin is higher than the above range, eccentricity may be generated during cable extrusion coating.

Antioxidants used in the present invention include di- (2-hydroxymethyl-3 [1-methylcyclohexyl] phenyl) methane, octadecyl-3- (3,5-di-tertiary-butyl-4-hydroxy Phenyl) propionate, 2,2'-thiodiethyl-bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], pentaerythritol-terrakis [ 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6-tertiary-butylphenyl), polymerization 2, 2 ', 4'-trimethyl-1,2-dihydroquinoline, tris- (2,4-di-tertiary-butylphenyl) phosphite, dilauryl ester of β, β'-thiodipropionic acid, β, β '-One or more mixtures of distearyl esters of thiodipropionic acid are selected to prepare the cable black coating compound, and the amount of the antioxidant added is 0.05-2.0 parts by weight based on 100 parts by weight of the base resin. More preferably 0.1-1. 0 weight part is preferable. When added below the above range, the thermal oxidation resistance is not sufficient, and when it is added above the above range, the effect of increasing the heat-resistant oxidation characteristic no longer appears large.

The carbon black used in the present invention has a particle size of 20 nm or less, pH 3.0-8.0, surface area 80-150 m 2 / g, and DBP absorbance 100-200cc / 100 g. It is 10-75 wt% with respect to the weight, and the amount finally contained in the black polyolefin compound for cable coating is 2-5 weight part with respect to 100 weight part of base resin, More preferably, 2-3 weight part is added. If the amount is less than the above range, the UV blocking effect is remarkably lowered. If it is added more than the above range, there is almost no increase in the UV blocking effect and rather, the mechanical properties are reduced.

In the present invention, the carbon black is prepared and used as a master batch, and the resin used as a carrier when preparing the master batch of carbon black should have good compatibility with the base resin. The resins used in the production of carbon black masterbatches are low density polyethylene, medium density polyethylene, high density polyethylene or polymerized from ethylene or ethylene and α-olefins having 4 or more carbon atoms in the range of 0.880-0.970 g / cm3, melt index of 0.1-10 g / 10 min. Low crystalline low pressure ultra low density polyethylene and linear low density polyethylene are suitable. The amount of carbon black master batch used can be up to 50-90 wt% of the total weight of the master batch. In particular, the low crystalline low pressure ultra low density polyethylene has a very good filling effect of carbon black, and when used as a carrier of the carbon black masterbatch, the amount used can be up to 20-90wt% of the total weight of the masterbatch, and also low crystalline low pressure Method Using a carbon black masterbatch made of 65 wt% or more ultra-low density polyethylene, it is possible to avoid the cable having excellent environmental stress cracking resistance without using a separate environmental stress cracking modifier when producing black compound through let-down. Taking black compound can be obtained.

In the present invention, it is possible to improve the dispersion and distribution of the carbon black during melt kneading of the carbon black master batch, and to improve the fluidity by lowering the melt viscosity of the master batch containing a large amount of carbon black, thereby improving the fluidity of the black coating compound through let-down. Lubricants that may be used to improve extrusion processability during fabrication and extrusion of final cable sheaths include metal salts of stearic acid or low molecular weight polyethylene waxes and low molecular weight polypropylene expanded or saturated fatty acids, unsaturated fatty acids and average molecular weights ranging from 1,700-8,000. Compounds or aluminum monoalkoxy compounds prepared therefrom may be used, and the addition amount is preferably 0.5-8 parts by weight based on 100 parts by weight of carbon black, but more preferably 3-5 parts by weight. If the amount is less than the above range, there is almost no effect as a lubricant, and if it is larger than the above range, it slips during kneading with the carbon black and the carrier resin, resulting in insufficient dispersion and distribution of the carbon black.

The lubricant used in the present invention may be mixed in advance with the carbon black and Henschel mixer before melt-kneading with the carrier resin for surface treatment of the carbon black, or may be collectively added together with the carrier resin, carbon black, and antioxidant in preparing the carbon black master batch. You can mix.

In the present invention, excellent compatibility with polyethylene as the base resin and excellent effect of modifying the environmental stress crack resistance, high heat resistance of the resin itself, high mechanical properties of the black compound for the final cable coating, environmental stress crack resistance And an environmental stress cracking modifier used to improve high temperature extrusion processability and a density 0.880- polymerized from ethylene and an α-olefin having 4 or more carbon atoms, such as butene-1, hexene-1, 4-methylpentene-1, and octene-1. Low crystalline low pressure method ultra low density polyethylene in the range of 0.91 g / cm 3 and 0.1-100 g / 10 min, the amount of which is 3-20 parts by weight based on 100 parts by weight of the base resin, and the effect of modifying sufficient stress cracking resistance in the environment below the above range. In the above range, it is not possible to obtain a sufficient effect of modifying environmental stress cracking resistance, but it is not preferable in terms of economy.

Hereinafter, a method of preparing a black polyethylene compound for cable coating of the present invention, a method of preparing a sample for measuring physical properties, and a method of testing physical properties will be described.

<Method of manufacturing black polyethylene compound for cable coating>

1. Preparation of Carbon Black Masterbatch

Put the polyethylene, antioxidant, carbon black, and lubricant as a carrier into the Banbury mixer maintained at 120-150 ℃, dry for 2-3 minutes to mix the components evenly, and then pressurized to bring the final melted compound to a temperature of 150 Melt kneading for 20-30 minutes to reach -180 ° C. The kneaded mixture is then kneaded several times in a roll mill and then fed into an extruder to produce a carbon black master batch.

2. Preparation of Black Coating Compound

Polyethylene base resin is kneaded and extruded so that the temperature of the molten compound is 170-230 ° C. when kneading in a continuous kneader together with a carbon black masterbatch and a low crystalline low pressure method ultra low density polyethylene to prepare a black compound for the final cable coating. .

<Method of preparing a sample for measuring the physical property>

1. Preparation of Press Molded Sheet

In order to test the environmental stress cracking resistance, using a press sheet molding machine set at 180 ° C., a heat molded for 10 minutes and then cooled to room temperature to prepare a press molded sheet having a thickness of 3 mm.

2. Manufacture of cable black sheath

In order to evaluate the mechanical properties and weather resistance, a black cable sheath was prepared as follows.

-Equipment: 120φ, L / D = 24, Zone Noil Extruder

-Screw R. P. M: 10

-Extruder temperature condition: C1 / C2 / C3 / C4 / C5 / NECK / HEAD / DIE = 170/175/180/180/180/180/180/175 (℃)

-Manufactured cable's outer diameter: 42.7mm

-Black cover thickness: 1.90mm

<Physical Properties Test Method Using Experimental Device>

1. Environmental stress crack resistance

A press molded sheet having a thickness of 3 mm was tested for 500 hours using a 100% IGEPAL CO-630 solution according to ASTM D-1693.

2. Tensile test after room temperature and heating aging

The extruded cable sheath was tested according to ASTM D-638 standard, and the properties after heating aging were aged at 168 hours in an air replaceable oven set at 100 ° C., and then tested according to the standard. Comparison was made with the tensile properties of the samples in the state.

3. Weather resistance

Extruded cable sheaths were aged at 2,000 hours using ATLAS XENON / SUNSHINE ARC WEATHER-O-METER according to ASTM D-2865 and then tested according to ASTM D-638. Comparison was made with the tensile properties of the samples.

4. Carbon Black Dispersibility

Using black compound for cable coating prepared in pellet form, the test was conducted according to ASTM D-3015 standard to evaluate carbon black dispersibility.

5. High temperature extrusion processability

-Extruder used: 3/4 ", single screw extruder (Hake Reomex-254), L / D = 25

Die type used: Pipe type (outer diameter = 20φ)

Screw rotation speed: 100 RPM

-Extruder Temperature Arrangement: C1 / C2 / C3 / C4 / DIE = 210/220/230/230/230 (℃)

The present invention will be described in more detail with reference to the following Examples.

Example 1

Oxidation based on 100 parts by weight of low density polyethylene (density 0.923 g / cm 3, melt index 0.3 g / 10 min, Mitsubishi Petrochemical, trade name: ZC-40) in one step according to the method for producing a black resin for cable coating according to the method 2.5 parts by weight of an inhibitor (Monsanto, trade name: SANTONOX-R) and 50 parts by weight of carbon black (CABOT, trade name: VULCAN-P) and 2 parts by weight of low molecular weight polyethylene oxide (Allied Chemical, trade name: AC617A) with lubricant A carbon black masterbatch is prepared by simultaneously mixing in a Banbury mixer set at -140 ° C, melt kneading for 20-30 minutes, and extruding.

7.8 parts by weight of carbon black masterbatch and low crystalline low pressure method ultra low density polyethylene (density 0.880 gcm, melt index 3.6 g / 10 min, Mitsui Petrochemical Co., Ltd.), product name: TAFMER A-4085) 3.3 parts by weight are kneaded and extruded with a continuous kneader to prepare a black compound for the final cable coating, and a press-formed sheet and a cable coating are manufactured according to the above-described sample production method and test method to evaluate and extrude the physical properties. Workability tests were carried out, and the test results are shown in Table 1 and Table 2.

Example 2

In step 1, a carbon black masterbatch was prepared using the same equipment, the same conditions, the same additives, and the addition amount (base resin, carbon black, antioxidant, lubricant) as in Example 1, and in step 2, ZC-40 100 as a base resin. 7.8 parts by weight of carbon black masterbatch and low crystalline low pressure method ultra low density polyethylene (density 0.880 g / cm 3, melt index 18 g / 10 min, Mitsui Petrochemical, trade name: TAFMER A-20090) 3.3 parts by weight in a continuous kneader Kneading and extrusion were carried out to prepare a black compound for the final cable coating, and a press formed sheet and a cable coating body were prepared according to the above-described sample preparation method and test method, and the physical property evaluation and extrusion processability test were performed. Table 1 and Table 2.

Example 3

In step 1, the same equipment as in Example 2, the same conditions, the same additives and the addition amount (carbon black, antioxidant, lubricant), but the base resin in the use of high-density polyethylene (density 0.958g / cm 3, melt index 0.4g / 10min instead of ZC-40) , Mitsui Petrochemical Co., Ltd., manufactured carbon black masterbatch using Hyzex 6200B>, 7.8 parts by weight of carbon black masterbatch and 3.3 parts by weight of TAFMER A-4085 based on 100 parts by weight of Hyzex 6200B as base resin in step 2. Kneading and extruding the parts with a continuous kneader to prepare a black compound for the final cable coating, and to prepare a press-formed sheet and cable coating in accordance with the above-described sample production method and test method, and carried out the physical property evaluation and extrusion process test, Each test result is shown in Table 1 and Table 2.

Example 4

In step 1, a carbon black masterbatch was prepared using the same equipment, the same conditions, the same additives, and the addition amount (base resin, carbon black, antioxidant, lubricant) as in Example 1, and in step 2, Hyzex 6200B 100 as a base resin. 7.8 parts by weight of carbon black masterbatch and 3.3 parts by weight of TAFMER A-20090 were kneaded and extruded with a continuous kneader to prepare a black compound for coating the final cable, and the press-formed sheet was prepared according to the above-described sample preparation method and test method. And a cable sheath was prepared to carry out physical property evaluation and extrusion test. The test results are shown in Table 1 and Table 2.

Comparative Example 1

50 parts by weight of carbon black (VULCAN-P) and 2.5 parts by weight of antioxidant (SANTONOX-R) and lubricant based on 100 parts by weight of ZC-40 in the first step according to the manufacturing method of the cable coating black compound presented in the above method 2 parts by weight of ISOPROPYL TRIISOSTEAROYL TITANATE (Ajino-Modo Co., Ltd., KR-TTS), and kneaded to prepare a carbon black masterbatch. Melt index 6.0g / 10min., Ethylene vinyl acetate copolymer (ATOCHEM, trade name: 9006) containing 28 wt% vinyl acetate, 3.3 parts by weight, 7.8 parts by weight of carbon black masterbatch, kneaded and extruded in a continuous kneader for final cable covering The black compound was prepared, and the press-formed sheet and the cable coating were prepared according to the above-described sample preparation method and test method, and the physical property evaluation and the extrusion processability test were performed. 2 is shown.

Comparative Example 2

In the first step, the carbon black masterbatch was prepared by using Hyzex 6200B instead of ZC-40, but using the same equipment, the same conditions, the same additives, and the addition amount (carbon black, antioxidant, lubricant) in step 1, 2 In the step, based on 100 parts by weight of the base resin, 7.8 parts by weight of carbon black masterbatch and 3.3 parts by weight of ethylene vinyl acetate copolymer (9006) were kneaded and kneaded with a continuous kneader to prepare a final black coating compound. According to the production method and test method of a sample, the press-formed sheet and the cable coating were prepared, and the physical property evaluation and the extrusion processability test were performed, and the test results are shown in Table 1 and Table 2.

TABLE 1

Physical property test results using experimental equipment

TABLE 2

Test result of extrusion processability using experimental equipment

Claims (29)

Low crystalline low pressure method ultra low density polyethylene (VLDPE) in the range of 0.880-0.910g / cm3 and melt index 0.1-100g / 10min, polymerized from polyethylene stress based on environmental stress cracking modifier ethylene and α-olefin having 4 or more carbon atoms And black with a particle size of 20 nm or less, pH 3.0-8.0, surface area of 80-150 m2 / g, carbon black with 100-200cc / 100g of DBP absorbency, antioxidant and lubricant. Polyethylene-based resin composition. The resin composition according to claim 1, wherein the polyethylene base resin is a low density polyethylene, a medium density polyethylene, a high density polyethylene, or a mixture thereof having a density of 0.910-0.970 g / cm3 and a melt index of 0.1-3.0 g / 10 min. The resin composition according to claim 1 or 2, wherein the polyethylene resin is 77-95 wt% based on the total coating resin composition. The method of claim 1, wherein the antioxidant is di- (2-hydroxymethyl-3 [1-methyl cyclohexyl] phenyl) methane, octadecyl-3- (3,5-di-tertiary-butyl-4-hydrate Hydroxyphenyl) propionate, 2,2'-thiodiethyl-bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-Di-tertiary-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6-tertiary-butylphenyl), polymerization 2 , 2 ', 4'-trimethyl-1,2-dihydroquinoline, tris- (2,4-di-tertiary-butylphenyl) phosphite, dilauryl ester of β, β'-thiodipropionic acid, β, Resin composition, characterized in that at least one selected from the group consisting of distearyl ester of β'- thiodipropionic acid. The resin composition according to claim 1 or 4, wherein the antioxidant is 0.05 to 2.0 parts by weight based on 100 parts by weight of the base resin. The resin composition according to claim 1, wherein the carbon black is 2-5 parts by weight based on 100 parts by weight of the base resin. The lubricant according to claim 1, wherein the lubricant is one of stearic acid metal salts or low molecular weight polyethylene waxes and low molecular weight polypropylene waxes or saturated fatty acids, unsaturated fatty acids and compounds prepared therefrom or aluminum monoalkoxy compounds having an average molecular weight in the range of 1,700-8,000. Resin composition made into. The resin composition according to claim 1 or 8, wherein the lubricant is 0.5-8 parts by weight based on 100 parts by weight of carbon black. The resin composition according to claim 1, wherein the low crystalline low pressure method ultra low density polyethylene is 3-20 parts by weight based on 100 parts by weight of the base resin. A carbon black master batch is prepared by mixing and melt kneading polyethylene, an antioxidant, carbon black, and a lubricant, and kneading and extruding a polyethylene base resin and a low crystalline low pressure method ultra low density polyethylene. The manufacturing method of the black polyethylene-type resin composition for electric wire coating. The method of claim 10, wherein the carrier polyethylene is a low density polyethylene, a medium density polyethylene, a high density polyethylene, polymerized from ethylene having a density of 0.880-0.970 g / cm 3 and a melt index of 0.1-10 g / 10 min, or ethylene and an α-olefin having 4 or more carbon atoms. Low crystalline low pressure method Ultra low density polyethylene or linear low density polyethylene production method characterized by the above-mentioned. The antioxidant of claim 10 wherein the antioxidant is di- (2-hydroxymethyl-3 [1-methylcyclohexyl] phenyl) methane, octadecyl-3- (3,5-di-tertiary-butyl-4-hydride Hydroxyphenyl) propionate, 2,2'-thiodiethyl-bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-Di-tertiary-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6-tertiary-butylphenyl), polymerization 2 , 2 ', 4'-trimethyl-1,2-dihydroquinoline, tris- (2,4-di-tertiary-butylphenyl) phosphite, dilauryl ester of β, β'-thiodipropionic acid, β, at least one selected from the group consisting of distearyl esters of β'-thiodipropionic acid. The method of claim 10, wherein the carbon black has a particle size of 20 nm or less, a pH of 3.0-8.0, a surface area of 80-150 m 2 / g, and a DBP absorbency of 100-200 cc / 100 g. The lubricant according to claim 10, wherein the lubricant is one of a stearic acid metal salt or a low molecular weight polyethylene wax and a low molecular weight polypropylene wax or a saturated fatty acid, an unsaturated fatty acid and a compound prepared therefrom or an aluminum monoalkoxy compound having an average molecular weight in the range of 1,700-8,000. Resin composition made into. The method according to claim 11, wherein the low crystalline low pressure method ultra low density polyethylene used as a carrier has a density of 0.880-0.910 g / cm 3 and a melt index of 0.1-10 g / 10 min. The method according to claim 11, wherein the low density polyethylene, the medium density polyethylene, the high density polyethylene, or the linear low density polyethylene used as the carrier has a density of 0.910-0.970 g / cm 3 and a melt index of 0.1-10 g / 10 min. The process according to claim 11 or 15, wherein the low crystalline low pressure method ultra low density polyethylene is 20-90 wt% with respect to the entire carbon black masterbatch. The method according to claim 10, wherein the content of carbon black is 10-75wt% based on the total amount of carbon black masterbatches. The method according to claim 11 or 16, wherein the low density polyethylene, the medium density polyethylene, the high density polyethylene or the linear low density polyethylene is 50-90 wt% based on the total amount of the carbon black masterbatch. 19. The method according to any one of claims 10, 13 and 18, wherein the content of carbon black is 10-45 wt% based on the total amount of carbon black masterbatches. The method according to claim 10 or 12, wherein the antioxidant is 0.05 to 2.0 parts by weight based on 100 parts by weight of the base resin. The method according to claim 10 or 14, wherein the lubricant is 0.5-8 parts by weight based on 100 parts by weight of carbon black. 15. The lubricant according to claim 10 or 14, wherein the lubricant is mixed with carbon black in advance before melt kneading the carrier resin, or mixed together with the carrier resin, carbon black and antioxidant in preparation of the carbon black master batch. Manufacturing method. The method according to claim 10, wherein the polyethylene base resin is low density polyethylene, medium density polyethylene, high density polyethylene, or a mixture thereof having a density of 0.910-0.970 g / cm 3 and melt index of 0.1-3.0 g / 10 min. 25. The method according to claim 10 or 24, wherein the polyethylene base resin is 77-95 wt% based on the total coating resin composition. The method according to claim 10, wherein the low crystalline low pressure ultra low density polyethylene has a density of 0.880-0.910 g / cm 3 and a melt index of 0.1-100 g / 10 min polymerized from ethylene and an α-olefin having 4 or more carbon atoms. The method according to claim 10 or 26, wherein the low crystalline low pressure method ultra low density polyethylene is 3-20 parts by weight based on 100 parts by weight of the base resin. The method according to claim 10, characterized in that the melt kneading for 20-30 minutes so that the temperature of the compound is 150-180 ℃ for the production of carbon black master batch. The method according to claim 10, wherein the carbon black masterbatch and the low crystalline low pressure method ultra low density polyethylene are added to the polyethylene base resin to melt kneading so that the temperature of the compound is 170 to 230 ° C.