KR20170109406A - Semiconductive composition and method for preparing the same - Google Patents
Semiconductive composition and method for preparing the same Download PDFInfo
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- KR20170109406A KR20170109406A KR1020160033491A KR20160033491A KR20170109406A KR 20170109406 A KR20170109406 A KR 20170109406A KR 1020160033491 A KR1020160033491 A KR 1020160033491A KR 20160033491 A KR20160033491 A KR 20160033491A KR 20170109406 A KR20170109406 A KR 20170109406A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
Abstract
The present invention relates to semiconductive compositions and processes for their preparation. More specifically, the present invention relates to a semiconductive composition capable of forming a semiconductive layer having excellent mechanical and electrical properties, excellent surface smoothness and deterioration due to excellent stability, and a method for producing the semiconductive composition .
Description
The present invention relates to semiconductive compositions and processes for their preparation. More specifically, the present invention relates to a semiconductive composition capable of forming a semiconductive layer having excellent mechanical and electrical properties, excellent surface smoothness and deterioration due to excellent stability, and a method for producing the semiconductive composition .
Typically, a high-voltage or ultra high-voltage power cable includes a conductor, an inner semiconductive layer surrounding it, an insulation layer surrounding the inner semiconductive layer, an outer semiconductive layer surrounding the insulation layer, A sheath layer disposed thereon, and the like.
Particularly, the inner semiconductive layer forms a gradient of insulation resistance in the insulation layer, thereby relieving local electric field concentration, thereby preventing insulation breakdown and shortening the life of the power cable due to deterioration of the insulation layer. In addition, the outer semiconductive layer performs a local field concentration mitigation function in the insulating layer like the inner semiconductive layer, and performs a shielding function.
Here, the inner semiconductive layer and the outer semiconductive layer may be formed of a semiconductive composition in which a conductive filler is dispersed in an insulating resin. In addition, since the conductive filler generally has fine particles of micrometer (탆) or nanometer (nm) size and tends to coagulate with each other in the insulating resin, in order to impart sufficient anti-conductive properties to the inner and outer semiconductive layers Should be included in the semiconductive composition in a substantial amount, for example 20 to 40% by weight in the case of carbon black.
When the conductive filler is contained in a substantial amount in the semiconductive composition, the surface smoothness of the semiconductive layer such as a large number of projections is formed on the surfaces of the inner and outer semiconductive layers formed by the semiconductive composition by aggregation thereof Whereby voids are generated between the inner semiconductive layer and the insulating layer or between the outer semiconductive layer and the insulating layer and the electric field locally concentrates on the voids so that the insulating breakdown due to the deterioration of the insulating layer And the life of the power cable is shortened.
Further, when stirring the semiconductive composition for a long period of time such that the conductive filler contained in the semiconductive composition is uniformly dispersed without aggregation, the semiconductive composition is exposed to high temperature, light, moisture, etc. for a long time, There is a problem that the function of the semiconductive layer formed from the semiconductive composition is deteriorated due to deterioration of the base resin constituting the electrically conductive composition and consequently the lifetime of the cable is shortened.
Accordingly, in the related art, excellent surface smoothness of the semiconductive layer is achieved through uniform dispersion of the conductive filler in the insulating resin while preventing the deterioration of the insulating resin, and at the same time, Research and development are underway to achieve semi-conductive characteristics.
However, by simply dispersing the conductive filler uniformly and minimizing the conductive filler content, the surface smoothness of the semiconductive layer, sufficient semiconducting properties, and mechanical properties can not be attained at the same time.
Therefore, a semiconductive composition for forming a semiconductive layer capable of simultaneously exhibiting excellent surface smoothness, sufficient semiconducting properties, and mechanical properties in a power cable and deteriorating its deterioration due to excellent stability is in desperate need.
It is an object of the present invention to provide a semiconductive composition capable of forming a semiconductive layer having excellent surface smoothness in a power cable and a method for producing the semiconductive composition.
It is another object of the present invention to provide a semiconductive composition capable of forming a semiconductive layer having sufficient semiconducting properties, particularly a desired volume resistivity and sufficient mechanical properties, in a power cable and a method for producing the same.
It is another object of the present invention to provide a semiconductive composition and a method for producing the same, which can maintain their function while suppressing deterioration even when they are stirred at a high temperature for a long time in order to uniformly disperse the conductive filler.
In order to solve the above problems,
A semiconductive composition comprising a base resin, a conductive filler and a stabilizer, wherein the base resin comprises a first resin comprising ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), or a combination thereof, and a low density polyethylene LDPE), wherein a mixing ratio of the first resin and the second resin is 7: 3 to 9: 1, and the conductive filler is a carbon nanotube based on the total weight of the semiconductive composition, (CNT), wherein the stabilizer comprises from 0.01 to 5% by weight of a light stabilizer, a heat stabilizer, or a combination thereof based on the total amount of the semiconductive composition do.
Wherein the melt index (MI) of the second resin measured at 190 캜 is 120% or more of the melt index (MI) measured at 190 캜 of the first resin.
The melt index (MI) of the first resin measured at 190 ° C. is 4 to 8 g / 10 min, and the melt index (MI) of the second resin measured at 190 ° C. is 6 to 10 g / 10 min ≪ / RTI > to provide a semiconductive composition.
And, the light stabilizer provides a semiconductive composition comprising a hindered amine light stabilizer, a hindered piperidine light stabilizer, or both.
On the other hand, in the semiconductive layer formed from the semiconductive composition, the volume resistivity Y (Ω · m) and the density of protrusions X (number / m 2) measured at 90 ° C. according to ASTM D 991 satisfy the following formula (1) A semiconductive composition is provided.
[Equation 1]
Y = aX b
In the above equation (1)
a is 0.03 to 0.034, and b is 2.7 to 2.8.
Furthermore, the present invention provides a semiconductive composition, wherein the volume resistivity is 200 Ω · m or less and the protrusion density is less than 10 / m 2.
Also, the carbon nanotube (CNT) has a diameter of 3 to 10 nm and a length of 5 to 500 탆.
And 0.1 to 1% by weight of a crosslinking agent based on the total weight of the composition.
Further, the present invention provides a semiconductive composition characterized in that the crosslinking agent is an organic peroxide.
On the other hand, a semiconductive composition is provided which comprises a dispersant, an antioxidant, a lubricant, a surfactant, a nucleating agent, a processing aid, or a combination thereof.
Here, the semiconductive composition is characterized in that the dispersant is an ester or amide surfactant.
The semiconductive composition according to the present invention can precisely control the type, shape and content of the conductive filler, thereby greatly improving the surface smoothness of the semiconductive layer formed therefrom, and at the same time, achieving the desired volume resistivity And mechanical properties at the same time.
In addition, the semiconductive composition according to the present invention can precisely control the kind, physical properties, content, and the like of the base resin, and further includes an additional stabilizer to provide an excellent effect that does not deteriorate even under prolonged agitation at a high temperature for uniform dispersion of the conductive filler .
The semiconductive composition according to the present invention may comprise a base resin, a conductive filler dispersed in the resin, and a stabilizer.
The base resin is not particularly limited as long as it can form a semiconductive layer included in the power cable, and can be appropriately selected from a base resin that is conventionally used for a semiconductive composition for forming a semiconductive layer of a power cable.
Examples of the base resin include polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene and polypropylene or polyolefins such as ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), and ethylene butyl acrylate But are not limited to, polyacrylates, polyesters, polycarbonates, polyurethanes, polyimides, polystyrenes, mixtures thereof, and the like.
The base resin may preferably be ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), or a combination thereof, which is excellent in the loading capacity of the conductive filler.
In particular, the base resin is preferably selected from the group consisting of ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), or a combination thereof, which has excellent loading capacity of the conductive filler, and low density polyethylene LDPE).
The blend ratio of ethylene ethyl acrylate (EEA) and / or ethylene butyl acrylate (EBA) to low density polyethylene (LDPE) may be 7: 3 to 9: 1. When the compounding ratio is less than 7: 3, the loading property of the conductive filler is lowered, so that the mechanical properties and moldability of the semiconductive composition are lowered and the surface properties of the semiconductive layer formed therefrom may be lowered. On the other hand, , The thermal stability of the semiconductive composition is lowered, and the semiconducting composition formed therefrom may have a deteriorated function such as a semiconductive property.
Herein, the ethylene ethyl acrylate (EEA) and the ethylene butyl acrylate (EBA) have a melt index (MI) of 4 to 8 g / 10 min measured at 190 ° C., and the low density polyethylene (LDPE) The melt index (MI) of the low density polyethylene (LDPE) may be in the range of 6 to 10 g / 10 min and the melt index (MI) of the ethylene ethyl acrylate (EEA) and the ethylene butyl acrylate Of the melt index (MI) of the thermoplastic elastomer (EBA), for example, 120 to 160%.
The conductive filler may include a carbon nanotube (CNT).
The carbon nanotubes (CNTs) are hexagonal carbon hexagons connected to each other to form a tube shape. Since the carbon nanotubes (CNTs) have a large aspect ratio in cross section and length, they are sufficient even if they are added in a relatively small amount as compared with other conductive fillers in the base resin And it is a main component for realizing the anti-conduction characteristic in the semiconductive composition according to the present invention because it can realize an excellent semiconductive property by forming an electrical network.
However, since the carbon nanotubes (CNTs) have a large aspect ratio, they tend to be entangled with each other like a thread in the base resin, thereby forming a plurality of protrusions on the surface of the semiconductive layer when extruded to form a semiconductive layer of the power cable, It is necessary to precisely control the shapes such as the diameter and the length and the amount of the additive.
Carbon nanotubes (CNTs) usable in the semiconductive compositions according to the present invention may have a diameter of from 3 to 10 nm and may have a single wall or multi-wall structure. In terms of realizing electrical characteristics, a single-wall structure is preferable, and in terms of cost, a multi-wall structure is preferable.
The carbon nanotube (CNT) may have a length of 5 to 500 탆. When the length of the carbon nanotube (CNT) is excessively short (less than 5 μm), it is difficult to realize a sufficient semi-conductive property and the carbon nanotube (CNT) must be added in an excess amount in order to realize a sufficient semi- There is a problem that the surface smoothness of the semiconductive layer is lowered and the manufacturing cost is increased.
On the other hand, when the length of the carbon nanotube (CNT) is excessively longer than 500 탆, it is difficult to uniformly disperse the carbon nanotube (CNT) in the base resin, There is a problem that the surface smoothness of the semiconductive layer is lowered and the mechanical properties such as elongation and the extrudability are lowered.
The carbon nanotubes (CNTs) are uniformly dispersed in the base resin and must be added in an amount exceeding a specific effective amount on the assumption that the carbon nanotubes (CNTs) have a shape such as a diameter, a length, One volume resistivity and surface smoothness can be achieved.
On the other hand, the present inventors have experimentally found that the above-mentioned effective content of the carbon nanotube (CNT) can be greatly different depending on whether or not the base resin is added with a crosslinking agent and the amount of the crosslinking agent added.
Further, the inventors of the present invention have found that, with the premise that the fine particles of the conductive filler are uniformly dispersed in the base resin constituting the semiconductive composition, a slight abrupt temperature change in the process of forming the semiconductive layer from the semiconductive composition, It is experimentally found that fine wrinkles and protrusions can be formed on the surface of the semiconductive layer formed by the different shrinkage and expansion ratio of the portion of the conductive filler where the fine particles are arranged and the portion not arranged, .
This is because the protrusions and the like are formed on the surface of the semiconductive layer formed from the semiconductive composition by aggregation of the conductive fillers in the base resin constituting the semiconductive composition so that the content of the conductive filler is minimized, It is a discovery of a completely different view from the conventional perception that the surface smoothness of the semiconductive layer can be improved by avoiding aggregation of the conductive filler and inducing uniform dispersion.
Further, the inventors of the present invention found that the fine wrinkles and protrusions lower the surface flatness of the semiconductive layer and consequently cause dielectric breakdown due to local electric field concentration of the insulating layer and shortening the lifetime of the cable. The difference in shrinkage rate and expansion ratio between adjacent regions on the surface of the semiconductive layer can be minimized by controlling the content to a specific effective amount or more and narrowing the gap between the fine particles of the uniformly dispersed conductive filler as much as possible, It is possible to solve the problems caused by fine wrinkles and protrusions.
Based on the above experimental findings, the semiconductive composition according to the present invention is characterized in that the conductive filler comprises carbon nanotubes (CNTs) having a shape such as the diameter and the length described above, and the fine particles of the conductive filler (90 캜) Y (Ω · m) of the semiconductive layer produced therefrom and the projection density X (number / m 2) indicating the surface smoothness satisfy the following equation As shown in Fig.
[Equation 1]
Y = aX b
In the above equation (1)
a is 0.03 to 0.034, and b is 2.7 to 2.8.
Specifically, the effective content of the carbon nanotube (CNT) by the amount of the crosslinking agent to be described later may be 6 to 8% by weight based on the total weight of the semiconductive composition. When the content of the carbon nanotubes (CNT) is less than 6% by weight, the surface density of the semiconductive layer formed from the semiconductive composition increases and the surface smoothness is lowered. When the content of carbon nanotubes is more than 8% by weight, There is a problem that the mechanical properties and the extrudability of the thermoplastic resin are deteriorated.
In addition, the semiconductive composition according to the present invention includes carbon nanotubes (CNTs) having a shape such as a diameter and a length as described above and being uniformly dispersed in the base resin as an electrically conductive filler with an effective content as described above, The desired volume resistivity of the semiconductive layer formed therefrom according to ASTM D 991 is at most about 90 캜, preferably about 200 Ωm or less, more preferably about 10 Ωm or less, and most preferably about 3 Ωm And the density of projections showing surface smoothness may be less than 10 pcs / m < 2 >.
The numerical range relating to the content of the carbon nanotubes (CNT) is a structure for achieving a reduction in the sharp volume resistivity of the semiconductive layer formed by the semiconductive composition, and not only is the critical significance recognized, When the content of the conductive filler is less than the specific effective content, the distance between the fine particles of the conductive filler in the base resin is distanced, whereby the excessive shrinkage ratio between the adjacent regions on the semiconductive layer surface and There is provided a very heterogeneous effect which solves the problem that fine wrinkles and projections are formed due to the difference in the expansion ratio and the surface smoothness of the semiconductive layer can be significantly lowered.
The semiconductive composition according to the present invention may further contain, as the conductive filler, carbon black such as a carbon nano plate (CNP), carbon nano flake (CNF), metal particles and the like in addition to the carbon nanotubes May be further included. The conductive filler not only performs the function of realizing the electrical characteristics of the semiconductive composition together with the carbon nanotubes (CNTs), but also disperses uniformly on the surface of the semiconductive layer, so that the shrinkage ratio and the expansion ratio The function of suppressing formation of fine wrinkles and protrusions that reduce the surface smoothness of the semiconductive layer can be additionally performed.
The conductive filler containing the carbon nanotubes (CNT) may be added directly to the base resin. However, in order to uniformly disperse the conductive filler in the base resin, %, Preferably at least 70% by weight, in a concentrated form and added in the form of a master batch prepared in the form of a pellet or the like.
The semiconductive composition according to the present invention may further comprise a stabilizer to suppress deterioration of the base resin or the like exposed to a long time at a high temperature when agitation for uniform dispersion of the conductive filler is performed at a high temperature for a long time.
The stabilizer may include a light stabilizer, a heat stabilizer, or a combination thereof. The light stabilizer may be selected from hindered amine series, hindered piperidine series light stabilizers and the like, preferably N, N'N ", N" -tetra Kiss (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4- yl) amino) triazin- -1, 10-diamine, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol and the like.
The heat stabilizer is not particularly limited, but tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6- methylphenyl] ethyl ester (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diyl bisphosphonate, bis (2,4- And the like.
The content of the stabilizer may be 0.01 to 5 wt% based on the total weight of the semiconductive composition. When the content of the stabilizer is less than 0.01% by weight, stability of the semiconductive composition is insufficient, and if the stabilizer is stirred at a high temperature for a long time, the semiconductive composition deteriorates to lower the function of the semiconductive layer formed therefrom. As a result, On the other hand, if it exceeds 5% by weight, the mechanical properties and moldability of the semiconductive composition may be lowered.
The semiconductive composition according to the present invention may further include a crosslinking agent for crosslinking the base resin in addition to the conductive filler. Since the olefin polymers and olefin copolymers corresponding to the base resin themselves form a semiconductive layer of the electric power cable, the mechanical strength, heat resistance and the like are insufficient. Therefore, the mechanical strength and the mechanical strength of the semiconductive layer, Heat resistance and the like can be improved.
As the crosslinking agent, a conventional crosslinking agent used for crosslinking the base resin can be used. For example, organic peroxides such as dicumyl peroxide (DCP) and di (t-butylperoxydisopropyl) benzene can be used . The organic peroxide is decomposed in a crosslinking process performed at 180 to 240 ° C to produce peroxide radicals, and the resulting peroxide radicals again induce a crosslinking reaction between the polymer chains of the base resin.
The amount of the crosslinking agent may be 0.1 to 1% by weight based on the total weight of the semiconductive composition, and when the amount of the crosslinking agent is less than 0.1% by weight, crosslinking of the base resin may be insufficient, , The effective amount of the carbon nanotube (CNT) may be unnecessarily increased to increase the amount of the carbon nanotube (CNT) added or to significantly reduce the electrical characteristics of the semiconductive layer.
The semiconductive composition according to the present invention may further contain other additives such as a dispersant, an antioxidant, a lubricant, a surfactant, a nucleating agent and a processing aid in addition to the conductive filler and the crosslinking agent.
The dispersant may deaggregate the conductive filler through steric stabilization of the conductive filler and generate the same charge on the conductive filler to generate an electric repulsive force between the conductive fillers to prevent re-agglomeration, so that uniformity of the conductive filler in the base resin It is possible to perform a function of assisting dispersion.
The type of the dispersant is not particularly limited and may be appropriately selected from among dispersants commonly used in semiconductive compositions for forming a semiconductive layer of a power cable. For example, an ester or amide surfactant may be used. The addition amount of the dispersant may be 0.1 to 10% by weight based on the total weight of the semiconductive composition.
The antioxidant functions to suppress deterioration due to oxidation of the semiconductive layer. The type of the antioxidant is not particularly limited and may be appropriately selected from among antioxidants commonly used in semiconductive compositions for forming a semiconductive layer of a power cable have.
As the antioxidant, for example, an amine-based antioxidant; Thioester-based antioxidants such as dialkyl esters, distearyl thiodipropionate, and dilauryl thiodipropionate; Tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene diphosphite, 2,2'-thiodiethylbis- [3- (3,5- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis- [3- Methyl-6-t-butylphenol), 2,2'-thiobis (6-t-butyl-4-methylphenol), triethylene glycol-bis- [3- (3- 4-hydroxy-5-methylphenyl) propionate]), and mixtures thereof, wherein the antioxidant is selected from the group consisting of a total of the semiconductive composition And may be 0.1 to 2% by weight based on the weight.
The present invention relates to a method of making a semiconductive composition. In the present invention, the method for producing the semiconductive composition is not particularly limited. For example, the base resin constituting the semiconductive composition is mixed with 6 to 8 wt% of carbon nanotubes (CNT), 0.01 to 5 wt% of a light stabilizer, 0.1 to 1 wt% of a crosslinking agent, 0.1 to 10 wt% of an antioxidant, 0.1 to 2% by weight of a dispersing agent, and other additives by using a mixing roll at about 70 to 100 캜 for about 5 minutes.
Here, the carbon nanotubes (CNTs) may be added directly or in the form of a master batch. In addition, the semi-rigid composition may be agitated using a kneader mixer, a twin screw extruder, or the like in order to uniformly disperse the carbon nanotubes (CNTs) in the base resin.
[Example]
Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
1. Production Example of Semiconductive Composition
Each component of the content shown in Table 1 below was kneaded at 70 to 100 ° C for 5 minutes using a mixing roll to prepare a semiconductive composition, followed by pressing (180 ° C, 200 kg / cm 2, 20 minutes). Five dumbbell specimens of the dumbbell shape as shown in the following figure were prepared for each of Example 1 and Comparative Examples 1 to 3, and were molded in a press (180 ° C, 200 kg / cm 2, 20 minutes) mm, a width of 30 mm, and a length of 64 mm were prepared for each of the examples and comparative examples, and a 1 mm thick tape-shaped semiconductive layer sample was prepared by using a T-die of a small extruder One for each of Examples and Comparative Examples.
2. Evaluation of Physical Properties of Semi-Conductive Layer
end. Measurement of tensile strength and elongation
Each of five dumbbell-shaped semiconductive layer specimens according to Example 1 and Comparative Examples 1 to 3 was pulled at a rate of 200 ± 10 mm / min using a tensile tester according to the standard ASTM D 638, and the load at the time of cutting the specimen The tensile strength was calculated by dividing the average load of at least three measured values by the cross-sectional area of the specimen. The difference between the gauge distance and the initial gauge distance at the time of cutting was divided by the initial gauge length, Respectively. Here, the tensile strength is 1.5 kgf / mm 2 or more, and the elongation is 180% or more.
I. Measurement of tensile strength and elongation after heating
Each of the five dumbbell-shaped semiconductive layer specimens according to Example 1 and Comparative Examples 1 to 3 was deteriorated at 121 DEG C for 168 hours, and then subjected to tensile testing at a rate of 200 10 mm / min using a tensile tester according to Specification ASTM D 638 The tensile strength was calculated by dividing the average load of at least three measured values by the cross-sectional area of the specimen, and then calculating the difference between the gauge distance and the initial gauge distance The elongation percentage was calculated by dividing by the gauge length and multiplying by 100. Here, the residual tensile strength and elongation percentage after deterioration should be 90% or more, respectively.
I. Measurement of volume resistivity
Each of five rectangular parallelepiped-shaped specimens according to each of the Examples and Comparative Examples was left in an oven preheated to 90 +/- 1 DEG C under a relative humidity of 50 +/- 5% according to the standard ASTM D991 for 10 minutes, After the measurement, the volume resistivity was calculated using the average value of the minimum values of the measured values. Here, the volume resistivity should be 10 Ω · m or less.
The measurement results of the tensile strength, elongation, and volume resistivity are shown in Table 1 below.
CNT
The tensile strength
Elongation rate
%
(90 DEG C)
- Resin 1: ethylene ethyl acrylate (manufacturer: Dupont; product name: EEA 2615 AC; MI: 6 g / 10 min)
- resin 2: low density polyethylene (trade name: LDPE XL610; MI: 8 g / 10 min) manufactured by Lotte Chemical Co.,
- CNT: Carbon nanotube (manufacturer: JEIO; product name: JC142P1 (HP))
- CNP: Carbon nanoplate (manufacturer: XG Science; product name: M-5)
- Stabilizer: Piperidine-based light stabilizer (Manufacturer: Songwon Industrial Co., Ltd .: UV119)
- Crosslinking agent: di (t-butylperoxyisopropyl) benzene
- Dispersant: Nonionic surfactant
As shown in Table 1, the semi-conductive composition of Comparative Example 1 contained no low-density polyethylene (LDPE) as a base resin and did not contain a light stabilizer, resulting in poor heat resistance and stability, The semi-conductive composition of Example 2 contained a light stabilizer and maintained its stability, so that the mechanical properties did not deteriorate after deterioration. However, the volume resistivity was greatly increased because it contained no low-density polyethylene (LDPE) as a base resin. It was confirmed that the composition did not contain a light stabilizer and thus the stability deteriorated and the mechanical properties after the deterioration greatly deteriorated.
In addition, it was confirmed that the semiconducting composition of Comparative Example 2 significantly reduced the elongation percentage of the semiconductive layer due to the excessive amount of the carbon nanotube (CNT).
On the other hand, it was confirmed that the semi-conductive composition of Example 1 according to the present invention improved both mechanical properties, semi-conductive properties, heat resistance and the like.
While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. . It is therefore to be understood that the modified embodiments are included in the technical scope of the present invention if they basically include elements of the claims of the present invention.
Claims (11)
A base resin, a conductive filler and a stabilizer,
Wherein the base resin comprises a first resin comprising ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA) or a combination thereof and a second resin comprising low density polyethylene (LDPE)
Wherein a mixing ratio of the first resin and the second resin is 7: 3 to 9: 1,
The conductive filler comprises 6 to 8% by weight of carbon nanotube (CNT) based on the total weight of the semiconductive composition,
Wherein the stabilizer comprises from 0.01 to 5% by weight of a light stabilizer, a heat stabilizer, or a combination thereof, based on the total weight of the semiconductive composition.
Wherein the melt index (MI) of the second resin measured at 190 占 폚 is at least 120% of the melt index (MI) measured at 190 占 폚 of the first resin.
The first resin has a melt index (MI) of 4 to 8 g / 10 min measured at 190 ° C. and a melt index (MI) of 6 to 10 g / 10 min measured at 190 ° C. of the second resin Lt; / RTI > composition.
Wherein the light stabilizer comprises a hindered amine light stabilizer, a hindered piperidine light stabilizer, or both.
Wherein the volume resistivity Y (Ω · m) measured at 90 ° C. according to ASTM D 991 and the density of protrusions X (number / m 2) measured in a semiconductive layer formed from the semiconductive composition satisfy the following formula Composition.
[Equation 1]
Y = aX b
In the above equation (1)
a is 0.03 to 0.034, and b is 2.7 to 2.8.
Wherein the volume resistivity is 200? 占 퐉 or less and the protrusion density is less than 10 / m2.
Wherein the carbon nanotube (CNT) has a diameter of 3 to 10 nm and a length of 5 to 500 mu m.
0.1 to 1% by weight, based on the total weight of the composition, of a cross-linking agent.
Wherein the cross-linking agent is an organic peroxide.
Antifoaming agents, dispersants, antioxidants, lubricants, surfactants, nucleating agents, processing aids, or combinations thereof.
Wherein the dispersant is an ester or amide surfactant.
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| KR20220158402A (en) | 2021-05-24 | 2022-12-01 | 주식회사 디와이엠 솔루션 | Semi-conductive composition for ehv power cable |
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|---|---|---|---|---|
| JP2002083516A (en) * | 2000-09-06 | 2002-03-22 | Nippon Unicar Co Ltd | Electrical insulating resin composition and electric wire/ cable covered with it |
| KR20100012591A (en) * | 2008-07-29 | 2010-02-08 | 동신대학교산학협력단 | Power cable having a semi-conductive shield |
| KR20150101642A (en) * | 2014-02-27 | 2015-09-04 | (주)경원소재 | Semiconductive composition and method for preparing the same |
-
2016
- 2016-03-21 KR KR1020160033491A patent/KR102046683B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002083516A (en) * | 2000-09-06 | 2002-03-22 | Nippon Unicar Co Ltd | Electrical insulating resin composition and electric wire/ cable covered with it |
| KR20100012591A (en) * | 2008-07-29 | 2010-02-08 | 동신대학교산학협력단 | Power cable having a semi-conductive shield |
| KR20150101642A (en) * | 2014-02-27 | 2015-09-04 | (주)경원소재 | Semiconductive composition and method for preparing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220158402A (en) | 2021-05-24 | 2022-12-01 | 주식회사 디와이엠 솔루션 | Semi-conductive composition for ehv power cable |
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| Publication number | Publication date |
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| KR102046683B1 (en) | 2019-11-20 |
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