WO2024045340A1 - Peel strength-improved semi-conductive shielding material, preparation method, article, and cable - Google Patents

Peel strength-improved semi-conductive shielding material, preparation method, article, and cable Download PDF

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Publication number
WO2024045340A1
WO2024045340A1 PCT/CN2022/130994 CN2022130994W WO2024045340A1 WO 2024045340 A1 WO2024045340 A1 WO 2024045340A1 CN 2022130994 W CN2022130994 W CN 2022130994W WO 2024045340 A1 WO2024045340 A1 WO 2024045340A1
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Prior art keywords
parts
resin
peel strength
shielding material
ethylene
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PCT/CN2022/130994
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French (fr)
Chinese (zh)
Inventor
侯帅
傅明利
黎小林
展云鹏
朱闻博
贾利川
惠宝军
冯宾
张逸凡
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南方电网科学研究院有限责任公司
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Publication of WO2024045340A1 publication Critical patent/WO2024045340A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the present invention relates to the technical field of high-voltage cables, and in particular to a semiconductive shielding material with improved peel strength, a preparation method, a product and a cable.
  • the semiconducting shielding layer is an important component. It mainly plays the role of preventing interface discharge between the insulation layer and the conductor and reducing the electrical stress intensity of the insulation layer.
  • the semiconductive shielding layer improves the cable's initial corona discharge performance by reducing the potential gradient between the stranded conductors and the metal shield, providing a more uniform electric field distribution for the insulation layer.
  • high voltage cables have higher requirements on the quality and reliability of semiconductive shielding layers.
  • the adhesion of the semi-conductive shielding layer to the insulation layer is an important influencing factor. If the adhesion is small, the semiconducting shielding layer and the insulating layer are easy to peel off. During the cable laying process, gaps may appear between the semiconducting shielding layer and the insulating layer due to stretching and other factors, and there will be gaps during long-term use. Factors such as temperature cause gaps between the semiconducting shielding layer and the insulating layer. When a gap occurs between the semiconductive shielding layer and the insulating layer, the partial discharge may continue to grow, and in severe cases, the insulating layer may even be broken down, causing cable damage.
  • the present application provides a semiconductive shielding material with improved peel strength, a preparation method, a product and a cable.
  • the semiconducting shielding material can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the service life of the cable.
  • the first aspect of this application provides a semiconductive shielding material with improved peel strength, including the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and maleic anhydride grafted polyethylene. 1 to 5 parts and 0.4 to 2.2 parts of cross-linking agent; wherein, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is ethylene-ethyl acrylate resin and one or both of ethylene-butyl acrylate resin.
  • the grafting rate of the maleic anhydride-grafted polyethylene is 0.8% to 1.2%.
  • the melt index of the maleic anhydride-grafted polyethylene is 2g/10min to 4g/10min.
  • the mass ratio of the low-density polyethylene resin and the ethylene-acrylic resin is 1:4 to 4:1.
  • the melt index of the low-density polyethylene resin is 0.25g/10min ⁇ 2g/10min.
  • the density of the low-density polyethylene resin is 0.918g/cm 3 to 0.932g/cm 3 .
  • the melt index of the ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 10g/min.
  • the ethylene-acrylic resin has an elongation at break of ⁇ 700%.
  • the oil absorption value of the conductive carbon black is 150ml/100g ⁇ 170ml/100g.
  • the ash content of the conductive carbon black is ⁇ 0.2%.
  • the conductive carbon black has a 325-mesh screen residue content of ⁇ 8 ppm.
  • the conductive carbon black does not contain sulfur impurities and silicon impurities.
  • the cross-linking agent is one or more of di-tert-butyl cumene peroxide, dicumyl peroxide and bis-25.
  • the raw material further includes processing aids.
  • the processing aid includes a dispersant, and the mass fraction of the dispersant is 0.6 to 2.5 parts.
  • the processing aid includes a coupling agent, and the mass fraction of the coupling agent is 1 to 2 parts.
  • the processing aid includes a lubricant, and the mass fraction of the lubricant is 1 to 2 parts.
  • the processing aid includes an antioxidant, and the mass fraction of the antioxidant is 0.3 to 0.7 parts.
  • the low-density polyethylene resin, the ethylene-acrylic resin, the conductive carbon black and the maleic anhydride-grafted polyethylene are mixed to obtain a mixture;
  • the mixture is extruded and pelletized to obtain pellets;
  • the pre-finished product is subjected to heat treatment.
  • the temperature of the mixing process is 45°C to 50°C.
  • the rotation speed of the mixing process is 150 rpm to 250 rpm.
  • the extrusion temperature is 150°C to 200°C.
  • the rotation speed of the extrusion host is 100 rpm to 150 rpm.
  • the temperature of the heat treatment is 50°C to 70°C.
  • the heating treatment time is 5h to 15h.
  • a semiconductive shielding product whose preparation raw materials include the semiconductive shielding material with improved peel strength as described in any of the above embodiments or the semiconductive shielding material with improved peel strength prepared by the preparation method as described in any of the above embodiments. .
  • a cable including a conductor, an insulating layer and a semiconductive shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting shielding layer is composed of the above It is made of the semiconductive shielding material with improved peel strength as described in any embodiment or the semiconductive shielding material with improved peel strength prepared by the preparation method as described in any of the above embodiments.
  • the raw materials of the above-mentioned peel strength improved semi-conductive shielding material include 58 to 68 parts by mass of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene and With 0.4 parts to 2.2 parts of cross-linking agent, under the ratio of raw materials, the low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility, and the conductive carbon black has good dispersion in the resin. .
  • the semiconducting shielding material When used in cables to prepare a semiconducting shielding layer, it can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the life of the cable. service life.
  • the base resin, conductive carbon black, maleic anhydride-grafted polyethylene and cross-linking agent are respectively 58 to 68 parts and 27 to 34 parts by mass.
  • the ratio of 0.4 to 2.2 parts, 1 to 5 parts, and 0.4 to 2.2 parts can better solve the problem of low-density polyethylene resin and ethylene-acrylic resin restricting the mechanical properties of semi-conductive shielding materials due to polarity differences, making semi-conductive shielding materials
  • the shielding material improves peel strength while taking into account good mechanical properties.
  • the peel strength-improved semiconductive shielding material includes the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, and cross-linking agent 0.4 parts to 2.2 parts; wherein, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. kind.
  • the low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility, and the conductive carbon black has good dispersion in the resin.
  • the semiconducting shielding material When used in cables to prepare a semiconducting shielding layer, it can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the life of the cable. service life.
  • low-density polyethylene resin is a non-polar molecule and ethylene-acrylic resin is a polar molecule.
  • the difference in polarity between the two may affect the tensile strength and breaking elongation of products made of semi-conductive shielding materials. It has adverse effects on mechanical properties such as length and ratio.
  • the mass parts of the matrix resin, conductive carbon black, maleic anhydride grafted polyethylene and cross-linking agent are respectively 58 to 68 parts, 27 to 34 parts, 1 to 5 parts and 0.4
  • the ratio of parts to 2.2 parts can better solve the problem of low-density polyethylene resin and ethylene-acrylic resin restricting the mechanical properties of semi-conductive shielding materials due to polarity differences, so that the semi-conductive shielding materials have good mechanical properties.
  • the use of low-density polyethylene resin can effectively reduce the volume resistivity of the semiconductive shielding material at 23°C and 90°C, and improve the electrical properties of the semiconducting shielding material.
  • the raw materials of this peel strength-improved semiconductive shielding material are: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, and 0.4 to 2.2 parts of joint agent; among them, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; ethylene-acrylic acid resin is one of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. Or both.
  • the mass parts of the matrix resin can be selected from 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, and 65 parts , 66 copies, 67 copies, 68 copies, etc. It is also understandable that the mass fraction of the matrix resin can be appropriately selected within the range of 58 to 68 parts.
  • the mass parts of conductive carbon black can be selected from 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts portions etc. It can also be understood that the mass fraction of conductive carbon black can also be other suitable choices in the range of 27 to 34 parts.
  • the mass parts of maleic anhydride grafted polyethylene can be selected from 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 servings, 4.5 servings, 5 servings, etc. It can also be understood that the mass fraction of maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 1 to 5 parts.
  • the mass parts of the cross-linking agent can be selected from 0.4 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts portions etc. It can also be understood that the mass fraction of the cross-linking agent can be appropriately selected within the range of 0.4 to 2.2 parts.
  • the low density polyethylene resin has a melting point higher than the melting point of the ethylene-acrylic resin. At this time, the melt expansion of ethylene-acrylic resin can be better suppressed by low-density polyethylene resin, which is beneficial to fixing the conductive network.
  • the grafting rate of maleic anhydride-grafted polyethylene is 0.8% to 1.2%.
  • the grafting rate of maleic anhydride-grafted polyethylene can be, but is not limited to, 0.8%, 0.9%, 1%, 1.1%, 1.2%, etc. It is understandable that the grafting rate of maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 0.8% to 1.2%.
  • the melt index of maleic anhydride-grafted polyethylene is 2g/10min to 4g/10min.
  • the melt index of maleic anhydride-grafted polyethylene is 2g/10min, 2.5g/10min, 3g/10min, 3.5g/10min, 4g/10min, etc.
  • the melt index of the maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 2g/10min to 4g/10min.
  • the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4 to 4:1.
  • the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4, 3:7, 2:3, 1:1, 2:1, 3:1, etc. It is understandable that the mass ratio of low-density polyethylene resin and ethylene-acrylic resin can be other suitable choices in the range of 1:4 to 4:1.
  • the melt index of low-density polyethylene resin is 0.25g/10min to 2g/10min.
  • the melt index of low-density polyethylene resin is 0.5g/10min, 0.6g/10min, 0.8g/10min, 1g/10min, 1.5g/10min, 1.8g/10min or 2g/10min, etc. It is understandable that the melt index of low-density polyethylene resin can also be appropriately selected within the range of 0.25g/10min ⁇ 2g/10min.
  • the density of the low-density polyethylene resin is 0.918g/cm 3 to 0.932g/cm 3 .
  • the density of low-density polyethylene resin is 0.918g/cm 3 , 0.92g/cm 3 , 0.925g/cm 3 , 0.928g/cm 3 , 0.93g/cm 3 , etc. It is understandable that the density of low-density polyethylene resin can also be appropriately selected within the range of 0.918g/cm 3 to 0.932g/cm 3 .
  • the melt index of ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 10g/min.
  • the melt index of ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 9g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 8g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg
  • the melt index under the condition is ⁇ 5g/min, etc.
  • the elongation at break of the ethylene-acrylic resin is ⁇ 700%.
  • the elongation at break of the ethylene-acrylic resin is ⁇ 800%; the elongation at break of the ethylene-acrylic resin is ⁇ 900%, etc.
  • the mass percentage of acrylate in the ethylene-acrylic resin is 15% to 20%.
  • the mass percentage of acrylate in the ethylene-acrylic resin is 15%, 16%, 17%, 18%, 19%, 20%, etc.
  • the mass percentage of acrylate in the ethylene-acrylic resin can also be appropriately selected in the range of 15% to 20%.
  • the ethylene-acrylic resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. At this time, the mass percentage of ethyl acrylate in the ethylene-ethyl acrylate resin is 15% to 20%. The mass percentage of butyl acrylate in ethylene-butyl acrylate resin is 15% to 20%.
  • the oil absorption value of conductive carbon black is 150ml/100g ⁇ 170ml/100g.
  • the oil absorption value of conductive carbon black is 150ml/100g, 160ml/100g, 170ml/100g, etc. It is understandable that the oil absorption value of conductive carbon black can also be selected within the range of 150ml/100g ⁇ 170ml/100g.
  • the conductive carbon black is a high-purity conductive carbon black.
  • the ash content of conductive carbon black is ⁇ 0.2%.
  • the ash content of the conductive carbon black is ⁇ 0.1%.
  • the ash content of the conductive carbon black is ⁇ 0.05%.
  • the 325 mesh sieve residue content of conductive carbon black is ⁇ 8ppm.
  • the 325 mesh screen residue content of the conductive carbon black is ⁇ 7ppm.
  • the 325 mesh screen residue content of the conductive carbon black is ⁇ 5ppm.
  • the 325-mesh screen residue content of the conductive carbon black is ⁇ 3ppm.
  • conductive carbon black does not contain sulfur impurities and silicon impurities.
  • the cross-linking agent is one or more of bis-tert-butylperoxycumylbenzene (BIPB), dicumyl peroxide (DCP) and bis-25.
  • BIPB bis-tert-butylperoxycumylbenzene
  • DCP dicumyl peroxide
  • the raw materials of the semiconductive shielding material with improved peel strength also include processing aids.
  • processing aids By adding processing aids, the processing properties of semi-conductive shielding materials can be improved and the overall performance of semi-conductive shielding materials can be further improved.
  • the processing aid includes a dispersant
  • the mass fraction of the dispersant is 0.6 to 2.5 parts.
  • the mass parts of the dispersant can be but are not limited to 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, etc. . It is understandable that the mass fraction of the dispersant can also be appropriately selected in the range of 0.6 to 2.5 parts.
  • the dispersant is one or more of ethylene bisstearamide (EBS), white oil and oleic acid amide.
  • the processing aid includes a coupling agent, and the mass part of the coupling agent is 1 to 2 parts.
  • the mass parts of the coupling agent are 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. It is understandable that the mass fraction of the coupling agent can also be appropriately selected in the range of 1 to 2 parts.
  • the coupling agent is a silane coupling agent. More specifically. Silane coupling agent can be KH550.
  • the processing aid includes a lubricant
  • the mass part of the lubricant is 1 to 2 parts.
  • the mass parts of lubricant are 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. It is understandable that the mass fraction of the lubricant can also be appropriately selected within the range of 1 to 2 parts.
  • the lubricant is at least one of zinc stearate and paraffin wax.
  • the processing aid includes an antioxidant, and the mass fraction of the antioxidant is 0.3 to 0.7 parts.
  • the mass parts of antioxidants are 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, etc. It is understandable that the mass fraction of the antioxidant can also be appropriately selected in the range of 0.3 to 0.7 parts.
  • the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 300. More specifically, the antioxidant may be mixed with antioxidant 1010 and antioxidant 300 in a mass ratio of 1:1.
  • the processing aid is a mixture of dispersants, coupling agents, lubricants, and antioxidants.
  • the semiconductive shielding material with improved peel strength includes the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and 1 part to 1 part of maleic anhydride grafted polyethylene. 5 parts, cross-linking agent 0.4 ⁇ 2.2 parts, dispersant 0.6 ⁇ 2.5 parts, coupling agent 1 ⁇ 2 parts, lubricant 1 ⁇ 2 parts and antioxidant 0.3 ⁇ 0.7 parts; among them, matrix resin It is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
  • the raw materials of the semiconductive shielding material with improved peel strength are: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and maleic anhydride grafted polyethylene 1 parts to 5 parts, cross-linking agent 0.4 to 2.2 parts, dispersant 0.6 to 2.5 parts, coupling agent 1 to 2 parts, lubricant 1 to 2 parts and antioxidant 0.3 to 0.7 parts; among them,
  • the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic resin; the ethylene-acrylic resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
  • Another embodiment of the present invention provides a method for preparing the above-mentioned peel strength-improved semiconductive shielding material.
  • the preparation method includes the following steps: mixing low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black and maleic anhydride-grafted polyethylene to obtain a mixture; extruding and pelletizing the mixture to obtain a cut Pellets; mix the cut pellets with a cross-linking agent to obtain a pre-finished product; heat-treat the pre-finished product.
  • the temperature of the mixing process is 45°C to 50°C.
  • the temperature of the mixing process can be 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, etc.
  • the rotation speed of the mixing process is 150rpm ⁇ 250rpm.
  • the rotation speed of mixing processing is 150rpm, 180rpm, 200rpm, 250rpm, etc. It will be appreciated that the mixing process can be carried out in a mixer.
  • the extrusion temperature is 150°C to 200°C; for example, the extrusion temperature can be 150°C, 160°C, 180°C, 190°C, 200°C, etc.
  • the extrusion host speed is 100rpm ⁇ 150rpm; for example, the extrusion host speed is 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, etc. It will be appreciated that extrusion can be performed in an extruder. Alternatively, the extruder may be a twin-screw extruder.
  • the temperature of the heat treatment is 50°C to 70°C; optionally, the temperature of the heat treatment is 50°C, 55°C, 60°C, 65°C, 70°C, etc.
  • the heat treatment time is 5h to 15h.
  • the heating treatment time is 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, etc.
  • the following steps are also included: keeping the pellets warm at 50°C to 70°C.
  • the insulation temperature is 50°C, 55°C, 60°C, 65°C, 70°C, etc.
  • the holding time is 3h to 6h.
  • the holding time is 3h, 4h, 5h, 6h, etc.
  • the grinding time is 8min ⁇ 20min. Specifically, the grinding time is 8 min, 10 min, 15 min or 20 min, etc. It will be appreciated that grinding can be performed in a grinder.
  • Low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black, maleic anhydride-grafted polyethylene and cross-linking agent are dried to remove moisture from each raw material. Further, when processing aids are included, the low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black, maleic anhydride grafted polyethylene, cross-linking agent and processing aids are dried to remove moisture in each raw material .
  • the raw materials for preparing the product include the above-mentioned semiconductive shielding material with improved peel strength or the semiconductive shielding material with improved peel strength prepared by the above preparation method.
  • the semi-conductive shielding product is made by extrusion molding of raw materials including the above-mentioned semi-conductive shielding material.
  • the semiconductive shielding product is a semiconductive shielding sleeve.
  • the semiconductive shielding product is a high-voltage cable semiconducting shielding product.
  • the raw materials for preparing the semiconductive shielding product also include insulating materials.
  • Semiconducting shielding products are made by extrusion molding of raw materials including the above-mentioned semiconducting shielding materials and insulation materials.
  • Another embodiment of the present invention provides a cable, including a conductor, an insulating layer and a semiconductive shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting shielding layer has the above peel strength It is made of an improved semi-conductive shielding material or a peel-strength-improved semi-conductive shielding material prepared by the above preparation method.
  • semiconductive shielding layers are located on both surfaces of the insulating layer.
  • the cable includes a conductor, an inner shielding layer, an insulation layer and an outer shielding layer arranged in sequence from the inside to the outside, where both the inner shielding layer and the outer shielding layer are semi-conductive shielding layers.
  • the raw materials for preparing the peel strength-improved semiconductive shielding material in this embodiment are: 62.5 parts of matrix resin, 30 parts of conductive carbon black, 1 part of maleic anhydride grafted polyethylene, 2 parts of dispersant, and even 2 parts of linking agent, 1 part of lubricant, 0.5 part of antioxidant and 1 part of cross-linking agent.
  • the matrix resin is low-density polyethylene resin and ethylene-ethyl acrylate resin, and the mass ratio of low-density polyethylene resin and ethylene-ethyl acrylate resin is 3:7.
  • the melt index of low-density polyethylene resin is 0.5g/10min, and the density of low-density polyethylene resin is 0.918g/cm 3 .
  • the mass percentage of ethyl acrylate in ethylene-ethyl acrylate resin is 17%, the melt index of ethylene-ethyl acrylate resin at 190°C and 2.16kg is 8.5g/min, and the elongation at break of ethylene-ethyl acrylate resin is 900%.
  • the oil absorption value of conductive carbon black is 158ml/100g, the ash content is ⁇ 0.2%, the residue content on 325 mesh screen is 5ppm, and it does not contain sulfur impurities and silicon impurities.
  • the grafting rate of maleic anhydride-grafted polyethylene is 1.2%, and the melt index of maleic anhydride-grafted polyethylene is 2.5g/10min.
  • the dispersant is ethylene bisstearamide.
  • the coupling agent is silane coupling agent KH550.
  • the lubricant is zinc stearate.
  • the antioxidant is a mixture of antioxidant 1010 and antioxidant 300 at a mass ratio of 1:1.
  • the preparation method of the semiconductive shielding material with improved peel strength includes the following steps:
  • S101 Dry low-density polyethylene resin, ethylene-ethyl acrylate resin, conductive carbon black, maleic anhydride-grafted polyethylene, cross-linking agent, dispersant, coupling agent, lubricant and antioxidant to remove various Moisture in raw materials.
  • S102 Mix low-density polyethylene resin, ethylene-ethyl acrylate resin, conductive carbon black, maleic anhydride-grafted polyethylene, dispersant, coupling agent, lubricant and antioxidant in a mixer , get the mixture.
  • the temperature of the mixing process is 45°C, and the rotation speed of the mixing process is 160 rpm.
  • S105 Grind the cross-linking agent in a grinder for 10 minutes.
  • the peel strength-improved semiconductive shielding material in this embodiment is obtained.
  • Example 2 Compared with Example 1, the difference in Example 2 is that the mass fraction of maleic anhydride-grafted polyethylene is 2 parts.
  • Example 3 Compared with Example 1, the difference in Example 3 is that the mass fraction of maleic anhydride-grafted polyethylene is 3 parts.
  • Comparative Example 1 Compared with Example 1, the difference of Comparative Example 1 is that the matrix resin is ethylene-ethyl acrylate resin, and the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
  • Comparative Example 2 Compared with Example 1, the difference of Comparative Example 2 is that the matrix resin is low-density polyethylene resin, and the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
  • Comparative Example 3 Compared with Example 1, the difference in Comparative Example 3 is that the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
  • the shielding materials obtained in the examples and comparative examples were pressed into test plates with a thickness of 1 mm. Then the test plates were tested for tensile strength, elongation at break, room temperature volume resistivity, 90°C volume resistivity and glass strength. The test results are shown in Table 1.
  • Comparative Examples 1 and 3 It can be seen from Comparative Examples 1 and 3 that using low-density polyethylene resin and ethylene-ethyl acrylate resin as the matrix resin can effectively improve the peel strength of the semiconductive shielding layer and the insulating layer. The reason may be due to the low-density polyethylene resin used. Vinyl resin is the base material of high-voltage AC cable insulation material. Its interface matching with the insulation layer is excellent, which increases its peel strength. Furthermore, after compounding low-density polyethylene resin and ethylene-ethyl acrylate resin, the electrical properties of the semiconductive shielding layer are better, but its mechanical properties have declined.
  • ethylene-ethyl acrylate resin is extremely Low-density polyethylene resin is a non-polar polymer, and the compatibility between the two is poor. When compounded at a high proportion, the tensile strength and elongation at break of the semi-conductive shielding material decrease. In Comparative Example 2, low-density polyethylene resin is used as the matrix resin. Although its electrical properties and peel strength are good, its mechanical properties are poor.

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Abstract

The present disclosure relates to a peel strength-improved semi-conductive shielding material, a preparation method, an article, and a cable. The peel strength-improved semi-conductive shielding material is prepared from the following raw materials in parts by mass: 58-68 parts of a matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene, and 0.4-2.2 parts of a cross-linking agent. Low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility under the proportioning of the raw materials, and the conductive carbon black has good dispersibility in the resin. When the semi-conductive shielding material is used in a cable for preparing a semi-conductive shielding layer, the adhesive force between the semi-conductive shielding layer and an insulating layer can be effectively increased, the peel strength between the semi-conductive shielding layer and the insulating layer is improved, and the service life of the cable is prolonged.

Description

剥离强度改善型半导电屏蔽料、制备方法、制品和电缆Semiconductive shielding material with improved peel strength, preparation method, product and cable
本申请要求于2022年08月30日提交中国专利局、申请号为2022110494089、发明名称为“剥离强度改善型半导电屏蔽料、制备方法、制品和电缆”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires the priority of the Chinese patent application submitted to the China Patent Office on August 30, 2022, with the application number 2022110494089 and the invention name "Peel Strength Improved Semiconducting Shielding Material, Preparation Method, Products and Cables", all of which The contents are incorporated into this application by reference.
技术领域Technical field
本发明涉及高压电缆技术领域，尤其是涉及一种剥离强度改善型半导电屏蔽料、制备方法、制品和电缆。The present invention relates to the technical field of high-voltage cables, and in particular to a semiconductive shielding material with improved peel strength, a preparation method, a product and a cable.
背景技术Background technique
随着电力工业的发展，高压电力电缆的需求量不断增加。在高压电缆的结构中，半导电屏蔽层是一个重要的组成部分，其主要起着防止绝缘层和导体间的界面放电，以及降低绝缘层电应力强度的作用。同时，半导电屏蔽层通过降低绞合导体与金属屏蔽间的电位梯度，为绝缘层提供更均匀的电场分布，提高了电缆起始电晕放电性能。相比于中低压电缆，高压电缆对半导电屏蔽层的质量和可靠性具有更高的要求。With the development of the power industry, the demand for high-voltage power cables continues to increase. In the structure of high-voltage cables, the semiconducting shielding layer is an important component. It mainly plays the role of preventing interface discharge between the insulation layer and the conductor and reducing the electrical stress intensity of the insulation layer. At the same time, the semiconductive shielding layer improves the cable's initial corona discharge performance by reducing the potential gradient between the stranded conductors and the metal shield, providing a more uniform electric field distribution for the insulation layer. Compared with medium and low voltage cables, high voltage cables have higher requirements on the quality and reliability of semiconductive shielding layers.
在改善高压电缆性能的过程中，半导电屏蔽层在绝缘层上的附着力是比较重要的影响因素。如果附着力较小，半导电屏蔽层和绝缘层易剥离，在电缆铺设的过程中，可能会由于拉伸等因素导致半导电屏蔽层和绝缘层之间出现空隙，并且在长期使用中还会因为温度等因素致使半导电屏蔽层和绝缘层之间产生空隙。当半导电屏蔽层和绝缘层之间出现空隙之后，局部放电量可能会不断增长，严重时甚至会导致绝缘层被击穿，导致电缆损坏。In the process of improving the performance of high-voltage cables, the adhesion of the semi-conductive shielding layer to the insulation layer is an important influencing factor. If the adhesion is small, the semiconducting shielding layer and the insulating layer are easy to peel off. During the cable laying process, gaps may appear between the semiconducting shielding layer and the insulating layer due to stretching and other factors, and there will be gaps during long-term use. Factors such as temperature cause gaps between the semiconducting shielding layer and the insulating layer. When a gap occurs between the semiconductive shielding layer and the insulating layer, the partial discharge may continue to grow, and in severe cases, the insulating layer may even be broken down, causing cable damage.
发明内容Contents of the invention
有鉴于此，本申请提供了一种剥离强度改善型半导电屏蔽料、制备方法、制品和电缆。所述半导电屏蔽料可以有效提高半导电屏蔽层和绝缘层之间附着力，改善半导电屏蔽层和绝缘层之间的剥离强度，延长电缆的使用寿命。In view of this, the present application provides a semiconductive shielding material with improved peel strength, a preparation method, a product and a cable. The semiconducting shielding material can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the service life of the cable.
本申请第一方面提供了一种剥离强度改善型半导电屏蔽料，包括如下质量份数的原料：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份以及交联剂0.4份～2.2份；其中，所述基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；所述乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。The first aspect of this application provides a semiconductive shielding material with improved peel strength, including the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and maleic anhydride grafted polyethylene. 1 to 5 parts and 0.4 to 2.2 parts of cross-linking agent; wherein, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is ethylene-ethyl acrylate resin and one or both of ethylene-butyl acrylate resin.
在其中一个实施例中，所述马来酸酐接枝聚乙烯的接枝率为0.8％～1.2％。In one embodiment, the grafting rate of the maleic anhydride-grafted polyethylene is 0.8% to 1.2%.
在其中一个实施例中，所述马来酸酐接枝聚乙烯的熔融指数为2g/10min～4g/10min。In one embodiment, the melt index of the maleic anhydride-grafted polyethylene is 2g/10min to 4g/10min.
在其中一个实施例中，所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂的质量比为1:4～4:1。In one embodiment, the mass ratio of the low-density polyethylene resin and the ethylene-acrylic resin is 1:4 to 4:1.
在其中一个实施例中，所述低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min。In one embodiment, the melt index of the low-density polyethylene resin is 0.25g/10min˜2g/10min.
在其中一个实施例中，所述低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3。 In one embodiment, the density of the low-density polyethylene resin is 0.918g/cm 3 to 0.932g/cm 3 .
在其中一个实施例中，所述乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤10g/min。In one embodiment, the melt index of the ethylene-acrylic resin at 190°C and 2.16kg is ≤10g/min.
在其中一个实施例中，所述乙烯-丙烯酸树脂的断裂伸长率≥700％。In one embodiment, the ethylene-acrylic resin has an elongation at break of ≥700%.
在其中一个实施例中，所述导电炭黑的吸油值为150ml/100g～170ml/100g。In one embodiment, the oil absorption value of the conductive carbon black is 150ml/100g～170ml/100g.
在其中一个实施例中，所述导电炭黑的灰分含量≤0.2％。In one embodiment, the ash content of the conductive carbon black is ≤0.2%.
在其中一个实施例中，所述导电炭黑的325目筛余物含量≤8ppm。In one embodiment, the conductive carbon black has a 325-mesh screen residue content of ≤ 8 ppm.
在其中一个实施例中，所述导电炭黑不含硫杂质和硅杂质。In one embodiment, the conductive carbon black does not contain sulfur impurities and silicon impurities.
在其中一个实施例中，所述交联剂为双叔丁基过氧异丙基苯、过氧化二异丙苯以及双25中的一种或多种。In one embodiment, the cross-linking agent is one or more of di-tert-butyl cumene peroxide, dicumyl peroxide and bis-25.
在其中一个实施例中，所述原料还包括加工助剂。In one embodiment, the raw material further includes processing aids.
在其中一个实施例中，所述加工助剂包括分散剂，所述分散剂的质量份数为0.6份～2.5份。In one embodiment, the processing aid includes a dispersant, and the mass fraction of the dispersant is 0.6 to 2.5 parts.
在其中一个实施例中，所述加工助剂包括偶联剂，所述偶联剂的质量份数为1份～2份。In one embodiment, the processing aid includes a coupling agent, and the mass fraction of the coupling agent is 1 to 2 parts.
在其中一个实施例中，所述加工助剂包括润滑剂，所述润滑剂的质量份数为1份～2份。In one embodiment, the processing aid includes a lubricant, and the mass fraction of the lubricant is 1 to 2 parts.
在其中一个实施例中，所述加工助剂包括抗氧剂，所述抗氧剂的质量份数为0.3份～0.7份。In one embodiment, the processing aid includes an antioxidant, and the mass fraction of the antioxidant is 0.3 to 0.7 parts.
一种上述任一实施例中所述的剥离强度改善型半导电屏蔽料的制备方法，包括如下步骤：A method for preparing the semiconductive shielding material with improved peel strength as described in any of the above embodiments, including the following steps:
将所述低密度聚乙烯树脂、所述乙烯-丙烯酸树脂、所述导电炭黑以及所述马来酸酐接枝聚乙烯进行混料处理，得到混合料；The low-density polyethylene resin, the ethylene-acrylic resin, the conductive carbon black and the maleic anhydride-grafted polyethylene are mixed to obtain a mixture;
将所述混合料挤出、切粒，得到切粒料；The mixture is extruded and pelletized to obtain pellets;
将所述切粒料与所述交联剂混合，得到预成品；Mix the pellets and the cross-linking agent to obtain a pre-finished product;
对所述预成品进行加热处理。The pre-finished product is subjected to heat treatment.
在其中一个实施例中，所述混料处理的温度为45℃～50℃。In one embodiment, the temperature of the mixing process is 45°C to 50°C.
在其中一个实施例中，所述混料处理的转速为150rpm～250rpm。In one embodiment, the rotation speed of the mixing process is 150 rpm to 250 rpm.
在其中一个实施例中，所述挤出的温度为150℃～200℃。In one embodiment, the extrusion temperature is 150°C to 200°C.
在其中一个实施例中，所述挤出的主机转速为100rpm～150rpm。In one embodiment, the rotation speed of the extrusion host is 100 rpm to 150 rpm.
在其中一个实施例中，所述加热处理的温度为50℃～70℃。In one embodiment, the temperature of the heat treatment is 50°C to 70°C.
在其中一个实施例中，所述加热处理的时间为5h～15h。In one embodiment, the heating treatment time is 5h to 15h.
一种半导电屏蔽制品，其制备原料包括上述任一实施例中所述的剥离强度改善型半导电屏蔽料或者上述任一实施例中所述的制备方法制备的剥离强度改善型半导电屏蔽料。A semiconductive shielding product whose preparation raw materials include the semiconductive shielding material with improved peel strength as described in any of the above embodiments or the semiconductive shielding material with improved peel strength prepared by the preparation method as described in any of the above embodiments. .
一种电缆，包括导体、绝缘层以及半导电屏蔽层；所述导***于所述绝缘层的内侧，所述半导电屏蔽层位于所述绝缘层的至少一个表面；所述半导电屏蔽层由上述任一实施例中所述的剥离强度改善型半导电屏蔽料或者上述任一实施例中所述的制备方法制备的剥离强度改善型半导电屏蔽料制成。A cable, including a conductor, an insulating layer and a semiconductive shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting shielding layer is composed of the above It is made of the semiconductive shielding material with improved peel strength as described in any embodiment or the semiconductive shielding material with improved peel strength prepared by the preparation method as described in any of the above embodiments.
上述剥离强度改善型半导电屏蔽料的原料包括质量份数分别为58份～68份的基体树脂、27份～34份的导电炭黑、1份～5份的马来酸酐接枝聚乙烯以及0.4份～2.2份的交联剂，在原料的配比下，基体树脂中的低密度聚乙烯树脂和乙烯-丙烯酸树脂具有良好的界面相容性，导电炭黑在树脂中具有良好的分散性。将该半导电屏蔽料应用于电缆中制备半导电屏蔽层时，可以有效提高半导电屏蔽层与绝缘层之间的附着力，改善半导电屏蔽层与绝缘层之间的剥离强度，延长电缆的使用寿命。The raw materials of the above-mentioned peel strength improved semi-conductive shielding material include 58 to 68 parts by mass of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene and With 0.4 parts to 2.2 parts of cross-linking agent, under the ratio of raw materials, the low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility, and the conductive carbon black has good dispersion in the resin. . When the semiconducting shielding material is used in cables to prepare a semiconducting shielding layer, it can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the life of the cable. service life.
进一步地，在上述剥离强度改善型半导电屏蔽料中，通过基体树脂、导电炭黑、马来酸酐接枝聚乙烯以及交联剂按照质量份数分别为58份～68份、27份～34份、1份～5份以及0.4份～2.2份的配比，较好地解决了低密度聚乙烯树脂和乙烯-丙烯酸树脂由于极性差异而制约半导电屏蔽料力学性能的问题，使得半导电屏蔽料在改善剥离强度的同时兼顾了良好的力学性能。Further, in the above-mentioned peel strength-improved semiconductive shielding material, the base resin, conductive carbon black, maleic anhydride-grafted polyethylene and cross-linking agent are respectively 58 to 68 parts and 27 to 34 parts by mass. The ratio of 0.4 to 2.2 parts, 1 to 5 parts, and 0.4 to 2.2 parts can better solve the problem of low-density polyethylene resin and ethylene-acrylic resin restricting the mechanical properties of semi-conductive shielding materials due to polarity differences, making semi-conductive shielding materials The shielding material improves peel strength while taking into account good mechanical properties.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此 本发明不受下面公开的具体实施例的限制。In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific implementation modes of the present invention are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways different from those described here. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the invention belongs. The terminology used herein in the description of the invention is for the purpose of describing specific embodiments only and is not intended to limit the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
本发明一实施例提供了一种剥离强度改善型半导电屏蔽料。该剥离强度改善型半导电屏蔽料包括如下质量份数的原料：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份以及交联剂0.4份～2.2份；其中，基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。在本实施例中原料的配比下，基体树脂中的低密度聚乙烯树脂和乙烯-丙烯酸树脂具有良好的界面相容性，导电炭黑在树脂中具有良好的分散性。将该半导电屏蔽料应用于电缆中制备半导电屏蔽层时，可以有效提高半导电屏蔽层与绝缘层之间的附着力，改善半导电屏蔽层与绝缘层之间的剥离强度，延长电缆的使用寿命。One embodiment of the present invention provides a semiconductive shielding material with improved peel strength. The peel strength-improved semiconductive shielding material includes the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, and cross-linking agent 0.4 parts to 2.2 parts; wherein, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. kind. Under the ratio of raw materials in this embodiment, the low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility, and the conductive carbon black has good dispersion in the resin. When the semiconducting shielding material is used in cables to prepare a semiconducting shielding layer, it can effectively improve the adhesion between the semiconducting shielding layer and the insulating layer, improve the peeling strength between the semiconducting shielding layer and the insulating layer, and extend the life of the cable. service life.
可以理解的是，低密度聚乙烯树脂为非极性分子，乙烯-丙烯酸树脂为极性分子，两者极性上的差异可能会对半导电屏蔽料制成的产品的拉伸强度和断裂伸长率等力学性能带来不利影响。在本实施例中，通过基体树脂、导电炭黑、马来酸酐接枝聚乙烯以及交联剂按照质量份数分别为58份～68份、27份～34份、1份～5份以及0.4份～2.2份的配比，较好地解决了低密度聚乙烯树脂和乙烯-丙烯酸树脂由于极性差异而制约半导电屏蔽料力学性能的问题，使半导电屏蔽料兼顾了良好的力学性能。另外，本实施例中通过低密度聚乙烯树脂的使用，可以有效降低半导电屏蔽料23℃和90℃的体积电阻率，改善半导电屏蔽料的电学性能。It can be understood that low-density polyethylene resin is a non-polar molecule and ethylene-acrylic resin is a polar molecule. The difference in polarity between the two may affect the tensile strength and breaking elongation of products made of semi-conductive shielding materials. It has adverse effects on mechanical properties such as length and ratio. In this embodiment, the mass parts of the matrix resin, conductive carbon black, maleic anhydride grafted polyethylene and cross-linking agent are respectively 58 to 68 parts, 27 to 34 parts, 1 to 5 parts and 0.4 The ratio of parts to 2.2 parts can better solve the problem of low-density polyethylene resin and ethylene-acrylic resin restricting the mechanical properties of semi-conductive shielding materials due to polarity differences, so that the semi-conductive shielding materials have good mechanical properties. In addition, in this embodiment, the use of low-density polyethylene resin can effectively reduce the volume resistivity of the semiconductive shielding material at 23°C and 90°C, and improve the electrical properties of the semiconducting shielding material.
本发明还有一实施例提供了一种剥离强度改善型半导电屏蔽料。按质量份数计，该剥离强度改善型半导电屏蔽料的原料为：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份以及交联剂0.4份～2.2份；其中，基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。在本实施例中，以基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份以及交联剂0.4份～2.2份作为原料，也可以获得良好剥离强度和力学性能的半导电屏蔽料。Another embodiment of the present invention provides a semiconductive shielding material with improved peel strength. In terms of parts by mass, the raw materials of this peel strength-improved semiconductive shielding material are: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, and 0.4 to 2.2 parts of joint agent; among them, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; ethylene-acrylic acid resin is one of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. Or both. In this embodiment, 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene and 0.4 to 2.2 parts of cross-linking agent are used as raw materials. Alternatively, Semi-conductive shielding material with good peel strength and mechanical properties.
可以理解的是，在剥离强度改善型半导电屏蔽料的原料中，基体树脂的质量份数可选为58份、59份、60份、61份、62份、63份、64份、65份、66份、67份、68份等。还可以理解的是，基体树脂的质量份数还可以在58份～68份范围内做其他合适的选择。It can be understood that in the raw materials of the peel strength improved semi-conductive shielding material, the mass parts of the matrix resin can be selected from 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, and 65 parts , 66 copies, 67 copies, 68 copies, etc. It is also understandable that the mass fraction of the matrix resin can be appropriately selected within the range of 58 to 68 parts.
可以理解的是，在剥离强度改善型半导电屏蔽料的原料中，导电炭黑的质量份数可选为27份、28份、29份、30份、31份、32份、33份、34份等。还可以理解的是，导电炭黑的质量份数还可以在27份～34份范围内做其他合适的选择。It can be understood that in the raw materials of the peel strength improved semi-conductive shielding material, the mass parts of conductive carbon black can be selected from 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts portions etc. It can also be understood that the mass fraction of conductive carbon black can also be other suitable choices in the range of 27 to 34 parts.
可以理解的是，在剥离强度改善型半导电屏蔽料的原料中，马来酸酐接枝聚乙烯的质量份数可选为1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。还可以理解的是，马来酸酐接枝聚乙烯的质量份数还可以在1份～5份范围内做其他合适的选择。It can be understood that in the raw materials of the peel strength improved semi-conductive shielding material, the mass parts of maleic anhydride grafted polyethylene can be selected from 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 servings, 4.5 servings, 5 servings, etc. It can also be understood that the mass fraction of maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 1 to 5 parts.
可以理解的是，在剥离强度改善型半导电屏蔽料的原料中，交联剂的质量份数可选为0.4份、0.5份、0.8份、1份、1.5份、1.8份、2份、2.2份等。还可以理解的是，交联剂的质量份数还可以在0.4份～2.2份范围内做其他合适的选择。It can be understood that in the raw materials of the peel strength improved semi-conductive shielding material, the mass parts of the cross-linking agent can be selected from 0.4 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts portions etc. It can also be understood that the mass fraction of the cross-linking agent can be appropriately selected within the range of 0.4 to 2.2 parts.
在一个具体的示例中，低密度聚乙烯树脂的熔点高于乙烯-丙烯酸树脂 的熔点。此时，可以通过低密度聚乙烯树脂对乙烯-丙烯酸树脂的熔融膨胀进行更好地抑制，有利于固定导电网络。In a specific example, the low density polyethylene resin has a melting point higher than the melting point of the ethylene-acrylic resin. At this time, the melt expansion of ethylene-acrylic resin can be better suppressed by low-density polyethylene resin, which is beneficial to fixing the conductive network.
在一个具体的示例中，马来酸酐接枝聚乙烯的接枝率为0.8％～1.2％。比如，马来酸酐接枝聚乙烯的接枝率可以是但不限定为0.8％、0.9％、1％、1.1％、1.2％等。可理解，马来酸酐接枝聚乙烯的接枝率还可以在0.8％～1.2％范围内做其他合适的选择。In a specific example, the grafting rate of maleic anhydride-grafted polyethylene is 0.8% to 1.2%. For example, the grafting rate of maleic anhydride-grafted polyethylene can be, but is not limited to, 0.8%, 0.9%, 1%, 1.1%, 1.2%, etc. It is understandable that the grafting rate of maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 0.8% to 1.2%.
在一个具体的示例中，马来酸酐接枝聚乙烯的熔融指数为2g/10min～4g/10min。可选地，马来酸酐接枝聚乙烯的熔融指数为2g/10min、2.5g/10min、3g/10min、3.5g/10min、4g/10min等。进一步可选地，马来酸酐接枝聚乙烯的熔融指数还可以在2g/10min～4g/10min范围内作其他合适的选择。In a specific example, the melt index of maleic anhydride-grafted polyethylene is 2g/10min to 4g/10min. Alternatively, the melt index of maleic anhydride-grafted polyethylene is 2g/10min, 2.5g/10min, 3g/10min, 3.5g/10min, 4g/10min, etc. Further optionally, the melt index of the maleic anhydride-grafted polyethylene can also be appropriately selected in the range of 2g/10min to 4g/10min.
在基体树脂中，作为低密度聚乙烯树脂和乙烯-丙烯酸树脂的用量示例，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比为1:4～4:1。比如，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比为1:4、3:7、2:3、1:1、2:1、3:1等。可理解的是，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比还可以在1:4～4:1范围内做其他合适的选择。In the matrix resin, as an example of the amounts of low-density polyethylene resin and ethylene-acrylic resin, the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4 to 4:1. For example, the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4, 3:7, 2:3, 1:1, 2:1, 3:1, etc. It is understandable that the mass ratio of low-density polyethylene resin and ethylene-acrylic resin can be other suitable choices in the range of 1:4 to 4:1.
作为低密度聚乙烯树脂的参数示例，低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min。譬如，低密度聚乙烯树脂的熔融指数为0.5g/10min、0.6g/10min、0.8g/10min、1g/10min、1.5g/10min、1.8g/10min或2g/10min等。可理解的是，低密度聚乙烯树脂的熔融指数还可以在0.25g/10min～2g/10min范围内做其他合适的选择。As an example of parameters of low-density polyethylene resin, the melt index of low-density polyethylene resin is 0.25g/10min to 2g/10min. For example, the melt index of low-density polyethylene resin is 0.5g/10min, 0.6g/10min, 0.8g/10min, 1g/10min, 1.5g/10min, 1.8g/10min or 2g/10min, etc. It is understandable that the melt index of low-density polyethylene resin can also be appropriately selected within the range of 0.25g/10min ~ 2g/10min.
可选地，低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3。譬如，低密度聚乙烯树脂的密度为0.918g/cm 3、0.92g/cm 3、0.925g/cm 3、0.928g/cm 3、0.93g/cm 3等。可理解的是，低密度聚乙烯树脂的密度还可以在0.918g/cm 3～0.932g/cm 3范围内做其他合适的选择。 Optionally, the density of the low-density polyethylene resin is 0.918g/cm 3 to 0.932g/cm 3 . For example, the density of low-density polyethylene resin is 0.918g/cm 3 , 0.92g/cm 3 , 0.925g/cm 3 , 0.928g/cm 3 , 0.93g/cm 3 , etc. It is understandable that the density of low-density polyethylene resin can also be appropriately selected within the range of 0.918g/cm 3 to 0.932g/cm 3 .
在一个具体的示例中，乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤10g/min。比如，乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤9g/min；乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤8g/min；乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤5g/min等。进一步地，乙烯-丙烯酸树脂的断裂伸长率≥700％。可选地，乙烯-丙烯酸树脂的断裂伸长率≥800％；乙烯-丙烯酸树脂的断裂伸长率≥900％等。In a specific example, the melt index of ethylene-acrylic resin at 190°C and 2.16kg is ≤10g/min. For example, the melt index of ethylene-acrylic resin at 190°C and 2.16kg is ≤9g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg is ≤8g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg The melt index under the condition is ≤5g/min, etc. Further, the elongation at break of the ethylene-acrylic resin is ≥700%. Optionally, the elongation at break of the ethylene-acrylic resin is ≥800%; the elongation at break of the ethylene-acrylic resin is ≥900%, etc.
进一步地，乙烯-丙烯酸树脂中丙烯酸酯的质量百分数为15％～20％。可选地，乙烯-丙烯酸树脂中丙烯酸酯的质量百分数为15％、16％、17％、18％、19％、20％等。进一步可选地，乙烯-丙烯酸树脂中丙烯酸酯的质量百分数还可以在15％～20％范围内做其他合适的选择。Further, the mass percentage of acrylate in the ethylene-acrylic resin is 15% to 20%. Alternatively, the mass percentage of acrylate in the ethylene-acrylic resin is 15%, 16%, 17%, 18%, 19%, 20%, etc. Further optionally, the mass percentage of acrylate in the ethylene-acrylic resin can also be appropriately selected in the range of 15% to 20%.
可理解的是，乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。此时，乙烯-丙烯酸乙酯树脂中丙烯酸乙酯的质量百分数为15％～20％。乙烯-丙烯酸丁酯树脂中丙烯酸丁酯的质量百分数为15％～20％。It can be understood that the ethylene-acrylic resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. At this time, the mass percentage of ethyl acrylate in the ethylene-ethyl acrylate resin is 15% to 20%. The mass percentage of butyl acrylate in ethylene-butyl acrylate resin is 15% to 20%.
在一个具体的示例中，导电炭黑的吸油值为150ml/100g～170ml/100g。比如，导电炭黑的吸油值为150ml/100g、160ml/100g、170ml/100g等。可理解，导电炭黑的吸油值还可以在150ml/100g～170ml/100g范围内作其他合适的选择。In a specific example, the oil absorption value of conductive carbon black is 150ml/100g～170ml/100g. For example, the oil absorption value of conductive carbon black is 150ml/100g, 160ml/100g, 170ml/100g, etc. It is understandable that the oil absorption value of conductive carbon black can also be selected within the range of 150ml/100g ~ 170ml/100g.
进一步地，导电炭黑为高纯净度型导电炭黑。具体地，导电炭黑的灰分含量≤0.2％。可选地，导电炭黑的灰分含量≤0.1％。进一步可选地，导电炭黑的灰分含量≤0.05％。导电炭黑的325目筛余物含量≤8ppm。可选地，导电炭黑的325目筛余物含量≤7ppm。进一步可选地，导电炭黑的325目筛余物含量≤5ppm。又一步可选地，导电炭黑的325目筛余物含量≤3ppm。再进一步地，导电炭黑不含硫杂质和硅杂质。Further, the conductive carbon black is a high-purity conductive carbon black. Specifically, the ash content of conductive carbon black is ≤0.2%. Optionally, the ash content of the conductive carbon black is ≤0.1%. Further optionally, the ash content of the conductive carbon black is ≤0.05%. The 325 mesh sieve residue content of conductive carbon black is ≤8ppm. Optionally, the 325 mesh screen residue content of the conductive carbon black is ≤7ppm. Further optionally, the 325 mesh screen residue content of the conductive carbon black is ≤5ppm. In another optional step, the 325-mesh screen residue content of the conductive carbon black is ≤3ppm. Furthermore, conductive carbon black does not contain sulfur impurities and silicon impurities.
在一个具体的示例中，交联剂为双叔丁基过氧异丙基苯(BIPB)、过 氧化二异丙苯(DCP)以及双25中的一种或多种。In a specific example, the cross-linking agent is one or more of bis-tert-butylperoxycumylbenzene (BIPB), dicumyl peroxide (DCP) and bis-25.
在一个具体的示例中，剥离强度改善型半导电屏蔽料的原料还包括加工助剂。通过加工助剂的加入，可以改善半导电屏蔽料的加工性格，进一步提高半导电屏蔽料的综合性能。In a specific example, the raw materials of the semiconductive shielding material with improved peel strength also include processing aids. By adding processing aids, the processing properties of semi-conductive shielding materials can be improved and the overall performance of semi-conductive shielding materials can be further improved.
可选地，加工助剂包括分散剂，分散剂的质量份数为0.6份～2.5份。比如，分散剂的质量份数可以是但不限定为0.6份、0.7份、0.8份、0.9份、1份、1.2份、1.5份、1.6份、1.8份、2份、2.2份、2.5份等。可理解，分散剂的质量份数还可以在0.6份～2.5份范围内作其他合适的选择。具体地，分散剂为乙撑双硬脂酰胺(EBS)、白油和油酸酰胺中的一种或多种。Optionally, the processing aid includes a dispersant, and the mass fraction of the dispersant is 0.6 to 2.5 parts. For example, the mass parts of the dispersant can be but are not limited to 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, etc. . It is understandable that the mass fraction of the dispersant can also be appropriately selected in the range of 0.6 to 2.5 parts. Specifically, the dispersant is one or more of ethylene bisstearamide (EBS), white oil and oleic acid amide.
可选地，加工助剂包括偶联剂，偶联剂的质量份数为1份～2份。比如，偶联剂的质量份数为1份、1.3份、1.5份、1.8份、2份等。可理解，偶联剂的质量份数还可以在1份～2份范围内作其他合适的选择。具体地，偶联剂为硅烷偶联剂。更具体地。硅烷偶联剂可以是KH550。Optionally, the processing aid includes a coupling agent, and the mass part of the coupling agent is 1 to 2 parts. For example, the mass parts of the coupling agent are 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. It is understandable that the mass fraction of the coupling agent can also be appropriately selected in the range of 1 to 2 parts. Specifically, the coupling agent is a silane coupling agent. More specifically. Silane coupling agent can be KH550.
可选地，加工助剂包括润滑剂，润滑剂的质量份数为1份～2份。比如，润滑剂的质量份数为1份、1.3份、1.5份、1.8份、2份等。可理解，润滑剂的质量份数还可以在1份～2份范围内作其他合适的选择。具体地，润滑剂为硬脂酸锌和石蜡中的至少一种。Optionally, the processing aid includes a lubricant, and the mass part of the lubricant is 1 to 2 parts. For example, the mass parts of lubricant are 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. It is understandable that the mass fraction of the lubricant can also be appropriately selected within the range of 1 to 2 parts. Specifically, the lubricant is at least one of zinc stearate and paraffin wax.
可选地，加工助剂包括抗氧剂，抗氧剂的质量份数为0.3份～0.7份。比如，抗氧剂的质量份数为0.3份、0.4份、0.5份、0.6份、0.7份等。可理解，抗氧剂的质量份数还可以在0.3份～0.7份范围内作其他合适的选择。具体地，抗氧剂为抗氧剂1010、抗氧剂168以及抗氧剂300中的一种或多种。更具体地，抗氧剂可以是由抗氧剂1010和抗氧剂300按质量比为1:1混合而成。Optionally, the processing aid includes an antioxidant, and the mass fraction of the antioxidant is 0.3 to 0.7 parts. For example, the mass parts of antioxidants are 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, etc. It is understandable that the mass fraction of the antioxidant can also be appropriately selected in the range of 0.3 to 0.7 parts. Specifically, the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 300. More specifically, the antioxidant may be mixed with antioxidant 1010 and antioxidant 300 in a mass ratio of 1:1.
在一个具体的示例中，加工助剂由分散剂、偶联剂、润滑剂以及抗氧剂混合而成。In a specific example, the processing aid is a mixture of dispersants, coupling agents, lubricants, and antioxidants.
在一个具体的示例中，剥离强度改善型半导电屏蔽料包括如下质量份数的原料：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份、交联剂0.4份～2.2份、分散剂0.6份～2.5份、偶联剂1份～2份、润滑剂1份～2份以及抗氧剂0.3份～0.7份；其中，基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。In a specific example, the semiconductive shielding material with improved peel strength includes the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and 1 part to 1 part of maleic anhydride grafted polyethylene. 5 parts, cross-linking agent 0.4~2.2 parts, dispersant 0.6~2.5 parts, coupling agent 1~2 parts, lubricant 1~2 parts and antioxidant 0.3~0.7 parts; among them, matrix resin It is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
在一个具体的示例中，按质量份数计，剥离强度改善型半导电屏蔽料的原料为：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份、交联剂0.4份～2.2份、分散剂0.6份～2.5份、偶联剂1份～2份、润滑剂1份～2份以及抗氧剂0.3份～0.7份；其中，基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。In a specific example, in terms of parts by mass, the raw materials of the semiconductive shielding material with improved peel strength are: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and maleic anhydride grafted polyethylene 1 parts to 5 parts, cross-linking agent 0.4 to 2.2 parts, dispersant 0.6 to 2.5 parts, coupling agent 1 to 2 parts, lubricant 1 to 2 parts and antioxidant 0.3 to 0.7 parts; among them, The matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic resin; the ethylene-acrylic resin is one or both of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
本发明还有一实施例提供了一种上述剥离强度改善型半导电屏蔽料的制备方法。该制备方法包括如下步骤：将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电炭黑以及马来酸酐接枝聚乙烯进行混料处理，得到混合料；将混合料挤出、切粒，得到切粒料；将切粒料与交联剂混合，得到预成品；对预成品进行加热处理。Another embodiment of the present invention provides a method for preparing the above-mentioned peel strength-improved semiconductive shielding material. The preparation method includes the following steps: mixing low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black and maleic anhydride-grafted polyethylene to obtain a mixture; extruding and pelletizing the mixture to obtain a cut Pellets; mix the cut pellets with a cross-linking agent to obtain a pre-finished product; heat-treat the pre-finished product.
在一个具体的示例中，混料处理的温度为45℃～50℃。比如，混料处理的温度可以是45℃、46℃、47℃、48℃、49℃、50℃等。混料处理的转速为150rpm～250rpm。比如，混料处理的转速为150rpm、180rpm、200rpm、250rpm等。可理解的是，混料处理可以在混料机中进行。In a specific example, the temperature of the mixing process is 45°C to 50°C. For example, the temperature of the mixing process can be 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, etc. The rotation speed of the mixing process is 150rpm ~ 250rpm. For example, the rotation speed of mixing processing is 150rpm, 180rpm, 200rpm, 250rpm, etc. It will be appreciated that the mixing process can be carried out in a mixer.
在一个具体的示例中，挤出的温度为150℃～200℃；比如，挤出的温度可以是150℃、160℃、180℃、190℃、200℃等。挤出的主机转速为100rpm～150rpm；比如，挤出的主机转速为100rpm、110rpm、120rpm、130rpm、140rpm、150rpm等。可理解的是，挤出可以在挤出机中进行。可选地，挤 出机可以是双螺杆挤出机。In a specific example, the extrusion temperature is 150°C to 200°C; for example, the extrusion temperature can be 150°C, 160°C, 180°C, 190°C, 200°C, etc. The extrusion host speed is 100rpm ~ 150rpm; for example, the extrusion host speed is 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, etc. It will be appreciated that extrusion can be performed in an extruder. Alternatively, the extruder may be a twin-screw extruder.
在一个具体的示例中，加热处理的温度为50℃～70℃；可选地，加热处理的温度为50℃、55℃、60℃、65℃、70℃等。进一步地，加热处理的时间为5h～15h。可选地，加热处理的时间为5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h等。通过加热处理，可以使交联剂被切粒料充分吸收，以提高半导电屏蔽料的性能。In a specific example, the temperature of the heat treatment is 50°C to 70°C; optionally, the temperature of the heat treatment is 50°C, 55°C, 60°C, 65°C, 70°C, etc. Further, the heat treatment time is 5h to 15h. Optionally, the heating treatment time is 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, etc. Through heat treatment, the cross-linking agent can be fully absorbed by the pellets to improve the performance of the semi-conductive shielding material.
在将切粒料与交联剂混合之前，还包括如下步骤：将切粒料在50℃～70℃保温。可选地，保温温度为50℃、55℃、60℃、65℃、70℃等。再进一步地，保温时间3h～6h。可选地，保温时间为3h、4h、5h、6h等。Before mixing the pellets and the cross-linking agent, the following steps are also included: keeping the pellets warm at 50°C to 70°C. Optionally, the insulation temperature is 50°C, 55°C, 60°C, 65°C, 70°C, etc. Furthermore, the holding time is 3h to 6h. Optionally, the holding time is 3h, 4h, 5h, 6h, etc.
在将切粒料与交联剂混合之前，还包括如下步骤：对交联剂进行研磨处理。研磨时间为8min～20min。具体地，研磨时间为8min、10min、15min或20min等。可理解的是，研磨可以在研磨机中进行。Before mixing the pellets and the cross-linking agent, the following steps are also included: grinding the cross-linking agent. The grinding time is 8min~20min. Specifically, the grinding time is 8 min, 10 min, 15 min or 20 min, etc. It will be appreciated that grinding can be performed in a grinder.
可以理解的是，在制备剥离强度改善型半导电屏蔽料中，将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电炭黑以及马来酸酐接枝聚乙烯混料处理之前还包括如下步骤：将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电炭黑、马来酸酐接枝聚乙烯以及交联剂烘干以去除各原料中的水分。进一步地，当包括加工助剂时，将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电炭黑、马来酸酐接枝聚乙烯、交联剂以及加工助剂烘干以去除各原料中的水分。It can be understood that in preparing the semi-conductive shielding material with improved peel strength, the following steps are included before processing the mixture of low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black and maleic anhydride-grafted polyethylene: Low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black, maleic anhydride-grafted polyethylene and cross-linking agent are dried to remove moisture from each raw material. Further, when processing aids are included, the low-density polyethylene resin, ethylene-acrylic resin, conductive carbon black, maleic anhydride grafted polyethylene, cross-linking agent and processing aids are dried to remove moisture in each raw material .
本发明还有一实施例提供了一种半导电屏蔽制品。该制品的制备原料包括上述剥离强度改善型半导电屏蔽料或者上述制备方法制备的剥离强度改善型半导电屏蔽料。可选地，半导电屏蔽制品由包括上述半导电屏蔽料的原料挤出成型制成。进一步可选地，半导电屏蔽制品为半导电屏蔽套。可选地，半导电屏蔽制品为高压电缆半导电屏蔽制品。Another embodiment of the present invention provides a semiconductive shielding product. The raw materials for preparing the product include the above-mentioned semiconductive shielding material with improved peel strength or the semiconductive shielding material with improved peel strength prepared by the above preparation method. Optionally, the semi-conductive shielding product is made by extrusion molding of raw materials including the above-mentioned semi-conductive shielding material. Further optionally, the semiconductive shielding product is a semiconductive shielding sleeve. Optionally, the semiconductive shielding product is a high-voltage cable semiconducting shielding product.
在一个具体的示例中，半导电屏蔽制品的制备原料中还包括绝缘料。半导电屏蔽制品由包括上述半导电屏蔽料和绝缘料的原料挤出成型制成。In a specific example, the raw materials for preparing the semiconductive shielding product also include insulating materials. Semiconducting shielding products are made by extrusion molding of raw materials including the above-mentioned semiconducting shielding materials and insulation materials.
本发明还有一实施例提供了一种电缆，包括导体、绝缘层以及半导电屏蔽层；导***于绝缘层的内侧，半导电屏蔽层位于绝缘层的至少一个表面；半导电屏蔽层由上述剥离强度改善型半导电屏蔽料或者上述制备方法制备的剥离强度改善型半导电屏蔽料制成。Another embodiment of the present invention provides a cable, including a conductor, an insulating layer and a semiconductive shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting shielding layer has the above peel strength It is made of an improved semi-conductive shielding material or a peel-strength-improved semi-conductive shielding material prepared by the above preparation method.
在一个具体的示例中，半导电屏蔽层位于绝缘层的两个表面。此时，电缆包括由内到外依次设置的导体、内屏蔽层、绝缘层和外屏蔽层，其中内屏蔽层和外屏蔽层均为半导电屏蔽层。In a specific example, semiconductive shielding layers are located on both surfaces of the insulating layer. At this time, the cable includes a conductor, an inner shielding layer, an insulation layer and an outer shielding layer arranged in sequence from the inside to the outside, where both the inner shielding layer and the outer shielding layer are semi-conductive shielding layers.
以下为具体实施例。The following are specific examples.
实施例1Example 1
按质量份数计，本实施例中剥离强度改善型半导电屏蔽料的制备原料为：基体树脂62.5份、导电炭黑30份、马来酸酐接枝聚乙烯1份、分散剂2份、偶联剂2份、润滑剂1份、抗氧剂0.5份以及交联剂1份。In terms of parts by mass, the raw materials for preparing the peel strength-improved semiconductive shielding material in this embodiment are: 62.5 parts of matrix resin, 30 parts of conductive carbon black, 1 part of maleic anhydride grafted polyethylene, 2 parts of dispersant, and even 2 parts of linking agent, 1 part of lubricant, 0.5 part of antioxidant and 1 part of cross-linking agent.
其中，基体树脂为低密度聚乙烯树脂和乙烯-丙烯酸乙酯树脂，低密度聚乙烯树脂和乙烯-丙烯酸乙酯树脂的质量比为3:7。低密度聚乙烯树脂的熔融指数为0.5g/10min，低密度聚乙烯树脂的密度为0.918g/cm 3。乙烯-丙烯酸乙酯树脂中丙烯酸乙酯的质量百分数为17％，乙烯-丙烯酸乙酯树脂在190℃和2.16kg下的熔融指数为8.5g/min，乙烯-丙烯酸乙酯树脂的断裂伸长率为900％。 Among them, the matrix resin is low-density polyethylene resin and ethylene-ethyl acrylate resin, and the mass ratio of low-density polyethylene resin and ethylene-ethyl acrylate resin is 3:7. The melt index of low-density polyethylene resin is 0.5g/10min, and the density of low-density polyethylene resin is 0.918g/cm 3 . The mass percentage of ethyl acrylate in ethylene-ethyl acrylate resin is 17%, the melt index of ethylene-ethyl acrylate resin at 190°C and 2.16kg is 8.5g/min, and the elongation at break of ethylene-ethyl acrylate resin is 900%.
导电炭黑的吸油值为158ml/100g、灰分含量＜0.2％、325目筛余物含量为5ppm，不含硫杂质和硅杂质。The oil absorption value of conductive carbon black is 158ml/100g, the ash content is <0.2%, the residue content on 325 mesh screen is 5ppm, and it does not contain sulfur impurities and silicon impurities.
马来酸酐接枝聚乙烯的接枝率为1.2％，马来酸酐接枝聚乙烯的熔融指数为2.5g/10min。The grafting rate of maleic anhydride-grafted polyethylene is 1.2%, and the melt index of maleic anhydride-grafted polyethylene is 2.5g/10min.
分散剂为乙撑双硬脂酰胺。偶联剂为硅烷偶联剂KH550。润滑剂为硬脂酸锌。抗氧剂为抗氧剂1010和抗氧剂300按质量比为1:1混合而成。The dispersant is ethylene bisstearamide. The coupling agent is silane coupling agent KH550. The lubricant is zinc stearate. The antioxidant is a mixture of antioxidant 1010 and antioxidant 300 at a mass ratio of 1:1.
本实施例中剥离强度改善型半导电屏蔽料的制备方法包括如下步骤：In this embodiment, the preparation method of the semiconductive shielding material with improved peel strength includes the following steps:
S101：将低密度聚乙烯树脂、乙烯-丙烯酸乙酯树脂、导电炭黑、马来酸酐接枝聚乙烯、交联剂、分散剂、偶联剂、润滑剂以及抗氧剂烘干以去除各原料中的水分。S101: Dry low-density polyethylene resin, ethylene-ethyl acrylate resin, conductive carbon black, maleic anhydride-grafted polyethylene, cross-linking agent, dispersant, coupling agent, lubricant and antioxidant to remove various Moisture in raw materials.
S102：将低密度聚乙烯树脂、乙烯-丙烯酸乙酯树脂、导电炭黑、马来酸酐接枝聚乙烯、分散剂、偶联剂、润滑剂以及抗氧剂在混料机中进行混料处理，得到混合料。混料处理的温度为45℃，混料处理的转速为160rpm。S102: Mix low-density polyethylene resin, ethylene-ethyl acrylate resin, conductive carbon black, maleic anhydride-grafted polyethylene, dispersant, coupling agent, lubricant and antioxidant in a mixer , get the mixture. The temperature of the mixing process is 45°C, and the rotation speed of the mixing process is 160 rpm.
S103：将混合料在双螺杆挤出机中挤出，切粒，得到切粒料。挤出的温度为180℃，挤出的主机转速为120rpm。S103: Extrude the mixture in a twin-screw extruder and dice it to obtain pelletized material. The extrusion temperature is 180°C, and the extrusion host speed is 120 rpm.
S104：将切粒料在65℃保温3h。S104: Keep the pellets at 65°C for 3 hours.
S105：将交联剂在研磨机中研磨10min。S105: Grind the cross-linking agent in a grinder for 10 minutes.
S106：将保温之后的切粒料与研磨之后的交联剂混合，得到预成品。S106: Mix the pellets after heat preservation and the cross-linking agent after grinding to obtain a pre-finished product.
S107：对预成品在65℃加热10h。S107: Heat the pre-finished product at 65°C for 10 hours.
加热之后得到本实施例中的剥离强度改善型半导电屏蔽料。After heating, the peel strength-improved semiconductive shielding material in this embodiment is obtained.
实施例2Example 2
与实施例1相比，实施例2的不同之处在于，马来酸酐接枝聚乙烯的质量份数为2份。Compared with Example 1, the difference in Example 2 is that the mass fraction of maleic anhydride-grafted polyethylene is 2 parts.
实施例3Example 3
与实施例1相比，实施例3的不同之处在于，马来酸酐接枝聚乙烯的质量份数为3份。Compared with Example 1, the difference in Example 3 is that the mass fraction of maleic anhydride-grafted polyethylene is 3 parts.
对比例1Comparative example 1
与实施例1相比，对比例1的不同之处在于，基体树脂为乙烯-丙烯酸乙酯树脂，马来酸酐接枝聚乙烯的质量份数为0份。Compared with Example 1, the difference of Comparative Example 1 is that the matrix resin is ethylene-ethyl acrylate resin, and the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
对比例2Comparative example 2
与实施例1相比，对比例2的不同之处在于，基体树脂为低密度聚乙烯树脂，马来酸酐接枝聚乙烯的质量份数为0份。Compared with Example 1, the difference of Comparative Example 2 is that the matrix resin is low-density polyethylene resin, and the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
对比例3Comparative example 3
与实施例1相比，对比例3的不同之处在于，马来酸酐接枝聚乙烯的质量份数为0份。Compared with Example 1, the difference in Comparative Example 3 is that the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
性能测试Performance Testing
将实施例和对比例中得到的屏蔽料分别压板制成厚度为1mm的测试板。然后对测试板分别测试拉伸强度、断裂伸长率、常温体积电阻率、90℃体积电阻率以及玻璃强度。测试结果如表1所示。The shielding materials obtained in the examples and comparative examples were pressed into test plates with a thickness of 1 mm. Then the test plates were tested for tensile strength, elongation at break, room temperature volume resistivity, 90°C volume resistivity and glass strength. The test results are shown in Table 1.
表1Table 1
Figure PCTCN2022130994-appb-000001
Figure PCTCN2022130994-appb-000001
从实施例1～3和对比例3可以看出，随着马来酸酐接枝聚乙烯的增加，测试板的力学性能有效提升，并且剥离强度从46N/2cm增强到了不可剥离，满足高压电缆绝缘层和半导电屏蔽层不可剥离的要求。并且马来酸酐接枝聚乙烯的使用对测试板的电气性能也有一定程度的改善，原因可能在于马来酸酐接枝聚乙烯起到了相容剂、分散剂和粘结剂的作用，进而提高导电炭 黑的在基体树脂中的分散性，以及提高半导电屏蔽层和绝缘层的附着性。It can be seen from Examples 1 to 3 and Comparative Example 3 that with the increase of maleic anhydride-grafted polyethylene, the mechanical properties of the test board are effectively improved, and the peel strength is enhanced from 46N/2cm to non-peelable, which meets the requirements of high-voltage cable insulation. layer and semi-conductive shielding layer are not peelable. Moreover, the use of maleic anhydride-grafted polyethylene also improves the electrical performance of the test board to a certain extent. The reason may be that maleic anhydride-grafted polyethylene acts as a compatibilizer, dispersant and adhesive, thereby improving conductivity. The dispersion of carbon black in the matrix resin and the adhesion of the semi-conductive shielding layer and the insulating layer are improved.
从对比例1和对比例3可知，采用低密度聚乙烯树脂和乙烯-丙烯酸乙酯树脂作为基体树脂，可以有效提升半导电屏蔽层和绝缘层的剥离强度，原因可能是由于采用的低密度聚乙烯树脂为高压交流电缆绝缘料基料，其与绝缘层的界面匹配性能优异，使得其剥离强度增加。进一步，采用低密度聚乙烯树脂和乙烯-丙烯酸乙酯树脂复配之后，半导电屏蔽层的电气性能更为优异，但是其力学性能有所下降，原因可能是由于乙烯-丙烯酸乙酯树脂为极性分子，低密度聚乙烯树脂为非极性高分子，两者相容性较差，在高比例复配时半导电屏蔽料的拉伸强度和断裂伸长率有所下降。对比例2中用低密度聚乙烯树脂作为基体树脂，虽然其电气性能和剥离强度较好，但是力学性能较差。It can be seen from Comparative Examples 1 and 3 that using low-density polyethylene resin and ethylene-ethyl acrylate resin as the matrix resin can effectively improve the peel strength of the semiconductive shielding layer and the insulating layer. The reason may be due to the low-density polyethylene resin used. Vinyl resin is the base material of high-voltage AC cable insulation material. Its interface matching with the insulation layer is excellent, which increases its peel strength. Furthermore, after compounding low-density polyethylene resin and ethylene-ethyl acrylate resin, the electrical properties of the semiconductive shielding layer are better, but its mechanical properties have declined. The reason may be that ethylene-ethyl acrylate resin is extremely Low-density polyethylene resin is a non-polar polymer, and the compatibility between the two is poor. When compounded at a high proportion, the tensile strength and elongation at break of the semi-conductive shielding material decrease. In Comparative Example 2, low-density polyethylene resin is used as the matrix resin. Although its electrical properties and peel strength are good, its mechanical properties are poor.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准，说明书可以用于解释权利要求的内容。The above-mentioned embodiments only express several implementation modes of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims, and the description can be used to interpret the content of the claims.

Claims (10)

  1. 一种剥离强度改善型半导电屏蔽料，其特征在于，包括如下质量份数的原料：基体树脂58份～68份、导电炭黑27份～34份、马来酸酐接枝聚乙烯1份～5份以及交联剂0.4份～2.2份；其中，所述基体树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；所述乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的一种或两种。A semiconductive shielding material with improved peel strength, characterized by including the following raw materials in parts by mass: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, and 1 part to 1 part of maleic anhydride grafted polyethylene. 5 parts and 0.4 to 2.2 parts of cross-linking agent; wherein, the matrix resin is compounded of low-density polyethylene resin and ethylene-acrylic resin; the ethylene-acrylic resin is ethylene-ethyl acrylate resin and ethylene- One or two types of butyl acrylate resin.
  2. 根据权利要求1所述的剥离强度改善型半导电屏蔽料，其特征在于，所述马来酸酐接枝聚乙烯满足以下特征中的一个或多个：The peel strength-improved semiconductive shielding material according to claim 1, wherein the maleic anhydride grafted polyethylene meets one or more of the following characteristics:
    (1)所述马来酸酐接枝聚乙烯的接枝率为0.8％～1.2％；(1) The grafting rate of the maleic anhydride-grafted polyethylene is 0.8% to 1.2%;
    (2)所述马来酸酐接枝聚乙烯的熔融指数为2g/10min～4g/10min。(2) The melt index of the maleic anhydride-grafted polyethylene is 2g/10min to 4g/10min.
  3. 根据权利要求1～2中任一项所述的剥离强度改善型半导电屏蔽料，其特征在于，包括以下特征中的一个或多个：The semiconductive shielding material with improved peel strength according to any one of claims 1 to 2, characterized in that it includes one or more of the following features:
    (1)所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂的质量比为1:4～4:1；(1) The mass ratio of the low-density polyethylene resin and the ethylene-acrylic resin is 1:4 to 4:1;
    (2)所述低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min；(2) The melt index of the low-density polyethylene resin is 0.25g/10min~2g/10min;
    (3)所述低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3； (3) The density of the low-density polyethylene resin is 0.918g/cm 3 ~ 0.932g/cm 3 ;
    (4)所述乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤10g/min；(4) The melt index of the ethylene-acrylic resin at 190°C and 2.16kg is ≤10g/min;
    (5)所述乙烯-丙烯酸树脂的断裂伸长率≥700％；(5) The elongation at break of the ethylene-acrylic resin is ≥700%;
    (6)所述导电炭黑的吸油值为150ml/100g～170ml/100g；(6) The oil absorption value of the conductive carbon black is 150ml/100g～170ml/100g;
    (7)所述导电炭黑的灰分含量≤0.2％；(7) The ash content of the conductive carbon black is ≤0.2%;
    (8)所述导电炭黑的325目筛余物含量≤8ppm；(8) The 325 mesh sieve residue content of the conductive carbon black is ≤8ppm;
    (9)所述导电炭黑不含硫杂质和硅杂质；(9) The conductive carbon black does not contain sulfur impurities and silicon impurities;
    (10)所述交联剂为双叔丁基过氧异丙基苯、过氧化二异丙苯以及双25中的一种或多种。(10) The cross-linking agent is one or more of di-tert-butyl cumene peroxide, dicumyl peroxide and bis-25.
  4. 根据权利要求1～3中任一项所述的剥离强度改善型半导电屏蔽料，其特征在于，所述原料还包括加工助剂，所述加工助剂满足以下特征中的一个或多个：The semiconductive shielding material with improved peel strength according to any one of claims 1 to 3, characterized in that the raw material further includes a processing aid, and the processing aid satisfies one or more of the following characteristics:
    (1)所述加工助剂包括分散剂，所述分散剂的质量份数为0.6份～2.5份；(1) The processing aid includes a dispersant, and the mass fraction of the dispersant is 0.6 to 2.5 parts;
    (2)所述加工助剂包括偶联剂，所述偶联剂的质量份数为1份～2份；(2) The processing aid includes a coupling agent, and the mass fraction of the coupling agent is 1 to 2 parts;
    (3)所述加工助剂包括润滑剂，所述润滑剂的质量份数为1份～2份；(3) The processing aid includes a lubricant, and the mass fraction of the lubricant is 1 to 2 parts;
    (4)所述加工助剂包括抗氧剂，所述抗氧剂的质量份数为0.3份～0.7份。(4) The processing aid includes an antioxidant, and the mass fraction of the antioxidant is 0.3 to 0.7 parts.
  5. 一种权利要求1～4中任一项所述的剥离强度改善型半导电屏蔽料的制备方法，其特征在于，包括如下步骤：A method for preparing the semiconductive shielding material with improved peel strength according to any one of claims 1 to 4, characterized in that it includes the following steps:
    将所述低密度聚乙烯树脂、所述乙烯-丙烯酸树脂、所述导电炭黑以及所述马来酸酐接枝聚乙烯进行混料处理，得到混合料；The low-density polyethylene resin, the ethylene-acrylic resin, the conductive carbon black and the maleic anhydride grafted polyethylene are mixed to obtain a mixture;
    将所述混合料挤出、切粒，得到切粒料；The mixture is extruded and pelletized to obtain pellets;
    将所述切粒料与所述交联剂混合，得到预成品；Mix the pellets and the cross-linking agent to obtain a pre-finished product;
    对所述预成品进行加热处理。The pre-finished product is subjected to heat treatment.
  6. 根据权利要求5所述的剥离强度改善型半导电屏蔽料的制备方法，其特征在于，所述混料处理满足以下特征中的一个或多个：The method for preparing a semiconductive shielding material with improved peel strength according to claim 5, wherein the mixing process satisfies one or more of the following characteristics:
    (1)所述混料处理的温度为45℃～50℃；(1) The temperature of the mixing process is 45°C to 50°C;
    (2)所述混料处理的转速为150rpm～250rpm。(2) The rotation speed of the mixing process is 150rpm to 250rpm.
  7. 根据权利要求5～6中任一项所述的剥离强度改善型半导电屏蔽料的制备方法，其特征在于，所述挤出满足以下特征中的一个或多个：The method for preparing a semiconductive shielding material with improved peel strength according to any one of claims 5 to 6, characterized in that the extrusion satisfies one or more of the following characteristics:
    (1)所述挤出的温度为150℃～200℃；(1) The extrusion temperature is 150°C to 200°C;
    (2)所述挤出的主机转速为100rpm～150rpm。(2) The rotation speed of the extrusion host is 100rpm to 150rpm.
  8. 根据权利要求5～7中任一项所述的剥离强度改善型半导电屏蔽料的制备方法，其特征在于，所述加热处理满足以下特征中的一个或多个：The method for preparing a semiconductive shielding material with improved peel strength according to any one of claims 5 to 7, wherein the heating treatment satisfies one or more of the following characteristics:
    (1)所述加热处理的温度为50℃～70℃；(1) The temperature of the heat treatment is 50°C to 70°C;
    (2)所述加热处理的时间为5h～15h。(2) The time of the heat treatment is 5h to 15h.
  9. 一种半导电屏蔽制品，其特征在于，其制备原料包括权利要求1～4中任一项所述的剥离强度改善型半导电屏蔽料或者权利要求5～8中任一项所述的制备方法制备的剥离强度改善型半导电屏蔽料。A semiconductive shielding product, characterized in that its preparation raw materials include the peel strength improved semiconducting shielding material according to any one of claims 1 to 4 or the preparation method according to any one of claims 5 to 8 Prepared semiconductive shielding material with improved peel strength.
  10. 一种电缆，其特征在于，包括导体、绝缘层以及半导电屏蔽层；所述 导***于所述绝缘层的内侧，所述半导电屏蔽层位于所述绝缘层的至少一个表面；所述半导电屏蔽层由权利要求1～4中任一项所述的剥离强度改善型半导电屏蔽料或者权利要求5～8中任一项所述的制备方法制备的剥离强度改善型半导电屏蔽料制成。A cable, characterized in that it includes a conductor, an insulating layer and a semiconducting shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting The shielding layer is made of the semiconducting shielding material with improved peel strength according to any one of claims 1 to 4 or the semiconducting shielding material with improved peel strength prepared by the preparation method according to any one of claims 5 to 8. .
PCT/CN2022/130994 2022-08-30 2022-11-10 Peel strength-improved semi-conductive shielding material, preparation method, article, and cable WO2024045340A1 (en)

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