WO2017182870A1 - Crosslinkable polymer composition comprising organic peroxide - Google Patents

Crosslinkable polymer composition comprising organic peroxide Download PDF

Info

Publication number
WO2017182870A1
WO2017182870A1 PCT/IB2017/000458 IB2017000458W WO2017182870A1 WO 2017182870 A1 WO2017182870 A1 WO 2017182870A1 IB 2017000458 W IB2017000458 W IB 2017000458W WO 2017182870 A1 WO2017182870 A1 WO 2017182870A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer composition
parts
weight
peroxide
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/IB2017/000458
Other languages
French (fr)
Inventor
Jun-Bae Jeon
Seong-Jin Kim
Young-Gu Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nexans SA
Original Assignee
Nexans SA
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 Nexans SA filed Critical Nexans SA
Priority to KR1020187033709A priority Critical patent/KR20180128504A/en
Publication of WO2017182870A1 publication Critical patent/WO2017182870A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/286—Chlorinated polyethylene
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/14—Peroxides
    • 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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethylene vinyl acetate copolymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • 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
    • H01B3/441—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 alkenes
    • 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
    • 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
    • H01B3/448—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 other vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables

Definitions

  • the present invention relates to a crosslinkable polymer composition comprising a mixture of organic peroxides, more particularly for the production of sheathing for cable or line.
  • present invention relates to a method for preparing sheathing for cable or line with the polymer composition of the present invention, which following production via mixing of the components is crosslinked, and more particularly compressed and crosslinked.
  • the present invention relates to a cable or line having sheathing that is produced with the polymer composition of the present invention.
  • Chemical and physical crosslinking reaction provides thermosetting properties for rubber.
  • Such crosslinking reaction typically enables rubber to have increased mechanical properties, thermal- or chemical-resistance.
  • the rubber crosslinking reaction can be divided depending on the crosslinking method, into sulfur crosslinking, organic peroxide crosslinking, radiation crosslinking, silane crosslinking and the like.
  • the organic peroxide crosslinking method is widely used for crosslinking rubber in cable industry, since its mechanism is relatively simple and the polymer produced by the method has an enhanced thermal-resistance.
  • Organic peroxide is degraded via light and heat to form free-radicals, and the activity can be determined depending on its decomposition temperature. As the decomposition temperature is lower, the crosslinking reaction occurs faster.
  • Crosslinking speed is an important factor in preparing cables and lines. When the crosslinking speed is increased, the extrusion line speed becomes faster, and thus the productivity is increased and the expenses can be reduced. However, as crosslinking speed is increased, the oxidation reaction occurs faster. In addition, if decomposition temperature is low, undesired scorch may occur during the procedure of mixing and extruding, which may decrease the mechanical property and workability of rubber.
  • Co-crosslinking agent activates organic peroxide crosslinking reaction so as to raise crosslinking speed or crosslinking density.
  • co-crosslinking agent may decrease scorch stability and other mechanical properties or decrease workability due to the increased adhesion with metal interface .
  • the present invention provides a cable or line with a crosslinked sheathing obtained from said
  • the present invention provides a method for producing sheathing for cable or line, from said crosslinkable polymer composition.
  • the present invention provides a crosslinkable polymer composition comprising an elastomeric polymer; an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide; and antioxidant.
  • the crosslinkable polymer composition of the present invention can be used for preparing sheathing for
  • the elastomeric polymer according to the present invention comprises chlorinated polyethylene (CPE) and ethylene vinyl acetate copolymer (EVA) .
  • the antioxidant of the present invention comprises phenol based antioxidant or UV stabilizer, preferably, both of them.
  • the polymer composition according to the present invention comprises the organic peroxide in an amount of 0.5 to 10 parts by weight, with respect to 100 parts by weight of elastomeric polymer.
  • the composition of the invention comprises dialkyl peroxide type peroxide in amount of 1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer, and peroxyketal type peroxide in an amount of 2 to parts by weight, preferably 5 to 10 parts by weight with respect to 100 parts by weight of elastomeric polymer.
  • the polymer composition according to present invention comprises antioxidant in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer.
  • the present invention provides a cable or line with a sheathing that is made of a crosslinkable polymer composition comprising elastomeric polymer, an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide, and
  • the present invention provides a cable or line with a crosslinked sheathing that is obtained from a crosslinkable polymer composition comprising elastomeric polymer, an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide, and antioxidant.
  • the present invention provides a method for produce a sheathing for electrical and/or optical cable or line, comprising :
  • step i) mixing the cross linkable polymer composition, and ii) crosslinking the mixture obtained from step i), and more preferably compressing the mixture obtained from step i) so as to crosslink the mixture.
  • the term "sheathing" means more particularly the outermost layer of a cable or line.
  • the crosslinkable polymer composition according to the present invention can guarantee a good crosslinking speed, which can increase extrusion line speed when producing a wire, and ultimately, can raise productivity.
  • the polymer composition according to the present invention can show an optimized scorch stability while guaranteeing a good crosslinking speed and good mechanical
  • composition can be used for preparing sheathing for electrical and/or optical cables or lines.
  • crosslinkable polymer composition according to the present invention comprises elastomeric polymer, organic
  • the polymer composition according to the present invention comprises an elastomeric polymer, preferably, chlorinated polyethylene (CPE) and ethylene vinyl acetate copolymer (EVA) .
  • CPE chlorinated polyethylene
  • EVA ethylene vinyl acetate copolymer
  • the chlorinated polyethylene is a polymer having polyethylene main chain with chlorine atoms randomly replacing the hydrogen atoms along the chain. By adding chlorine atoms, the polymer has an enhanced fire retardant and advantageous chemical resistance and thermo-resistance .
  • the ethylene vinyl acetate copolymer is a copolymer that is produced via polymerization of ethylene monomer and vinyl acetate monomer.
  • the physical properties of EVA are determined depending on the degree of polymerization and content of vinyl acetate, and typically EVA presents good chemical- resistance, weather resistance, and ozone-resistance.
  • EVA has vinyl acetate content from 20 to 70%, and more preferably from 25 to 40%.
  • the polymer composition according to the present invention comprises organic peroxide as a crosslinking agent.
  • Organic peroxide may generally be considered as derivatives of hydrogen peroxide (H 2 O 2 ) in which one or both of hydrogen atoms is/are replaced by organic group (s) .
  • Said organic peroxide produces free radicals by light or heat, and the radials form c-c linkage with adjacent polymer chains, so that the rubber that presents enhanced mechanical strength, thermo-resistance, chemical resistance and electrical properties can be produced.
  • the organic peroxide according to the present invention comprises a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide. Said mixture provides a rapid
  • the dialkyl peroxide type peroxide is selected from the group consisting of Dicumyl peroxide, 2 , 5-dimethyl-2 , 5-Di- ( t-butylperoxy ) hexane and Bis(t- butylperoxy isopropyl ) enzene, and preferably is Bis(t- butylperoxy isopropyl ) benzene .
  • peroxyketal type peroxide is 1 , 4-bis- ( t-butylperoxy ) -3 , 3 , 5-trimethylcyclohexane or n-butyl 4, 4-di (t-butylperoxy) valerate, and preferably n-butyl 4,4-di(t- butylperoxy) valerate .
  • the content of organic peroxide in the composition according to the present invention is 0.5 to 10 parts by weight, with respect to 100 parts by weight of elastomeric polymer.
  • the composition comprises:
  • the polymer composition according to the present invention comprises antioxidant.
  • the antioxidant can prevent polymer composition from oxidation, and enhance weather- resistant /thermos-resistant properties, and scorch stability.
  • the antioxidant according to the present invention is selected from the group consisting of:
  • UV stabilizer i.e., benzotriazole based UV stabilizer such as 2 , 4-di-tert-butyl-6- ( 5-chlorobenzotriazol-2-yl ) phenol; 2- ( 2H-benzotriazole-2-yl ) -p-cresol ; 2-(2H- benzotriazole-2-yl ) -4, 6-bis ( 1-methyl-l-phenylethyl ) ; 2- ( 2H-benzotriazole-2-yl ) -4, 6-ditertpentylphenol ) , - Amine based antioxidant (i.e., octylated diphenylamine, 2,2, 4-trimethyl-l , 2-dihydroquinoline (TMQ) ) ,
  • TMQ 2-dihydroquinoline
  • Cyclic acetal based antioxidant i.e., 3,9-di-3- cyclohexen-l-yl-2 , 4, 6, 10-tetraoxaspiro [5.5] undecane ) , and - a combination thereof.
  • the antioxidant according to the present invention includes phenol based antioxidant or UV stabilizer, and preferably, includes both of them.
  • the phenol based antioxidant can prevent scorch stability of the composition from decreasing while the crosslinking speed is increasing.
  • the phenol based antioxidant and UV stabilizer can enhance the mechanical properties of the polymer composition.
  • the content of antioxidant in polymer composition is 0.1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer.
  • the polymer composition according to the present invention may comprise phenol based antioxidant and UV stabilizer in an amount of 0.1 to 2.5 parts by weight with respect to 100 parts by weight of elastomeric polymer, separately.
  • the polymer composition according to the present invention may optionally further comprises organic additives and/or
  • the organic additives may include compatibilizer , plasticizer, pigments, coupling agents, or crosslinking aid agents.
  • the organic additives may include compatibilizer , plasticizer, pigments, coupling agents, or crosslinking aid agents.
  • the compatibilizer e.g., compatibilizer, plasticizer, pigments, coupling agents, or crosslinking aid agents.
  • the organic additives may include compatibilizer , plasticizer, pigments, coupling agents, or crosslinking aid agents.
  • the organic additives may include compatibilizer , plasticizer, pigments, coupling agents, or crosslinking aid agents.
  • inorganic additives may include metal-based inorganic additives and ceramic-based inorganic additives, such as carbon black, calcium carbonate (CaCC>3) , talc, china clay, graphite, silica, mica, antimony trioxide, lead oxide, aluminum hydroxide,
  • magnesium hydroxide magnesium oxide, zinc oxide
  • the content of organic additives is 100 parts by weight or less, preferably 50 parts by weight or less, with respect to 100 parts by weight of
  • the cable according to the present invention is a cable having sheathing as defined according to standard HD 22.1 EM 7.
  • said cable can be used as a wind turbine power cable.
  • the sheathing that is made of polymer composition according to the present invention can be used as inner sheath and/or outer sheath of the cable.
  • the inner sheath can be positioned between insulation and braid, and the outer sheath can be positioned at outermost part of the cable.
  • Another object of the present invention is to provide a method for preparing a sheathing for electrical and/or optical cables or lines, comprising:
  • step ii) crosslinking the mixture obtained from step i), and more preferably compressing the mixture obtained from step i) so as to crosslink the mixture.
  • the sheathing for cable and line according to the present invention can be produced by mixing the crosslinkable polymer composition comprising aforementioned components, using for example two-roll mill.
  • the organic and/or inorganic additives disclosed before may be further added to said mixture depending on the particular properties industrially required to the crosslinkable polymer composition for sheathing.
  • composition may be compressed in mold under the high temperature so as to be crosslinked to form a crosslinked product.
  • the crosslinking procedure is performed under the temperature of, for example, 150 ° C or more, particularly 150 ° C to 220 ° C, with the pressure of, preferably 12 to 22 MPa, more preferably 16 to 20MPa, by heating, for example using water or inorganic salt as a
  • the method according to the present invention has high crosslinking speed, which can increase productivity.
  • the crosslinkable composition is prepared using the components and the mixing ratio as shown
  • antioxidant (Anox-70) 0.5
  • the elastomeric polymer in Table 1 being a mixture of CPE and EVA .
  • UV stabilizing antioxidant as 2,4 ditertbutyl-6- ( 5- chlorobenzotriazol-2-yl ) phenol commercialized by Ciba with the reference Tinuvin 327;
  • the mechanical properties such as tensile strength (TS) and Elongation at break (EB) of crosslinked product was determined by preparing dumbbell-shaped species as defined in the standard DIN 53504. S2, and then using a universal tensile strength tester under the condition as defined in standard IEC 60811-1-1. When both values of the tensile strength and the elongation at break are higher, the mechanical properties are considered to better on the whole.
  • crosslinking speed polymer composition was prepared using the components and mixing ratio in Table 2 according to the method that is described in the representative preparation example.
  • the polymer compositions thus obtained were determined on the crosslinking speed and scorch stability according to the measurement method described before. And the results are
  • - phr refers to parts per 100 parts of elastomeric polymer, the elastomeric polymer in Table 2 being a mixture of CPE and EVA,
  • Vulkanox HS/LG is a trade name of amine based antioxidant as 2 , 2 , 4-trimethyl-l , 2-dihydroquinoline (TMQ) commercialized by Lanxess,
  • Vulkazon AFS/LG is a trade name of a cyclic acetal based antioxidant as 3 , 9-di-3-cyclohexen-l-yl-2 , 4 , 6 , 10-tetraoxaspiro
  • composition according to examples 1 and 2 were shown to have enhanced scorch stability compared to that of comparative example 2 which does not comprise dialkyl peroxide type peroxide.
  • polymer composition was prepared using the components and mixing ration in Table 3 according to the method that is described in the representative preparation example.
  • the polymer compositions thus obtained were determined on the crosslinking speed, scorch stability and mechanical
  • - phr refers to parts per 100 parts of elastomeric polymer, the elastomeric polymer in Table 3 being a mixture of CPE and EVA, - Octamine is a trade name of amine based antioxidant as octylated diphenylamine, commercialized by CROMPTON Corporation
  • antioxidant shows enhanced mechanical properties compared with that of composition according to example 3 which comprises only phenol based antioxidant.
  • composition comprising 1 phr of
  • dialkylperoxide and 6.0 phr of peroxyketal according to example 5 is shown to have higher crosslinking speed compared to the
  • composition comprising 1.3 phr of dialkylperoxide and 4.0 phr of peroxyketal according to example 4.
  • compositions according to comparative example 1 and example 12 of the present invention are compositions according to comparative example 1 and example 12 of the present invention.
  • the composition according to example 12 of the present invention is shown to have about 20% increased crosslinking speed with good scorch stability and mechanical properties (tensile strength) , compared to the composition according to the comparative example 1.
  • the results show that according to present invention, the composition having fast crosslinking speed while guaranteeing optimized scorch stability and physical property can be produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

The present invention relates to a crosslinkable polymer composition for use as a sheathing for electrical and/or optical cable or lines, to a cable and/or line with the claimed polymer composition, and to a method for preparing a sheathing for cable and/or line. The crosslinkable polymer composition according to the présent invention comprises an elastomeric polymer, a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide, and antioxidant.

Description

CROSSLINKABLE POLYMER COMPOSITION COMPRISING ORGANIC PEROXIDE
Field of the invention
The present invention relates to a crosslinkable polymer composition comprising a mixture of organic peroxides, more particularly for the production of sheathing for cable or line.
In addition, present invention relates to a method for preparing sheathing for cable or line with the polymer composition of the present invention, which following production via mixing of the components is crosslinked, and more particularly compressed and crosslinked.
Furthermore, the present invention relates to a cable or line having sheathing that is produced with the polymer composition of the present invention.
Background of the invention
Chemical and physical crosslinking reaction provides thermosetting properties for rubber. Such crosslinking reaction typically enables rubber to have increased mechanical properties, thermal- or chemical-resistance. The rubber crosslinking reaction can be divided depending on the crosslinking method, into sulfur crosslinking, organic peroxide crosslinking, radiation crosslinking, silane crosslinking and the like.
Among them, the organic peroxide crosslinking method is widely used for crosslinking rubber in cable industry, since its mechanism is relatively simple and the polymer produced by the method has an enhanced thermal-resistance. Organic peroxide is degraded via light and heat to form free-radicals, and the activity can be determined depending on its decomposition temperature. As the decomposition temperature is lower, the crosslinking reaction occurs faster. Crosslinking speed is an important factor in preparing cables and lines. When the crosslinking speed is increased, the extrusion line speed becomes faster, and thus the productivity is increased and the expenses can be reduced. However, as crosslinking speed is increased, the oxidation reaction occurs faster. In addition, if decomposition temperature is low, undesired scorch may occur during the procedure of mixing and extruding, which may decrease the mechanical property and workability of rubber.
One of methods commonly used for raising crosslinking speed, is adding a co-crosslinking agent. Co-crosslinking agent activates organic peroxide crosslinking reaction so as to raise crosslinking speed or crosslinking density. However, if co- crosslinking agent is added to the polymer excessively, it may decrease scorch stability and other mechanical properties or decrease workability due to the increased adhesion with metal interface .
Therefore, there still remains in the related art demands for crosslinkable polymer composition having rapid crosslinking speed, while maintaining good scorch stability.
Prior Art
[Patent Publication No .1 ] US 4180531 (December 25, 1975)
Brief description of the invention
It is an object of the present invention to provide a crosslinkable polymer composition, more particularly for use in sheathing for electrical and/or optical cable or line, having good crosslinking speed and scorch stability.
It is another object of the present invention to provide a cable or line with a sheathing made of said crosslinkable
polymer composition.
More particularly, the present invention provides a cable or line with a crosslinked sheathing obtained from said
crosslinkable polymer composition.
It is another object of the present invention to provide a method for producing sheathing for cable or line, from said crosslinkable polymer composition. In order to achieve the object, the present invention provides a crosslinkable polymer composition comprising an elastomeric polymer; an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide; and antioxidant. The crosslinkable polymer composition of the present invention can be used for preparing sheathing for
electric and/or optical cables or lines.
In one embodiment, the elastomeric polymer according to the present invention comprises chlorinated polyethylene (CPE) and ethylene vinyl acetate copolymer (EVA) .
In another embodiment, the antioxidant of the present invention comprises phenol based antioxidant or UV stabilizer, preferably, both of them.
In one preferable embodiment, the polymer composition according to the present invention comprises the organic peroxide in an amount of 0.5 to 10 parts by weight, with respect to 100 parts by weight of elastomeric polymer.
In another preferable embodiment, the composition of the invention comprises dialkyl peroxide type peroxide in amount of 1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer, and peroxyketal type peroxide in an amount of 2 to parts by weight, preferably 5 to 10 parts by weight with respect to 100 parts by weight of elastomeric polymer.
In another preferable embodiment, the polymer composition according to present invention comprises antioxidant in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer.
In addition, in order to achieve the object, the present invention provides a cable or line with a sheathing that is made of a crosslinkable polymer composition comprising elastomeric polymer, an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide, and
antioxidant .
More particularly, the present invention provides a cable or line with a crosslinked sheathing that is obtained from a crosslinkable polymer composition comprising elastomeric polymer, an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide, and antioxidant.
Furthermore, the present invention provides a method for produce a sheathing for electrical and/or optical cable or line, comprising :
i) mixing the cross linkable polymer composition, and ii) crosslinking the mixture obtained from step i), and more preferably compressing the mixture obtained from step i) so as to crosslink the mixture.
In the present invention, the term "sheathing" means more particularly the outermost layer of a cable or line.
Advantageous effects
The crosslinkable polymer composition according to the present invention can guarantee a good crosslinking speed, which can increase extrusion line speed when producing a wire, and ultimately, can raise productivity.
In addition, the polymer composition according to the present invention, can show an optimized scorch stability while guaranteeing a good crosslinking speed and good mechanical
properties, so that the composition can be used for preparing sheathing for electrical and/or optical cables or lines.
Detailed description of the invention
Hereinafter, the invention will be described in more detail. The crosslinkable polymer composition according to the present invention comprises elastomeric polymer, organic
peroxide and antioxidant.
Elastomeric polymer The polymer composition according to the present invention comprises an elastomeric polymer, preferably, chlorinated polyethylene (CPE) and ethylene vinyl acetate copolymer (EVA) .
The chlorinated polyethylene (CPE) is a polymer having polyethylene main chain with chlorine atoms randomly replacing the hydrogen atoms along the chain. By adding chlorine atoms, the polymer has an enhanced fire retardant and advantageous chemical resistance and thermo-resistance .
The ethylene vinyl acetate copolymer (EVA) is a copolymer that is produced via polymerization of ethylene monomer and vinyl acetate monomer. The physical properties of EVA are determined depending on the degree of polymerization and content of vinyl acetate, and typically EVA presents good chemical- resistance, weather resistance, and ozone-resistance.
In a preferred embodiment, EVA has vinyl acetate content from 20 to 70%, and more preferably from 25 to 40%.
Organic peroxide
The polymer composition according to the present invention comprises organic peroxide as a crosslinking agent. Organic peroxide may generally be considered as derivatives of hydrogen peroxide (H2O2) in which one or both of hydrogen atoms is/are replaced by organic group (s) . Said organic peroxide produces free radicals by light or heat, and the radials form c-c linkage with adjacent polymer chains, so that the rubber that presents enhanced mechanical strength, thermo-resistance, chemical resistance and electrical properties can be produced.
The organic peroxide according to the present invention comprises a mixture of dialkyl peroxide type peroxide and peroxyketal type peroxide. Said mixture provides a rapid
crosslinking speed and proper scorch stability to the polymer composition .
In one preferable embodiment, the dialkyl peroxide type peroxide is selected from the group consisting of Dicumyl peroxide, 2 , 5-dimethyl-2 , 5-Di- ( t-butylperoxy ) hexane and Bis(t- butylperoxy isopropyl ) enzene, and preferably is Bis(t- butylperoxy isopropyl ) benzene .
In another preferable embodiment, peroxyketal type peroxide is 1 , 4-bis- ( t-butylperoxy ) -3 , 3 , 5-trimethylcyclohexane or n-butyl 4, 4-di (t-butylperoxy) valerate, and preferably n-butyl 4,4-di(t- butylperoxy) valerate .
In another preferable embodiment, the content of organic peroxide in the composition according to the present invention is 0.5 to 10 parts by weight, with respect to 100 parts by weight of elastomeric polymer. In another preferable embodiment, the composition comprises:
- dialkyl peroxide type peroxide in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of
elastomeric polymer, and
- peroxyketal type peroxide in an amount of 2 to 10 parts by weight, preferably 5 to 10 parts by weight, with respect to 100 parts by weight of elastomeric polymer.
Antioxidant
The polymer composition according to the present invention comprises antioxidant. The antioxidant can prevent polymer composition from oxidation, and enhance weather- resistant /thermos-resistant properties, and scorch stability.
In one embodiment, the antioxidant according to the present invention is selected from the group consisting of:
- phenol based antioxidant (i.e., 2 , 2'thiodiethylene bis
[ 3- ( 3 , 5-di-t-butyl-4-hydroxyphenyl ) propionate ; 1,3,5- trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4- hydroxybenzyl ) benzene } ; 2,2' -methylenebis ( 6-t-butyl-4- methylphenol ) ; Pentaerythritol tetrakis ( 3 , 5-di-tert- butyl-4-hydroxyhydrocinnamate ) ) ,
- UV stabilizer (i.e., benzotriazole based UV stabilizer such as 2 , 4-di-tert-butyl-6- ( 5-chlorobenzotriazol-2-yl ) phenol; 2- ( 2H-benzotriazole-2-yl ) -p-cresol ; 2-(2H- benzotriazole-2-yl ) -4, 6-bis ( 1-methyl-l-phenylethyl ) ; 2- ( 2H-benzotriazole-2-yl ) -4, 6-ditertpentylphenol ) , - Amine based antioxidant (i.e., octylated diphenylamine, 2,2, 4-trimethyl-l , 2-dihydroquinoline (TMQ) ) ,
- Cyclic acetal based antioxidant (i.e., 3,9-di-3- cyclohexen-l-yl-2 , 4, 6, 10-tetraoxaspiro [5.5] undecane ) , and - a combination thereof.
In one preferable embodiment, the antioxidant according to the present invention includes phenol based antioxidant or UV stabilizer, and preferably, includes both of them. Particularly, the phenol based antioxidant can prevent scorch stability of the composition from decreasing while the crosslinking speed is increasing. Also, the phenol based antioxidant and UV stabilizer can enhance the mechanical properties of the polymer composition.
In one preferable embodiment, the content of antioxidant in polymer composition is 0.1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer. In another preferable embodiment, the polymer composition according to the present invention may comprise phenol based antioxidant and UV stabilizer in an amount of 0.1 to 2.5 parts by weight with respect to 100 parts by weight of elastomeric polymer, separately.
Other additives
The polymer composition according to the present invention may optionally further comprises organic additives and/or
inorganic additives. Preferably, the organic additives may include compatibilizer , plasticizer, pigments, coupling agents, or crosslinking aid agents. In preferable embodiment, the
inorganic additives may include metal-based inorganic additives and ceramic-based inorganic additives, such as carbon black, calcium carbonate (CaCC>3) , talc, china clay, graphite, silica, mica, antimony trioxide, lead oxide, aluminum hydroxide,
magnesium hydroxide, magnesium oxide, zinc oxide
In one non-limited embodiment, the content of organic additives is 100 parts by weight or less, preferably 50 parts by weight or less, with respect to 100 parts by weight of
elastomeric polymer, and the content of inorganic additives is
300 parts by weight or less, preferably 150 parts by weight with respect to 100 parts by weight of elastomeric polymer.
Cable or line
Another object of the invention is to provide an electrical and/or optical cable or line with a sheathing that is made of polymer composition according to the present invention. In one embodiment, the cable according to the present invention is a cable having sheathing as defined according to standard HD 22.1 EM 7. Preferably, said cable can be used as a wind turbine power cable. In another embodiment, the sheathing that is made of polymer composition according to the present invention can be used as inner sheath and/or outer sheath of the cable. Preferably, the inner sheath can be positioned between insulation and braid, and the outer sheath can be positioned at outermost part of the cable. The cable comprising said layer (s) has outstanding
flexibility and features such as weather resistance, oil
resistance and cold resistance so as to protect cable from
surrounding environment .
Preparation method for sheathing of cable or line
Another object of the present invention is to provide a method for preparing a sheathing for electrical and/or optical cables or lines, comprising:
i) mixing the cross linkable polymer composition according to the present invention, and
ii) crosslinking the mixture obtained from step i), and more preferably compressing the mixture obtained from step i) so as to crosslink the mixture.
The sheathing for cable and line according to the present invention can be produced by mixing the crosslinkable polymer composition comprising aforementioned components, using for example two-roll mill. The organic and/or inorganic additives disclosed before may be further added to said mixture depending on the particular properties industrially required to the crosslinkable polymer composition for sheathing.
In addition, said mixture of crosslinkable polymer
composition may be compressed in mold under the high temperature so as to be crosslinked to form a crosslinked product. Preferably, the crosslinking procedure is performed under the temperature of, for example, 150°C or more, particularly 150°C to 220°C, with the pressure of, preferably 12 to 22 MPa, more preferably 16 to 20MPa, by heating, for example using water or inorganic salt as a
thermal fluid.
The method according to the present invention has high crosslinking speed, which can increase productivity.
Hereinafter, the present invention is described in further detail in the following Examples which are not in any way intended to limit the scope of the invention as claimed. In addition, it will appear to a person skilled in the art that various modifications may be made to the disclosed embodiments, and that such modifications are intended to be within the scope of the present invention.
Example
Preparation of crosslinkable polymer composition and its crosslinked product (representative example of preparation)
As a representative example of the method for preparing a crosslinkable polymer composition and its crosslinked product according to the invention, the crosslinkable composition is prepared using the components and the mixing ratio as shown
Table 1. [Table 1]
Figure imgf000010_0001
antioxidant (Tinuvin 327) 0.5
antioxidant (Anox-70) 0.5
Dialkyl peroxide (PBP-98 ) 1.0
peroxyketal (Luperox 230XL- 6
40SP)
In Table 1, phr refers to parts per 100 parts of
elastomeric polymer, the elastomeric polymer in Table 1 being a mixture of CPE and EVA .
Firstly, we mixed:
- CPE with a chlorine content of 36% commercialized by
HANGZHOU KELICHEM under the reference CM 3610;
- EVA with a vinyl acetate content of 28% commercialized by Dupont with the reference Elvax 265;
- UV stabilizing antioxidant as 2,4 ditertbutyl-6- ( 5- chlorobenzotriazol-2-yl ) phenol commercialized by Ciba with the reference Tinuvin 327;
- phenol based antioxidant as 2 , 2 ' thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl ) propionate] ,
commercialized by Addivant with the reference Anox-70;
- A dialkylperoxide as Bis ( t-butylperoxy isopropyl ) benzene commercialized by NOF with the reference PBP-98;
- A peroxyketal peroxides as n-butyl 4,4-di(t- butylperoxy) valerate commercialized by Arkema with the reference Luperox 230XL-40SP,
, with the ratio in Table 1, using a two-roll mill at 80°C for 15 minutes.
The mixture thus obtained was compressed under 170°C/15MPa and crosslinked for a period of time of tcgo defined below. And subsequently the pressure was released and the obtained composite was cooled in the air. As a result, the crosslinked product of crosslinkable polymer composition of the present invention was made . Evaluation method for crosslinking speed of polymer composition
In order to measure the crosslinking speed of polymer composition, the ODR (Oscillation disk rheometer) test under the condition as defined in ASTM D2084 standard was carried out and determine the time tC9o taken to reach to 90% of the maximum ODR torque value, which is increased as the crosslinking reaction is occurred. It is considered that the lower tC9o represents the faster crosslinking speed.
Evaluation method for scorch stability of polymer
composition
In order to measure scorch stability of polymer composition, Money viscometer test defined in standard ASTM D1646 was carried out, and determined the scorch time (t5) which is a time required for the increase of 5 points from minimum viscosity value of mixture in molten status. It is considered that the higher scorch time (t5) represents the higher scorch stability. Evaluation method for mechanical properties of crosslinked product of polymer composition
The mechanical properties such as tensile strength (TS) and Elongation at break (EB) of crosslinked product was determined were determined by preparing dumbbell-shaped species as defined in the standard DIN 53504. S2, and then using a universal tensile strength tester under the condition as defined in standard IEC 60811-1-1. When both values of the tensile strength and the elongation at break are higher, the mechanical properties are considered to better on the whole.
Properties determined using different polymer compositions or their crosslinked products 1
In order to identify the effects of peroxides on
crosslinking speed, polymer composition was prepared using the components and mixing ratio in Table 2 according to the method that is described in the representative preparation example. The polymer compositions thus obtained were determined on the crosslinking speed and scorch stability according to the measurement method described before. And the results are
presented in the following Table 2.
[Table 2 ]
Figure imgf000013_0001
In Table 2,
- phr refers to parts per 100 parts of elastomeric polymer, the elastomeric polymer in Table 2 being a mixture of CPE and EVA,
- Vulkanox HS/LG is a trade name of amine based antioxidant as 2 , 2 , 4-trimethyl-l , 2-dihydroquinoline (TMQ) commercialized by Lanxess,
- Vulkazon AFS/LG is a trade name of a cyclic acetal based antioxidant as 3 , 9-di-3-cyclohexen-l-yl-2 , 4 , 6 , 10-tetraoxaspiro
[ 5.5 ] undecane commercialized by Lanxess, and
- the meaning of other abbreviations described in Table 2 is as defined above in the present specification.
As shown in Table 2, the polymer composition according to ample 1 and 2 were shown to have crosslinking speed relatively faster than that comparative example 1 which does not comprise peroxyketal type peroxide. In addition, in spite of fast
crosslinking speed, the composition according to examples 1 and 2 were shown to have enhanced scorch stability compared to that of comparative example 2 which does not comprise dialkyl peroxide type peroxide.
Properties determined using different polymer compositions or their crosslinked products 2
In order to identify the effect of antioxidant on scorch stability, polymer composition was prepared using the components and mixing ration in Table 3 according to the method that is described in the representative preparation example.
The polymer compositions thus obtained were determined on the crosslinking speed, scorch stability and mechanical
properties according to the measurement method described before. And the results are presented in the following Table 3.
[Table 3 ]
Figure imgf000014_0001
strength (MPa)
Elongation at 533 - 534 - 550 312 367 351
break ( % )
In Table 3,
- phr refers to parts per 100 parts of elastomeric polymer, the elastomeric polymer in Table 3 being a mixture of CPE and EVA, - Octamine is a trade name of amine based antioxidant as octylated diphenylamine, commercialized by CROMPTON Corporation
- the meaning of other abbreviations described in Table 2 is as defined above in the present specification. As shown in Table 3, among the compositions according to the comparative examples 3 to 7 which comprise only peroxyketal type peroxide as crosslinking agent, compositions having phenol based antioxidant are shown to have the highest scorch stability. In addition, the composition according to example 4 which
comprises both phenol based antioxidant and uv stabilizing
antioxidant shows enhanced mechanical properties compared with that of composition according to example 3 which comprises only phenol based antioxidant.
Furthermore, the composition comprising 1 phr of
dialkylperoxide and 6.0 phr of peroxyketal according to example 5 is shown to have higher crosslinking speed compared to the
composition comprising 1.3 phr of dialkylperoxide and 4.0 phr of peroxyketal according to example 4.
Comparison of mechanical properties between the
compositions according to comparative example 1 and example 12 of the present invention
The mechanical properties of the compositions according to comparative example 1 and the example 12 are disclosed in the following Table 4.
[Table 4] component/test Comparative example 1 Example 12
Peroxide Dialkylperoxide dialkylperoxide +
peroxyketal
Antioxidant TMQ + cyclic acetal Phenol based
based antioxidant antioxidant +
benzotriazole based UV stabilizer
TC 90(min) 7.3 5.8
Mooney scorch t5 >60 48
( 125 °C )
Tensile strength 10.0 11.3
(half curing) 1}
Tensile strength 11.7 11.2
(optimum curing)2'
1) is performed according to compression moulding at 170°C/15MPa for 5 minutes
2) is performed according to compression moulding at 170°C/15MPa for 13 minutes
As shown Table 4, the composition according to example 12 of the present invention is shown to have about 20% increased crosslinking speed with good scorch stability and mechanical properties (tensile strength) , compared to the composition according to the comparative example 1.
Accordingly, the results show that according to present invention, the composition having fast crosslinking speed while guaranteeing optimized scorch stability and physical property can be produced.

Claims

Claims
1. A crosslinkable polymer composition, comprising:
- an elastomeric polymer;
- an organic peroxide comprising a mixture of dialkyl peroxide type peroxide and peroxiketal type peroxide; and
- an antioxidant.
2. The crosslinkable polymer composition according to claim 1, wherein the elastomeric polymer comprises chlorinated
polyethylene (CPE) and ethylene vinyl acetate copolymer (EVA) .
3. The crosslinkable polymer composition according to claim 1 or 2, wherein the antioxidant comprises phenol based
antioxidant.
4. The crosslinkable polymer composition according to any one of the preceding claims, wherein the antioxidant comprises phenol based antioxidant and UV stabilizer.
5. The crosslinkable polymer composition according to any one of the preceding claims, wherein the composition comprises the organic peroxide in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of elastomeric polymer, and the antioxidant in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of elastomeric polymer.
6. The crosslinkable polymer composition according to any one of the preceding claims, wherein the composition comprises 1 to 5 parts by weight of dialkyl type peroxide with respect to 100 parts by weight of elastomeric polymer, and 5 to 10 parts by weight of peroxyketal type peroxide with respect to 100 parts by weight of elastomeric polymer.
7. Electrical and/or optical cable or line with a sheathing made of a polymer composition according to any one of the preceding claims.
8. Electrical and/or optical cable or line with a
crosslinked sheathing obtained from a polymer composition according to any one of the preceding claims.
9. Method for preparing a sheathing for electrical and/or optical cable or line, comprising:
i) mixing the crosslinkable polymer composition according to any one of the preceding claims; and
ii) crosslinking the mixture obtained from step i), and more preferably compressing the mixture obtained from step i) so as to crosslink the mixture.
PCT/IB2017/000458 2016-04-22 2017-03-28 Crosslinkable polymer composition comprising organic peroxide Ceased WO2017182870A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020187033709A KR20180128504A (en) 2016-04-22 2017-03-28 Crosslinkable polymer composition comprising organic peroxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160049322A KR20170120876A (en) 2016-04-22 2016-04-22 Crosslinkable polymer composition comprising organic peroxide
KR10-2016-0049322 2016-04-22

Publications (1)

Publication Number Publication Date
WO2017182870A1 true WO2017182870A1 (en) 2017-10-26

Family

ID=58672631

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2017/000458 Ceased WO2017182870A1 (en) 2016-04-22 2017-03-28 Crosslinkable polymer composition comprising organic peroxide

Country Status (2)

Country Link
KR (2) KR20170120876A (en)
WO (1) WO2017182870A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180531A (en) 1976-11-16 1979-12-25 Dominic Alia Processible and vulcanizable polar polymers
JPH1126791A (en) * 1997-07-08 1999-01-29 Du Pont Mitsui Polychem Co Ltd Protective sheet for solar cell module
US20090159129A1 (en) * 2006-04-05 2009-06-25 Bridgestone Corporation Sealing film for solar cell and solar cell using the sealing film
KR20120040359A (en) * 2010-10-19 2012-04-27 삼성토탈 주식회사 Composition of ethylene vinyl acetate copolymer for solar cell encapsulant
US20130062096A1 (en) * 2010-06-03 2013-03-14 Suh Joon Han Strippable Insulation Shield for Cables

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180531A (en) 1976-11-16 1979-12-25 Dominic Alia Processible and vulcanizable polar polymers
US4180531B1 (en) 1976-11-16 1987-03-10
JPH1126791A (en) * 1997-07-08 1999-01-29 Du Pont Mitsui Polychem Co Ltd Protective sheet for solar cell module
US20090159129A1 (en) * 2006-04-05 2009-06-25 Bridgestone Corporation Sealing film for solar cell and solar cell using the sealing film
US20130062096A1 (en) * 2010-06-03 2013-03-14 Suh Joon Han Strippable Insulation Shield for Cables
KR20120040359A (en) * 2010-10-19 2012-04-27 삼성토탈 주식회사 Composition of ethylene vinyl acetate copolymer for solar cell encapsulant

Also Published As

Publication number Publication date
KR20180128504A (en) 2018-12-03
KR20170120876A (en) 2017-11-01

Similar Documents

Publication Publication Date Title
CA2943155C (en) Crosslinkable polymeric compositions with n, n, n', n', n", n"-hexaallyl-1,3,5-triazine-2,4,6-triamine crosslinking coagent, methods for making the same, and articles made therefrom
EP2938669B1 (en) Methods for making cross-linkable polymeric compositions and for producing a coated conductor
EP2576689B1 (en) Strippable insulation shield for cables
KR102448281B1 (en) Method for manufacturing a cable with a cross-linked insulating layer and the cable
WO2015149222A1 (en) Crosslinkable polymeric compositions with diallyl isocyanurate crosslinking coagents, methods for making the same, and articles made therefrom
US20130148932A1 (en) Cold temperature-resistant chloroprene casing mixture
CA3097761A1 (en) Polymeric composition containing a light stabilizer
WO2019009294A1 (en) Resin composition, resin coating material, wire harness for automobile, and production method for wire harness for automobile
CN107924737A (en) Wire and Cable
JP2011080020A (en) Non-halogen flame-retardant resin composition, manufacturing method therefor, and electric cable using the same
KR101774449B1 (en) Insulating Material Composition For Automotive Electric Cables With Excellent Abrasion Resistance And Flame Retardant
WO2016021611A1 (en) Silane-grafted composition and method for producing same, as well as wire and cable using said composition
JP2012241041A (en) Non-halogen flame-retardant rubber composition and rubber-coated wire and cable
WO2017182870A1 (en) Crosslinkable polymer composition comprising organic peroxide
CN105623166B (en) Halogen-free flame-retardant resin composition and high-voltage cable
JP5655595B2 (en) Flame-retardant composition having peelability, method for producing flame-retardant resin, and insulated wire
KR20200143540A (en) Composition for aerial cable outer insulation, aerial cable including areial cable outer insulation manufactured therefrom and manufactuing method of the same
KR101821482B1 (en) Flame-retardant elastomer composition and a preparation method thereof
JP5776389B2 (en) Flame retardant composition having peelability and heat resistance, method for producing flame retardant resin, and insulated wire
JP6295050B2 (en) Ethylene propylene rubber composition, cable and molded article formed from the composition
JP6720565B2 (en) Insulated wire and cable
KR101506326B1 (en) Polymer resin composition for preparing insulating material having reinforced thermal stability
JP2012146458A (en) Radiation resistant electric wire and cable
WO2010132766A2 (en) Improved insulation compositions containing zinc stabilizers
KR101687796B1 (en) Sheath Composition For Electric Cable And Electric Cable Using The Same

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187033709

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17722147

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17722147

Country of ref document: EP

Kind code of ref document: A1