KR101837498B1 - Halogen-Free Flame Retarding Resin Composition Having Improved Leading-in and Insulated Electric Wire Using the same - Google Patents

Abstract

The present invention relates to a halogen-free flame-retardant resin composition having improved drawability, and more particularly, to an insulation wire using the halogen-free flame retardant resin composition. More particularly, the present invention relates to an halogen-free flame retardant resin composition having improved flame retardancy and mechanical properties, Free halogen-free flame retardant resin composition and an insulated wire using the halogen-free flame retardant resin composition.
The halogen-free flame-retardant resin composition of the present invention having improved drawability includes a base resin comprising a polyethylene resin and a polyolefin-based elastomer, a non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide, wherein the polyolefin- And a second polyolefin elastomer having a melt index of 3.0 to 4.0 g / 10 min is mixed with the first polyolefin elastomer having a melt index of 1.0 to 2.0 g / 10 min, as a copolymer of? -Olefin having a? .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant resin composition having improved lead-in properties and an insulated wire using the halogen-

The present invention relates to a halogen-free flame-retardant resin composition having improved drawability, and more particularly, to an insulation wire using the halogen-free flame retardant resin composition. More particularly, the present invention relates to an halogen-free flame retardant resin composition having improved flame retardancy and mechanical properties, Free halogen-free flame retardant resin composition and an insulated wire using the halogen-free flame retardant resin composition.

Electric wires used for general electrical work or electrical equipment wiring, indoor wiring, etc., have excellent heat resistance, flame retardancy, water resistance, chemical resistance, insulation, cold resistance and oil resistance .

In addition, the wires for indoor wiring such as electric lamps, electric heaters, etc. are installed in a way that they are drawn out from certain points such as a ceiling, a wall, and a floor, In this case, the electric wire drawn into the ceiling, the wall, and the floor is transported through a conduit made of a material such as PVC, which protects the electric wire and guides the electric wire until it is drawn.

The wires conveyed through the conduit may be difficult to transport when exhibiting excessive flexibility or stiffness and may be difficult to transfer due to friction with the inner wall of the conduit or with other incoming wires, It may be more difficult to transport it if it is transported through a conduit in a bent area according to the structure of a building, a ceiling of a facility, a wall, and a floor.

Therefore, the wire has flexibility and rigidity suitable for transportation and minimizes the friction between the wire and the inner wall of the conduit or another wire to be fed together, so that the surface friction coefficient of the insulating layer constituting the wire is improved It needs to be low enough. In addition, in order to improve the durability of the electric wire, there is a case where the surface of the electric wire is coated with lubricating oil or the like and the installation work is carried out. In this case, the insulating layer constituting the electric wire should have improved oil resistance against lubricating oil and the like.

Polyvinyl chloride has been widely used for electric wires because of its excellent flame retardancy and tensile properties. However, since phthalate plasticizer is included in recent years, development of a resin replacing polyvinyl chloride has been demanded due to recent human hazard. In addition, halogen-free flame retardant products that are safe and do not use heavy metal compounds such as lead, cadmium, and hexavalent chromium and are environmentally friendly with less environmental pollution are required.

Korean Unexamined Patent Publication No. 2014-0122998 discloses a non-halogen flame-retarded insulated wire having a conductor and an insulating layer covering the conductor, wherein the insulating layer comprises 40 to 65 parts by mass of high-density polyethylene having a melt flow rate of 0.60 or less, 25 to 30 parts by mass of an ethylene-based resin, 10 to 30 parts by mass of an ethylene-based elastomer, and 10 to 30 parts by mass of a styrene-based elastomer, wherein a polyphenylene ether- Halogen-free flame-retardant insulated wire comprising a crosslinked product of a resin composition containing 6 to 25 parts by mass of a polyfunctional monomer and 1 to 10 parts by mass of a polyfunctional monomer ", Korean Patent Publication No. 2004-0098415 discloses" 50 to 200 parts by weight of a metal hydroxide-based inorganic flame retardant based on 100 parts by weight of a matrix resin having a blend ratio of ethylene copolymer resin of 2: 8 to 8: 2; 0.5 to 20 parts by weight of an antioxidant and 0.1 to 3.0 parts by weight of a phenolic metal deactivator are disclosed.

Recently, such polyvinyl chloride has been replaced by other resins such as polyolefin. However, since it has no self-extinguishing property, it is difficult to secure flame retardancy. When a flame retardant is used for ensuring flame retardancy, the coefficient of friction is high. There is a problem with poor lead-in when inserting the wire.

As a result, the inventors of the present invention have found that the flame retardant resin composition used for electric wires is composed of a base resin including a polyethylene resin and a polyolefinic elastomer, a non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide When the base resin is composed of a polyethylene resin and a polyolefin-based elastomer and their melt index is limited to a specific range, the flame retardancy is excellent, the flexibility is excellent, the friction coefficient is low, It was confirmed that the wire could be manufactured, and the present invention was completed.

An object of the present invention is to provide a halogen-free flame-retardant crosslinked insulated electric wire having a low coefficient of friction and excellent drawability and excellent flexibility and mechanical properties, and a halogen-free flame retardant resin composition for the production thereof.

In order to achieve the above object, the present invention provides a polyolefin elastomer composition comprising a base resin comprising a polyethylene resin and a polyolefinic elastomer, a non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide, olefin is a mixture of a first polyolefin elastomer having a melt index of 1.0 to 2.0 g / 10 min and a second polyolefin elastomer having a melt index of 3.0 to 4.0 g / 10 min. Thereby providing an improved halogen-free flame-retardant resin composition.

In the present invention, the polyethylene resin may be a low-density polyethylene having a melt index of 1.0 to 3.0 g / 10 min, or a low-density polyethylene and a high-density polyethylene having a melt index of 0.1 to 2.0 g / 10 min.

In the present invention, the non-halogen flame retardant is a metal hydroxide surface-treated with silane.

In the present invention, the crosslinking agent may be at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, vinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, vinyldibromosilane, At least one silane-based cross-linking agent selected from the group consisting of butoxy silane; Dicumyl peroxide, benzoyl peroxide, lauryl peroxide, t-butyl cumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2,5- Hexane, and di-t-butyl peroxide; Or from the group consisting of triallyl isocyanurate, trimethallyl isocyanurate, triacryloformate, triallyl trimellurate, tris (diallylamine) -S-triazine and trimethylolpropane trimethacrylate And is at least one triolefin-based crosslinking agent selected.

In the present invention, when the cross-linking agent is a silane-based cross-linking agent, t-butylcumylperoxide, dicumylperoxide, methylethylketoneperoxide, 2,5-dimethyl-2,5-di (t- At least one crosslinking auxiliary selected from the group consisting of hexane, di-t-butyl peroxide, t-butyl peroxybenzoate and?,? -Bis (t-butylperoxyisopropyl) .

In the present invention, when the cross-linking agent is a silane cross-linking agent, dibutyltin dilaurate, dibutyl dimaleate, dibutyltin acetate, dibutyltin octoate, tin octoate, tin acetate, lead naphthenate, zinc At least one cross-linking catalyst selected from the group consisting of octoate, titanium ester, tetrabutyl titanate, ethylamine, hexylamine and piperidine.

In the present invention, the metal stearate is at least one selected from the group consisting of magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, lithium stearate, sodium stearate and barium stearate.

In the present invention, the fatty acid amide is at least one selected from the group consisting of laurin amide, palmitamide, stearoamide, behenamide, 12-hydroxystearoamide, oleamide and erucamide .

In the present invention, the halogen-free flame retardant resin composition further comprises at least one additive selected from the group consisting of a silicone oil, an antioxidant, a UV stabilizer, a foaming agent, a processing stabilizer, a pigment and a filler.

In the present invention, the halogen-free flame retardant resin composition preferably contains 100 to 300 parts by weight of a non-halogen flame retardant, 100 to 300 parts by weight of a crosslinking agent 0.1 to 10 parts by weight, metal stearate 0.1 to 10 parts by weight, and fatty acid amide 0.1 to 10 parts by weight.

In the present invention, the halogen-free flame retardant resin composition further comprises a polyolefin-based copolymer grafted with maleic anhydride.

The present invention also provides an insulated electric wire, which is manufactured from the halogen-free flame retardant resin composition having improved drawability.

The wires and cables produced from the halogen-free flame retardant resin composition according to the present invention have not only excellent flame retardancy, but also excellent flexibility, low friction coefficient and excellent mechanical properties.

In the present invention, the flame retardant resin composition used in the wire is composed of a base resin comprising a polyethylene resin and a polyolefinic elastomer, a non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide, wherein the base resin is a polyethylene resin And a polyolefin-based elastomer, it is possible to produce an insulated wire which is excellent in flame retardancy, excellent in flexibility, low in friction coefficient, and excellent in mechanical properties.

(A) a polyolefin elastomer obtained by mixing a first polyolefin elastomer having a melt index of 1.0 to 2.0 g / 10 min and a second polyolefin elastomer having a melt index of 3.0 to 4.0 g / 10 min, and (b) ) Low density polyethylene having a melt index of 1.0 to 3.0 g / 10 minutes may be used alone or in combination with high density polyethylene having a melt index of 0.1 to 2.0 g / 10 minutes. A non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide The mixture was melt kneaded and extruded to prepare a test specimen which can be used as a sheath for electric wires, and the properties of the specimen were evaluated. As a result, it was confirmed that the coefficient of friction was low, the extrusion appearance and the hot set characteristics were excellent, and the pulling performance was improved.

Therefore, the present invention, in one aspect, comprises a base resin comprising a polyethylene resin and a polyolefin-based elastomer, a non-halogen flame retardant, a crosslinking agent, a metal stearate and a fatty acid amide, wherein the polyolefin- Olefin copolymer having a melt index of 1.0 to 2.0 g / 10 min and a second polyolefin-based elastomer having a melt index of 3.0 to 4.0 g / 10 min, wherein the first polyolefin elastomer and the second polyolefin elastomer have a melt index Free flame retardant resin composition.

The polyolefin-based elastomer may be a copolymer of ethylene and an? -Olefin having 3 or more carbon atoms for facilitating thermal crosslinking performed during extrusion and promoting mechanical strength and crosslinking reaction, more specifically ethylene Propylene-1-butene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene- Propylene-1-octene copolymer rubber, an ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, an ethylene-propylene-dicyclopentadiene copolymer rubber, an ethylene- 1,4-hexadiene copolymer rubber and ethylene-propylene-5-vinyl-2-norbornene copolymer rubber may be used alone or in combination.

In the present invention, the polyolefin-based elastomer has a melt index of 1.0 to 2.0 g / 10 min measured at 190 占 폚 and 2.16 kg according to ASTM D1238 and a first polyolefin elastomer measured at 190 占 폚 and 2.16 kg according to ASTM D1238 And a second polyolefin elastomer having a melt index of 3.0 to 4.0 g / 10 min. The mixture may be mixed at a weight ratio of 4: 6 to 6: 4. In this range, It is possible to provide a composition having excellent flowability and mechanical properties.

In the present invention, the polyethylene resin is used as a matrix resin, and when combined with the polyolefin-based elastomer and other components, it can impart sufficient flame retardancy and fluidity. The polyethylene resin may be any one or more selected from linear low density polyethylene, low density polyethylene, medium density polyethylene and high density polyethylene, preferably low density polyethylene alone or a mixture of low density polyethylene and high density polyethylene.

More preferably, the low-density polyethylene having a melt index of 1.0 to 3.0 g / 10 min measured at 190 占 폚 and 2.16 kg according to ASTM D1238, or a low-density polyethylene having a melt index measured at 190 占 폚 and 2.16 kg according to ASTM D1238 of 0.1 To 2.0 g / 10 min. The mixing ratio may be a mixture of low density polyethylene 3 to 7: high density polyethylene 7 to 3 weight ratio.

In the present invention, the content of the polyethylene resin and the polyolefin-based elastomer is not limited. However, in order to further improve the object of the present invention, the content of the polyethylene resin and the polyolefin- 60% by weight is preferably used.

In the present invention, the non-halogen flame retardant is used for imparting flame retardancy, and it is preferable to use a metal hydroxide surface-treated with silane. Specifically, aluminum hydroxide, aluminum trioxide, magnesium hydroxide, magnesium oxide Hydroxides, hydrates, calcium hydroxides and calcium oxide hydrates may be used, which have been surface-treated with vinyl silane. When the metal hydroxide is surface-treated with vinylsilane, the vinylsilane is hydrolyzed and attached by chemical bonding to the surface of the metal hydroxide by the condensation reaction, and the silane group reacts with the base resin to secure excellent dispersibility Do. The content of the non-halogen flame retardant is preferably 100 to 300 parts by weight based on 100 parts by weight of the base resin.

In the present invention, the crosslinking agent may be a silane crosslinking agent, an organic peroxide crosslinking agent, or a triolefin crosslinking agent depending on the crosslinking method such as water flow method, chemical crosslinking method and electron beam irradiation crosslinking method. Vinyltriethoxysilane, vinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, vinyldibromosilane, vinyltri n butoxysilane, and the like can be exemplified, and examples thereof include vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, The organic peroxide crosslinking agent is selected from the group consisting of dicumyl peroxide, benzoyl peroxide, lauryl peroxide, t-butyl cumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2,5-dimethyl- t-butylperoxy) hexane, and di-t-butyl peroxide. The triolefin-based crosslinking agent may be triallyl isocyanurate, trimethallyl isocyanurate, Acrylic formate, triallyl trimellitic acrylate, tris (diallylamine) -S- triazine, trimethylolpropane trimethacrylate and the like can be mentioned Methacrylate, but the embodiment is not limited thereto.

The amount of the crosslinking agent is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the base resin in order to prevent scratching due to crosslinking during extrusion.

When the cross-linking agent is a silane-based cross-linking agent such as vinyltrimethoxysilane, the base resin may react with the cross-linking agent to graft vinyl silane and may be crosslinked by exposure to moisture or moisture in the presence of a cross-linking catalyst.

Therefore, when the cross-linking agent is a silane-based cross-linking agent, a cross-linking catalyst and a cross-linking aid may be further added to facilitate cross-linking.

Wherein the crosslinking catalyst is selected from the group consisting of dibutyltin dilaurate, dibutyl dimaleate, dibutyl tin acetate, dibutyl tin octoate, tin octoate, tin acetate, lead naphthenate, zinc octoate, titanium ester, tetrabutyl titanate , Ethylamine, hexylamine, piperidine and the like, but are not limited thereto. The content of the crosslinking catalyst is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the base resin.

The above-mentioned crosslinking aid is intended to facilitate the bonding of the silane crosslinking agent and the base resin, and it is preferable to use a crosslinking agent such as t-butyl cumyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl- (Peroxy) hexane, di-t-butyl peroxide, t-butyl peroxybenzoate, and?,? - bis (t-butylperoxyisopropyl) benzene. The content of the crosslinking aid is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the base resin.

In the present invention, the metal stearate and the fatty acid amide are used for lowering the frictional coefficient to improve the pull-in property of the wire, and by using them, the coefficient of friction can be further lowered, and the extruded appearance and hot set characteristics can be improved .

Examples of the metal stearate include, but are not limited to, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, lithium stearate, sodium stearate and barium stearate. The content of the metal stearate is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the base resin.

In the present invention, the fatty acid amide may be exemplified by laurin amide, palmitamide, stearoamide, behenamide, 12-hydroxystearoamide, oleamide, erucamide and the like. The content of the fatty acid amide is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the base resin.

The halogen-free flame retardant resin composition according to the present invention may further contain additives such as a silicone oil, an antioxidant, a UV stabilizer, a filler, a blowing agent, a processing stabilizer, and a pigment as necessary. The content of each of the additives is preferably within a range that does not impair the flame retardancy while achieving the desired physical properties, and may be selected from 0.01 to 5 parts by weight based on 100 parts by weight of the base resin have.

The silicone oil is used for suppressing aggregation of the composition and improving water resistance. Examples of the silicone oil include dimethylsilicone oil in which both the side chain and the terminal of the polysiloxane are methyl groups, methylphenyl silicone oil in which part of the side chain of the polysiloxane is phenyl group, Methylhydrogen silicone oil and the like, and copolymers thereof, and examples thereof include amine-modified, epoxy-modified, alicyclic epoxy-modified, carboxyl-modified, carbinol Modified silicone oil modified with phenol-modified or aralkyl-modified silicone oil, which is modified with a higher fatty acid amide, a silanol-modified, diol-modified, phenol-modified or aralkyl-modified silicone oil May be used.

The antioxidant is used for preventing decomposition during processing and improving the heat resistance to retard aging in a high temperature environment, and one or more selected from the group consisting of phenol, phosphorus, amine, sulfur and metal can be used. The phenolic antioxidants may be sterically hindered phenolic stabilizers, for example, 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, tetrabis (methylene-3- (3,5- Bis (3,5-di-t-butyl-4-hydroxyhydrocinnamoyl) hydrazine (1,2- hydrazine, 4,4'-thiobis (2-t-butyl-5-methylphenol), 2,2'-thiodiethylbis- [3- (3,5- Hydroxyphenyl) propionate], pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 4,4'-thiobis (6-t-butyl-4-methylphenol), triethylene glycol-bis- [3- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 6,6 Butyl-2,2'-thiodi-p-cresol, 1,3,5-tris (4-t- butyl-3-hydroxy-2,6-xylyl) methyl- 3,5,6-triazine-2,4,6- (1H, 3H, 5H) -thione and dioctadecyl 3,3'-thiodipropionate can be used.

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.

The UV stabilizer is used to prevent oxidation by UV. The UV stabilizer may be 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, , 5'-methylenebis (2-hydroxy-4-methoxybenzophenone), and other 2-hydroxybenzophenones; Di (tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4- -Hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole; 2- (2'-hydroxyphenyl) benzotriazoles such as benzotriazole; Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; Cyanoacrylates such as ethyl- alpha -cyano-beta, beta -diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; Di (tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) Phenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -s-triazine, and the like, but the present invention is not limited thereto.

Examples of the filler include, but are not limited to, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite for preventing aging, reinforcing, and increasing the amount of the filler.

The halogen-free flame-retardant resin composition according to the present invention is a polyolefin-based copolymer grafted with maleic anhydride, if necessary, in order to ensure compatibility between the base resin and the non-halogen flame retardant and to further improve properties such as flow- May be further included. Specific examples of the polyolefin-based copolymer include ethylene vinyl acetate (EVA), polyethylene-based and polypropine-based copolymer resins, and the like. These may be used singly or in combination of two or more, but are not limited thereto. The graft ratio may be 0.1 to 15% by weight, and specifically may be a polypropylene resin having a graft ratio of maleic anhydride of 0.1 to 15% by weight. The content of the polyolefin-based copolymer grafted with maleic anhydride may be in the range of 0.1 to 15 parts by weight based on 100 parts by weight of the base resin, but is not limited thereto.

The halogen-free flame retardant resin composition according to the present invention satisfies the physical properties with a friction coefficient of 0.6CoF or less according to ASTM 1894, and therefore has a low coefficient of friction in the production of electric wires and is excellent in drawability and excellent in flexibility and mechanical properties. Wires can be provided.

Accordingly, the present invention relates to an insulated wire which is manufactured from a halogen-free flame retardant resin composition having improved drawability from a different viewpoint.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The following physical properties were measured as follows.

(1) Tensile strength / elongation: measured at a tensile speed of 200 mm / min in accordance with IEC 60811-501

(2) Properties after heating: According to IEC 60811-401, the dumbbell specimens were allowed to stand at 135 ° C for 168 hours, and then the changes in tensile strength and elongation were measured

(3) HOT SET: Hot (20 N / cm ² , 15 min) / Set (0 N / cm ² ) by applying a load of 20 N / cm ² at 200 ° C according to the method of IEC 60811-507, 5 min) to evaluate the crosslinking properties. That is, the extruded specimens were allowed to stand for 4 hours in water at 80 ° C, and the elongation length and shrinkage length were measured at 200 ° C with and without load, and the degree of crosslinking with time was compared. That is, it is an increased percentage of the specimen left standing at 80 ° C in water for 4 hours under the hot condition (elongated length) / (length of the original specimen) × 100, and the set is set at the temperature without being subjected to the load (reduced length) / (Original length) × 100, which indicates the degree of crosslinking at room temperature

(4) Extrudability: When extruded using an extruder, the appearance is smooth and the degree of goodness is evaluated

(5) Coefficient of friction: Measured according to ASTM 1894

(6) Melt index (base resin): measured at 190 占 폚 and 2.16 kg according to ASTM D1238

(7) Pattern viscosity: measured according to ASTM D 1646 ML1 + 4 140 ° C

(8) Oxygen index: measured according to ASTM D 2863

(9) Hardness: Measured according to ASTM D 2240.

[Example 1]

Ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF810) 20 having a density of 0.921 g / cm ³ and a melt index of 2.0 g / 10 min and having a melt index of 1.2 g / 10 min and containing 50% by weight of low density polyethylene (LG Chem, LUTENE CB2030) 150 parts by weight of silane-coated magnesium hydroxide (Kyowa, Kisuma 5P) was added to 100 parts by weight of a base resin mixed with an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF840) , 0.5 part by weight of a phenolic antioxidant (Ciba, IR-1035), 0.5 part by weight of a thiophenol antioxidant (chemchura, TBM 6), 0.5 part by weight of a UV stabilizer (Ciba 0.3 part by weight of a metal antioxidant (Ciba, MD-1024), 0.2 part by weight of magnesium stearate, 0.3 part by weight of erucamide (AKZO NOBEL, Armoslip E), 0.5 part by weight of vinyltrimethoxysilane Momentive, A171) and 0.5 part by weight of dicumyl peroxide were mixed and kneaded in a 3 l / batch kneader [DISPERSION KNEA DER, FINE MACHINERY INDUSTRY CO., LTD.) At 190 DEG C for 20 minutes to prepare a compound composition.

Thereafter, 98.2% by weight of the compound composition and 1.8% by weight of dibutyltin dilaurate as a crosslinking catalyst were injected into an extruder (EXTRUDER, Fine Machinery Co., Ltd., Korea) having a diameter of 50 mm. The hopper was melted and kneaded at a temperature of 150 占 폚, a temperature of the cylinder 1 of 155 占 폚, a temperature of the cylinder 2 of 160 占 폚 and a die of 165 占 폚, extruded using a T-die (T-DIE) The test specimens were prepared as sheath for electric wire. The physical properties of the specimen were measured and the results are shown in Table 1.

[Example 2]

Density polyethylene having a density of 0.921 g / cm ³ and a melt index of 2.0 g / 10 min, a density of 0.945 g / cm ³ and a melt index of 0.27 g / 10 min (low-density polyethylene (LG Chem, LUTENE® CB2030) Olefin copolymer (Mitsuichem, DF810) having a melt index of 3.6 g / 10 min and a melt index of 1.2 g / 10 min, And 30 wt% of an elastomer (Mitsuichem, DF840) were mixed and used. The properties of the prepared specimens were measured and the results are shown in Table 1.

[Example 3]

A linear low density polyethylene filament graft copolymer (Dupont, LLDPE-g (trade name)) obtained by grafting maleic anhydride having a melt index of 1.5 g / 10 min and an MA content of 1.0 wt% based on 100 parts by weight of the base resin in Example 1 -MA, Fusabond E588) was further used in place of 10 parts by weight. The properties of the prepared specimens were measured and the results are shown in Table 1.

[Example 4]

In Example 2, a linear low density polyethylene filament graft copolymer (Dupont, LLDPE-g, manufactured by Dupont Co., Ltd.) in which maleic anhydride having a melt index of 1.5 g / 10 min and an MA content of 1.0 wt% -MA, Fusabond E588) were further used in place of 10 parts by weight of the above-mentioned mixture. The properties of the prepared specimens were measured and the results are shown in Table 1.

[Example 5]

As a base resin, the density 0.921g / cm ^3, melt index 2.0g / 10 minutes density polyethylene (LG Chemical, LUTENE® CB2030) 20% by weight, density 0.965g / cm ^3, melt index 1.0g / 10 min High-density polyethylene (SK 20 wt% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF810) having a melt index of 1.2 g / 10 min and a melt index of 3.6 g / 10 min .; ethylene-alpha-olefin copolymer A specimen was prepared in the same manner as in Example 1 except that 30 wt% of coalesced elastomer (Mitsuichem, DF840) was used. The physical properties of the prepared specimens were measured and the results are shown in Table 2.

[Example 6]

As a base resin, the density 0.921g / cm ^3, melt index 2.0g / 10 minutes density polyethylene (LG Chemical, LUTENE® CB2030) 20% by weight, density 0.956g / cm ^3, melt index 2.0g / 10 min High-density polyethylene (SK Olefin copolymer elastomer (Mitsuichem, DF810) having a melt index of 1.2 g / 10 min and a melt index of 3.6 g / 10 min, A specimen was prepared in the same manner as in Example 1, except that 30 wt% of a copolymer elastomer (Mitsuichem, DF840) was used. The physical properties of the prepared specimens were measured and the results are shown in Table 2.

[Example 7]

Ethylene-alpha-olefin copolymer elastomer (Mitsuichem, Japan) having a density of 0.923 g / cm ³ , a melting point of 1.0 g / 10 min and a melt index of 1.2 g / 10 min as a base resin, containing 50% by weight of low density polyethylene (LG Chem, Seetec BF315) Except that 30 wt% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF840) having a melt index of 3.6 g / 10 min was used in place of the ethylene / alpha-olefin copolymer elastomer (DF810) . The physical properties of the prepared specimens were measured and the results are shown in Table 2.

[Example 8]

Ethylene-alpha-olefin copolymer elastomer (Mitsuichem, Japan) having a density of 0.921 g / cm ³ , a melting point of 3.0 g / 10 min and a melt index of 1.2 g / 10 min as a base resin, 50% by weight of low density polyethylene (LG Chem, Seetec BF500) Except that 30 wt% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF840) having a melt index of 3.6 g / 10 min was used in place of the ethylene / alpha-olefin copolymer elastomer (DF810) . The physical properties of the prepared specimens were measured and the results are shown in Table 2.

Properties Example 1 Example 2 Example 3 Example 4 Room temperature Tensile Strength (MPa) 17.3 16.7 17.5 17.8 Elongation (%) 160 160 170 175 After heating
(135 DEG C, 168 hrs) Tensile Residue (%) 110.1 111.9 115.1 114.1 Renal survival rate (%) 91.1 92.2 90.4 91.3 Hot set
(HOT SET) Hot (%) 70.0 75.0 70.0 70.0 Set (%) 7.0 8.0 7.0 7.0 Extrusion evaluation Discharge amount (g / min) 43.2 50.2 47.4 52.0 Long-term extrudability (minute) More than 40 minutes More than 40 minutes More than 40 minutes More than 40 minutes Coefficient of friction
ASTM 1894 CoF 0.49 0.42 0.45 0.39 Pattern viscosity ML1 + 4 140 C 40.4 50.2 45.2 52.2 Oxygen index % 33.0 33.0 32.0 33.0 Hardness Shore A 98 98 98 98 Shore D 54 56 55 56

As shown in Table 1, the specimens prepared from the halogen-free flame-retardant resin compositions of Examples 1 to 4 exhibited a room temperature elongation of not less than 125%, a tensile remainder after heating and an elongation percentage of 60 to 140% HOT 100% or less, SET 15% or less, long-term extrudability 40 min or more, and coefficient of friction (ASTM 1984) 0.6CoF or less.

Properties Example 5 Example 6 Example 7 Example 8 Room temperature Tensile Strength (MPa) 16.4 16 17.6 17 Elongation (%) 165 170 167 160 After heating
(135 DEG C, 168 hrs) Tensile Residue (%) 111.8 113.5 114.1 110.1 Renal survival rate (%) 91.6 89.1 90.2 91.2 Hot set
(HOT SET) Hot (%) 80.0 90.0 60.0 90.0 Set (%) 10.0 12.5 5.0 10.0 Extrusion evaluation Discharge amount (g / min) 52.0 55.0 42.1 44.5 Long-term extrudability (minute) More than 40 minutes More than 40 minutes More than 40 minutes More than 40 minutes Coefficient of friction
ASTM 1894 CoF 0.45 0.46 0.5 0.49 Pattern viscosity ML1 + 4 140 C 48.0 45.2 45.3 37.1 Oxygen index % 33.0 33.0 33.0 33.0 Hardness Shore A 98 98 98 98 Shore D 56 56 54 54

As shown in Table 2, the specimens prepared from the halogen-free flame-retardant resin compositions of Examples 5 to 8 exhibited a room temperature elongation of not less than 125%, a tensile residual rate after heating and an elongation percentage of 60 to 140% HOT 100% or less, SET 15% or less, long-term extrudability 40 min or more, and coefficient of friction (ASTM 1984) 0.6CoF or less.

[Comparative Example 1]

A specimen was prepared in the same manner as in Example 1 except that magnesium-stearate was not used in Example 1, and physical properties were measured.

[Comparative Example 2]

Specimens were prepared in the same manner as in Example 1 except that the erucamide was not used in Example 1, and the physical properties were measured.

[Comparative Example 3]

In Example 1, specimens were prepared in the same manner as in Example 1 except that magnesium-stearate and erucamide were not used, and the physical properties of the specimens were measured.

[Comparative Example 4]

In the same manner as in Example 1, except that magnesium-stearate and erucamide were not used and 1.0 part by weight of polyolefin wax (Excerex 30050B) was added to 100 parts by weight of base resin in Example 1, And the physical properties thereof were measured. The results are shown in Table 3.

[Comparative Example 5]

Ethylene-alpha-olefin copolymer elastomer (Mitsuichem Co., Ltd.) having a melt index of 1.2 g / 10 min and a density of 0.921 g / cm ³ and a melt index of 2.0 g / 10 min as a base resin, 50 wt.% Low density polyethylene (LG Chem, LUTENE CB2030) DF810) was used in place of 50% by weight of a polypropylene resin, and the properties were measured.

[Comparative Example 6]

Ethylene-alpha-olefin copolymer elastomer (Mitsuichem, Japan) having a density of 0.921 g / cm ³ and a melt index of 2.0 g / 10 min as a base resin and containing 50% by weight of low density polyethylene (LG Chem, LUTENE CB2030) and a melt index of 3.6 g / DF840) in an amount of 50% by weight based on the total weight of the composition, and the properties of the specimens were measured in the same manner as in Example 1,

Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Room temperature Tensile Strength (MPa) 17.1 18.5 15.1 18.0 19.1 14.1 Elongation (%) 156 154 170 166 120 170 After heating
(135 DEG C, 168 hrs) Tensile Residue (%) 109.1 109.1 112.3 110.5 70.3 107.7 Renal survival rate (%) 90.1 94.1 95.8 92.1 60.1 94.4 Hot set
(HOT SET) Hot (%) 80.0 60.0 50.0 70.0 30.0 120.0 Set (%) 10.0 5.0 5.0 7.0 0.0 15.0 Extrusion evaluation Discharge amount (g / min) 40.1 46.2 40.0 39.5 40.3 43.2 Long-term extrudability (minute) More than 40 minutes More than 40 minutes More than 40 minutes More than 40 minutes 10 minutes More than 40 minutes Coefficient of friction
ASTM 1894 CoF 0.70 0.79 0.90 0.85 0.53 0.56 Pattern viscosity ML1 + 4 140 C 42.1 44.3 46.8 36.0 60.4 35.2 Oxygen index % 33.0 34.0 32.0 32.5 33.0 32.0 Hardness Shore A 98 98 98 98 98 98 Shore D 54 54 54 54 54 54

As shown in Table 3, Comparative Example 1 in which no metal stearate was used, Comparative Example 2 in which no fatty acid amide was used, Comparative Example 3 in which metal stearate and fatty acid amide were not used, and metal stearate and fatty acid amide Comparative Example 4 in which polyolefin wax was used and Comparative Example 5 in which the coefficient of friction (ASTM 1984) was more than 0.6CoF and the polyolefin elastomer was not mixed and used one by one was used at room temperature Elongation and long-term extrudability were lower than the standards, and Comparative Example 6 was found to have poor hot set characteristics.

[Comparative Example 7]

A specimen was prepared in the same manner as in Example 1 except that 100 weight% of low density polyethylene (LG Chem, LUTENE CB2030) having a density of 0.921 g / cm ³ and a melt index of 2.0 g / 10 min was used as the base resin. The results are shown in Table 4.

[Comparative Example 8]

Alpha-olefin copolymer elastomer (Mitsuichem Co., Ltd.) having a density of 0.921 g / cm ³ , a melting point of 0.4 g / 10 min and a melt index of 1.2 g / 10 min as low-density polyethylene (LG Chem, Lutene bf0300) Except that 30 wt% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF840) having a melt index of 3.6 g / 10 min was used in an amount of 20 wt% Respectively. The properties of the prepared specimens were measured and the results are shown in Table 4.

[Comparative Example 9]

An ethylene-alpha-olefin copolymer elastomer (Mitsuichem Co., Ltd.) having a melt index of 1.2 g / 10 minutes and 50% by weight of low density polyethylene (LG Chem, Seetec BF511) having a density of 0.924 g / cm ³ and a melt index of 4.0 g / Except that 30 wt% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF840) having a melt index of 3.6 g / 10 min was used in an amount of 20 wt% Respectively. The properties of the prepared specimens were measured and the results are shown in Table 4.

[Comparative Example 10]

(Polyethylene terephthalate) having a density of 0.921 g / cm ³ and a melting point of 2.0 g / 10 min as a base resin, 20 wt% of low density polyethylene (LG Chem, LUTENE CB2030), a density of 0.961 g / cm ³ and a melt index of 5.5 g / 20 weight% of an ethylene-alpha-olefin copolymer elastomer (Mitsuichem, DF810) having a melt index of 1.2 g / 10 min and a melt index of 3.6 g / 10 min .; an ethylene-alpha-olefin A specimen was prepared in the same manner as in Example 1, except that 30 wt% of a copolymer elastomer (Mitsuichem, DF840) was used. The properties of the prepared specimens were measured and the results are shown in Table 4.

[Comparative Example 11]

As a base resin, the density 0.921g / cm ^3, melt index 2.0g / 10 minutes density polyethylene (LG Chemical, LUTENE® CB2030) 20% by weight, density 0.954g / cm ^3, a melt index 0.075g / 10 min High-density polyethylene (SK Olefin copolymer (Mitsuichem Co., DF810) having a melt index of 1.2 g / 10 min and a melt index of 3.6 g / 10 min, which comprises 30% by weight of ethylene-alpha-olefin copolymer elastomer A test piece was prepared in the same manner as in Example 1, except that 30 wt% of an elastomer (Mitsuichem, DF840) was used. The properties of the prepared specimens were measured and the results are shown in Table 4.

Properties Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Room temperature Tensile Strength (MPa) 10.2 14.3 13.2 15.5 10.1 Elongation (%) 54 102 190 185 70 After heating
(135 DEG C, 168 hrs) Tensile Residue (%) 20.0 70.3 109.1 130.2 109.1 Renal survival rate (%) 20.1 60.1 90.1 95.1 90.1 Hot set
(HOT SET) Hot (%) Broken 30.0 Broken 150.0 Broken Set (%) Broken 2.5 Broken 30.0 Broken Extrusion evaluation Discharge amount (g / min) 40.1 40.1 30.1 34.1 40.1 Long-term extrudability (minute) More than 40 minutes 5 minutes More than 40 minutes More than 40 minutes 5 minutes Coefficient of friction
ASTM 1894 CoF 0.55 0.51 0.52 0.43 0.52 Pattern viscosity ML1 + 4 140 C 34.1 60.4 30.1 40.1 68.1 Oxygen index % 31.0 33.0 33.0 33.0 33.0 Hardness Shore A 98 98 98 98 98 Shore D 54 54 54 56 56

As shown in Table 4, Comparative Example 7 in which the polyolefin-based elastomer was not used and only low-density polyethylene was used as the base resin exhibited the following properties: the room temperature elongation, the tensile residual rate after heating, the elongation percentage, Comparative Example 8 in which low density polyethylene having a melt index of 0.4 g / 10 minutes was used did not satisfy the room temperature elongation and long term extrudability, and Comparative Example 9 using a low density polyethylene having a melt index of 4.0 g / 10 minutes showed a hot set ) Comparative Example 11 using high density polyethylene having a poor melting point and a high melting point and a high melting point of 5.5 g / 10 minutes also showed poor hot set characteristics and Comparative Example 11 using high density polyethylene having a melt index of 0.075 g / The extrudability was lowered, and it was confirmed that the hot set characteristic was poor.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

A base resin including a polyethylene resin and a polyolefin-based elastomer, a non-halogen-based flame retardant, a cross-linking agent, a metal stearate and a fatty acid amide,
The polyethylene resin is a mixture of low-density polyethylene having a melt index of 1.0 to 3.0 g / 10 min and high-density polyethylene having a melt index of 0.1 to 2.0 g / 10 min at a weight ratio of 3 to 7: 7 to 3,
Wherein the polyolefin-based elastomer is a copolymer of ethylene and an? -Olefin having 3 or more carbon atoms, the first polyolefin-based elastomer having a melt index of 1.0 to 2.0 g / 10 min and a second polyolefin-based elastomer having a melt index of 3.0 to 4.0 g / Elastomer in a weight ratio of 4 to 6: 6 to 4,
100 to 300 parts by weight of a non-halogen flame retardant, 0.1 to 10 parts by weight of a crosslinking agent, 0.1 to 10 parts by weight of a metal stearate, and 0.1 to 10 parts by weight of a polyolefin- 10 to 10 parts by weight of a fatty acid amide and 0.1 to 10 parts by weight of a fatty acid amide.
delete The halogen-free flame retardant resin composition according to claim 1, wherein the non-halogen flame retardant is a metal hydroxide surface-treated with silane.
The method of claim 1, wherein the crosslinking agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, vinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, vinyldibromosilane, and vinyltri At least one silane-based crosslinking agent selected from the group consisting of normal butoxy silane; Dicumyl peroxide, benzoyl peroxide, lauryl peroxide, t-butyl cumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2,5- Hexane, and di-t-butyl peroxide; Or from the group consisting of triallyl isocyanurate, trimethallyl isocyanurate, triacryloformate, triallyl trimellurate, tris (diallylamine) -S-triazine and trimethylolpropane trimethacrylate Wherein the halogen-free flame-retardant resin composition is at least one selected from triolefin-based crosslinking agents.
5. The method according to claim 4, wherein when the cross-linking agent is a silane-based cross-linking agent, t-butylcumylperoxide, dicumylperoxide, methylethylketoneperoxide, 2,5- ) At least one crosslinking auxiliary selected from the group consisting of hexane, di-t-butyl peroxide, t-butyl peroxybenzoate and?,? -Bis (t-butylperoxyisopropyl) Wherein the halogen-free flame-retardant resin composition is a halogen-free flame retardant resin composition.
5. The method of claim 4, wherein when the cross-linking agent is a silane-based cross-linking agent, dibutyltin dilaurate, dibutyl dimaleate, dibutyl tin acetate, dibutyl tin octoate, tin octoate, tin acetate, Free flame retardant resin composition according to any one of claims 1 to 3, further comprising at least one crosslinking catalyst selected from the group consisting of zinc octoate, titanium ester, tetrabutyl titanate, ethylamine, hexylamine and piperidine.
The method according to claim 1, wherein the metal stearate is at least one selected from the group consisting of magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, lithium stearate, sodium stearate and barium stearate A halogen-free flame retardant resin composition having improved drawability.
The pharmaceutical composition according to claim 1, wherein the fatty acid amide is at least one selected from the group consisting of laurin amide, palmitamide, stearoamide, behenamide, 12-hydroxystearoamide, oleamide and erucamide Free flame retardant resin composition.
The halogen-free flame-retardant resin composition according to claim 1, further comprising at least one additive selected from the group consisting of silicone oil, antioxidant, UV stabilizer, blowing agent, processing stabilizer, pigment and filler .
delete The halogen-free flame-retardant resin composition according to claim 1, further comprising a polyolefin-based copolymer grafted with maleic anhydride.
An insulated wire produced by the halogen-free flame retardant resin composition according to any one of claims 1, 3, 4, 5, 6, 7, 8, 9, and 11.