KR101542110B1 - Flame-retardant resin composition for extrusion, insulater prepared using the same, and electrical wire and cable thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a high temperature water-resistant flame retardant resin composition for extrusion, an insulator produced using the same, and electric wires and cables containing the same. In one embodiment, 100 parts by weight of the base resin (A), 80 to 160 parts by weight of the flame retardant (B) and 1 to 10 parts by weight of the antioxidant (C) 40 to 70% by weight of a thermoplastic elastomer (A2) and 5 to 25% by weight of a compatibilizer (A3), wherein the thermoplastic elastomer (A2) comprises a polypropylene-based elastomer and a styrene-ethylene- (SEBS) elastomer in a weight ratio of 1: 2 to 1: 5, and the compatibilizer (A3) comprises a polyolefin-based copolymer resin in which at least one of maleic anhydride and phthalic anhydride is grafted, Wherein the flame retardant (B) comprises at least one of (B1) phosphorus flame retardant, (B3) nitrogen flame retardant and (B4) phosphorus nitrogen flame retardant, wherein the phosphorus flame retardant (B1) and the phosphorus nitrogen flame retardant (B4) Silicon-based coupling agents including vinyl silane, titanate-based coupling agents, Fatty acid, metal hydrate, amine or its metal salt, and the higher fatty acid is stearic acid, oleic acid, palmitic acid, behenic acid or a combination thereof.

Description

FIELD OF THE INVENTION The present invention relates to a high temperature water-resistant flame retardant resin composition for extrusion, an insulator manufactured using the same, and electric wires and cables containing the same. BACKGROUND ART [0002]

TECHNICAL FIELD The present invention relates to a high temperature water-resistant flame retardant resin composition for extrusion, an insulator produced using the same, and electric wires and cables containing the same. More particularly, the present invention relates to a high-temperature water-resistant flame-retardant resin composition for extrusion which is environment-friendly and excellent in flame retardance and mechanical properties without halogen components, an insulator manufactured using the same, and electric wires and cables containing the same.

PVC (polyvinyl chloride) has excellent flame retardance and tensile properties, and is excellent in economical efficiency and widely used in automobile and appliance wires. Generally, phthalate plasticizers will be included in the production of wires containing PVC resin. Recently, due to environmental problems, phthalate plasticizers and PVC hazards, the use of PVC is gradually decreased And the development of a resin capable of coping with the physical properties of PVC resin is required.

In addition, these PVCs are produced by using antimony trioxide (Sb ₂ O ₃ ) together as a flame retardant adjuvant, but in the case of such wires containing antimony trioxide, toxic gases including carcinogenic substances are generated during combustion Use is regulated.

In this regard, Korean Patent Laid-Open Publication No. 2005-0038307 discloses a method for forming a sheath and a cable excellent in thermal stability and flame retardancy, including PVC resin, phosphorus-based flame retardant plasticizer, bromine- However, there is a problem that harmful substances are generated in the PVC resin, the phthalate plasticizer and the antimony trioxide contained in the composition when the sheath and the cable are burned.

On the other hand, additives such as base resins, flame retardants and plasticizers are very important for replacing PVC having self-flame resistance and securing excellent economic efficiency, flame retardancy and tensile properties.

Recently, polyolefin (Poly olefin) has been used as a substitute for such PVC, but there has been a great difficulty in securing flame retardancy because there is no self-extinguishing property.

Examples of the flame retardant that can be added to impart flame retardancy to the polyolefin base resin include halogen flame retardants, phosphorus flame retardants, and inorganic flame retardants (metal hydroxides). Br (bromine) and Cl (chlorine) are used as flame retardants in the case of the above-mentioned F because the binding force of F (fluorine), Br (bromine), Cl (chlorine) and I It is very strong and does not generate radicals, and I is not suitable as a flame retardant used at high temperature because it is easily decomposed even at a low temperature because of its weak binding force. As a result, Br and Cl are mainly used as flame retardants, and bromine flame retardants having excellent cost effectiveness are mainly used. Such a halogen-based flame retardant has an advantage of obtaining a sufficient flame retardant effect even when a very small amount of the halogen-based flame retardant is added as compared with an inorganic material, and thus it is widely used in electric and electronic products requiring an impact resistance. Despite its many advantages, however, its use is regulated because of its environmentally harmful properties.

Phosphorous flame retardants are the most noticeable flame retardants as the regulations on the use of halogen flame retardants are getting into full swing. Representative mechanism is the formation of expansion char (Char). It is a highly effective flame retardant which extinguishes by burning up and blocking oxygen. However, it has poor thermal stability and compatibility with resins, and is particularly poor in high temperature water resistance, so that it may absorb moisture upon exposure to water vapor and precipitate on the wire surface.

The most commonly used inorganic flame retardants are aluminum hydroxide and magnesium hydroxide. The two flame retardants are the main mechanism of flame retardant, which is the cooling effect that is absorbed by the endothermic process during the process of releasing water during decomposition. In addition, although metal hydroxide flame retardants are environmentally friendly, they must be used in a considerably large amount to obtain high-grade flame retardants such as UL-V0, which can adversely affect high impact strength, especially electrical properties, in the final product. have.

Particularly, when a high flame retardancy property such as a VW-1 test pass is required, which is one of the most severe flame-retardant test, a flame retardant content of 30 wt% or more and more preferably 50 wt% or more is added to the base resin, There is a problem that it is affected.

Accordingly, the present inventors have repeatedly conducted studies to obtain a flame retardant and other mechanical properties of PVC by using a phosphorous-based flame retardant which can obtain a dramatic effect with a minimum amount of input. In addition, The present invention has been completed based on this finding.

An object of the present invention is to provide a high temperature water-resistant flame retardant resin composition for extrusion which is environmentally friendly, has excellent flame retardancy, mechanical strength and high temperature water resistance.

Another object of the present invention is to provide a high temperature water-resistant flame retardant resin composition for extrusion which is excellent in appearance, extrudability, workability and economy, and can prevent surface stickiness.

It is still another object of the present invention to provide an insulator produced by using the high temperature water-resistant flame retardant resin composition for extrusion.

It is still another object of the present invention to provide a method of manufacturing an electric wire and a cable including the insulator.

One aspect of the present invention relates to a high temperature water-resistant flame retardant resin composition for extrusion. In one embodiment, the high temperature water-resistant flame retardant resin composition for extrusion comprises 100 parts by weight of the base resin (A), 80 to 160 parts by weight of the flame retardant (B) and 1 to 10 parts by weight of the antioxidant (C) Wherein the resin comprises 15 to 40% by weight of the polyolefin resin (A1), 40 to 70% by weight of the thermoplastic elastomer (A2) and 5 to 25% by weight of the compatibilizer (A3), wherein the thermoplastic elastomer (A2) And a styrene-ethylene-butylene-styrene (SEBS) elastomer in a weight ratio of 1: 2 to 1: 5, wherein the compatibilizing agent (A3) is at least one of maleic anhydride and phthalic anhydride Wherein the flame retardant (B) comprises at least one of (B1) a phosphorus flame retardant, (B3) a nitrogen flame retardant, and (B4) a phosphorus-nitrogen flame retardant, The phosphorus-nitrogen-based flame retardant (B4) Based coupling agents, titanate-based coupling agent, a higher fatty acid, a metal hydrate, an amine or a metal salt thereof as would a coating, the higher fatty acid is characterized in that stearic acid, oleic acid, palmitic acid, behenic acid, or a combination thereof.

In one embodiment, the polyolefin-based resin (A1) has a melt index (MI) of 2.0 to 4.5 g / 10 min, a tensile strength of 2.5 to 3.8 kgf / mm 2, and a melting point (Tm) of 150 to 180 ° C A first polypropylene resin; (A12) a second polypropylene resin having a melt index of 1.0 to 1.5 g / 10 min, a tensile strength of 4.0 to 8.0 kgf / mm 2 and a melting point (Tm) of 160 to 200 캜; And (A13) a third polypropylene resin having a melt index of 0.1 to 0.8 g / 10 min, a tensile strength of 1.0 to 2.3 kgf / mm 2 and a melting point (Tm) of 140 ° C to 180 ° C; And the like.

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In one embodiment, the graft ratio of the compatibilizing agent (A3) is 0.5 to 15% by weight.

In one embodiment, the antioxidant (C) comprises at least one of phenol, phosphorus, sulfur, amine and metal.

In one embodiment, the lubricant further comprises 0.1 to 8 parts by weight of the lubricant (D) and 0.1 to 8 parts by weight of the flame-retardant auxiliary (E) per 100 parts by weight of the base resin (A).

In one embodiment, the lubricant (D) comprises at least one of a fluorine-based, silicone-based, amide-based, zinc-based and fatty acid-based lubricant. (SnO), zinc borate, and zinc stearate.

In one embodiment, the composition further comprises 0.5 to 30 parts by weight of paraffinic oil (F) per 100 parts by weight of the base resin (A).

Another aspect of the present invention relates to an insulator comprising the composition.

Another aspect of the present invention relates to a wire including the insulator.

Another aspect of the present invention relates to a cable comprising the insulator.

The insulator including the high-temperature water-resistant flame retardant resin composition for extrusion according to the present invention is environmentally friendly because it does not emit pollutants during combustion, has excellent mechanical strength and high temperature water resistance, is excellent in appearance, extrudability, workability and economy, It is possible to achieve a high flame retardancy of UL 758 and 1581 as VW-1 grade and to prevent surface stickiness by minimizing the use of oil during extrusion. In addition, Residual rate and tensile residual rate), and the electric wire and cable including the insulator including the high temperature water-resistant flame retardant resin composition for extrusion can be used for automobile, electronic equipment and construction.

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 high temperature water-resistant flame retardant resin composition for extrusion. In one embodiment, the high temperature water-resistant flame retardant resin composition for extrusion comprises (A) a base resin, (B) a flame retardant and (C) an antioxidant, Wherein the thermoplastic elastomer (A2) comprises at least one of a polyethylene-based, a polypropylene-based and a styrene-based elastomer; and the compatibilizer (A3) is at least one selected from the group consisting of maleic anhydride (B1) phosphorus flame retardant, (B2) metal hydroxide flame retardant, (B3) nitrogen flame retardant, and (B3) at least one of maleic anhydride and phthalic anhydride. Wherein the phosphorus flame retardant (B1), the metal hydroxide flame retardant (B2) and the phosphorus nitrogen flame retardant (B4) are at least one of phosphorus-based flame retardant (B4) A titanate-based coupling agent, a higher fatty acid, a metal hydrate, an amine or a metal salt thereof.

Hereinafter, the high temperature water-resistant flame retardant resin composition for extrusion according to the present invention will be described in detail.

(A) Base resin

The base resin (A) may include (A1) a polyolefin resin, (A2) a thermoplastic elastomer, and (A3) a compatibilizer.

(A1) polyolefin resin

The polyolefin-based resin (A1) may be included in the present invention to replace the conventional polyvinyl chloride (PVC) resin to secure eco-friendliness while securing economy and hardness due to heat resistance and low specific gravity.

Examples of the polyolefin resin (A1) used in the present invention include ethylene vinyl acetate (EVA), ethylene methacrylate (EMA), polyethylene (PE), and polypropylene Propylene) may be used.

In one embodiment, polypropylene can be used as the polyolefin-based resin (A1). The polypropylene is a widely used general-purpose resin and it is economical and has a high melting point (Tm) of about 160 ° C and has high heat resistance in the state of not being crosslinked, and thus has suitable characteristics as a wire material.

At this time, the polypropylene may be used alone, or a mixture of two or more polypropylene having different melt index may be used. In one embodiment, the melt index (MI) is from 2.0 to 4.5 g / 10 min (ASTM D1238, 230 DEG C, 2.16 kg measurement standard), the tensile strength is 2.5 to 3.8 kgf / mm < 2 >, the elongation is 400 to 550% (Tm) of 150 占 폚 to 180 占 폚; (A12), a melt index of 1.0 to 1.5 g / 10 min (ASTM D1238, 230 DEG C, 2.16 kg measurement standard), a tensile strength of 4.0 to 8.0 kgf / A second polypropylene resin; (A13) a melt index of 0.1 to 0.8 g / 10 min (ASTM D1238, 230 DEG C, 2.16 kg measurement standard), a tensile strength of 1.0 to 2.3 kgf / A third polypropylene resin; Etc. may be used. These may be used singly or in combination of two or more, but are not limited thereto. When the polyolefin-based resin (A1) of the above-mentioned type is applied, it is excellent in heat resistance and tensile strength, and is excellent in moldability, and may be preferable in terms of balance.

The polyolefin resin (A1) may be contained in an amount of 10 to 50% by weight based on the total weight of the base resin (A). Preferably 10 to 40% by weight. More preferably 15 to 30% by weight. When the content is within the above range, excellent heat resistance and tensile strength can be obtained, and moldability can be excellent.

(A2) Thermoplastic elastomer

The thermoplastic elastomer (A2) may be included to improve the toughness, impact resistance and low-temperature characteristics of the base resin (A) and to improve the flexibility of the present invention by controlling the hardness of the polyolefin-based resin (A1).

The thermoplastic elastomer (A2) may include at least one of a polyethylene-based elastomer, a polypropylene-based elastomer, and a styrene-based elastomer. In one embodiment, a polypropylene based elastomer having a propylene group introduced therein and a styrene-ethylene-butylene-styrene (SEBS) elastomer can be mixed and used. When the thermoplastic elastomer (A2) of the above type is used, it is excellent in compatibility with the polyolefin-based resin (A1), and flexibility can be imparted to the present invention. The polypropylene-based elastomer may be an ethylene-propylene (EP) elastomer based on polypropylene.

The polypropylene-based ethylene-propylene (EP) elastomer is a product prepared by introducing ethylene into polypropylene and adjusting its hardness. The polypropylene-based elastomer is added to the polyolefin-based resin (A1) Flexibility can be imparted.

In an embodiment, the polypropylene-based elastomer may have a melt index of 1.4 to 2.0 g / 10 min (ASTM D1238, 230 ° C, 2.16 kg measurement standard) and a Shore A hardness of 40 to 70.

The SEBS is included for the purpose of improving the impact strength and toughness of the polyolefin resin (A1), and the SEBS has a chemical structure similar to that of the polyolefin resin (A1) such as the polypropylene resin, And the disadvantage of the polyolefin-based resin (A1) can be improved without deteriorating the physical properties. In addition, the addition of the SEBS causes a phenomenon that the flame retardant (B) easily breaks when the flame retardant (B) is high in the present invention, and this phenomenon can be prevented by increasing the impact strength.

In an embodiment, the SEBS may have a melt index of 0.5 to 1.3 g / 10 min (ASTM D1238, 230 ° C, 2.16 kg measurement standard) and a Shore A hardness of 40 to 70.

In one embodiment, the thermoplastic elastomer (A2) may comprise a polypropylene-based elastomer and a styrene-ethylene-butylene-styrene (SEBS) elastomer in a weight ratio of 1: 2 to 1: 5. More specifically, the polypropylene-based ethylene-propylene (EP) elastomer and the styrene-ethylene-butylene-styrene (SEBS) elastomer may be contained at a weight ratio of 1: 2 to 1: 5. Preferably in a weight ratio of 1: 2 to 1: 3.5. Within the above range, compatibility, flexibility and impact resistance can be excellent without deteriorating the physical properties such as heat resistance of the present invention.

The thermoplastic elastomer (A2) may be contained in an amount of 10 to 80% by weight based on the total weight of the base resin (A). Preferably 10 to 70% by weight. More preferably from 30 to 65% by weight. When included in the above range, compatibility, flexibility and impact resistance can be excellent without deteriorating physical properties such as heat resistance of the present invention.

(A3) compatibilizer

The compatibilizer (A3) may be included for the purpose of ensuring compatibility between the base resin (A) and the flame retardant (B). In one embodiment, the compatibilizer (A3) may be a polyolefin-based copolymer resin obtained by grafting at least one of maleic anhydride and phthalic anhydride.

As the polyolefin-based copolymer resin, ethylene vinyl acetate (EVA), polyethylene-based and polypropine-based copolymer resins can be used. These may be used singly or in combination of two or more, but are not limited thereto.

When the compatibilizer (A3) is included in the base resin (A), the flame retardant (B) may be chemically bonded to prevent deterioration of physical properties due to the injection of the flame retardant (B).

In one embodiment, the grafting rate of the compatibilizing agent (A3) may be 0.5 to 15% by weight. More specifically, as the compatibilizing agent (A3), at least one of a polypropylene resin having a graft ratio of maleic anhydride of 0.5 to 15 wt% and SEBS having a graft ratio of maleic anhydride of 0.5 to 15 wt% may be used. 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 compatibilizer (A3) may be contained in an amount of 5 to 40% by weight based on the total weight of the base resin (A). Preferably 10 to 20% by weight. More preferably from 10 to 15% by weight. When included in the above range, it is excellent in compatibility with the polyolefin resin (A1), the thermoplastic elastomer (A2) and the flame retardant (B) without lowering the mechanical strength such as rigidity and impact resistance of the present invention, May be possible.

(B) Flame retardant

The flame retardant (B) may be included for the purpose of preventing decomposition of raw materials during processing of the present invention, securing flame retardancy (vertical flame retardancy) and improving high temperature water resistance. In one embodiment, the flame retardant (B) may include at least one of (B1) phosphorus flame retardant, (B2) metal hydroxide flame retardant, (B3) nitrogen flame retardant and (B4) phosphorus-nitrogen flame retardant.

When the flame retardant (B) of the above type is applied, it is excellent in flame retardancy and high temperature water resistance, and does not contain antimony and halogen components, so that it can be environmentally friendly without generating harmful components in burning.

Examples of the phosphorus flame retardant (B1) include triphenyl phosphate, trialkylphenyl phosphate, tricrecylphosphate, propylated triphenylphosphate, butylated triphenylphosphate butylated triphenyl phosphate, triethylphosphate, tributyl phosphate, resorcinoldiphosphate, bisphenoldiphosphate, dimethyl methyl phosphonate, polyphosphate ester ( polyethyleneterephthalate, polyphosphate ester, oligomeric organophosphate, ethylpyrocardecolphosphate, dipyrrocadecol biphosphate, polyethylene ethyleneoxy phosphate, methylneopentylphosphate, pentaerythritol diethyl One or more of pentaeritritoldiethylphosphate, pentaeritritoldiphenylphosphate, methylneopentylphosphonate, dicyclopentyldiphosphate and dineopentylbiphosphate may be used. have.

As the metal hydroxide-based flame retardant (B2), at least one selected from magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₃ ) and calcium hydroxide (Ca (OH) ₂ )

The nitrogen-based flame retardant (B3) may include at least one of melamine, melamine cyanurate and triphenylisocyanurate. In addition, the nitrogen-based flame retardant (B3) is relatively inexpensive and can be economically superior.

The phosphorus-based flame retardant (B4) may include at least one of melamine phosphate, melamine pyrophosphate, ammonium polyphosphate and alkylamine phosphate.

The phosphorus flame retardant (B1), the metal hydroxide flame retardant (B2), and the phosphorus nitrogen flame retardant (B4) may be selected from the group consisting of metal hydrates (metal hydroxides), silicone coupling agents including vinylsilane, titanate coupling agents, , An amine or a metal salt thereof. As the metal hydrate, Mg (OH) ₂ , Al (OH) ₃ and Ca (OH) ₂ may be used. As the higher fatty acid, stearic acid, oleic acid, palmitic acid and behenic acid may be used. It does not.

The surface-coated metal hydroxide-based flame retardant (B2) may have a particle size of 0.01 탆 to 2 탆 and a specific surface area of 5 mm 2 / g to 100 mm 2 / g. Preferably, the particle size is from 0.1 탆 to 1 탆, and the specific surface area is from 5 mm 2 / g to 50 mm 2 / g. More preferably, the particle size may be 0.3 탆 to 0.8 탆 and the specific surface area may be 15 mm 2 / g to 30 mm 2 / g. Can be evenly dispersed in the base resin (A) and other components while lengthening the effect duration in the above range.

As described above, since the coating is excellent in high temperature water resistance and hygroscopicity, it is possible to prevent deterioration of the properties of compounds and electric wires. Particularly, it is excellent in compatibility with the base resin (A) in the production of wires including the coated flame retardant (B), and the phenomenon that the flame retardant (B) precipitates on the surface of the wire even when exposed to water vapor at 85 캜 for 7 days Can be prevented.

In one embodiment, a phosphorus-nitrogen type flame retardant (B4) coated with a metal hydrate may be used as the flame retardant (B).

In another embodiment, the metal hydroxide flame retardant (B2) and the coated phosphorus-nitrogen flame retardant (B4) may be mixed with the flame retardant (B) at a weight ratio of 1: 0.5 to 1: 3. When applied as described above, the synergistic effect between the flame retardant components is excellent, and the flame retardant effect can be more excellent.

In one embodiment, the flame retardant (B) may be contained in an amount of 80 to 160 parts by weight based on 100 parts by weight of the base resin (A). And preferably 100 to 150 parts by weight. More preferably 100 to 130 parts by weight. When the content is included in the above amount, the flame retardant effect of the present invention can be sufficiently realized, and excellent high temperature water resistance and hygroscopicity can be obtained, and mechanical property deterioration due to excessive addition can be prevented. When the flame retardant (B) is contained in an amount less than 80 parts by weight, the flame retardancy is lowered. When the flame retardant (B) is contained in an amount of more than 160 parts by weight, the electrical properties of the electric wire deteriorate and the mechanical properties such as tensile strength and elongation .

(C) Antioxidant

In the present invention, the antioxidant (C) prevents degradation of the composition of the present invention and improves heat resistance, thereby delaying the aging of wires and cables manufactured according to the present invention in a high temperature environment.

In the present invention, the antioxidant (C) may be selected from phenol, phosphorus, amine, sulfur and metal.

Examples of the phenolic antioxidants include sterically hindered phenolic stabilizers such as alkylated monophenols, polyphenols or alkylation products of dienes and polyphenols, but are not limited thereto. Do not.

For example, 2,6-di-tetra-butyl-4-methylphenol, octadecyl-3- (3,5-di- -Bis (4'-hydroxy-3'-t-butylphenyl) butanoic acid) glycol ester and tetrabis (methylene-3- ) Methane and 1,2-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamoyl) hydrazine ), But the present invention is not limited thereto.

As the phosphorus antioxidant, phosphorus ester compounds, aromatic phosphine compounds, and the like may be used, but the present invention is not limited thereto.

As the amine antioxidant, N, N'-di-2-naphthyl-p-phenylenediamine and the like can be used, but the present invention is not limited thereto.

Examples of the sulfur-containing antioxidant include diaryl 3,3-thiodipropionate, diamylmethyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thioiodipropionate, pentaerythritol-tetrakis- (beta -lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) 8,10-tetraoxaspiro [5,5] undecane, and the like, but the present invention is not limited thereto.

As the metal-based antioxidant, nickel N, N-dibutyldithiocarbamate and the like can be used, but the present invention is not limited thereto.

In one embodiment, the antioxidant (C) may be used in a weight ratio of phenol-based and sulfur-based antioxidant of 1: 0.5 to 1: 2. In the above range, synergistic effects are exhibited with excellent compatibility with the composition of the present invention, so that the operation for extrusion or injection is easy, and the effect of preventing aging, deterioration and decomposition of the polymer can be greatly increased.

In one embodiment, the antioxidant (C) may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base resin (A). Preferably 1.5 to 8 parts by weight. More preferably 1.5 to 5 parts by weight. When the antioxidant (C) is contained in an amount of less than 1 part by weight, the heat resistance is lowered to cause deterioration of the product, If it exceeds 10 parts by weight, the physical properties of the present invention may deteriorate.

Further, in the present invention, 0.1 to 8 parts by weight of the lubricant (D) and 0.1 to 8 parts by weight of the flame-retardant auxiliary (E) may be further added to 100 parts by weight of the base resin (A).

(D) a lubricant

The lubricant (D) may be included for the purpose of improving the fluidity and processability of the composition of the present invention. As the lubricant (D) in the present invention, a conventional lubricant may be used. For example, fluorine-based, silicone-based, amide-based, zinc-based and fatty acid-based lubricants can be used. These may be used singly or in combination of two or more, but are not limited thereto.

The lubricant (D) may be included in an amount of 0.1 to 8 parts by weight based on 100 parts by weight of the base resin (A). Preferably 0.1 to 5 parts by weight. Within the above range, the workability can be excellent without impairing the physical properties of the present invention.

(E) Flame Retarding Agent

The flame-retardant auxiliary (E) may be included in the present invention for the purpose of preventing the deterioration of the mechanical properties and heat resistance of the coating together with the improvement of the flame retardancy. In one embodiment, the flame retardant auxiliary (E) may be at least one selected from the group consisting of silicone gum, zinc oxide (ZnO), tin oxide (SnO), zinc borate and zinc stearate.

The flame-retardant auxiliary (E) may be included in an amount of 0.1 to 8 parts by weight based on 100 parts by weight of the base resin (A). Preferably 0.1 to 5 parts by weight. The flame retardant effect can be expected within the above range, and the mechanical properties and heat resistance of the coating can be prevented from deteriorating.

In the present invention, 0.5 to 30 parts by weight of (F) paraffinic oil may be further added to 100 parts by weight of the base resin (A).

(F) Paraffinic oil

The paraffinic oil (F) may be included for the purpose of improving the mixing workability by improving the softness and fluidity of the high temperature water-resistant flame retardant resin composition for extrusion. The paraffinic oils may be those having a paraffin content of 50 wt% or more for good compatibility and thermal stability.

In one embodiment, the paraffinic oil (F) may be included in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the base resin (A). Preferably 15 to 30 parts by weight. In the above range, the moldability and workability are excellent, and the surface stickiness of the wire according to the present invention can be prevented.

Further, the high temperature water-resistant flame retardant resin composition for extrusion of the present invention may further contain the (G) additive within a range not affecting the characteristics of the present invention.

In one embodiment, the additive (G) may comprise at least one of an anti-drip agent and a surface modifier.

The anti-drip agent may be included in the flame retardant test to prevent the insulator made of the composition from melting. For example, it is possible to use a copolymer of triglycidyl isocyanurate, an epoxidized novolac resin, and a copolymer of tetrafluoroethylene, tetrafluoroethylene and hexafluoropropylene, fluorocarbon resin of tetrafluoroethylene and perfluoro Fluoro-based resins such as polyvinylidene fluoride, polyvinylidene fluoride, and the like.

The surface modifier may be included for the purpose of enhancing the scratch resistance during the production of the insulator according to the present invention and improving the appearance by smoothing the surface. In one embodiment, the surface modifier may include a silicone rubber compound. More specifically, the silicone rubber compound may be polydimethylsiloxane (PDMS, poly (dimethyl siloxane)), but is not particularly limited, and the silicone rubber compound may be a silicone rubber compound containing the polydimethylsiloxane, silicone oil, It can also be used as a master batch.

In one embodiment, the additive (G) may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the base resin (A). Preferably 0.5 to 5 parts by weight. Within the above range, the flame retardancy, high-temperature water resistance, and physical properties of the present invention can be improved without deteriorating appearance, workability and scratch resistance.

Another aspect of the present invention relates to an insulator comprising the high temperature water-resistant flame retardant resin composition for extrusion. The insulator does not contain a halogen component and an antimony component, and is environmentally friendly because no harmful components are generated at the time of combustion. The insulator has excellent mechanical properties such as a residual heat ratio (elongation percentage and tensile residual rate) and is VW-1 rated according to UL 758, It has vertical flame retardancy and excellent in high temperature water resistance. There is no substance to be deposited on the surface even when exposed to water vapor at 85 ° C for 7 days, and addition of oil component is minimized, thereby preventing sticky surface of the insulator.

In the present invention, the thickness of the insulator can be changed according to the thickness of the internal conductor line. For example, the thickness of the insulator may be 0.05 mm to 5 mm, but is not limited thereto.

Another aspect of the present invention relates to electric wires and cables comprising the insulator. In one embodiment, the total outer diameter of the wires and cables may be between 1.0 mm and 40 mm, but is not limited thereto.

The electric wires and cables can be used for automobiles, electronic devices, architectural use, and the like.

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 2 and Comparative Examples 1 to 6

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A) Base resin

(A1) polyolefin resin

(A11) A resin having high transparency and having a melt index of 4.0 g / 10 min (ASTM D1238, 230 DEG C, 2.16 kg measurement standard), a tensile strength of 2.7 kgf / Propylene resin was used. (A12) A second polypropylene resin having a melt index of 1.0 g / 10 min, a tensile strength of 4 kgf / mm 2, an elongation of 500% and a Tm of 150 캜 or more was used as the highly crystalline resin. (A13) A third polypropylene resin having a melt index of 0.8 g / 10 min, a tensile strength of 1 kgf / mm 2, an elongation of 500% and a Tm of 140 캜 or higher was used.

(A2) Thermoplastic elastomer

(A21) A polypropylene-based elastomer having a melt index of 1.5 g / 10 min (ASTM D1238, 230 DEG C, 2.16 kg measurement basis) and Shore A 66 was used. (A22) Melt index: 1.0 g / 10 min Styrene-ethylene-butylene-styrene (SEBS) elastomer having hardness -Shore A 65 was used as the measurement standard (ASTM D1238, 230 DEG C,

(A3) compatibilizer

(A31) A polypropylene resin having a graft ratio of maleic anhydride of 0.5% to 15% was used. (A32) SEBS elastomer having a graft ratio of maleic anhydride of 0.5% to 15% was used.

(B) Flame retardant

(B11) phosphorus-nitrogen flame retardant coated with a metal hydrate was used.

(B12) surface-coated phosphorus-nitrogen flame retardant. (B21) Vinylsilane coated Mg (OH) ₂ was used. (B22) Mg (OH) ₂ which is not surface-coated was used (B3) melamine cyanurate was used.

(C) Antioxidant

(C1) Phenol-based antioxidant AO-60 (pentaetritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) ) Dodecylthiourea of ADEKA manufactured by ADEKA under the trade name of AO-412 (2,2-bis [(3- (dodecylthio) -1-oxopropoxy) methyl] propane- (C3) A phenol-based metal antioxidant (1024 FG) manufactured by SONGWON Co., Ltd. was used.

(D) Lubricant: TR 016 from STRUKTOL was used.

(E) Flame retardant aid: silicone gum was used.

(F) paraffinic oil was used.

(G) Additive

(G1) Polytetrafluoroethylene (PTFE) was used as an anti-drip agent.

(G2) A silicon master batch (M / B) containing polydimethylsiloxane (PDMS) as a surface modifier was used.

The above Examples 1 to 3 and Comparative Examples 1 to 6 were kneaded using a kneader and a roll mill in accordance with the components and contents of the following Table 1 and then kneaded at 150 ° C for 1 minute using a single extruder. After the extrusion, the extrudate was cooled and pelletized. The pelletized primary extrudate was secondarily extruded using a wire extruder, and the pellet was secondarily extruded to a thickness of 0.3 mm in thickness to prepare an insulator having an outer diameter of 1.6 mm.

Example Comparative Example One 2 3 One 2 3 4 5 6 (A) Base resin (A11) 25 25 - 20 25 - 20 - 20 (A12) - - - - - 25 - 25 - (A13) - - 25 - - - - - - (A21) 15 15 15 20 25 20 20 20 20 (A21) 50 50 50 45 50 45 50 45 50 (A31) 10 - 5 15 - - - 10 10 (A32) - 10 5 - - 10 10 - - (B) Flame retardant (B11) 100 70 70 - - 100 40 180 70 (B12) - - - 100 80 - - - - (B21) - 30 - - - - - - 20 (B22) - - - - 20 - - - (B3) - - 30 - - - - - 10 (C) Antioxidant (C1) One 0.5 One One One 5 One One 3 (C2) - One One - - 3 - - 3 (C3) 0.5 0.5 One 0.5 0.5 5 0.5 0.5 3 (D) a lubricant One One One One One One One One One (E) Flame Retarding Agent 2 2 2 2 2 2 2 2 2 (F) Paraffinic oil 25 25 25 - 25 25 - - - (G) Additive (G1) - - One One - - One One One (G2) 2 2 2 One 2 2 One One One

(Unit: parts by weight)

Experimental Example 1

The properties of the above Examples 1 to 3 and Comparative Examples 1 to 6 were evaluated according to the following evaluation criteria and are shown in Table 2 below.

(1) Flame retardancy: Evaluated based on whether or not VW-1 has a vertical flame retardancy defined in accordance with UL 758 standard. Specifically, after arranging the insulators of Examples 1 to 3 and Comparative Examples 1 to 6 vertically, the flame was applied five times for 15 seconds every 15 seconds with a predetermined vertical flame in the lower portion. When the burning length of the insulator after the application of the flame was 600 mm or less, it was judged to be?, And when it was exceeded, it was judged to be X.

(2) Tensile strength (kgf / mm < 2 >) and elongation (%): Each of the specimens of Examples 1 to 3 and Comparative Examples 1 to 6 was taken at 150 mm each, Then, the insulator is vertically stretched at a speed of 500 mm / min using a material tester (tensile and elongation measurement tester). The elongation length is measured on the basis of the above-mentioned gauge, converted to% of the gauge 20 mm, and the elongation is measured. The tensile load at the point where the insulator is broken is divided by the sectional area of the insulator. When the measured tensile strength was 0.563 kgf / mm < 2 > or more, it was judged to be X when the measured tensile strength was 0.563 kgf / mm < 2 >, and when the elongation was measured to be 200%

(3) Heat resistance (tensile residual rate (%) and residual percentage of elongation (%)): Each of the specimens of Examples 1 to 3 and Comparative Examples 1 to 6 was taken at 150 mm each, and 20 mm marker was taken. The insulator is then aged for 180 seconds at a temperature of 168 占 폚 (heat resistance 1), 200 占 폚 X 168h (heat resistance 2) and 232 占 폚 X 168h (heat resistance 3). The sample is vertically stretched at a speed of 500 mm / min using a material tester (tensile and elongation rate measuring tester). The elongation length was measured on the basis of the gauge, converted to% of the gauge 20 mm, and the elongation was measured and compared with the room temperature elongation. The tensile load at the point where the insulator is broken is divided by the cross-sectional area of the insulator, and the tensile strength is calculated and then compared with the tensile strength at room temperature. In the case of the tensile residual rate, X was determined to be 75% or more of the room temperature property, and X was determined to be 75% or less.

(4) Evaluation of High Temperature Water Resistance (High Temperature Moisture Resistance): The above Examples 1 to 3 and Comparative Examples 1 to 6 were aged for one week at a temperature of 85 占 폚 and a humidity of 90%. In the case where the flammability agent contained in the above Examples and Comparative Examples is highly hygroscopic, the flammable agent may be transferred to the surface to cause a blooming phenomenon that forms white spots or protrusions on the surface, and the flammable agent may melt due to humidity and become sticky , And the state of the surface of the insulator of the examples and comparative examples was observed. When no abnormality was found, it was judged as?, When the surface of the insulator was sticky or when the flame retardant component was precipitated on the surface.

Example Comparative Example One 2 3 One 2 3 4 5 6 Flammability ○ ○ ○ ○ X ○ X ○ ○ The tensile strength ○ ○ ○ ○ ○ X X X X Elongation ○ ○ ○ ○ ○ X X X X Heat resistance Tensile Residue ○ ○ ○ X X X X X X Renal survival rate ○ ○ ○ X ○ X X X X High temperature water resistance ○ ○ ○ X X ○ X ○ ○

The results are shown in Table 2. Referring to Table 2, Examples 1 to 3 of the present invention have excellent physical properties such as tensile strength, heat resistance, low temperature, insulation, and flame retardancy of the produced insulators. However, It was found that the flame retardant component was precipitated on the surface of the insulator, the flame retardancy was lowered, and the physical properties such as tensile strength, elongation and heat resistance were lowered.

Claims (12)

100 parts by weight of the base resin (A), 80 to 160 parts by weight of the flame retardant (B) and 1 to 10 parts by weight of the antioxidant (C)
Wherein the base resin (A) comprises 15 to 40% by weight of the polyolefin resin (A1), 40 to 70% by weight of the thermoplastic elastomer (A2) and 5 to 25% by weight of the compatibilizer (A3)
The thermoplastic elastomer (A2) comprises a polypropylene-based elastomer and a styrene-ethylene-butylene-styrene (SEBS) elastomer in a weight ratio of 1: 2 to 1: 5,
The compatibilizing agent (A3) may be selected from the group consisting of maleic anhydride and
Phthalic acid anhydride, and at least one grafted polyolefin-based copolymer resin,
The flame retardant (B) comprises at least one of (B1) a phosphorus flame retardant, (B3) a nitrogen-based flame retardant, and (B4)
The phosphorus flame retardant (B1) and phosphorus-nitrogen flame retardant (B4) are coated with a silicon-based coupling agent including vinyl silane, a titanate-based coupling agent, a higher fatty acid, a metal hydrate, an amine or a metal salt thereof,
Wherein the higher fatty acid is stearic acid, oleic acid, palmitic acid, behenic acid, or a combination thereof.
delete The polyolefin resin (A1) according to claim 1, wherein the polyolefin resin (A1)
(A11) a first polypropylene resin having a melting point (MI) of 2.0 to 4.5 g / 10 min, a tensile strength of 2.5 to 3.8 kgf / mm 2 and a melting point (Tm) of 150 ° C to 180 ° C;
(A12) a second polypropylene resin having a melt index of 1.0 to 1.5 g / 10 min, a tensile strength of 4.0 to 8.0 kgf / mm 2 and a melting point (Tm) of 160 to 200 캜; And
(A13) a third polypropylene resin having a melt index of 0.1 to 0.8 g / 10 min, a tensile strength of 1.0 to 2.3 kgf / mm 2 and a melting point (Tm) of 140 to 180 캜; Wherein the flame retardant resin composition contains at least one of the following components.
delete The flame-retardant resin composition according to claim 1, wherein the graft ratio of the compatibilizing agent (A3) is 0.5 to 15% by weight.
The flame-retardant resin composition according to claim 1, wherein the antioxidant (C) comprises at least one of phenol, phosphorus, sulfur, amine and metal.
The flame-retardant resin composition according to claim 1, further comprising 0.1 to 8 parts by weight of the lubricant (D) and 0.1 to 8 parts by weight of the flame-retardant auxiliary (E) per 100 parts by weight of the base resin (A).
The lubricant (D) according to claim 7, wherein the lubricant (D) comprises at least one of fluorine, silicon, amide,
Wherein the flame retardant auxiliary (E) comprises at least one of silicone gum, zinc oxide (ZnO), tin oxide (SnO), zinc borate and zinc stearate.
The flame-retardant resin composition according to claim 1, further comprising (F) 0.5 to 30 parts by weight of a paraffinic oil based on 100 parts by weight of the base resin (A).
An insulator made from the flame retardant resin composition of any one of claims 1, 3, and 9 to 9.
An electric wire comprising the insulator of claim 10.
A cable characterized by comprising the insulator of claim 10.