KR100373852B1 - Silane crosslinkable black polyethylene composition and manufacturing method for wire and cable application - Google Patents

Abstract

The present invention relates to a black water crosslinking resin composition for electric wire and a method for manufacturing the same, and more particularly, a crosslinking aid and a water crosslinking agent serving as an intermediate medium for chemically grafting a silane compound and a silane to a polyethylene resin, which is a base resin. A water-crosslinkable black resin composition for outdoor medium and low voltage cable containing a catalyst for shortening time, carbon black, an antioxidant and a mixture of polydimethylsiloxane or a mixture of polydimethylsiloxane and polyethylene glycol. By using polyethylene glycol and a separate process of chemically bonding the silane compound and polyethylene, and using a two-component system using a catalyst, the extrusion processability and cable surface are not only excellent in the medium and low voltage power cable extrusion for outdoor use, but also uniform and excellent mechanical properties. , The number of black Scoring For dental wires and to get excellent insulator electrical properties relates to a bridge resin composition and a method of manufacturing the same.

Description

{Silane crosslinkable black polyethylene composition and manufacturing method for wire and cable application}

The present invention relates to a black water crosslinking resin composition for electric wires and a method of manufacturing the same, and more particularly, to a polyethylene resin, which is a base resin, with a silane compound, a crosslinking aid, a catalyst, carbon black, an antioxidant, a polydimethylsiloxane, or a polydimethylsiloxane. A crosslinkable black resin composition for outdoor low and medium voltage power cable insulation containing a mixture of polyethylene glycol, comprising polydimethylsiloxane and polyethylene glycol as an additive, and a separate process and catalyst for chemically bonding the silane compound and polyethylene. Black water-crosslinking resin composition for electric wires that can obtain an excellent insulator and excellent surface property as well as excellent extrudeability and cable surface when extruding medium and low voltage power cables for outdoor use by mixing two-component system, and That manufacture It is about a method.

Outdoor low and medium voltage power cables are overhead wires, ie simple wires with a single layer of material with two functions of insulator and sheath on a conductor consisting of conductor only. Outdoor low and medium voltage power cable should not only have excellent weather resistance and oxidation resistance as a cover material, but also have excellent electrical characteristics such as withstand voltage characteristics in order to function as an insulator. Existing resin compositions used in the manufacture of medium and low voltage power cables for outdoor use include a crosslinking agent for imparting heat resistance by chemical crosslinking, but premature decomposition in an extruder forms premature crosslinks called scotch, making extrusion difficult and There is a problem that adversely affects the appearance and properties.

Therefore, in order to compensate for the disadvantages of the low-voltage power cable for outdoor use by the chemical crosslinking method of adding the crosslinking agent and to improve the productivity, the silane is impregnated with the silane in the resin composition instead of the chemical crosslinking in order to improve the productivity. A method of using a crosslinking method in which a grafted onto polyethylene and extruded cable is exposed to moisture to crosslink is disclosed (US Pat. No. 4,117,195).

This cross-linking method has a lower binding energy than chemical cross-linking method, and it is mainly limited to extrusion insulation of overhead wires because it is difficult to exclude the influence of water because it passes through water, and it is preferable to use it at a relatively low voltage (1 class). Do. However, it is difficult to secure the uniformity of physical properties of the final product due to the uneven reaction of silane and polyethylene in the extruder during the manufacture of outdoor low and medium voltage power cables by silane impregnation, and not only the problem that the scorch occurs during long-term work, but also the master batch form When carbon black is added, there are problems of weather resistance and crack generation due to dispersion nonuniformity.

In the present invention, in order to solve the problems of the above-mentioned crosslinkable black resin composition for the insulation of the medium-low voltage power cable for outdoor use, a combination of a suitable silane compound, a crosslinking aid, a catalyst, carbon black, and an antioxidant in polyethylene resin In order to reduce the extrusion load and improve the electrical properties of the final insulator, polydimethylsiloxane and polyethylene glycol are used in the preparation of the resin composition, and the step of chemically grafting the silane compound to the polyethylene is separately introduced. It is an object of the present invention to provide a black water-crosslinking resin composition for electric wires capable of producing an insulator having excellent time uniformity, excellent mechanical properties, excellent scratch resistance and crack resistance.

In order to achieve the above object, the black water-based crosslinking resin composition of the present invention has a crosslinking aid of 0.01 to 3.0 parts by weight based on 100 parts by weight of polyethylene, and a crosslinking aid serving as an intermediate medium for chemically grafting the silane to polyethylene. 1.0 parts by weight, 0.01 to 0.1 parts by weight of catalyst for shortening the crosslinking time, 0.3 to 3.0 parts by weight of carbon black, 0.1 to 0.6 parts by weight of antioxidant and polydimethylsiloxane alone or a mixture of polydimethylsiloxane and polyethylene glycol 0.1 to 0.6 It is composed of parts by weight, and the silane compound and the crosslinking aid are characterized in that it is included through a separate step of chemically grafting on polyethylene.

In addition, the present invention includes a method for producing a black water crosslinking resin for the wire, a mixture of a crosslinking aid and an antioxidant acting as an intermediate medium for chemically grafting polyethylene, silane compound, silane to polyethylene in a twin screw extruder Adding a step to prepare a graft copolymer having a graft ratio of 5 to 15%;

Separately preparing a catalyst master batch for shortening the crosslinking time by putting polyethylene, a catalyst, and an antioxidant as a carrier and kneading for 30 minutes in a batch type kneader maintained at 110 to 130 ° C;

Separately, carbon black micropores are impregnated with polydimethylsiloxane or a mixture of polydimethylsiloxane and polyethylene glycol, and then kneaded together with polyethylene resin in a batch type kneader maintained at 110 to 130 ° C., and an antioxidant is added to carbon black. Manufacturing a master batch;

Mixing and extruding the graft copolymer prepared in each of the above steps with 1 to 10% by weight of carbon black master batch and 2 to 5% by weight of catalyst master batch; And a method for producing a black water crosslinking resin for an electric wire, including a step of water crosslinking the extrudate in hot water.

The present invention will be described in more detail as follows.

As a base resin of the black water crosslinking resin composition according to the present invention, that is, the resin composition for insulation of low and medium voltage power cables for outdoor use, a polyethylene resin, for example, may be polymerized from ethylene and an α-olefin having 3 to 8 carbon atoms. One or more blends selected from ultra low density polyethylene, low density polyethylene, medium density polyethylene, linear low density polyethylene, and high density polyethylene having a melt index of 0.5 to 6.0 g / 10 minutes and a density of 0.910 to 0.960 g / cm 3 can be used.

The silane compound used in the present invention is an additive that is chemically bonded to polyethylene and serves as a functional group for crosslinking of outdoor low and medium voltage cables. Such silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, vinyldibromosilane, vinyltrinomalbutoxysilane, and the like. It is contained in 0.5-3.0 weight part with respect to 100 weight part of polyethylene resins in the black water crosslinking resin composition for electric power cable insulation. If the content is out of the above range, there is a problem that hot elongation is greatly reduced or physical properties such as scorch stability during extrusion are greatly reduced.

In addition, the crosslinking aid according to the present invention is added as an intermediate mediator that chemically grafts polyethylene and silane. Such crosslinking aids include t-butyl cumyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide , t-butyl peroxy benzoate, α, α-bis (t-butyl peroxy isopropyl) benzene and the like are used, and 0.01 to 100 parts by weight of the polyethylene resin in the black water crosslinking composition for medium and low voltage power cable insulation for outdoor use. It is contained in 1.0 weight part.

In addition, the catalyst used in the present invention is added for the economic advantage of shortening the crosslinking time when crosslinking by exposure to moisture after manufacture of outdoor low-voltage power cable for outdoor use, that is, water crosslinking. Such catalysts include dibutyl tin dilaurate, dibutyl tin dimaleate, dibutyl tin diacetate, dibutyl tin dioctoate, tetrabutyl titanate, hexylamine, dibutylamine, and the like. It is contained in 0.01-0.1 weight part with respect to 100 weight part of polyethylene resins in a black crosslinked resin composition. It is used as a master batch to add a certain ratio during the manufacture of the medium-low voltage power cable for outdoor use, the amount of the catalyst used in the production of the catalyst master batch is preferably 0.1 to 2.0% by weight of the weight before the master batch.

Meanwhile, the carbon black used in the present invention is a filler for imparting weather resistance to outdoor low and medium voltage power cables, and has a particle size of 15 to 30 nm, a surface area of 80 to 150 m 2 / g, an apparent density of 0.350 to 0.360 g / cm 3, and a pH of 8.0. It has the following characteristics. Such carbon black is added in an amount of 0.3 to 3.0 parts by weight based on 100 parts by weight of polyethylene resin in the black water crosslinking composition for outdoor low and medium voltage power cable insulation, and is used by adding a fixed ratio in the final medium and low voltage power cable manufacturing by master batch. The amount of carbon black used in preparing the carbon black master batch is preferably 15 to 50% by weight of the weight before the master batch.

In addition, the antioxidant used in the present invention not only inhibits oxidation of the insulator which is directly or indirectly received after the processing of outdoor low and medium voltage power cables, but also early crosslinking that may occur during the chemical reaction of the silane compound, the crosslinking aid and polyethylene. It is an additive having a function of suppressing the phenomenon. Such antioxidants include, but are not limited to, phenolic antioxidants such as pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 2,2 '-Thiodiethylbis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], octadecyl-3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 4,4'-thiobis (6-t-butyl-m-cresol), triethylene glycol-bis-3 (3-t-butyl-4-hydroxy-5-methylphenyl Used in the form of a single or a combination of propionate and ester-based antioxidants, such as dilauryl thiodipropionate, and the like, with respect to 100 parts by weight of polyethylene resin in the black water crosslinking composition for medium and low voltage power cable insulation for outdoor use. It is preferable to contain in 0.1-0.6 weight part.

In addition, the polydimethylsiloxane or a mixture of polydimethylsiloxane and polyethylene glycol used in the present invention reduces the processing load and internal frictional heat applied to the extruder when processing the medium and low voltage power cables for outdoor use, and withstands the economical voltage characteristics of the medium and low voltage power cables for outdoor use. It is an additive added to improve the electrical characteristics of the. It is preferable that such a mixture of polydimethylsiloxane or polydimethylsiloxane and polyethylene glycol is contained at 0.1 to 0.6 parts by weight based on 100 parts by weight of polyethylene resin in the outdoor medium and low voltage cable cable composition. If the content is less than 0.1 parts by weight, no additive effect is observed, and if the content is more than 0.6 parts by weight, non-uniformity of the extrusion amount occurs. Moreover, when using polydimethylsiloxane and polyethylene glycol in combination, 0.1-0.4 weight part of polydimethylsiloxane and 0.05-0.2 weight part of polyethyleneglycol are preferable with respect to 100 weight part of polyethylene resins.

Polydimethylsiloxane suitable for the purpose of the present invention as described above is used in the range of the average molecular weight 10,000 ~ 100,000, polyethylene glycol is preferably used in the range of the average molecular weight 200 ~ 10,000, by combining polydimethylsiloxane and polyethylene glycol It can be used, and if necessary, polydimethylsiloxane can also be used alone. Since polydimethylsiloxane and polyethylene glycol are relatively viscous liquids, polydimethylsiloxane and polyethylene glycol were impregnated into micropores of carbon black using a Henschel mixer prior to preparing the carbon black master batch to improve dispersion in the final composition. After the production of the master batch together with the carbon black, it is preferable to add and use at a predetermined ratio during the production of outdoor low-voltage power cable.

In the present invention, the water-reversible black resin for insulation of the medium-low voltage power cable for outdoor use using the base resin and the additive described above is manufactured by the following three processes.

In the first step, a graft copolymer (a compound in which a silane compound is chemically bonded to polyethylene) is produced. A mixture of polyethylene, a silane compound, a crosslinking aid and an antioxidant is introduced into a twin screw extruder to chemically convert the silane compound to polyethylene. The graft copolymer is prepared by binding. In this case, the prepared graft copolymer may have a graft ratio of 5 to 15%, preferably 8 to 12% (a measure of the amount of the silane compound chemically bonded to polyethylene). And the operation temperature of an extruder is suitably set so that the temperature of the graft copolymer of a molten state may have a range of 180-280 degreeC.

In the second step, the final catalyst master batch is prepared by kneading for 30 minutes by adding polyethylene, a catalyst, and an antioxidant as a carrier to a batch type kneader in which a heating medium is maintained at 110 to 130 ° C. as a step of preparing a catalyst master batch to shorten the crosslinking time. do.

The third process is a process for producing a carbon black master batch, which consists of the following two step process. First, in step 1, carbon black is charged to the Henschel mixer at room temperature, and then evenly sprayed with a liquid mixture of polydimethylsiloxane or polydimethylsiloxane and polyethylene glycol, and then stirred at high speed for 20 to 30 minutes to give polydimethylsiloxane or polydimethylsiloxane and polyethylene. The mixture of glycols is impregnated into the micropores of carbon black.

In the second step, the same polyethylene resin as that of the base resin of the black low-crosslinked resin composition for outdoor low-voltage power cable insulation, which is a carrier, is put into a batch type kneader in which the heating medium is maintained at 110 to 130 ° C, and then polydimethylsiloxane or Carbon black impregnated with a mixture of polydimethylsiloxane and polyethylene glycol is added and kneaded at a temperature of 140 to 180 ° C for 30 minutes. After adding the antioxidant to the kneaded product again, the mixture was kneaded for 10 minutes to prepare a carbon black master batch.

The graft copolymer, the catalyst masterbatch and the carbon black masterbatch prepared in each of the three processes described above are tumbler or Henschel mixer depending on the required level and the crosslinking condition of the carbon black content of the outdoor medium and low voltage power cable finally produced. It is used to mix in an appropriate ratio, such as using a graft copolymer, wherein the carbon black master batch contains 1 to 10% by weight of the total weight, the catalyst master batch to contain 2 to 5% by weight. Preferably, a cable can be produced using an extruder from such a mixture. When the cable is immersed in hot water and subjected to water crosslinking, a black water crosslinking resin for electric wires according to the present invention can be obtained.

The black water crosslinking resin of the present invention prepared as described above has excellent extrusion processability and cable surface when extruding medium and low voltage power cables for outdoor use, and exhibits excellent insulation properties with excellent mechanical properties, scorch resistance, and electrical properties. Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

Example 1

In order to prepare the graft copolymer, 2.0 parts by weight of vinyltrimethoxysilane and 100 parts by weight of dicumyl peroxide in 100 parts by weight of low density polyethylene (LG Chem, Lutene LDPE: Density 0.920, Melt Index 2.0) were used in a twin screw extruder. , 0.1 parts by weight of an antioxidant (Shibagai Co., Irganox 1076) was added to the reaction extruded to prepare a graft copolymer. At this time, the operating conditions were adjusted so that the temperature of the graft copolymer in the molten state has a range of 220 ~ 240 ℃, to prepare a graft copolymer having a graft ratio of 8 to 12%.

On the other hand, dibutyltindilaura is used as a catalyst for 100 parts by weight of low density polyethylene (LG Chemical, Lutene LDPE: Density 0.920, Melt Index 2.0) in a Benbury mixer maintained at 110 to 130 ° C to prepare a catalyst master batch. 0.5-2.0 weight part of rates, 0.1-0.15 weight part of antioxidant (Shibagaiki Co., Irganox 1076) were put, and it knead | mixed for 30 minutes, and prepared the catalyst masterbatch.

In order to prepare a carbon black master batch, the Henschel mixer maintained at room temperature in one step has a particle size of 15 to 30 nm, a surface area of 80 to 150 m 2 / g, an apparent density of 0.350 to 0.360 g / m 3, and a pH of 8.0 or less. 9A32), and evenly spray 30 parts by weight of a liquid mixture of polydimethylsiloxane and polyethylene glycol (weight ratio of 7: 3) with respect to 100 parts by weight of carbon black, and then stir at high speed at 1,000 rpm for 20 minutes for polydimethylsiloxane and Polyethylene glycol was impregnated into the micropores of carbon black. After mixing and mixing 45 parts by weight of carbon black prepared in step 1 with 100 parts by weight of a low density polyethylene (LG Chemical, Lutene LDPE: density 0.920, melt index 2.0) in a Banbury mixer which is a batch mixer in two steps, 1.0 parts by weight of an antioxidant (Igana Corporation, Irganox 1076) was added to 100 parts by weight of the kneaded material, and finally kneaded to prepare a carbon black master batch containing carbon black, antioxidant, polydimethylsiloxane, and polyethylene glycol.

After preparing each of the above-mentioned process in a tumbler mixer for 9 minutes by weight of the graft copolymer, 4% by weight of the catalyst master batch and 4.2% by weight of the carbon black master batch, and mixed for 5 minutes, the mixture was Under the same conditions, a 1 ㎸ outdoor cable having a final carbon black content of 1% by weight was prepared, and the prepared cable was immersed in 90 ° C. water for 3 hours to perform crosslinking. The properties were then evaluated and the results are shown in Table 1 below.

* 1㎸ Outdoor cable manufacturing condition

Instrument: 90 Φ, L / D 24

Screw: L / D 24 standard single screw, compression ratio 3: 1

Die: Compression Die

Wire Rod: 1㎸, 385QMM

Extruder Temperature: C1 / C2 / C3 / C4 / C5 / Neck / Head / Die = 160/170/180/180/190/200/200/200 ℃

Speed: 40 m / min

Example 2

In the same manner as in Example 1, but did not add a mixture of polydimethylsiloxane and polyethylene glycol in the production of the carbon black master batch, only polydimethylsiloxane was added to prepare a 1 ㎸ outdoor cable using a single screw extruder. The properties were then evaluated and the results are shown in Table 1 below.

Example 3

In the same manner as in Example 1, 2.5 parts by weight of vinyltrimethoxysilane was added to prepare a graft copolymer having a graft ratio of 12 to 13%, and a 1 ㎸ outdoor cable was manufactured using a single screw extruder. The properties were then evaluated and the results are shown in Table 1 below.

Comparative example

Instead of preparing the graft copolymer using the twin screw extruder in Example 2, a mixture of the same composition as in the graft copolymer in Example 2 was added to a Henschel mixer maintained at 80 ° C. for 30 minutes. After stirring, the silane, the crosslinking aid, and the antioxidant were impregnated into the low density polyethylene, and then a 1 kV outdoor cable was manufactured using a single screw extruder. The properties were then evaluated and the results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Comparative example Tensile Strength (㎏ / ㎠) 150-170 150-170 155-175 110 to 150 % Elongation 310-340 310 to 350 300-330 300-360 Tensile Strength Residual Rate after Heating (%) 97 96 99 85 Elongation at rest after heating (%) 95 94 97 81 Hot Elongation (%) 70-90 70-90 60 to 80 90 to 150 Set elongation (%) 0 to 5 0 to 5 0 to 5 5 to 15 Extrusion Load (A) 70 90 72 85 Extrusion appearance Smoothness good Smoothness Scorch generation Withstand voltage characteristics (㎸ / ㎜) 40 34 41 30 Weatherability (%) 98 88 99 81 Crack resistance (time) 1,500 1,000 1,500 500 Scotch stability (minutes) 60 40 55 25

1) Hot / set elongation: measured by IEC 840 method. Smaller value means better physical property.

2) Tensile strength / elongation residual rate after heating: After aging the specimen in 135 ℃ oven for 7 days, the tensile strength / elongation is measured and displayed as the residual ratio compared to room temperature characteristics. The larger the value, the better the heat resistance.

3) Withstand voltage characteristics: 1mm specimens were prepared by extrusion molding and measured according to ASTM D149 method.

4) Weather resistance: According to ASTM D1435 method, the specimen is accelerated and aged at weather-O-meter, and the tensile strength is measured and displayed as the residual ratio to the tensile strength at room temperature. The larger the value, the better the weather resistance.

5) Crack resistance: It is evaluated by the environmental stress crack resistance measured according to ASTM D1693 method, and it means the time elapsed until the first crack occurred after soaking 10 specimens in 10% solution of Igepal. Larger value means better crack resistance.

6) Scotch Stability: It is the time that crosslinking degree reaches 5% by mixing each composition at 180 ℃ and 30 rpm using Haake mixer and measuring the crosslinking degree according to time. Meaning.

As described above, the black water-crosslinking resin for electric wire according to the present invention uses a polydimethylsiloxane and polyethylene glycol, and uses a separate process of chemically bonding the silane compound and polyethylene, and a mixture of a two-component system using a catalyst. When extruding power cables, not only the extrusion processability and the cable surface are excellent, but also the excellent uniformity, excellent mechanical properties, scorch resistance and electrical properties are excellent.

Claims (9)

(Correction) 0.01 to 1.0 parts by weight of a crosslinking aid serving as an intermediate medium for chemically grafting the silane to polyethylene, 0.01 to 1.0 parts by weight of a silane compound, and a catalyst for shortening the crosslinking time with respect to 100 parts by weight of polyethylene. It is composed of parts by weight, 0.3 to 3.0 parts by weight of carbon black, 0.1 to 0.6 parts by weight of antioxidant and 0.1 to 0.6 parts by weight of polydimethylsiloxane alone or a mixture of polydimethylsiloxane and polyethylene glycol, provided that the silane compound and the crosslinking aid Black water cross-linking resin composition for electric wire, characterized in that it is included through a separate step of grafting . The polyethylene resin according to claim 1, wherein the polyethylene resin has a melt index of 0.5 to 6.0 g / 10 min, a density of 0.910 to 0.960 g / cm3 polymerized from ethylene and an α-olefin having 3 to 8 carbon atoms, a low density polyethylene, and a medium density. Black water-crosslinking resin composition for a wire, characterized in that one or more blends selected from polyethylene, linear low density polyethylene and high density polyethylene. The method of claim 1, wherein the silane compound is selected from vinyltrimethoxysilane, vinyltriethoxysilane, vinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, vinyldibromosilane, and vinyltrinormal butoxysilane. Black water crosslinking resin composition for electric wires to The crosslinking aid according to claim 1, wherein the crosslinking aid is t-butyl cumyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, di-t Black water-crosslinking resin composition for electric wires, characterized in that it is selected from -butyl peroxide, t-butyl peroxy benzoate and α-bis (t-butyl peroxy isopropyl) benzene. The wire according to claim 1, wherein the catalyst is selected from dibutyl tin dilaurate, dibutyl tin dimaleate, dibutyl tin diacetate, dibutyl tin dioctoate, tetrabutyl titanate, hexylamine and dibutylamine. Black water crosslinking resin composition. The black water crosslinked resin composition according to claim 1, wherein the carbon black has a particle size of 15 to 30 nm, a surface area of 80 to 150 m 2 / g, an apparent density of 0.350 to 0.370 g / cm 3, and a pH of 8.0 or less. The black water-based crosslinking resin composition according to claim 1, wherein the polydimethylsiloxane is in the range of an average molecular weight of 10,000 to 100,000, and the polyethylene glycol is an average molecular weight of 200 to 10,000. The black water-crosslinking resin for electric wire according to claim 1, wherein the mixture of polydimethylsiloxane and polyethylene glycol contains 0.1 to 0.4 parts by weight of polydimethylsiloxane and 0.05 to 0.2 parts by weight of polyethylene glycol based on 100 parts by weight of polyethylene resin. Composition. (Correction) A graft copolymer having a graft ratio of 5 to 15% was prepared by introducing a mixture of a crosslinking aid and an antioxidant , which serves as an intermediate for chemically grafting polyethylene, silane compound, and silane to polyethylene in a twin screw extruder. Process of doing; Separately preparing a catalyst master batch for shortening the crosslinking time by putting polyethylene, a catalyst, and an antioxidant as a carrier and kneading for 30 minutes in a batch type kneader maintained at 110 to 130 ° C; Separately, carbon black micropores are impregnated with polydimethylsiloxane or a mixture of polydimethylsiloxane and polyethylene glycol, and then kneaded together with polyethylene resin in a batch type kneader maintained at 110 to 130 ° C., and an antioxidant is added to carbon black. Manufacturing a master batch; Mixing and extruding the graft copolymer prepared in each of the above steps with 1 to 10% by weight of carbon black master batch and 2 to 5% by weight of catalyst master batch; And The manufacturing method of the black water crosslinking resin for electric wires including the process of carrying out the water crosslinking of the said extrudate in hot water .