WO2010013851A1 - Resin composition for coating material of electrical cables and electrical cables using the same - Google Patents

Resin composition for coating material of electrical cables and electrical cables using the same Download PDF

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Publication number
WO2010013851A1
WO2010013851A1 PCT/KR2008/004382 KR2008004382W WO2010013851A1 WO 2010013851 A1 WO2010013851 A1 WO 2010013851A1 KR 2008004382 W KR2008004382 W KR 2008004382W WO 2010013851 A1 WO2010013851 A1 WO 2010013851A1
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WO
WIPO (PCT)
Prior art keywords
group
electrical cables
mixtures
compound
based plasticizer
Prior art date
Application number
PCT/KR2008/004382
Other languages
French (fr)
Inventor
Do-Hyun Park
Original Assignee
Ls Cable Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ls Cable Ltd. filed Critical Ls Cable Ltd.
Priority to PCT/KR2008/004382 priority Critical patent/WO2010013851A1/en
Priority to CN200880130606.XA priority patent/CN102112542B/en
Publication of WO2010013851A1 publication Critical patent/WO2010013851A1/en

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Classifications

    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • 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
    • H01B3/443—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 from vinylhalogenides or other halogenoethylenic compounds
    • 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
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L27/22—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 modified by chemical after-treatment
    • C08L27/24—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 modified by chemical after-treatment halogenated

Definitions

  • the present invention relates to a resin composition for coating material of electrical cables and electrical cables using the same.
  • the present invention relates to a resin composition for coating material of electrical cables that is capable of forming a bedding layer with excellent tensile strength and flame retardancy, and electrical cables using the same.
  • electrical cables having a woven layer on a bedding layer are generally used, and the woven layer is formed by weaving a zinc-plated iron wire, a zinc-plated steel wire or a copper-coated iron wire.
  • JIS Japanese Industrial Standards
  • cables installed in dangerous areas or areas with risk of explosion necessarily had a woven layer therein or thereon.
  • the woven layer increases the outer diameter of electrical cables and decreases flexibility of the electrical cables, which makes it difficult to install the electrical cables in narrow spaces.
  • the woven layer requires additional processes in the manufacture of electrical cables, resulting in a rise of manufacturing cost.
  • the woven layer is formed by weaving a fine iron wire, if the iron wire is irregularly woven in a weaving process, faults often occur.
  • the woven layer increases the total weight of electrical cables.
  • the electrical cables, for example, used in ships have difficult in satisfying specific cable weight standard required by ship owners and manufacturers in these days.
  • a resin composition for coating material of electrical cables comprises a base resin selected from the group consisting of polyvinyl chloride (PVC) resin, chlorinated PVC resin and composite resins thereof; 30 to 80 parts by weight of a plasticizer based on 100 parts by weight of the base rein, selected from the group consisting of a phthalate-based plasticizer, a phosphate -based plasticizer, a fatty acid-based plasticizer, a mellitate- based plasticizer and a polymer-based plasticizer, and mixtures thereof; 1 to 50 parts by weight of a metal hydroxide flame-retardant based on 100 parts by weight of the base rein; and 1 to 50 parts by weight of a secondary flame-retardant based on 100 parts by weight of the base rein, selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, and mixtures thereof.
  • PVC polyvinyl chloride
  • the phthalate-based plasticizer is selected from the group consisting of di- isononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate and diisooctyl phthalate, and mixtures thereof
  • the phosphate-based plasticizer is selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate, and mixtures thereof
  • the fatty acid-based plasticizer is selected from the group consisting of DOA (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate), and mixtures thereof, the mellitate-based plastic
  • the antimony compound is antimony trioxide
  • the tin compound is selected from the group consisting of a compound of zinc hydroxide and tin, a compound of zinc and tin, and mixtures thereof.
  • the resin composition for coating material of electrical cables further comprises a stabilizer selected from the group consisting of lead-based material, nonlead-based material, epoxy stearate and metallic soap material, and mixtures thereof, or a filler selected from the group consisting of calcium carbonate, clay and talc, and mixtures.
  • the present invention provides an electrical cable comprising a bedding layer formed using the resin composition for coating material of electrical cables.
  • the bedding layer has a tensile strength of 2.0 kgf/mm 2 or more and an oxygen index more than 23%.
  • the resin composition for coating material of electrical cables according to the present invention has excellent tensile strength and flame retardancy, and a bedding layer of an electrical cable, formed using the resin composition meets function and characteristics of a woven layer as well as function and characteristics of a bedding layer. Accordingly, the electrical cable comprising a bedding layer formed using the resin composition for coating material of electrical cables according to the present invention eliminates the need for a woven layer, and thus has reduction in the outer diameter and weight, and consequently the manufacturing unit cost.
  • FIGs. 1 and 2 are schematic cross-sectional views of a conventional electrical cable.
  • FIG. 3 is a schematic cross-sectional view of an electrical cable according to an embodiment of the present invention.
  • a resin composition for coating material of electrical cables according to the present invention comprises a base resin, a plasticizer, a flame-retardant and a secondary flame-retardant.
  • the base resin includes thermoplastic resins which are deformable when heated, for example, PVC, chlorinated PVC (CPVC), and a combination thereof.
  • PVC has a degree of polymerization of 800 to 1700. If the degree of polymerization is below the minimum limit, a polymer has a low molecular weight, making it to secure a sufficient tensile strength. If the degree of polymerization exceeds the maximum limit, heat resistance and mechanical characteristics such as tensile strength and so on are excellent, but high temperature is required during a compounding or extruding process. Disadvantageously, it results in whole deterioration of extrudability.
  • PVC or CPVC is a linear or straight-chain polymer, in which a force between molecules restricts the motion of the polymer chain to maintain the rigid state, making modification difficult.
  • a thermal motion of PVC polymer molecules increases and a reaction therebetween, and as a result, a predetermined gap creates between PVC polymer molecules.
  • plasticizer molecules go into the gap between molecules and prevent the PVC polymer molecules from coming close with each other.
  • PVC polymer molecules have positive and negative polarities within, while plasticizer molecules also have such polar and non-polar parts.
  • the PVC polymer molecules and the plasticizer molecules are electrically attracted to each other, and the non-polar parts widen the distance among the polymer molecules.
  • the plasticizer may be a phthalate-based plasticizer, a phosphate-based plasticizer, a fatty acid-based plasticizer, a mellitate-based plasticizer or a polymer- based plasticizer.
  • the phthalate-based plasticizer is preferably at least one selected from the group consisting of diisononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate and diisooctyl phthalate.
  • the phosphate-based plasticizer is preferably at least one selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate.
  • the fatty acid-based plasticizer is preferably at least one selected from the group consisting of DOA (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate).
  • the mellitate-based plasticizer is preferably at least one selected from the group consisting of TOTM (Tri-2-ethylhexyl Trimellitate), mixed TOTM (Tri-2-ethylhexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate).
  • TOTM Tri-2-ethylhexyl Trimellitate
  • mixed TOTM Tri-2-ethylhexyl Trimellitate
  • TINTM Tri-isononyl Trimellitate
  • TIDTM Tri-isodecyl Trimellitate
  • the polymer-based plasticizer is preferably at least one selected from the group consisting of saturated polyester resin (polyester resin having a low degree of polymerization), unsaturated polyester resin, elastomer, epoxy [ESO (Epoxidized Soybean Oil), ELO (Epoxidized Linseed Oil)], an extender-type, glycol ester, citrate and chlorinated paraffin.
  • the content of the plasticizer is 30 to 80 parts by weight based on 100 parts by weight of the base resin. If the content of the plasticizer is below the minimum limit, it reduces the plasticizing effects of the plasticizer on PVC, and results in an increase of stiffness and reduction of flexibility, extrudability and mechanical characteristics, in particular, elongation. And, electrical cables without a woven layer will exhibit worse cold resistance than conventional electrical cables. If the content of the plasticizer exceeds the maximum limit, it results in deterioration of heat resistance and the mechanical characteristics, in particular, tensile strength.
  • the flame -retardant may be metal hydroxide, preferably aluminum hydroxide, magnesium hydroxide, a compound of magnesium hydroxide and carbonate, hy- drotalcite, or a compound of huntite and magnesium hydroxide.
  • the content of the flame -retardant is 1 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the flame-retardant is below the minimum limit, it does not secure sufficient flame retardancy of electrical cables and oxygen index represented as flame retardancy of the material characteristics.
  • the secondary flame-retardant may be any one selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, or mixtures selected arbitrarily therefrom.
  • the antinomy compound is antimony trioxide
  • the tin compound is a compound of zinc hydroxide and tin or a compound of zinc and tin.
  • the content of the secondary flame- retardant is preferably 1 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the secondary flame-retardant is below the minimum limit, flame retardancy resulted from the synergy effect with the flame-retardant is not expected.
  • the content of the secondary flame-retardant exceeds the maximum limit, it does not lead to increased flame retardancy in proportion to the increased content of the secondary flame-retardant, but rather remarkably reduces extrudability and tensile strength due to an excessive amount of inorganic substances. And, a rise in content of the secondary flame-retardant increases the unit cost of the material.
  • the stabilizer is preferably any one selected from the group consisting of lead stabilizer, nonlead stabilizer, epoxy stearate and metallic soap material, or mixtures selected arbitrarily therefrom.
  • the content of the stabilizer is 1 to 15 parts by weight based on 100 parts by weight of the base resin. If the content of the stabilizer is below the minimum limit, heat resistance of the material reduces remarkably, and consequently, the required characteristics are not satisfied. If the content of the stabilizer exceeds the maximum limit, heat resistance improvement resulted from the increased content of the stabilizer is not expected, and tensile strength reduces.
  • the filler is preferably any one selected from the group consisting of calcium carbonate, clay and talc, or mixtures selected arbitrarily therefrom.
  • the content of the filler is 3 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the filler is below the minimum limit, the decrease in the unit cost of the material resulted from addition of a low-cost filler is not expected. If the content of the filler exceeds the maximum limit, tensile strength and elongation reduce remarkably due to an excessive amount of inorganic substances, and extrudability also deteriorates.
  • FIGs. 1 and 2 are schematic cross-sectional views of a conventional electrical cable.
  • FIG. 3 is a schematic cross-sectional view of an electrical cable according to the present invention.
  • the conventional electrical cable includes a plurality of central conductors 101 and an insulating layer 103 surrounding each conductor 101.
  • a bedding layer 107 wholly surrounds the conductors 101 surrounded by the insulating layers 103.
  • a woven layer 109 surrounds the outer surface of the bedding layer 107, and is made of copper or tin-plated copper.
  • a sheath of PVC resin may be formed along the outer periphery of the woven layer 109 (See FIG. 1).
  • the PVC resin used in the sheath has flame-retardant grade according to IEC (International Elec- trotechnical Commission) 60332-3 Cat. C.
  • the electrical cable of the present invention includes a bedding layer 207, but does not include the woven layer 109 of the conventional electrical cable.
  • the bedding layer 207 is made of the resin composition for coating material of electrical cables according to the present invention.
  • the bedding layer 207 made of the resin composition for coating material of electrical cables according to the present invention has a tensile strength at normal temperature of 2.0 kgf/mm 2 or more and an oxygen index of more than 23%, and thus can act as a woven layer in addition to as a bedding layer intrinsically.
  • the woven layer can be removed from the electrical cable, so that the electrical cable has reduction in the outer diameter and weight and consequently the manufacturing unit cost. If a woven layer is removed from a conventional electrical cable, the electrical cable cannot have flame retardancy according to IEC 60332-3 Cat. C.
  • each composition of examples 1 to 6 and comparative examples 1 to 3 was prepared according to the ingredients and contents of Table 1.
  • Each material specimen and electrical cable was manufactured using the compositions, and evaluate in various aspects for specifying the technical effects of the present invention.
  • Examples 1 to 6 and Comparative examples 1 to 3 [33] A specimen for measuring the material characteristics was manufactured by mix- milling the ingredients of Table 1 using an open roller of about 130 0 C and molding using a press of 170 0 C for 5 minutes. And, an electrical cable comprising a conductor 201, an insulating layer 203, a bedding layer 207 and a sheath 211 was manufactured using a composition prepared according to the ingredients and content of Table 1, and is configured as shown in FIG. 3. The manufactured specimen was tested in aspects of mechanical characteristics at normal temperature, mechanical characteristics after heating, oxygen index and weight loss after heating, and the electrical cable was evaluated in aspects of cold resistance, flame retardancy and tension resistance.
  • 'resin a' is PVC having a degree of polymerization of 800 or more
  • 'resin b' is chlorinated PCV
  • 'resin c' is PVC having a degree of polymerization less than 800.
  • 'plasticizer a' is DINP
  • 'plasticizer b' is TOTM
  • 'stabilizer' is tribasic lead sulfate (TLS)
  • 'filler' is calcium carbonate
  • 'flame-retardant' is a compound of huntite and magnesium hydroxide having a weight ratio of x:y
  • 'secondary flame-retardant' is anytimony trioxide.
  • the electrical cable was pulled by a tensile force of 500 kgf.
  • the tension resistance is determined based on whether or not the insulation performance of an insulating layer is deteriorated and a sheath is damaged. [50] Table 2
  • PVC having a degree of polymerization of 800 or more satisfied the tensile strength of 2.0 kgf/mm 2 or more and elongation of 150% or more, required by the present invention.
  • the examples 1 to 6 satisfied the weight loss of 1.5 mg/cm 2 or less, required by the present invention.
  • the examples 1 to 6 satisfied the cold resistance and tension resistance required when installing electrical cables.
  • the examples 1 to 6 using a metal hydroxide flame-retardant and a secondary flame-retardant, singularly or in combination thereof satisfied the oxygen index more than 23% and flame-retardancy of electrical cables, required by the present invention.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Organic Insulating Materials (AREA)

Abstract

Disclosed are a resin composition for coating material of electrical cables and electrical cables using the same. The resin composition comprises 100 parts by weight of a base resin selected from the group consisting of polyvinyl chloride resin, chlorinated polyvinyl chloride resin and composite resins thereof; 30 to 80 parts by weight of a plasticizer selected from the group consisting of a phthalate-based plasticizer, a phosphate-based plasticizer, a fatty acid-based plasticizer, a mellitate-based plasticizer and a polymer-based plasticizer, and mixtures thereof; 1 to 50 parts by weight of a metal hydroxide flame-retardant; and 1 to 50 parts by weight of a secondary flame-retardant selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, and mixtures thereof.

Description

Description
RESIN COMPOSITION FOR COATING MATERIAL OF ELECTRICAL CABLES AND ELECTRICAL CABLES USING
THE SAME
Technical Field
[1] The present invention relates to a resin composition for coating material of electrical cables and electrical cables using the same. In particular, the present invention relates to a resin composition for coating material of electrical cables that is capable of forming a bedding layer with excellent tensile strength and flame retardancy, and electrical cables using the same. Background Art
[2] Electrical cables for power, control, signaling and so on, in particular, used in ships, should be prevented from deforming due to tensile force and lateral pressure on installation. For this purpose, electrical cables having a woven layer on a bedding layer are generally used, and the woven layer is formed by weaving a zinc-plated iron wire, a zinc-plated steel wire or a copper-coated iron wire. Conventionally, JIS (Japanese Industrial Standards) cables installed in dangerous areas or areas with risk of explosion necessarily had a woven layer therein or thereon. However, the woven layer increases the outer diameter of electrical cables and decreases flexibility of the electrical cables, which makes it difficult to install the electrical cables in narrow spaces. And, the woven layer requires additional processes in the manufacture of electrical cables, resulting in a rise of manufacturing cost. As mentioned above, because the woven layer is formed by weaving a fine iron wire, if the iron wire is irregularly woven in a weaving process, faults often occur. Furthermore, the woven layer increases the total weight of electrical cables. The electrical cables, for example, used in ships have difficult in satisfying specific cable weight standard required by ship owners and manufacturers in these days.
[3] So far, various structural designs of electrical cables have been suggested to ensure tension resistance and flame retardancy without a woven layer. However, the suggestions did not produce satisfactory results.
[4] One of attempts to ensure tension resistance of electrical cables without a woven layer is development and application of polymer materials with excellent mechanical characteristics, in particular, tensile strength. However, polymer materials with excellent tensile strength have low flame retardancy, resulting in poor flame retardancy of electrical cables. And, polymer materials with excellent tensile strength have high stiffness, resulting in reduced flexibility of electrical cables, which make it difficult to install the electrical cables. Meanwhile, if polymer materials are added with a large amount of organic and inorganic flame-retardants for flame retardancy, generally the polymer materials have the reduced tensile strength.
[5] Accordingly, studies have been steadily made in the related field to develop inventive flame-retardant polymer materials that meet functions and characteristics of both a bedding layer and a woven layer. The present invention is devised under this technical background. Disclosure of Invention Technical Problem
[6] Therefore, it is an object of the invention to provide a resin composition for coating material of electrical cables that meets functions and characteristics of both a bedding layer and a woven layer and eliminates the need for the woven layer, and electrical cables using the same. Technical Solution
[7] In order to achieve the object, a resin composition for coating material of electrical cables according to the present invention comprises a base resin selected from the group consisting of polyvinyl chloride (PVC) resin, chlorinated PVC resin and composite resins thereof; 30 to 80 parts by weight of a plasticizer based on 100 parts by weight of the base rein, selected from the group consisting of a phthalate-based plasticizer, a phosphate -based plasticizer, a fatty acid-based plasticizer, a mellitate- based plasticizer and a polymer-based plasticizer, and mixtures thereof; 1 to 50 parts by weight of a metal hydroxide flame-retardant based on 100 parts by weight of the base rein; and 1 to 50 parts by weight of a secondary flame-retardant based on 100 parts by weight of the base rein, selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, and mixtures thereof.
[8] Preferably, the phthalate-based plasticizer is selected from the group consisting of di- isononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate and diisooctyl phthalate, and mixtures thereof, the phosphate-based plasticizer is selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate, and mixtures thereof, the fatty acid-based plasticizer is selected from the group consisting of DOA (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate), and mixtures thereof, the mellitate-based plasticizer is selected from the group consisting of TOTM (Tri-2-ethyl hexyl Trimellitate), mixed TOTM (Tri-2-ethyl hexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate), and mixtures thereof, and the polymer-based plasticizer is selected from the group consisting of saturated polyester resin having a low degree of polymerization, unsaturated polyester resin, elastomer, ESO (Epoxidized Soybean Oil), ELO (Epoxidized Linseed Oil), an extender-type, glycol ester, citrate and chlorinated paraffin, and mixtures thereof. And, preferably the antimony compound is antimony trioxide, and the tin compound is selected from the group consisting of a compound of zinc hydroxide and tin, a compound of zinc and tin, and mixtures thereof. Preferably, the resin composition for coating material of electrical cables further comprises a stabilizer selected from the group consisting of lead-based material, nonlead-based material, epoxy stearate and metallic soap material, and mixtures thereof, or a filler selected from the group consisting of calcium carbonate, clay and talc, and mixtures. In addition to the resin composition for coating material of electrical cables, the present invention provides an electrical cable comprising a bedding layer formed using the resin composition for coating material of electrical cables. Preferably, the bedding layer has a tensile strength of 2.0 kgf/mm2 or more and an oxygen index more than 23%.
Advantageous Effects
[9] The resin composition for coating material of electrical cables according to the present invention has excellent tensile strength and flame retardancy, and a bedding layer of an electrical cable, formed using the resin composition meets function and characteristics of a woven layer as well as function and characteristics of a bedding layer. Accordingly, the electrical cable comprising a bedding layer formed using the resin composition for coating material of electrical cables according to the present invention eliminates the need for a woven layer, and thus has reduction in the outer diameter and weight, and consequently the manufacturing unit cost. Brief Description of Drawings
[10] These and other features, aspects, and advantages of preferred embodiments of the present invention will be more fully described in the following detailed description, taken accompanying drawings.
[11] FIGs. 1 and 2 are schematic cross-sectional views of a conventional electrical cable.
[12] FIG. 3 is a schematic cross-sectional view of an electrical cable according to an embodiment of the present invention.
[13] <Reference Numerals of Essential Parts in the Drawings>
[14] 101 , 201...conductor 103 , 203...insulating laye
[15] 107, 207...bedding layer 109...woven layer
[16] l l l, 211...sheath
Mode for the Invention
[17] A resin composition for coating material of electrical cables according to the present invention comprises a base resin, a plasticizer, a flame-retardant and a secondary flame-retardant.
[18] The base resin includes thermoplastic resins which are deformable when heated, for example, PVC, chlorinated PVC (CPVC), and a combination thereof. Preferably, PVC has a degree of polymerization of 800 to 1700. If the degree of polymerization is below the minimum limit, a polymer has a low molecular weight, making it to secure a sufficient tensile strength. If the degree of polymerization exceeds the maximum limit, heat resistance and mechanical characteristics such as tensile strength and so on are excellent, but high temperature is required during a compounding or extruding process. Disadvantageously, it results in whole deterioration of extrudability.
[19] PVC or CPVC is a linear or straight-chain polymer, in which a force between molecules restricts the motion of the polymer chain to maintain the rigid state, making modification difficult. However, when heated, a thermal motion of PVC polymer molecules increases and a reaction therebetween, and as a result, a predetermined gap creates between PVC polymer molecules. At this time, plasticizer molecules go into the gap between molecules and prevent the PVC polymer molecules from coming close with each other. PVC polymer molecules have positive and negative polarities within, while plasticizer molecules also have such polar and non-polar parts. The PVC polymer molecules and the plasticizer molecules are electrically attracted to each other, and the non-polar parts widen the distance among the polymer molecules.
[20] Preferably, the plasticizer may be a phthalate-based plasticizer, a phosphate-based plasticizer, a fatty acid-based plasticizer, a mellitate-based plasticizer or a polymer- based plasticizer. The phthalate-based plasticizer is preferably at least one selected from the group consisting of diisononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate and diisooctyl phthalate. The phosphate-based plasticizer is preferably at least one selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate. The fatty acid-based plasticizer is preferably at least one selected from the group consisting of DOA (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate). The mellitate-based plasticizer is preferably at least one selected from the group consisting of TOTM (Tri-2-ethylhexyl Trimellitate), mixed TOTM (Tri-2-ethylhexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate).
[21] The polymer-based plasticizer is preferably at least one selected from the group consisting of saturated polyester resin (polyester resin having a low degree of polymerization), unsaturated polyester resin, elastomer, epoxy [ESO (Epoxidized Soybean Oil), ELO (Epoxidized Linseed Oil)], an extender-type, glycol ester, citrate and chlorinated paraffin.
[22] Preferably, the content of the plasticizer is 30 to 80 parts by weight based on 100 parts by weight of the base resin. If the content of the plasticizer is below the minimum limit, it reduces the plasticizing effects of the plasticizer on PVC, and results in an increase of stiffness and reduction of flexibility, extrudability and mechanical characteristics, in particular, elongation. And, electrical cables without a woven layer will exhibit worse cold resistance than conventional electrical cables. If the content of the plasticizer exceeds the maximum limit, it results in deterioration of heat resistance and the mechanical characteristics, in particular, tensile strength.
[23] The flame -retardant may be metal hydroxide, preferably aluminum hydroxide, magnesium hydroxide, a compound of magnesium hydroxide and carbonate, hy- drotalcite, or a compound of huntite and magnesium hydroxide. Preferably, the content of the flame -retardant is 1 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the flame-retardant is below the minimum limit, it does not secure sufficient flame retardancy of electrical cables and oxygen index represented as flame retardancy of the material characteristics. If the content of the flame-retardant exceeds the maximum limit, flame retardancy is sufficiently expected due to the increased content of the flame-retardant, however, it results in deterioration of extrudability, tensile strength, elongation and heat resistance due to an excessive amount of inorganic substances.
[24] The secondary flame-retardant may be any one selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, or mixtures selected arbitrarily therefrom. Preferably, the antinomy compound is antimony trioxide, and the tin compound is a compound of zinc hydroxide and tin or a compound of zinc and tin. The content of the secondary flame- retardant is preferably 1 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the secondary flame-retardant is below the minimum limit, flame retardancy resulted from the synergy effect with the flame-retardant is not expected. If the content of the secondary flame-retardant exceeds the maximum limit, it does not lead to increased flame retardancy in proportion to the increased content of the secondary flame-retardant, but rather remarkably reduces extrudability and tensile strength due to an excessive amount of inorganic substances. And, a rise in content of the secondary flame-retardant increases the unit cost of the material.
[25] The stabilizer is preferably any one selected from the group consisting of lead stabilizer, nonlead stabilizer, epoxy stearate and metallic soap material, or mixtures selected arbitrarily therefrom. Preferably, the content of the stabilizer is 1 to 15 parts by weight based on 100 parts by weight of the base resin. If the content of the stabilizer is below the minimum limit, heat resistance of the material reduces remarkably, and consequently, the required characteristics are not satisfied. If the content of the stabilizer exceeds the maximum limit, heat resistance improvement resulted from the increased content of the stabilizer is not expected, and tensile strength reduces.
[26] The filler is preferably any one selected from the group consisting of calcium carbonate, clay and talc, or mixtures selected arbitrarily therefrom. Preferably, the content of the filler is 3 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the filler is below the minimum limit, the decrease in the unit cost of the material resulted from addition of a low-cost filler is not expected. If the content of the filler exceeds the maximum limit, tensile strength and elongation reduce remarkably due to an excessive amount of inorganic substances, and extrudability also deteriorates.
[27] FIGs. 1 and 2 are schematic cross-sectional views of a conventional electrical cable.
FIG. 3 is a schematic cross-sectional view of an electrical cable according to the present invention.
[28] Referring to FIGs. 1 and 2, the conventional electrical cable includes a plurality of central conductors 101 and an insulating layer 103 surrounding each conductor 101. A bedding layer 107 wholly surrounds the conductors 101 surrounded by the insulating layers 103. A woven layer 109 surrounds the outer surface of the bedding layer 107, and is made of copper or tin-plated copper. And, a sheath of PVC resin may be formed along the outer periphery of the woven layer 109 (See FIG. 1). Generally, the PVC resin used in the sheath has flame-retardant grade according to IEC (International Elec- trotechnical Commission) 60332-3 Cat. C.
[29] As shown in FIG. 3, the electrical cable of the present invention includes a bedding layer 207, but does not include the woven layer 109 of the conventional electrical cable. The bedding layer 207 is made of the resin composition for coating material of electrical cables according to the present invention. The bedding layer 207 made of the resin composition for coating material of electrical cables according to the present invention has a tensile strength at normal temperature of 2.0 kgf/mm2 or more and an oxygen index of more than 23%, and thus can act as a woven layer in addition to as a bedding layer intrinsically. Thus, the woven layer can be removed from the electrical cable, so that the electrical cable has reduction in the outer diameter and weight and consequently the manufacturing unit cost. If a woven layer is removed from a conventional electrical cable, the electrical cable cannot have flame retardancy according to IEC 60332-3 Cat. C.
[30]
[31] Hereinafter, each composition of examples 1 to 6 and comparative examples 1 to 3 was prepared according to the ingredients and contents of Table 1. Each material specimen and electrical cable was manufactured using the compositions, and evaluate in various aspects for specifying the technical effects of the present invention.
[32] Examples 1 to 6 and Comparative examples 1 to 3 [33] A specimen for measuring the material characteristics was manufactured by mix- milling the ingredients of Table 1 using an open roller of about 130 0C and molding using a press of 170 0C for 5 minutes. And, an electrical cable comprising a conductor 201, an insulating layer 203, a bedding layer 207 and a sheath 211 was manufactured using a composition prepared according to the ingredients and content of Table 1, and is configured as shown in FIG. 3. The manufactured specimen was tested in aspects of mechanical characteristics at normal temperature, mechanical characteristics after heating, oxygen index and weight loss after heating, and the electrical cable was evaluated in aspects of cold resistance, flame retardancy and tension resistance.
[34] Table 1 [Table 1] [Table ]
Figure imgf000008_0001
[35] In Table 1, 'resin a' is PVC having a degree of polymerization of 800 or more, 'resin b' is chlorinated PCV and 'resin c' is PVC having a degree of polymerization less than 800. And, 'plasticizer a' is DINP, 'plasticizer b' is TOTM, 'stabilizer' is tribasic lead sulfate (TLS), 'filler' is calcium carbonate, 'flame-retardant' is a compound of huntite and magnesium hydroxide having a weight ratio of x:y, and 'secondary flame-retardant' is anytimony trioxide.
[36] Characteristics evaluation [37] The specimens and electrical cables according to examples and comparative examples were evaluated in the following aspects, and the evaluation results are shown in Table 2.
[38] Characteristics at normal temperature
[39] According to IEC 60811-1-1 standard, tensile strength and elongation were measured when a tensile rate was 500 mm/min. The tensile strength and elongation requirements are 2.0 kgf/mm2 or more and 150% or more, respectively. [40] Weight loss after heating
[41] The specimen was placed at 100 0C for 168 hours and heated per unit surface area, and the weight loss was measured. The weight loss requirement is 1.5 mg/cm2 or less. [42] Oxygen index
[43] Flame retardancy of the specimen was measured according to ASTM D 2863 specifications. The oxygen index should be 24% or more. [44] Cold resistance
[45] Cold resistance of the electrical cable was measured according to IEC 811-1 standard. The cold resistance requirement is -25 0C or less. [46] Flame retardancy
[47] Flame retardancy of the electrical cable was measured according to IEC 332-3 Cat. A flame test.
[48] Tension resistance
[49] The electrical cable was pulled by a tensile force of 500 kgf. The tension resistance is determined based on whether or not the insulation performance of an insulating layer is deteriorated and a sheath is damaged. [50] Table 2
[Table 2] [Table ]
Figure imgf000010_0001
[51] According to the measurement results, the examples 1 to 6 using PVC or chlorinated
PVC having a degree of polymerization of 800 or more satisfied the tensile strength of 2.0 kgf/mm2 or more and elongation of 150% or more, required by the present invention. And, after heating at 100 0C, the examples 1 to 6 satisfied the weight loss of 1.5 mg/cm2 or less, required by the present invention. Furthermore, the examples 1 to 6 satisfied the cold resistance and tension resistance required when installing electrical cables. In addition, the examples 1 to 6 using a metal hydroxide flame-retardant and a secondary flame-retardant, singularly or in combination thereof, satisfied the oxygen index more than 23% and flame-retardancy of electrical cables, required by the present invention.
[52] On the contrary, the comparative examples 1 and 2 using a low molecular weight of
PVC having a low degree of polymerization showed the reduced heat resistance after heating and consequently a large weight change in the evaluation of durability. And, the comparative examples 1 and 2 using a large amount of plasticizer added to the low molecular weight of PVC had a very low tensile strength. Thus, it is not expected that electrical cables manufactured using the compositions of the comparative examples 1 and 2 will exhibit high strength.
[53] The comparative example 3 using the same resin of the comparative example 1 and a high molecular weight of plasticizer did not satisfy the weight loss requirement after heating. And, the comparative example 3 had a low tensile strength, and thus could not ensure tension resistance of electrical cables. As a result, the comparative example 3 did not ensure a long-term reliability of electrical cables. [54] Hereinabove, the preferred embodiments of the present invention are described.
However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Claims

Claims
[1] A resin composition for coating material of electrical cables, comprising: a base resin being selected from the group consisting of polyvinyl chloride resin having a degree of polymerization of 800 to 1700, chlorinated polyvinyl chloride resin and composite resins thereof; based on 100 parts by weight of the base rein,
30 to 80 parts by weight of a plasticizer selected from the group consisting of a phthalate -based plasticizer, a phosphate -based plasticizer, a fatty acid-based plasticizer, a mellitate-based plasticizer and a polymer-based plasticizer, and mixtures thereof;
1 to 50 parts by weight of a metal hydroxide flame-retardant; and
1 to 50 parts by weight of a secondary flame-retardant selected from the group consisting of antinomy compound, boron-based compound, tin compound and molybdenum compound, and mixtures thereof.
[2] The resin composition for coating material of electrical cables according to claim
1, wherein the phthalate-based plasticizer is selected from the group consisting of diisononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate and diisooctyl phthalate, and mixtures thereof, wherein the phosphate-based plasticizer is selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate, and mixtures thereof, wherein the fatty acid-based plasticizer is selected from the group consisting of DOA (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate), and mixtures thereof, wherein the mellitate-based plasticizer is selected from the group consisting of TOTM (Tri-2-ethylhexyl Trimellitate), mixed TOTM (Tri-2-ethylhexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate), and mixtures thereof, and wherein the polymer-based plasticizer is selected from the group consisting of saturated polyester resin having a low degree of polymerization, unsaturated polyester resin, elastomer, ESO (Epoxidized Soybean Oil), ELO (Epoxidized Linseed Oil), an extender-type, glycol ester, citrate and chlorinated paraffin, and mixtures thereof.
[3] The resin composition for coating material of electrical cables according to claim
1, wherein the antimony compound is antimony trioxide, and wherein the tin compound is selected from the group consisting of a compound of zinc hydroxide and tin and a compound of zinc and tin, and mixtures thereof. [4] The resin composition for coating material of electrical cables according to claim
1, further comprising: a stabilizer selected from the group consisting of lead-based material, nonlead- based material, epoxy stearate and metallic soap material, and mixtures thereof. [5] The resin composition for coating material of electrical cables according to claim
1, further comprising: a filler selected from the group consisting of carbonate, clay and talc, and mixtures. [6] An electrical cable, comprising: one or more central conductors; an insulating layer surrounding each conductor; a bedding layer wholly surrounding one or more insulating layers and formed using the resin composition for coating material of electrical cables, defined in any one of claims 1 to 5; and a sheath surrounding the bedding layer. [7] The electrical cable according to claim 6, wherein the bedding layer has a tensile strength of 2.0 kgf/mm2 or more and an oxygen index more than 23%.
PCT/KR2008/004382 2008-07-28 2008-07-28 Resin composition for coating material of electrical cables and electrical cables using the same WO2010013851A1 (en)

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