KR101723677B1 - Flame-retardant insulating composition, and electrical wire and cable prepared using the same - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to a flame retardant coating composition, and to electric wires and cables manufactured using the same. The flame retardant coating composition comprises (A) a base resin; (B) a flame retardant; And (C) an antioxidant, wherein the base resin (A) comprises (A1) 35 to 65% by weight of a polypropylene resin, (A2) 25 to 45% by weight of a thermoplastic elastomer, and (A3) Wherein the thermoplastic elastomer (A2) comprises an ethylene-propylene-diene (EPDM) elastomer, a maleic acid (maleic anhydride) Ethylene-butylene-styrene (SEBS) elastomer and maleic anhydride grafted styrene-ethylene-butylene-styrene elastomer (Ma-g-SEBS ). ≪ / RTI >

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame-retardant coating composition, and a wire and a cable produced using the same. BACKGROUND ART [0002]

FIELD OF THE INVENTION The present invention relates to a flame retardant coating composition, and to electric wires and cables manufactured using the same.

In recent years, due to the deterioration of high temperature and high performance of the vehicle, wires used in a space such as a vehicle having a narrow internal space and a high fire risk must have flexibility, heat resistance and flame retardancy. For example, High heat resistance grade is required.

Conventionally, PVC (polyvinyl chloride) and XLPE (crosslinked polyethylene) wires have been mainly used as a flame retardant coating agent. In the case of PVC wires, however, toxic gases are generated by halogen during combustion, In the case of XLPE, there is a problem that it is impossible to recycle by passing through an electron beam cross-linking process.

Accordingly, there is a need for an environmentally-friendly insulating material which does not contain halogen as an insulating material, has excellent flame retardancy, and has desired mechanical and chemical properties, and polypropylene resin has been widely used as an alternative thereto. Polypropylene has an advantage in that heat resistance and mechanical strength can be satisfied without crosslinking and recycling is possible.

However, the polypropylene resin is very vulnerable to flame retardance, so that when a large amount of a flame retardant is added, the mechanical properties are lowered and whitening occurs when the wire is bent.

The background art of the present invention is disclosed in Korean Patent Laid-Open Publication No. 2009-0106129 (published on October 10, 2009, entitled "Semiconductive polyvinyl chloride resin composition and wire using the same").

An object of the present invention is to provide a flame retardant coating composition excellent in mechanical strength, flame retardancy and heat resistance.

Another object of the present invention is to provide a flame retardant coating composition excellent in low temperature characteristics and abrasion resistance.

It is still another object of the present invention to provide a flame retardant coating composition that prevents bleaching during bending, has excellent bending resistance, and is free from the generation of toxic gases and is excellent in environmental compatibility.

Another object of the present invention is to provide a flame retardant coating composition having excellent productivity and economical efficiency.

It is still another object of the present invention to provide electric wires and cables manufactured using the flame retardant coating composition.

One aspect of the present invention relates to a flame retardant coating composition. The flame retardant coating composition comprises (A) a base resin; (B) a flame retardant; And (C) an antioxidant, wherein the base resin (A) comprises (A1) 35 to 65% by weight of a polypropylene resin, (A2) 25 to 45% by weight of a thermoplastic elastomer, and (A3) Wherein the polypropylene resin (A1) has a melt index of 0.1 to 1.5 g / 10 min and the thermoplastic elastomer (A2) is an ethylene-propylene-diene (EPDM) elastomer, a maleic anhydride grafted Ethylene-butylene-styrene elastomer (Ma-g-EPDM) elastomer, styrene-ethylene-butylene-styrene (SEBS) elastomer and maleic anhydride grafted styrene-ethylene- Or more.

In one embodiment, the polypropylene resin (A1) is a polypropylene terpolymer resin composed of an ethylene-propylene-alpha (alpha) olefin, a polypropylene block copolymer resin composed of ethylene-propylene, Propylene random copolymer resin.

In one embodiment, the thermoplastic elastomer (A2) may have a glass transition temperature (Tg) of -35 캜 or less.

In one embodiment, the thermoplastic elastomer (A2) may be partially crosslinked.

In one embodiment, the thermoplastic elastomer (A2) comprises an ethylene-propylene-diene (EPDM) elastomer and a maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomer in a weight ratio of 1: 0.1 to 1: can do,

In one embodiment, the coupling agent (A3) may comprise a polypropylene copolymer resin grafted with at least one of maleic anhydride and phthalic anhydride.

In one embodiment, 50 to 110 parts by weight of the flame retardant (B) and 0.5 to 15 parts by weight of the antioxidant (C) may be added to 100 parts by weight of the base resin (A).

In an embodiment wherein the flame retardant (B) comprises one or more of magnesium hydroxide (Mg (OH) _2), aluminum hydroxide (Al (OH) ₃₎ and calcium hydroxide (Ca (OH) _2), the flame retardant (B) May be surface-treated with at least one of a silicone-based coupling agent, a titanate-based coupling agent, a fatty acid, a metal hydroxide, an amine and a metal salt of an amine.

In one embodiment, the antioxidant (C) may include one or more of phenolic compounds, phosphorus compounds, sulfur compounds, amine compounds, and metal antioxidants.

In one embodiment, 0.1 to 15 parts by weight of the flame retardant aid (D) and 0.1 to 10 parts by weight of the lubricant (E) may be further added to 100 parts by weight of the base resin (A).

In one embodiment, the flame retardant aid D comprises at least one of antimony trioxide, zinc oxide (ZnO), tin oxide (SnO), zinc borate, and zinc stearate, and the lubricant (E) Amide-based, zinc-based, and fatty acid-based lubricants.

Another aspect of the invention relates to an insulator made from the flame retardant coating composition.

Another aspect of the present invention relates to a wire produced using the flame retardant coating composition.

Another aspect of the present invention relates to a cable made using the flame retardant coating composition.

The flame retardant coating composition according to the present invention is excellent in mechanical strength, flame retardancy and heat resistance, has excellent low temperature characteristics and abrasion resistance, prevents whitening at the time of bending of an insulator and has excellent bending resistance. And can be particularly suitable for use in a 125 ° C electric wire for automobiles.

1 shows a partially crosslinked thermoplastic elastomer according to one embodiment of the present invention.
2 shows a process for producing a flame retardant coating composition according to one embodiment of the present invention.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be exemplary, self-explanatory, allowing for equivalent explanations of the present invention.

One aspect of the present invention relates to a flame retardant coating composition. In one embodiment, the flame retardant coating composition comprises (A) a base resin; (B) a flame retardant; And (D) an antioxidant, wherein the base resin (A) comprises (A) 35 to 65% by weight of a polypropylene resin, (A2) 25 to 45% by weight of a thermoplastic elastomer, and (A3) And the thermoplastic elastomer (A2) has a melt index of 0.1 g / 10 min to 2.5 g / 10 min (ASTM D1238, 190 캜, 2.16 kg measurement standard), and the thermoplastic elastomer (A2) Ethylene-propylene-diene (EPDM) elastomers, maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomers, styrene-ethylene-butylene- styrene (SEBS) elastomers and maleic anhydride grafted styrene- -Butylene-styrene elastomer (Ma-g-SEBS).

Hereinafter, the flame retardant coating composition according to the present invention will be described in detail.

(A) Base resin

The base resin (A) of the present invention comprises (A1) a polypropylene type resin; (A2) a thermoplastic elastomer; And (A3) a coupling agent.

(A1) polypropylene resin

The polypropylene resin (A1) is included for the purpose of ensuring the abrasion resistance and flame retardancy of the present invention. In one embodiment, the polypropylene resin (A1) includes a polypropylene terpolymer resin composed of an ethylene-propylene-alpha (alpha) olefin, a polypropylene block copolymer resin composed of ethylene-propylene and ethylene- And a polypropylene random copolymer resin.

When the polypropylene-based (A1) resin of the above kind is applied, the effect of improving the low-temperature characteristics is excellent, the flame retardancy is secured by the relatively small amount of the flame retardant loading and the amount of the thermoplastic elastomer to be described later can be relatively reduced, Wear characteristics can be excellent. For example, a polypropylene block copolymer resin composed of ethylene-propylene. In one embodiment of the present invention, the ethylene-propylene-alpha (alpha) olefin may be ethylene-propylene-butene.

The polypropylene resin (A1) used is one having a melt index of 0.1 g / 10 min to 2.5 g / 10 min (ASTM D1238, 190 ° C, 2.16 kg measurement standard). The filler loading property is excellent at the melt index within the above range, and the relatively low amount of flame retardant loading ensures excellent flame retardancy and excellent mechanical properties. When the polypropylene resin (A1) having a melt index of less than 0.1 g / 10 min is applied, the flame retardancy may be lowered. When the melt index is more than 2.5 g / 10 min, flame retardancy and compatibility of the coating composition of the present invention are lowered, and mechanical properties may be deteriorated. For example, the melt index may be from 0.1 g / 10 min to 1.5 g / 10 min.

The polypropylene resin (A1) is contained in an amount of 35 to 65% by weight based on the total weight of the base resin (A). When it is included in the above range, it can be excellent in flex resistance, flame retardancy, abrasion resistance and mechanical properties. When the polypropylene resin (A1) is contained in an amount of less than 35% by weight, the flame retardancy and abrasion resistance of the present invention are lowered. When the polypropylene resin (A1) is contained in an amount exceeding 65% by weight, the mechanical properties and low temperature characteristics of the present invention may be deteriorated. For example, 40 to 55% by weight.

(A2) Thermoplastic elastomer

The thermoplastic elastomer (A2) is included for the purpose of improving the loading characteristics of the flame retardant component included in the present invention and improving flame retardancy, heat resistance, flexibility and low temperature characteristics.

In one embodiment, the thermoplastic elastomer (A2) may include an ethylene-propylene-diene (EPDM) elastomer, a maleic anhydride grafted Ethylene Propylene Diene Monomer (Ma-g-EPDM Styrene-ethylene-butadiene-styrene (SEBS) elastomer and maleic anhydride-grafted maleic anhydride grafted styrene-ethylene-butadiene-styrene elastomer, Ma-g-SEBS).

When the maleic anhydride grafted ethylene-propylene-diene and the maleic anhydride grafted styrene-ethylene-butylene-styrene elastomer are used, the graft ratio may be from 0.5% to 25%. In the above range, compatibility with the components contained in the composition, mixing property and processability can be excellent.

In one embodiment, the Mooney viscosity of the ethylene-propylene-diene and maleic anhydride grafted ethylene-propylene-diene may be 5 to 50 ML (1 + 4) 125 ° C. The processability, compatibility and mechanical properties can be excellent at the Mooney viscosity in the above range. For example, 20-35 ML (1 + 4) 125 [deg.] C.

The hardness (shore A) of the styrene-ethylene-butylene-styrene and the maleic anhydride styrene-ethylene-butylene-styrene may be 45 to 90. The hardness in the above range can provide excellent processability, compatibility, and mechanical properties. For example, from 60 to 85 days.

In one embodiment, the thermoplastic elastomer (A2) may have a glass transition temperature (Tg) of -35 占 폚 or lower. Under these conditions, low-temperature bending property and mechanical properties can be excellent. For example, a glass transition temperature (Tg) of -35 ° C to -55 ° C can be used. As another example, a glass transition temperature (Tg) of -37 ° C to -50 ° C can be used.

In one embodiment, the amorphous thermoplastic elastomer (A2) can be used. When the amorphous thermoplastic elastomer (A2) is used, whitening phenomenon that may occur upon bending of the insulator made of the polypropylene type resin (A1) can be improved.

In one embodiment, the thermoplastic elastomer (A2) may be partially crosslinked. The partial crosslinking means that at least a part of the rubber, which is the soft part, is crosslinked among the thermoplastic elastomer (A2) composed of a rubber which is a soft segment and a plastic which is a hard segment.

As described above, the flame retardant coating composition containing the partially crosslinked thermoplastic elastomer (A2) can be recycled in the production of the insulator, and the heat resistance of the crosslinked polyethylene (XLPE) level can be improved And a crosslinking degree of 50% or more can be ensured.

In one embodiment, the thermoplastic elastomer (A2) comprises an ethylene-propylene-diene (EPDM) elastomer and a maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomer in a weight ratio of 1: 0.1 to 1: can do. When it is included in the above weight ratio, it is excellent in compatibility and mixing property, and can be excellent in stretchability, flame retardancy and low temperature bending property at the same time. For example, in a weight ratio of 1: 1 to 1: 3.

In one embodiment, the thermoplastic elastomer (A2) comprises a styrene-ethylene-butadiene-styrene (SEBS) elastomer and a maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomer In a weight ratio of 1: 0.1 to 1: 5. When it is included in the above weight ratio, it is excellent in compatibility and mixing property, and can be excellent in stretchability, flame retardancy and low temperature bending property at the same time. For example, in a weight ratio of 1: 1 to 1: 3.

In one embodiment, the thermoplastic elastomer (A2) is contained in an amount of 25% by weight to 45% by weight based on the total weight of the base resin (A). When it is included in the above range, it is excellent in compatibility with the composition component of the present invention and is excellent in low temperature characteristics, flame retardancy and heat resistance. When the thermoplastic elastomer (A2) is contained in an amount of less than 25% by weight, the low temperature property and mechanical properties of the present invention may be deteriorated. When the thermoplastic elastomer (A2) is contained in an amount exceeding 45% by weight, flame retardancy and heat resistance may be deteriorated. For example, 30% by weight to 45% by weight.

(A3) Coupling agent

The coupling agent (A3) is included for the purpose of enhancing the compatibility and mixing property of the flame retardant coating composition of the present invention to secure processability and physical properties. In one embodiment, the coupling agent (A3) may be a polypropylene copolymer resin grafted with at least one of maleic anhydride and phthalic anhydride. In the present invention, the coupling agent (A3) can be suitably selected from those having a high graft ratio of maleic anhydride and phthalic anhydride and a low graft ratio. In one embodiment, the grafting rate of the coupling agent (A3) may be from 0.5% to 35%. The bonding properties with other components of the present invention can be improved under the above conditions, so that workability and physical properties can be excellent.

The coupling agent (A3) may have a melt index of 100 to 250 g / 10 min (ASTM D1238, 190 DEG C, 2.16 kg measurement standard).

In one embodiment, the coupling agent (A3) is contained in an amount of 10% by weight to 35% by weight based on the total weight of the base resin (A). When included in the above range, the bonding properties between the composition components of the present invention are improved, and the properties such as workability, tensile strength and elongation can be excellent. When the amount of the coupling agent (A3) is less than 10% by weight, the processability is deteriorated. When the coupling agent (A3) is contained in an amount exceeding 35% by weight, flame retardancy, low temperature characteristics and mechanical properties may be deteriorated. For example, 15 to 30% by weight.

(B) Flame retardant

The flame retardant (B) is included for the purpose of ensuring heat resistance, flame retardancy and water resistance. In one embodiment, the flame retardant (B) may be a surface-treated inorganic hydroxide flame retardant. The surface treatment may be performed to ensure the water resistance and compatibility with the resin component of the present invention, and to coat the surface of the flame retardant (B).

In one embodiment, the flame retardant (B) may include at least one of magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₃ ) and calcium hydroxide (Ca (OH) ₂ ). The flame retardant (B) may be at least one selected from the group consisting of a silicone-based coupling agent, a titanate-based coupling agent, a fatty acid, a metal hydroxide, an amine and a metal salt of an amine. In one embodiment, the fatty acid may comprise one or more of stearic acid, oleic acid, palmitic acid, and behenic acid.

In one embodiment, the average size of the flame retardant (B) may be between 0.1 μm and 20 μm. As used herein, the term " size " means the maximum length. When the flame retardant in the above range is included, the flame retardant component can be easily dispersed in the base resin (A), and the bending resistance and flexibility of the insulator can be excellent. For example, a flame retardant (B) having an average size of 0.5 μm to 10 μm can be used.

The specific surface area (BET method) of the flame retardant (B) may be 5 mm 2 / g to 100 mm 2 / g.

The flame retardant (B) may be contained in an amount of 50 to 110 parts by weight based on 100 parts by weight of the base resin (A). When included in the above range, whitening can be prevented when the insulator is bent without deteriorating the electrical characteristics, elongation, durability and flexibility of the present invention, and excellent flame retardancy and heat resistance, . For example, 80 to 110 parts by weight.

(C) Antioxidant

The antioxidant (C) is included in the present invention for the purpose of prevention of aging and deterioration phenomenon, and metal inactivation effect. In an embodiment, the antioxidant may include at least one of phenol, phosphorus, sulfur, amine and metal antioxidants.

Examples of the phenolic antioxidants include sterically hindered phenolic stabilizers such as alkylated monophenol compounds, alkylthiomethylphenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, tocopherol compounds, A thiodiphenyl ether compound and an alkylidene bisphenol compound.

The phosphorus antioxidant may include at least one of a phosphorus-based ester compound and an aromatic phosphine compound.

Examples of the amine antioxidant include N, N'-diisopropyl-p-phenylenediamine, N, N'-di-tert-butylphenylenediamine, N, N'-bis (1,4-dimethylpentyl) phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'- , N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) Phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N- Phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine and N, N'-dimethyl-N, N'-di- Butyl-p-phenylenediamine.

Examples of the sulfur-containing antioxidant include diaryl 3,3-thiodipropionate, diamylmethyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis- (beta -lauryl-thio-propionate) and 3,9-bis (2-dodecylthioethyl) 8,10-tetraoxaspiro [5,5] undecane.

The metal-based antioxidant may include at least one of a copper-based antioxidant, a molybdenum-based antioxidant, lead chloride, magnesium chloride, and zinc chloride.

In an embodiment, the antioxidant (C) may include a phenolic antioxidant and a phenolic antioxidant in a weight ratio of 1: 0.5 to 10. When it is included in the above weight ratio, synergistic effect is exhibited with excellent compatibility with the composition of the present invention, and workability at the time of extrusion or injection is excellent, and the effect of preventing aging, deterioration and decomposition of polymer can be greatly increased. For example, in a weight ratio of 1: 1 to 3.

In an embodiment, the antioxidant (C) may be added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the base resin (A). Within the above range, the effect of preventing aging and deterioration can be excellent without impairing the physical properties of the present invention. For example, 0.5 to 8 parts by weight. For example, 1.5 to 3 parts by weight.

In one embodiment of the present invention, the flame retardant coating composition may further comprise a flame retardant auxiliary (D) and a lubricant (E).

(D) Flame retardant

The flame-retardant auxiliary (D) may be included in the present invention for the purpose of improving flame retardancy. In one embodiment, the flame-retardant auxiliary (D) may include at least one of antimony trioxide, zinc oxide (ZnO), tin oxide (SnO), zinc borate and zinc stearate.

The flame-retardant auxiliary (D) may be included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the base resin (A). When the content is within the above range, the mechanical properties of the present invention are not deteriorated, and the flame retardancy can be excellent. For example, 0.5 to 12 parts by weight. For example, 1 part by weight to 5 parts by weight.

(E) Lubricant

The lubricant (E) improves the dispersibility of the flame retardant (B) and the like contained in the composition of the present invention and improves workability. In one embodiment, the lubricant (E) may include at least one of ester, silicone, fatty acid and amide lubricants.

Examples of the ester-based lubricant include butyl stearate, glycerol monostearate, and montan wax. The montanic wax may be a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms.

As the silicone type lubricant, silicone oil, silicone wax, or the like can be used. The silicone wax may mean an alkyl dimethicone compound having 30 to 45 carbon atoms.

The fatty acid-based lubricant may include at least one of stearic acid, oleic acid, an animal higher fatty acid, and a vegetable higher fatty acid. For example, it may include at least one of butyl stearate, glycerol mono stearate, glycerine monooleate and stearyl stearate.

Examples of the amide-based lubricant include zinc-amide-based lubricants, ethylene-bis-stearamide, ethylenebis (oleamide), and erucamide. Or the like.

In one embodiment, an ester-based lubricant and a silicone-based lubricant may be used as the lubricant (E). More specifically, montan wax and silicone wax can be used. When the lubricant of the above kind is used, it is excellent in external appearance and lubricity, and the dispersibility of the flame retardant (B) component is excellent, and the workability can be improved.

The lubricant (E) may be added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the base resin (A). When the content is in the above range, it is excellent in appearance and lubricity, and the dispersibility of the flame retardant (B) component is excellent, and the workability can be improved. For example, 0.3 part by weight to 3 parts by weight. For example, 0.5 to 2 parts by weight.

(F) Additive

In another embodiment of the present invention, the flame retardant coating composition may further comprise (F) an additive. The additive (F) may include at least one of carbon black, a processing improver, silicone gum, an antidrip agent and a pigment.

The silicone gum may be included for the purpose of improving dispersibility and mixing of the composition of the present invention.

The drip inhibitor prevents dripping (dropping) during combustion, and in the specific example, polytetrafluoroethylene (PTFE) can be used as the drip preventive agent.

The pigment may be included for the purpose of coloring the present invention. For example, titanium dioxide (TiO ₂ ) or the like can be used.

The processing improvement agent may be included for the purpose of improving the restoring force, workability, releasability and abrasion resistance at high temperatures. Silicon or silicone resin may be used as the processing improver. In one embodiment, the silicone resin may be a siloxane resin. For example, the siloxane resin may be selected from the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenylcyclotetrasiloxane and octaphenyl Cyclotetrasiloxane. ≪ / RTI >

In one embodiment, the processing modifier can be used in the form of a silicon (siloxane) master batch. For example, it may be used in the form of a masterbatch containing a resin such as silicone resin and polypropylene.

The additive (F) may be added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the base resin (A). The drip-preventing effect can be excellent in the above range.

The flame retardant coating composition of the present invention is excellent in mechanical strength, flame retardancy and heat resistance, is excellent in low temperature characteristics and abrasion resistance, is economical because it can be recycled, has excellent bending resistance by preventing whitening during bending of insulator, So that the environmental friendliness can be excellent.

Another aspect of the invention relates to an insulator made using the flame retardant coating composition. In one embodiment, the insulator may be made of a partially cross-linked thermoplastic elastomer (A2) to ensure heat resistance and mechanical properties at the level of conventional cross-linked polyethylene (XLPE) without performing a crosslinking step such as electron beam crosslinking. In one embodiment, the degree of crosslinking of the insulator may be at least 50%. For example, from 65% to 75%.

The method of manufacturing the insulator includes: kneading the flame retardant coating composition described above; And extruding the kneaded composition to produce an insulator.

The kneading may be performed at a temperature of 150 ° C to 250 ° C using a melt mixing apparatus such as a conventional extruder or a Banbury mixer. For example, it can be kneaded at 200 ° C to 235 ° C. The extrusion may be carried out using a conventional wire extruder.

The kneaded composition may be pelletized into an extruder to produce an extrusion molded article. In one embodiment, the pellet-form composition may be injected into an extruder and extruded into an outer diameter portion of the inner conductor to form an extrusion molded article.

In one embodiment, the thickness of the insulator may vary depending on the thickness of the inner conductor. For example, it may be 0.05 mm to 5 mm, but is not limited thereto.

Another aspect of the present invention relates to a wire produced using the flame retardant coating composition. The wire may comprise an insulator made using the flame retardant coating composition. For example, the electric wire may include an inner conductor; And an insulating layer surrounding the inner conductor, wherein the insulating layer is formed using the flame-retardant coating composition of the present invention. In one embodiment, the inner conductor may include one or more of tin, copper, aluminum, and alloys thereof.

Another aspect of the present invention relates to a cable made using the flame retardant coating composition. In one embodiment, the cable may comprise an insulator made using the flame retardant coating composition. For example, the cable may comprise an inner conductor; An insulating layer surrounding the inner conductor; And a sheath layer surrounding the insulating layer, wherein the insulating layer is formed using the flame-retardant coating composition of the present invention.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Examples 1 to 3 and Comparative Examples 1 to 4

Specific specifications of the components of the flame-retardant coating composition used in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention are as follows.

(A) Base resin

(A1) polypropylene resin

(A11) a melt index: 5g / 10min (ASTM D 1238 standard, 190 ℃, 2.16Kg measurement), density: 0.91g / cm ³ (23 ℃ measurement), tensile strength: 260kgf / cm ^2, elongation at break over 500%, the heat A polypropylene random copolymer resin composed of ethylene-propylene was used, which had a deformation temperature of 105 캜 and a flexural modulus of 12,000 kgf / cm ² .

(A12) a melt index: 4g / 10min (ASTM D 1238 standard, 190 ℃, 2.16Kg measurement), density: 0.9g / cm ³ (23 ℃ measurement), yield stress: 275kgf / cm ^2, elongation: 500% or more, A heat distortion temperature of 105 DEG C, and a flexural modulus of 10,500 kgf / cm < ^{2 &} gt ;.

(A13) Melt index: 0.5 g / 10 min (ASTM D 1238 Measured at 2.16 Kg based on 190 캜) Density: 0.9 g / cm ³ (at 23 캜) Impact strength: 5 kgfcm / cm ² Tensile strength: : 100%, a flexural modulus of elasticity of 1500 MPa and a thermal deformation temperature of 100 DEG C was used.

(A2) Thermoplastic elastomer

(A21) Mooney viscosity: 25 ML (1 + 4) 125 ℃, ^{density: 0.88 g / cm 3 (23} ℃ measurement), crystallinity: 12%, and the critical temperature (Tc): a 36 ℃, as shown in Figure 1, A partially crosslinked ethylene-propylene-diene (EPDM) elastomer was used.

(A22) an off-white gum pellets (Off-White Rubbery pellet) form Mooney viscosity: 30 ML (1 + 4) 125 ℃, density: 0.87g / cm ³ (23 ℃ measured), maleic anhydride graft ratio: 5 to 15%, bulk density: 0.6g / cm ^3, a glass transition temperature (Tg): -37 ℃, and also the cross-section as shown in one of maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomer Were used.

(A 23) Styrene / Rubber ratio: 33/67%, density: 0.91 g / cm ³ (measured at 23 ° C), tensile strength: 4000 psi or more, elongation: 800% or more and hardness (Shore A) A styrene-ethylene-butylene-styrene (SEBS) elastomer was used.

(A24) Density: 0.92 g / cm ³ (measured at 23 캜) A melt index of 5.0 g / 10 min (measured at 190 占 폚, 2.16 Kg as measured by ASTM D 1238), a shore A of 84, an elongation of 600%, and a maleic anhydride grafting rate of 1 to 15% Maleic anhydride grafted styrene-ethylene-butylene-styrene (Ma-g-SEBS) elastomer was used.

(A25) density: 0.970g / cm ³ (23 ℃ measurement), hardness (Shore A): 69, brittle temperature (Brittleness Temperature) is -60 ℃ a thermoplastic vulcanized material (poly completely cross-linked ethylene-propylene-based propylene- Diene (EPDM) dispersed elastomer, TPV) was used.

(A3) Coupling agent

(A31) an off-white, and pellet form, melt index: 250g / 10min (ASTM D 1238 standard, 190 ℃, 2.16Kg measurement), maleic anhydride graft ratio: 5 to 20%, density: 0.91g / cm ³ (23 Maleic anhydride grafted polypropylene copolymer resin having a bulk density of 0.6 g / cm < ³ > and a melting point of 160 DEG C to 170 DEG C was used.

(A32) a pellet form, melt index: 115g / 10min (ASTM D 1238 standard, 190 ℃, 2.16kg measured), density: 0.91g / cm ³ (23 ℃ measurement), melting point: 160 ℃ ~ 170 ℃ and maleic Maleic anhydride grafted polypropylene copolymer resin having an acid anhydride graft ratio of 1% was used.

(B) Flame retardant: Mg (OH) ₂ having an average size of 1 mu m surface-treated with vinylsilane was used.

(C) Antioxidant: (C1) Irganox 1010 (manufactured by BASF) was used as a phenol antioxidant. (C2) Phenol-based antioxidant Irganox 1024 (BASF) was used.

(D) Flame Retarding Agent: Zinc borate having an average size of 1 탆 was used.

(E) Lubricant: A zinc-amide lubricant was used.

(F) Additive: (F1) silicone gum was used. (F2) A silicon master batch containing a polypropylene resin and a silicone (siloxane) resin at a weight ratio of 1: 1 was used as a processing improvement agent. (F3) PTFE (polytetrafluoroethylene) was used as an anti-drip agent. The TiO ₂ in (F4) was used as pigment.

FIG. 2 illustrates a process for producing a pellet using the flame-retardant coating composition according to one embodiment of the present invention. Referring to FIG. 2, the contents and components of the examples and comparative examples according to Table 1 were put into an extruder (Twin Screw Extruder), kneaded at a melting temperature of 184 ° C after compounding and dried at a die temperature of 220 ° C And extruded into pellets. The pellets were poured into a 50 mm Single Screw Extruder and extruded to extrude the insulator into an outer diameter of a conductor of 1.0 mm and an insulation thickness of 0.3 mm to prepare a wire sample.

The following Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated for physical properties as described below, and the results are shown in Table 2 below.

(1) elongation percentage 1 (%): Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated for elongation percentage based on ES911110 standard. The standard value should be 125% or more. Elongation percentage 2 (%): The insulators of Examples 1 to 3 and Comparative Examples 1 to 4, in which conductors were removed, were subjected to aging at 158 占 폚 for 168 hours based on UL 1581/758 125 占 폚 heat resistance criterion. The elongation percentage standard value after aging should be 100% or more.

(2) Tensile strength 1 (kgf / mm ² ): Tensile strengths of Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated based on ES911110 standard. The reference value should not be less than 1.60 kgf / mm ² . Tensile Strength 2 (kgf / mm ² ): UL 1581/758 125 캜 Insulation of Examples 1 to 3 and Comparative Examples 1 to 4, in which conductors were removed, The strength was measured. The standard value of the tensile strength after aging should be 70% or more of the normal temperature.

(3) Heat resistance: Examples 1 to 3 and Comparative Examples 1 to 4 were heated and bent at 165 DEG C for 240 hours, and then evaluated for pass and fail by observing whether or not they lasted for 1 minute at 1000 V (heat resistance 1). According to JASO D619 standards, Examples 1 to 3 and Comparative Examples 1 to 4 were heated at 200 占 폚 for 30 minutes, and the surface was evaluated for melting and cracking, and evaluated as Pass and Fail (heat resistance 2).

(4) Flame retardancy: Samples of about 300 mm in length were taken in Examples 1 to 3 and Comparative Examples 1 to 4 according to ES911110 standards, and supported horizontally. The burning time of the sample was measured after the front end of the reducing salt adjusted to a length of about 130 mm and a length of about 35 mm of the oxidizing salt of flame was applied for a prescribed time from the center of the sample and the flame was removed. The reference value should be extinguished within 70 seconds.

(5) Oil resistance: Examples 1 to 3 and Comparative Examples 1 to 4 were immersed in oil at 50 占 폚 for 20 hours, and after bending, whether or not to withstand 1 minute at 1000 V was evaluated and evaluated as Pass and Fail.

(6) Low temperature: Examples 1 to 3 and Comparative Examples 1 to 4 were kept at -45 占 폚 for 3 hours, and then evaluated for pass and fail by observing whether or not they lasted for 1 minute at 1000 V after bending.

(7) Abrasion resistance: About 710 g of Scrape abrasion resistance was measured according to ISO 6722 standards for Examples 1 to 3 and Comparative Examples 1 to 4. The standard value should be 200 or more.

(8) Whitening phenomenon: Examples 1 to 3 and Comparative Examples 1 to 4 were bent 180 degrees, and color change was observed.

(9) Appearance: The surface states of Examples 1 to 3 and Comparative Examples 1 to 4 were checked and evaluated as good and bad.

(10) Extrusion characteristics: The problems of extrusion of Examples 1 to 3 and Comparative Examples 1 to 4 were confirmed and evaluated as good and bad.

(11) Stripability: The peeling properties of the coatings of the wires according to Examples 1 to 3 and Comparative Examples 1 to 4 were observed and evaluated as good and bad.

(12) High temperature pressure test: For Examples 1 to 3 and Comparative Examples 1 to 4, heating was carried out for 4 hours while being weighed at 125 DEG C, immersed in ice water for 10 seconds, And evaluated as Pass and Fail.

(13) Low temperature bending test: For Examples 1 to 3 and Comparative Examples 1 to 4, it was held at -40 占 폚 for 4 hours, and it was confirmed whether or not it was able to withstand 1 kV for 1 minute and evaluated as Pass and Fail .

(14) Low Temperature Shock Test: The samples of Examples 1 to 3 and Comparative Examples 1 to 4 were kept at -15 占 폚 for 4 hours, dropped at a rate of 100 g, checked for 1 minute at a voltage of 1 kv, And Fail.

(15) Short-term heat resistance: Examples 1 to 3 and Comparative Examples 1 to 4 were heated at 150 DEG C for 240 hours in accordance with ISO 6722 standards, bent at -25 DEG C, and checked whether they were able to withstand 1 kV for 1 minute And evaluated as Pass and Fail.

(16) Long-term heat resistance: Examples 1 to 3 and Comparative Examples 1 to 4 were heated at 125 ° C for 3,000 hours in accordance with ISO 6722 standard, bent at room temperature, checked whether they could withstand 1 kV for 1 minute, Fail.

(17) Thermal overload: Examples 1 to 3 and Comparative Examples 1 to 4 were heated at 175 占 폚 for 6 hours, bent at room temperature, and then evaluated for pass and fail by confirming whether they were able to withstand 1 kV for 1 minute. Respectively.

(18) Fluid compatibility: Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated in terms of Pass and Fail by checking whether or not they were able to withstand a voltage of 1 kV for 1 minute after putting them into a liquid.

(19) Low-temperature Flexibility: Examples 1 to 3 and Comparative Examples 1 to 4 were taken as 610 mm in length and maintained in a low-temperature bath at -55 ± 2 ° C for 4 hours. Then, a load of 0.68 kg was applied to the wire in a low- , Wound around a cylinder having an outer diameter of 25.4 mm three times to examine the degree of damage of the surface, and evaluated by Pass and Fail. It should also withstand 1,000V X 1min in water.

(20) Ozone resistance: Examples 1 to 3 and Comparative Examples 1 to 4 were wound on a standard round bar, left in an ozone chamber for 192 hours, and crack formation was confirmed and evaluated as Pass and Fail.

(21) Water temperature resistance (.mm): 48dV was added for 7 days under conditions of NaCl 10g / L and temperature 85 ° for Examples 1 to 3 and Comparative Examples 1 to 4, and the volume resistance was measured. The withstand voltage is applied 5 times repeatedly, and the reference value should not be destroyed above 10 ⁹ .mm.

(22) Insulation resistance (.mm): According to ISO 6722 standards, the samples of Examples 1 to 3 and Comparative Examples 1 to 4 were immersed in hot water at 70 캜 for 2 hours, and the resistance was measured by applying 500 V. The reference value shall not be destroyed above 10 ⁹ .mm.

(23) Temperature humidity cycling: Examples 1 to 3 and Comparative Examples 1 to 4 were wound on a standard round bar and repeated 40 times at -40 ° C and 80% relative humidity. After confirming whether or not they lasted for 1 minute at 1000V, Fail.

(24) Crosslinking degree (%): In Examples 1 to 3 and Comparative Examples 1 to 4, 0.1 g of the insulator sample was taken as a balance, put into a test tube, and xylene was added. This was heated in a thermostatic chamber at 120 DEG C for 24 hours, and then the sample was taken out, dried for 6 hours in a 100 DEG C drier, taken out, cooled to room temperature, and the mass was measured. The gel fraction was determined as a percentage of the mass before the test, .

With reference to the results of Table 2, it was confirmed that TPV (a material in which a fully crosslinked EPDM is finely dispersed in a PP base) in the case of Comparative Examples 1 and 2 was used to measure two degrees of crosslinking degree and heat resistance And the amount of the flame retardant for ensuring the flame retardancy was increased, and the elongation and the elongation after aging were low. It was also found that Comparative Examples 3 and 4, which were out of the range of the melt index of the polypropylene resin (A1) of the present invention, had a low flame retardancy. In Comparative Examples 3 and 4, the measured values of the degree of crosslinking and the heat resistance 2 were superior to those of Comparative Examples 1 and 2 using partially crosslinked Ma-g-EPDM. However, in order to ensure flame retardancy, , And the elongation and the elongation after aging were poor.

In Examples 1 to 3, a polypropylene type block copolymer having a melt index of 0.5 g / 10 min was used and flame retardancy according to ISO standards was passed. Compared with Comparative Examples 1 to 4, low temperature characteristics, elongation characteristics, And other mechanical properties. It was also confirmed that the electrical characteristics were excellent. In addition, using the partially crosslinked Ma-g-EPDM, the cross-linking degree was about 70%, and the heat resistance 2 (JASO D618) was evaluated only for the XLPE wire.

Thus, it can be seen that the flame retardant coating composition according to the present invention is suitable for a 125 ° C electric wire capable of realizing the characteristics of a crosslinked electric wire without conducting electron beam crosslinking or chemical crosslinking.

Claims (14)

(A) a base resin; (B) a flame retardant; And (C) an antioxidant,
The base resin (A) comprises (A1) 35 to 65% by weight of a polypropylene resin, (A2) 25 to 45% by weight of a thermoplastic elastomer, and (A3) 10 to 35% by weight of a coupling agent,
The polypropylene resin (A1) has a melt index of 0.1 g / 10 min to 2.5 g / 10 min (ASTM D1238, 190 DEG C, 2.16 kg measurement standard)
The thermoplastic elastomer (A2) is characterized by comprising an ethylene-propylene-diene (EPDM) elastomer and a maleic anhydride grafted ethylene-propylene-diene (Ma-g-EPDM) elastomer in a weight ratio of 1: 0.1 to 1: By weight.
The polypropylene resin composition according to claim 1, wherein the polypropylene resin (A1) is a polypropylene terpolymer resin composed of ethylene-propylene-alpha olefin, a polypropylene block copolymer resin composed of ethylene-propylene and a polypropylene Random copolymer resin. ≪ RTI ID = 0.0 > 11. < / RTI >
The flame-retardant coating composition according to claim 1, wherein the thermoplastic elastomer (A2) has a glass transition temperature (Tg) of -35 캜 or less.
The flame-retardant coating composition according to claim 1, wherein the thermoplastic elastomer (A2) is partially crosslinked.
delete The flame-retardant coating composition according to claim 1, wherein the coupling agent (A3) comprises a polypropylene copolymer resin grafted with at least one of maleic anhydride and phthalic anhydride.
The flame-retardant coating composition according to claim 1, which comprises 50 to 110 parts by weight of the flame retardant (B) and 0.1 to 15 parts by weight of the antioxidant (C), based on 100 parts by weight of the base resin (A).
The method of claim 1, wherein the flame retardant (B) comprises one or more of magnesium hydroxide (Mg (OH) _2), aluminum hydroxide (Al (OH) ₃₎ and calcium hydroxide (Ca (OH) _2),
The flame retardant (B) is surface-treated with at least one of a silicone-based coupling agent, a titanate-based coupling agent, a fatty acid, a metal hydroxide, an amine and a metal salt of an amine.
The flame-retardant coating composition according to claim 1, wherein the antioxidant (C) comprises at least one of phenolic compounds, phosphorous compounds, sulfur compounds, amine compounds and metal antioxidants.
The flame-retardant coating composition according to claim 1, further comprising 0.1 to 15 parts by weight of a flame-retardant auxiliary (D) and 0.1 to 10 parts by weight of a lubricant (E), based on 100 parts by weight of the base resin (A).
The method of claim 10, wherein the flame retardant auxiliary (D) comprises at least one of antimony trioxide, zinc oxide (ZnO), tin oxide (SnO), zinc borate, and zinc stearate,
Wherein the lubricant (E) comprises at least one of fluorine, silicon, amide, zinc and fatty acid lubricants.
An insulator made from the flame retardant coating composition of any one of claims 1 to 4, 6 to 11.
An electric wire comprising the insulator of claim 12.
A cable comprising the insulator of claim 12.

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