WO2024241401A1 - 絶縁層用樹脂組成物および絶縁電線 - Google Patents

絶縁層用樹脂組成物および絶縁電線 Download PDF

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Publication number
WO2024241401A1
WO2024241401A1 PCT/JP2023/018836 JP2023018836W WO2024241401A1 WO 2024241401 A1 WO2024241401 A1 WO 2024241401A1 JP 2023018836 W JP2023018836 W JP 2023018836W WO 2024241401 A1 WO2024241401 A1 WO 2024241401A1
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Prior art keywords
mass
parts
insulating layer
polyvinyl chloride
resin composition
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Ceased
Application number
PCT/JP2023/018836
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English (en)
French (fr)
Japanese (ja)
Inventor
奈侑 梁川
太郎 藤田
遼太 福本
丈 八木澤
明美 鈴木
賢治 堀
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to PCT/JP2023/018836 priority Critical patent/WO2024241401A1/ja
Priority to JP2025521618A priority patent/JPWO2024241401A1/ja
Publication of WO2024241401A1 publication Critical patent/WO2024241401A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H01B3/44—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 vinyl resins; acrylic resins

Definitions

  • This disclosure relates to a resin composition for an insulating layer and an insulated wire.
  • Vinyl chloride resins have excellent electrical insulation, voltage resistance, and heat resistance, and are used as insulating materials for wires and cables in the fields of automobiles and electrical and electronic equipment.
  • phthalate esters, trimellitate esters, adipate polyesters, cyclohexanedicarboxylate esters, etc. have been disclosed as plasticizers for such polyvinyl chloride compositions (see Patent Document 1).
  • the resin composition for insulating layers disclosed herein contains a resin component, a plasticizer, an inorganic filler, and a flame retardant, the resin component being mainly composed of polyvinyl chloride, the plasticizer being epoxidized soybean oil, acetylated castor oil, epoxidized linseed oil, or a combination thereof, the content of the plasticizer being 20 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polyvinyl chloride, and the content of the inorganic filler being 5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the polyvinyl chloride.
  • FIG. 1 is a schematic cross-sectional view of an insulated wire according to one embodiment of the present disclosure.
  • Biomass such as plant seed oil, is organic matter produced by living organisms through photosynthesis using solar energy from water and carbon dioxide, and is a carbon-neutral resource that does not increase new carbon dioxide in the atmosphere.
  • the inventors have found that when a material derived from biomass, such as seed oil, is used as a plasticizer for the insulating layer, the insulating performance is reduced compared to plasticizers derived from fossil resources, such as petroleum. From the standpoint of safety, insulating materials used in electric wires are required to have good insulating performance.
  • the purpose of this disclosure is to provide a resin composition for an insulating layer and an insulated wire that can reduce the environmental impact and improve the insulating performance and flexibility of the insulating layer.
  • the resin composition for insulating layer comprises: (1) A composition comprising a resin component, a plasticizer, an inorganic filler and a flame retardant, the resin component being mainly composed of polyvinyl chloride, the plasticizer being epoxidized soybean oil, acetylated castor oil, epoxidized linseed oil or a combination thereof, the content of the plasticizer being 20 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polyvinyl chloride, and the content of the inorganic filler being 5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the polyvinyl chloride.
  • the resin composition for insulating layers can reduce the environmental load by using epoxidized soybean oil, acetylated castor oil, epoxidized linseed oil, or a combination of these as the plasticizer.
  • the content of the plasticizer in the resin composition for insulating layers is 20 parts by mass or more and 100 parts by mass or less per 100 parts by mass of polyvinyl chloride, which is the main component of the resin components, and the content of the inorganic filler is 5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of polyvinyl chloride, so that the insulating layer can maintain good flexibility while improving the insulating performance.
  • the resin composition for insulating layers can reduce the environmental load and improve the insulating performance and flexibility of the insulating layer.
  • the "main component” refers to the component with the highest content, and may be, for example, 80% by mass or more.
  • the inorganic filler may be clay, calcium carbonate, talc, magnesium carbonate, or a combination thereof.
  • clay, calcium carbonate, talc, magnesium carbonate, or a combination thereof as the inorganic filler, the insulating performance of the insulating layer can be further improved.
  • the flame retardant may be antimony trioxide, a bromine-based flame retardant, or melamine cyanurate, and the content of the flame retardant may be 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the polyvinyl chloride.
  • antimony trioxide a bromine-based flame retardant, or melamine cyanurate
  • the content of the flame retardant is 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the polyvinyl chloride, the extrusion moldability and mechanical properties of the insulating layer can be sufficiently maintained while improving the flame retardant effect.
  • the insulated electric wire of the present disclosure is an insulated electric wire comprising a linear conductor and one or more insulating layers laminated on the outer peripheral surface of the conductor and composed of the resin composition for insulating layers described in any one of (1) to (3) above.
  • the insulated wire has one or more insulating layers that use the resin composition for the insulating layer, which reduces the environmental impact and improves the insulating performance and flexibility of the insulating layer. Therefore, the insulated wire can improve safety and workability.
  • the average degree of polymerization of polyvinyl chloride may be 1000 or more and 3000 or less, or 1200 or more and 2500 or less. By having the average degree of polymerization of polyvinyl chloride within the above range, an insulating layer having excellent flexibility and tensile strength can be formed.
  • the average degree of polymerization is the number average degree of polymerization measured by gel permeation chromatography (GPC).
  • the resin composition for an insulating layer contains a plasticizer, which can improve the flexibility and processability of the insulating layer.
  • the viscosity of the plasticizer at 25°C may be from 100 mPa ⁇ s to 1000 mPa ⁇ s or from 200 mPa ⁇ s to 800 mPa ⁇ s, from the viewpoint of migration to the polyvinyl chloride, which is the main component, and processability.
  • the lower limit of the plasticizer content per 100 parts by mass of polyvinyl chloride is 20 parts by mass, may be 35 parts by mass, or may be 40 parts by mass. If the plasticizer content is less than 20 parts by mass, it may be difficult to improve the flexibility of the resulting insulating layer.
  • the upper limit of the plasticizer content per 100 parts by mass of polyvinyl chloride is 100 parts by mass, may be 60 parts by mass, or may be 55 parts by mass. If the plasticizer content exceeds 100 parts by mass, the insulating performance of the resulting insulating layer may be reduced.
  • the insulating layer resin composition contains an inorganic filler, which can improve the insulating performance of the resulting insulating layer.
  • an inorganic filler various known inorganic fillers can be used, such as clay, calcium carbonate, talc, magnesium carbonate, calcium hydroxide, barium sulfate, calcium sulfate, strontium sulfate, titanium dioxide, magnesium silicate, magnesium oxide, magnesium hydroxide, fumed silica, or a combination thereof.
  • clay, calcium carbonate, talc, magnesium carbonate, or a combination thereof may be used.
  • the lower limit of the inorganic filler content per 100 parts by mass of polyvinyl chloride is 5 parts by mass, may be 7 parts by mass, or may be 10 parts by mass. If the content of the inorganic filler is less than 5 parts by mass, it may be difficult to improve the insulating performance of the resulting insulating layer.
  • the upper limit of the inorganic filler content per 100 parts by mass of polyvinyl chloride is 40 parts by mass, may be 20 parts by mass, or may be 17 parts by mass. If the content of the inorganic filler exceeds 40 parts by mass, the flexibility of the resulting insulating layer may be reduced.
  • the flame retardant imparts flame retardancy to the insulating layer using the resin composition for insulating layer.
  • the flame retardant include halogen-based flame retardants such as chlorine-based flame retardants and bromine-based flame retardants.
  • the flame retardants include halogen-based flame retardants such as antimony trioxide, antimony pentoxide, zinc borate, bromine-based flame retardants, and chlorine-based flame retardants, as well as non-halogen-based flame retardants such as metal hydroxides, nitrogen-based flame retardants, and phosphorus-based flame retardants. Flame retardants can be used alone or in combination of two or more.
  • An example of a bromine-based flame retardant is decabromodiphenylethane.
  • An example of a chlorine-based flame retardant is chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenol, or perchlorpentacyclodecane.
  • An example of a metal hydroxide is magnesium hydroxide or aluminum hydroxide.
  • An example of a nitrogen-based flame retardant is melamine cyanurate, triazine, isocyanurate, urea, or guanidine.
  • An example of a phosphorus-based flame retardant is metal phosphinate, phosphaphenanthrene, melamine phosphate, ammonium phosphate, phosphate ester, or polyphosphazene.
  • the flame retardant may be antimony trioxide, a bromine-based flame retardant, or melamine cyanurate, from the viewpoint of further improving the flame retardancy of the resulting insulating layer.
  • the content of the antimony trioxide may be 1 part by mass or more and 20 parts by mass or less, or 3 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the polyvinyl chloride.
  • the content of the bromine-based flame retardant may be 1 part by mass or more and 20 parts by mass or less, or 3 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the polyvinyl chloride.
  • the content of the melamine cyanurate may be 1 part by mass or more and 20 parts by mass or less, or 10 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the polyvinyl chloride.
  • Stabilizer In order to suppress thermal and oxidative degradation of polyvinyl chloride, various stabilizers can be added to the resin composition for insulating layer.
  • a non-lead-based stabilizer that does not contain lead may be used in order to reduce the environmental load.
  • the non-lead-based stabilizer include basic inorganic acid salts or their calcined products, hydrotalcite, calcium stearate, zinc stearate, and calcium-zinc composite stabilizers.
  • the stabilizers can be used alone or in combination of two or more types.
  • the resin composition for insulating layer may contain, in addition to the above-mentioned resin components, plasticizer, inorganic filler, flame retardant and stabilizer, other components such as antioxidants, crosslinking agents, ultraviolet absorbers, colorants, processability improvers and other modifiers, either alone or in combination of two or more thereof.
  • the resin composition for insulating layers reduces the environmental impact while improving the insulating performance and flexibility of the insulating layer.
  • the insulated wire includes a linear conductor and one or more insulating layers laminated on the outer peripheral surface of the conductor and using the resin composition for insulating layers.
  • the conductor may be one or more.
  • Fig. 1 is a schematic cross-sectional view of an insulated wire according to an embodiment of the present disclosure. As shown in Fig. 1, the insulated wire 1 includes a linear conductor 2 and one insulating layer 3 laminated on the outer peripheral surface of the conductor 2.
  • the conductor 2 is, for example, a round wire having a circular cross section, but may also be a rectangular wire having a square cross section or a twisted wire made by twisting together a plurality of wires.
  • the material of the conductor 2 is preferably a metal with high electrical conductivity and high mechanical strength.
  • metals include copper, copper alloys, aluminum, aluminum alloys, nickel, silver, soft iron, steel, and stainless steel.
  • the conductor 2 can be a material in which these metals are formed into a wire shape, or a multilayer structure in which such a wire shape is further coated with another metal, such as a nickel-coated copper wire, a silver-coated copper wire, a copper-coated aluminum wire, or a copper-coated steel wire.
  • the lower limit of the average cross-sectional area of the conductor 2 may be 0.01 mm2 or 0.1 mm2 .
  • the upper limit of the average cross-sectional area of the conductor 2 may be 30 mm2 or 25 mm2 . If the average cross-sectional area of the conductor 2 is less than the lower limit, the volume of the insulating layer 3 relative to the conductor 2 becomes large, and the volume efficiency of a coil or the like formed using the insulated wire 1 may be reduced. On the other hand, if the average cross-sectional area of the conductor 2 exceeds the upper limit, the insulating layer 3 must be formed thick in order to sufficiently reduce the dielectric constant, and the insulated wire 1 may become unnecessarily large in diameter.
  • the "average cross-sectional area" of the conductor 2 means an average value obtained by measuring the cross-sectional area of 10 arbitrary points of the conductor 2.
  • the insulating layer 3 is formed on the outer peripheral surface of the conductor 2 by extrusion molding using the above-mentioned resin composition for insulating layer.
  • the lower limit of the volume resistivity of the insulating layer 3 may be 1.0 ⁇ 10 15 ⁇ cm or 5.0 ⁇ 10 15 ⁇ cm. If the volume resistivity of the insulating layer 3 is less than the above lower limit, sufficient insulating performance may not be obtained.
  • Volume resistivity refers to the electrical resistance value measured by a double ring electrode method based on JIS-K6271:2008.
  • the lower limit of the average thickness of the insulating layer 3 may be 50 ⁇ m or 100 ⁇ m.
  • the upper limit of the average thickness of the insulating layer 3 may be 1500 ⁇ m or 1000 ⁇ m. If the average thickness of the insulating layer 3 is less than the lower limit, the insulating performance may be reduced. Conversely, if the average thickness of the insulating layer 3 exceeds the upper limit, the volumetric efficiency of a cable or the like formed using the insulated electric wire 1 may be reduced.
  • the "average thickness" of the insulating layer 3 refers to the average value obtained by measuring the thickness at 10 arbitrary points of the insulating layer 3. If a plurality of insulating layers 3 are provided, the average thickness of each insulating layer 3 is calculated, and this average value is regarded as the average thickness.
  • the insulating layer is formed by extrusion molding.
  • the method for producing the insulated wire includes a step of extrusion coating the insulating layer resin composition on the outer peripheral surface of the conductor.
  • the insulated wire has one or more insulating layers that use the resin composition for the insulating layer, which reduces the environmental impact as described above and improves the insulating performance and flexibility of the insulating layer. Therefore, the insulated wire having the insulating layer can improve safety and workability.
  • the conductor can also be made of a twisted wire made by twisting together several metal wires. In this case, several types of metal wires may be combined. The number of twists is generally seven or more.
  • the insulated wire may have a primer layer laminated directly onto the conductor.
  • This primer layer is preferably made of a cross-linked resin such as ethylene that does not contain metal hydroxide.
  • plasticizers used are as follows: Plasticizer: Epoxidized soybean oil (ADEKA Cizer o-130P) Epoxidized linseed oil (ADEKA Cizer o-180P)
  • the flexibility of the resin compositions for insulating layers No. 1 to No. 15 was evaluated by the 2% secant modulus.
  • the secant modulus was measured by the following procedure. A test piece having a thickness of 1 mm and a length of 100 mm was prepared from each resin composition for insulating layers using a hot press machine, and the load at 2% elongation when pulled in the length direction at a tensile speed of 50 mm/min using a tensile tester was divided by the cross-sectional area to measure the value, and the value was multiplied by 50 to obtain the 2% secant modulus value (MPa).
  • secant modulus is the slope of the line connecting a point on a stress-strain curve to the origin, and is an index of the ease of distortion, and the smaller the measured value, the more excellent the flexibility. If the secant modulus is 90 MPa or less, it is considered to be acceptable.
  • the flame retardancy evaluation of the resin compositions for insulating layers No. 1 to No. 15 was carried out by the following procedure.
  • the VW-1 vertical flame retardancy test described in UL1581 1080 was carried out. Specifically, five 40 cm electric wires were prepared, and a burner flame was applied to each sample at an angle of 20 degrees, and 15 seconds of ignition and 15 seconds of rest were repeated five times. If the fire was extinguished within 60 seconds, the absorbent cotton placed at the bottom was not burned by the falling combustion material, and the craft paper attached to the top of the sample was not burned or scorched, it was judged as passing (A). If even one of the five samples did not meet the passing level, it was judged as failing (B).
  • volume resistivity (Insulation performance evaluation by volume resistivity) A test sample measuring ⁇ 100 mm ⁇ t2.5 mm was prepared from each resin composition for the insulating layer using a heat press machine, and electrical resistance was measured using the double ring electrode method defined in JIS-K6271:2008. Volume resistivity ( ⁇ cm) was calculated from the measured value. A volume resistivity of 1 ⁇ 10 15 ⁇ cm or more was considered to be acceptable.
  • No. 1 in which the epoxidized soybean oil content is less than 20 parts by mass per 100 parts by mass of the polyvinyl chloride, had a very high 2% secant modulus.
  • No. 2 and No. 4 in which the clay content is less than 5 parts by mass per 100 parts by mass of the polyvinyl chloride, had low volume resistivity.
  • No. 7 in which the clay content is more than 40 parts by mass per 100 parts by mass of the polyvinyl chloride, had a high 2% secant modulus.
  • No. 8 in which the epoxidized soybean oil content is more than 100 parts by mass per 100 parts by mass of the polyvinyl chloride, had a low volume resistivity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
PCT/JP2023/018836 2023-05-19 2023-05-19 絶縁層用樹脂組成物および絶縁電線 Ceased WO2024241401A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013534924A (ja) * 2010-06-23 2013-09-09 ダウ グローバル テクノロジーズ エルエルシー ヒマシ油の精製アセチル化誘導体およびこれを含む組成物
JP2015522684A (ja) * 2012-06-26 2015-08-06 ダウ グローバル テクノロジーズ エルエルシー 可塑剤および可塑化ポリマー組成物
JP2016519168A (ja) * 2013-03-11 2016-06-30 ダウ グローバル テクノロジーズ エルエルシー 炭酸カルシウム及び焼成粘土の相乗的ブレンド
JP2016526083A (ja) * 2013-05-29 2016-09-01 ダウ グローバル テクノロジーズ エルエルシー ジアルキル２，５−フランジカルボキシレート可塑剤及び可塑化ポリマー組成物
CN112480573A (zh) * 2020-12-11 2021-03-12 深圳市帝源新材料科技股份有限公司 改性聚氯乙烯电缆材料及其制备方法和电缆

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013534924A (ja) * 2010-06-23 2013-09-09 ダウ グローバル テクノロジーズ エルエルシー ヒマシ油の精製アセチル化誘導体およびこれを含む組成物
JP2015522684A (ja) * 2012-06-26 2015-08-06 ダウ グローバル テクノロジーズ エルエルシー 可塑剤および可塑化ポリマー組成物
JP2016519168A (ja) * 2013-03-11 2016-06-30 ダウ グローバル テクノロジーズ エルエルシー 炭酸カルシウム及び焼成粘土の相乗的ブレンド
JP2016526083A (ja) * 2013-05-29 2016-09-01 ダウ グローバル テクノロジーズ エルエルシー ジアルキル２，５−フランジカルボキシレート可塑剤及び可塑化ポリマー組成物
CN112480573A (zh) * 2020-12-11 2021-03-12 深圳市帝源新材料科技股份有限公司 改性聚氯乙烯电缆材料及其制备方法和电缆

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