KR101938006B1 - Resin composition for cables with excellent flexibility, abrasion resistance and flame retardancy - Google Patents

Abstract

The present invention relates to a resin composition for wire. Particularly, the present invention relates to a resin composition for electric wire having excellent flexibility, abrasion resistance, flame retardancy, heat resistance, cold resistance and the like according to ISO 6722.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin composition for cables having excellent flexibility, abrasion resistance and flame retardancy,

The present invention relates to a resin composition for wire. Particularly, the present invention relates to a resin composition for electric wire having excellent flexibility, abrasion resistance, flame retardancy, heat resistance, cold resistance and the like according to ISO 6722.

Wires or cables are generally made up of conductors and insulators and can be designed with a variety of standard conductors, insulator materials, sheath materials, and other additive materials. In addition, the insulator material and the sheath material should satisfy the test specifications for various physical properties required according to the use environment of the electric wire or cable.

Particularly, according to the design standards and various test regulations stipulated by the international standard ISO 6722, the automobile manufacturer and the harness manufacturer, the polymer material adopted in the automotive wires has excellent mechanical properties and electrical insulation as well as excellent flexibility, abrasion resistance, flame retardancy, Heat resistance, oil resistance, chemical resistance and the like are required.

However, the physical properties required for the polymer material of the automobile electric wire may be in trade-off with each other, and the improvement of specific physical properties may cause deterioration of other properties. Specifically, when a resin having high toughness and crystallinity is used in order to ensure wear resistance of a polymer material, the flexibility of the polymer material is lowered, and in order to secure cold resistance of the polymer material, a low glass transition temperature The flexibility is excellent, but the heat resistance, abrasion resistance, workability of the harness and the like are deteriorated.

Further, in response to the demand of eco-friendly products, an inorganic flame retardant such as a metal hydroxide can be used instead of a halogen-based flame retardant for discharging toxic gas upon combustion. However, the metal hydroxide-based inorganic flame retardant has a flame retardancy lower than that of a conventional halogen- The physical properties of most of the other polymeric materials deteriorate when added in a large amount in order to ensure sufficient flame retardancy.

As described above, it is extremely difficult in the technical field to simultaneously satisfy the physical properties required in automobile wires, namely excellent flexibility, abrasion resistance, flame retardancy, cold resistance, heat resistance, oil resistance and chemical resistance.

Actually, as stipulated in ISO 6722, the heat resistant grade of the polymer material constituting the electric wire located under the hood of an automobile engine is mainly classified into Class 3 (125 ° C) or Class 4 (150 ° C), and conventionally, thermoplastic polyester resin, A crosslinked polyethylene resin to which a halogen flame retardant is applied, and a halogenated resin such as polyvinyl chloride have been used.

However, the thermoplastic polyester resin is excellent in resistance to gas and oil, mechanical strength, resistance to decomposition catalyzed by copper, but is cracked when exposed to hot salty water and ruptures when exposed to a humid temperature cycle There is a problem that it can rupture prematurely due to hydrolysis.

In addition, the halogen element contained in the crosslinked polyethylene resin or the halogenated resin to which the halogen flame retardant is applied is a tendency to specify a reduction in the use of such a halogen substance in many countries in practice due to a negative influence on the environment such as emission of toxic gas during combustion.

Accordingly, there is a demand for development of polymeric materials for electric wires and resin compositions constituting them, which satisfy all the physical properties such as excellent flexibility, abrasion resistance, flame retardance, cold resistance and heat resistance according to ISO 6722, .

It is an object of the present invention to provide a resin composition for electric wires which satisfies all the properties such as excellent flexibility, abrasion resistance, flame retardancy, cold resistance and heat resistance according to ISO 6722.

It is another object of the present invention to provide a resin composition for electric wires which does not contain a halogen-based resin, a halogen-based flame retardant and the like, which cause environmental problems.

In order to solve the above problems,

A mixture obtained by blending a modified polyolefin resin grafted with a polyethylene resin, a polyolefin elastomer resin and maleic anhydride is contained as a base resin, and the content of the polyethylene resin is 10 to 50 Wherein the content of the polyolefin elastomer resin is 20 to 80 parts by weight and the content of the maleic anhydride grafted modified polyolefin resin is 10 to 30 parts by weight,

Wherein the polyethylene resin has a flexural modulus (5% flexural modulus measured according to ASTM D790) of 6,000 to 14,000 kgf / cm2, and the flexural modulus of the polyolefin elastomer resin (2% flexural modulus measured according to ASTM D790 (Modulus of elasticity of 5% measured according to ASTM D790) of the modified polyolefin-based resin grafted with maleic anhydride is from 4,000 to 14,000 kgf / cm < 2 > A resin composition for wire,

Further, the polyethylene resin has a flexural modulus (5% flexural modulus measured according to ASTM D790) of 8,000 to 13,000 kgf / cm2 and a flexural modulus (2% flexural modulus measured according to ASTM D790) of the polyolefin elastomeric resin (Modulus of elasticity) of 40 to 200 kgf / cm < 2 >, and the modulus of bending elasticity of the modified polyolefin resin grafted with maleic anhydride (5% flexural modulus measured according to ASTM D790) is 6,000 to 13,000 kgf / To provide a resin composition for wire,

The glass transition temperatures of the polyethylene resin and the polyolefin elastomer resin are respectively from -70 to 0 캜 and the glass transition temperature of the modified polyolefin resin grafted with maleic anhydride is from -30 to 10 캜. And,

The glass transition temperatures of the polyethylene resin and the polyolefin elastomer resin are respectively -50 to -15 ° C and the glass transition temperature of the modified polyolefin resin grafted with maleic anhydride is -20 to 0 ° C Provided is a resin composition for wire,

Further, the present invention provides a resin composition for electric wire, wherein the crystallinity of the modified polyethylene resin, the polyolefin elastomer resin and the modified polyolefin resin grafted with maleic anhydride are respectively 15 to 80%

Wherein the modified polyolefin resin grafted with the polyethylene resin, the polyolefin elastomer resin and the maleic anhydride has a crystallinity of 20 to 60%, respectively,

The content of the copolymer in the polyolefin elastomer resin is 5 to 40% by weight based on the total weight of the polyolefin elastomer resin.

Here, the content of the copolymer in the polyolefin elastomer resin is 10 to 25% by weight, based on the total weight of the polyolefin elastomer resin,

The present invention also provides a resin composition for electric wire, wherein the copolymer is ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylate, ethylene butyl acrylate, ethylene butene, ethylene octene copolymer or a combination thereof,

The content of the maleic anhydride in the maleic anhydride-grafted modified polyolefin resin is 0.3 to 10% by weight, based on the total weight of the grafted maleic anhydride-modified polyolefin resin. And,

Further, the composition further comprises 0.5 to 4 parts by weight of the primary antioxidant, 0.5 to 4 parts by weight of the secondary antioxidant and 0.3 to 4 parts by weight of the antioxidant, based on 100 parts by weight of the base resin, Is from 200 to 700 g / mol,

Here, the content of the first antioxidant is 1 to 3 parts by weight, the content of the second antioxidant is 1 to 3 parts by weight, the content of the antioxidant is 0.5 to 3 parts by weight based on 100 parts by weight of the base resin , And the molecular weight of the anti-oxidizing agent is 300 to 600 g / mol.

The present invention also provides a resin composition for electric wire, which comprises 100 to 180 parts by weight of a flame retardant and 5 to 40 parts by weight of an auxiliary flame retardant based on 100 parts by weight of the base resin,

Wherein the content of the auxiliary flame retardant is 10 to 30 parts by weight based on 100 parts by weight of the base resin,

Further, the flame retardant is a metal hydroxide-based inorganic flame retardant that is not surface-treated or surface-treated with a silane, amine, stearic acid, or fatty acid, and the auxiliary flame retardant is melamine cyanurate, zinc borate, tin- And a resin composition for wire,

And further comprising at least one additive selected from lubricants, crosslinking aids, reinforcing agents, releasing agents, UV absorbers, stabilizers, pigments, dyes, colorants, antistatic agents, foaming agents and metal deactivators, Wherein the resin composition is 3 to 10 parts by weight based on 100 parts by weight of the resin,

Here, a resin composition for electric wire is provided, which comprises a triacrylate-based material as a crosslinking aid,

Also, a conductor; And an insulating coating made from the resin composition for wires and coated on the conductor,

Here, an automotive wire is provided.

INDUSTRIAL APPLICABILITY The resin composition for wires according to the present invention is required to be used as a polymeric material for electric wires but is excellent in properties that are in trade-off with each other, that is, excellent flexibility, abrasion resistance, flame retardancy, cold resistance and heat resistance Effect.

In addition, the resin composition for electric wire according to the present invention is environmentally friendly because it does not contain a halogen-based resin and halogen-based flame retardant which cause environmental problems.

The resin composition for wire according to the present invention is a base resin obtained by blending a polyethylene resin, a polyolefin elastomer resin and a modified polyolefin resin grafted with maleic anhydride.

The polyethylene resin improves the abrasion resistance of the wire produced from the base resin. The polyethylene resin includes various polyethylene resins according to various known polymerization methods. That is, the polyethylene resin may be a linear low density polyethylene (LLDPE), a low density polyethylene (LDPE), a medium density polyethylene (MDPE), a high density polyethylene resin (HDPE), or a combination thereof, and may be a polyethylene homopolymer, And may be a combination thereof.

The bending elastic modulus of the polyethylene resin may be 6,000 to 14,000 kgf / cm 2, preferably 8,000 to 13,000 kgf / cm 2. If the bending elastic modulus is less than 8,000 kgf / cm 2, the cold resistance and flexibility of the manufactured wire are improved but the workability of the harness may be lowered. If the bending elastic modulus is more than 13,000 kgf / cm 2, the cold resistance and flexibility of the wire are lowered, have.

The bending elastic modulus can be measured according to ASTM D790. Specifically, a specimen manufactured with a specimen of 3.2 mm × 12.7 mm × 125 mm is supported at two lower points in a lying down state, and a point at which a 5% deformation of the specimen length occurs at a constant speed at a point between the two points Find the modulus of elasticity at the point of breaking before 5%.

The content of the polyethylene resin may be 10 to 50 parts by weight based on 100 parts by weight of the base resin. If the content of the polyethylene resin is less than 10 parts by weight, the abrasion resistance of the produced wire may be deteriorated. If the content is more than 50 parts by weight, flexibility of the wire may be deteriorated.

In addition, the polyolefin elastomer resin improves the filler loading of the base resin and the cold resistance and flexibility of the wire produced from the base resin.

In the polyolefin elastomer, the polyolefin is a polymer composed of a monomer having the formula C _n H _2n , and is not particularly limited and includes polyethylene, polypropylene, polyisobutylene and the like. Polyolefin resins of this general structure and methods for their production are well known in the art and are disclosed, for example, in U.S. Patent Nos. 2,933,480 and 4,584,334.

The polyolefin elastomer resin comprises a copolymer of the polyolefin and one or more rubbers. Preferably, the polyolefin elastomer resin is selected from the group consisting of ethylene ethyl acrylate (EEA), ethylene vinyl acetate (EVA), ethylene methacrylate (EMA), ethylene butyl acrylate (EBA), ethylene butene (EB) ) System and the like.

The content of the copolymer in the polyolefin elastomer resin may be 5 to 40% by weight, preferably 10 to 25% by weight. If the content of the copolymer is less than 10% by weight, filler loading of the resin composition, cold resistance and flexibility of the produced wire may be deteriorated. If the content is more than 25% by weight, the abrasion resistance of the wire may be deteriorated.

The flexural modulus of the polyolefin elastomer resin may be 20 to 400 kgf / cm 2, preferably 40 to 200 kgf / cm 2. If the bending modulus of elasticity is less than 40 kgf / cm 2, harness workability of a manufactured wire may be deteriorated. If the bending elastic modulus is more than 200 kgf / cm 2, the cold resistance and flexibility of the wire may be deteriorated and the loadability of the filler may be deteriorated.

The bending elastic modulus can be measured by the same method as that for obtaining the bending elastic modulus of the polyethylene resin except that the elastic modulus at the point where the 2% deformation of the specimen length occurs or the point at which the deformation occurs before 2% is obtained.

The content of the polyolefin elastomer resin may be 20 to 80 parts by weight based on 100 parts by weight of the base resin. If the content of the polyolefin elastomer resin is less than 20 parts by weight, the cold resistance and flexibility of the produced wire may be deteriorated. If the content is more than 80 parts by weight, the abrasion resistance of the wire may be deteriorated.

In addition, the modified polyolefin-based resin in which the maleic anhydride is grafted improves the abrasion resistance of the wire made from the base resin, and increases the interfacial bonding force of the additionally added flame retardant and resin.

In the modified polyolefin-based resin in which the maleic anhydride is grafted, the polyolefin-based resin includes polyethylene, polypropylene, and the like, and is not particularly limited, and may be a homopolymer, a copolymer, or a combination thereof. In the modified polyolefin-based resin in which the maleic anhydride is grafted, the polyolefin-based resin may be substantially the same as or different from the polyolefin resin in the polyolefin elastomer.

Methods for grafting maleic anhydride to a polyolefin-based resin are known in the art. For example, a polyolefin-based resin grafted with maleic anhydride can be obtained by reacting maleic anhydride with a polyolefin resin under the presence of oxygen, air, hydrogen peroxide or other free radical initiator, and heating conditions.

In the modified polyolefin-based resin wherein the maleic anhydride is grafted, the maleic anhydride may be grafted to the polyolefin-based resin at 0.3 to 10% by weight. If the content of the maleic anhydride is less than 0.3% by weight, the mechanical properties and abrasion resistance of the produced wire may be deteriorated. If the content of the maleic anhydride exceeds 10% by weight, the cold resistance of the wire may be deteriorated.

The modulus of bending elasticity of the modified polyolefin-based resin grafted with maleic anhydride may be 4,000 to 14,000 kgf / cm 2, preferably 6,000 to 13,000 kgf / cm 2. If the bending elastic modulus is less than 6,000 kgf / cm 2, the cold resistance of the manufactured wire is increased but the harness workability may be lowered. If the bending elastic modulus is more than 13,000 kgf / cm 2, the cold resistance and flexibility of the wire may be lowered and whitening may occur.

The bending elastic modulus of the modified polyolefin-based resin grafted with maleic anhydride can be measured by the same method as described above.

The content of the modified polyolefin-based resin grafted with maleic anhydride may be preferably 10 to 30 parts by weight based on 100 parts by weight of the base resin. When the content of the maleic anhydride-grafted modified polyolefin-based resin is less than 10 parts by weight, the abrasion resistance of the produced wire may be deteriorated. If the content is more than 30 parts by weight, the cold resistance and flexibility of the wire may be deteriorated.

The glass transition temperature (Tg) of the polyethylene resin and the polyolefin elastomer resin may be -70 to 0 占 폚, preferably -50 to -15 占 폚. When the polyethylene resin and the polyolefin elastomer resin have a glass transition temperature of less than -50 ° C, the produced wire has excellent cold resistance but may deteriorate abrasion resistance. When the glass transition temperature is higher than -15 ° C, the cold resistance of the wire may be deteriorated.

The glass transition temperature of the modified polyolefin-based resin grafted with maleic anhydride may be -30 to 10 ° C, preferably -20 to 0 ° C. When the glass transition temperature of the maleic anhydride-grafted modified polyolefin-based resin is less than -30 ° C, the produced wire is excellent in cold resistance but may deteriorate in mechanical properties and abrasion resistance, and when it is more than 0 ° C, .

The glass transition temperature can be measured using Differential Scanning Calorimetry (DSC) according to ISO 1135762. Specifically, a graph of the relationship between the temperature of the sample and the heat flow to be supplied is obtained while gradually increasing the temperature of the DSC sample at a constant rate, and an extension line is drawn on the graph before and after the change in the slope of the graph, The glass transition temperature can be obtained at the point where it meets the graph.

The crystallinity of each of the polyethylene resin, the polyolefin elastomer resin and the maleic anhydride grafted modified polyolefin resin may be 15 to 80%, preferably 20 to 60%. When the degree of crystallinity is less than 20%, the abrasion resistance of a manufactured wire is deteriorated. When the degree of crystallization is more than 60%, abrasion resistance is excellent but whitening phenomenon and flexibility may be deteriorated.

The resin composition for wires according to the present invention may further comprise an antioxidant to improve the heat resistance of the wire to be produced. The antioxidant includes a primary antioxidant such as a phenol-based or amine-based antioxidant that directly participates in the oxidation reaction to prevent oxidation, and a secondary antioxidant such as sulfur and phosphorus that inactivates the metal serving as a catalyst for the oxidation reaction . The antioxidant suppresses the decomposition of the polymer covering the conductor by the copper ion of the conductor when the use temperature of the wire increases, thereby securing the heat resistance of the wire.

The content of the primary antioxidant may be 0.5 to 4 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the base resin. If the content of the first antioxidant is less than 1 part by weight, the heat resistance of the produced wire may be insufficient, and if it is more than 3 parts by weight, blooming may occur on the surface of the wire.

The content of the secondary antioxidant may be 0.5 to 4 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the base resin. If the content of the secondary antioxidant is less than 1 part by weight, the heat resistance of the produced wire may be insufficient, and if it is more than 3 parts by weight, blooming may occur on the surface of the wire.

In addition, the resin composition for electric wire according to the present invention may further comprise an antioxidant in addition to the antioxidant. The antioxidation agent suppresses the oxidation reaction in which copper ions from the conductor constituting the electric wire decompose the polymer covering the conductor at a high temperature, which is the temperature at which the electric wire is used, and an anti-oxidizing agent such as a urea system is widely known have.

The amount of the anti-oxidizing agent may be 0.3 to 4 parts by weight, preferably 0.5 to 3 parts by weight based on 100 parts by weight of the base resin. If the amount of the antioxidant is less than 0.5 part by weight, the electric wire may have insufficient heat resistance. If the antioxidant is more than 2 parts by weight, blooming may occur on the wire surface.

The main component of the antioxidant may have a molecular weight of 200 to 700 g / mol, preferably 300 to 600 g / mol. If the molecular weight is less than 300 g / mol, the desired anti-oxidizing performance may not be obtained. If the molecular weight is more than 600 g / mol, the anti-oxidizing property is excellent but dispersion failure and blooming may occur.

The resin composition for wires according to the present invention may further include a flame retardant to improve the flame retardancy of the electric wire to be produced. The flame retardant may preferably be a metal hydroxide-based inorganic flame retardant which is a non-halogen flame retardant. Examples of the metal hydroxide-based inorganic flame retardant include aluminum hydroxide, magnesium hydroxide and the like.

The metal hydroxide-based inorganic flame retardant may be used by surface treatment or non-surface treatment with silane such as vinyl silane, amine-based such as vinyl amine, stearic acid, fatty acid, etc., or may be used alone or in combination of two or more. Preferably, the metal hydroxide-based inorganic flame retardant has a particle size of 0.5 to 30 μm and a specific surface area (BET) of 3 to 20 mm 2 / g.

For example, the non-surface-treated magnesium hydroxide is commercially available from Konoshima Chemical Co. Ltd. under the product names of Magseeds N1, N2 and N3, and the surface- The product name of MAGNIFIN from Albemarle Corporation, Kyowa Chemical Industry to KISUMA product name, Sakai Chemical Company to MGZ product name, Martin Marietta Magnesia Specialties to Magnesium (Magshield).

The content of the metal hydroxide-based inorganic flame retardant may be 100 to 180 parts by weight based on 100 parts by weight of the base resin. When the content of the inorganic flame retardant is less than 100 parts by weight, the flexibility and cold resistance of the electric wire to be produced are improved, but the flame retardancy may be insufficient. When the content is more than 180 parts by weight, the flame retardancy of the electric wire is excellent, Other physical properties may be deteriorated.

The inorganic flame retardant may be used together with an auxiliary flame retardant such as melamine cyanurate, zinc borate, and tin-based flame retardant. When the auxiliary flame retardant is used together, its content may be 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the base resin. If the content of the auxiliary flame retardant is less than 10 parts by weight, the flame retardancy of the produced wire may be insufficient. If the auxiliary flame retardant is more than 30 parts by weight, an additional cost may be incurred such as an increase in the price of the wire,

The resin composition for electric wire according to the present invention may contain a high molecular weight wax, a low molecular weight wax, a polyolefin wax, a paraffin wax, a paraffin oil, stearic acid, a metal soap, an organic silicone, a fatty acid ester, Stabilizers, dyes, dyes, colorants, antistatic agents, foaming agents, metal deactivators, and the like, or combinations thereof, in addition to the above-mentioned additives.

The content of the other additives may be 3 to 10 parts by weight based on 100 parts by weight of the base resin.

A typical method for producing a resin composition for electric wire according to the present invention is a method for producing a resin composition for electric wire, which comprises a modified polyolefin-based resin grafted with a polyethylene resin, a polyolefin elastomer and a maleic anhydride constituting the base resin, an antioxidant, And melt mixing the additives in a melt mixing apparatus such as a compounding extruder or a Banbury mixer.

Further, the melt-mixed mixture is melt-filtered through at least one filter having an opening with a diameter of 20 to 150 micrometers, preferably 30 to 130 micrometers, more preferably 40 to 110 micrometers, to remove particulate impurities . The melt filtration process may be performed through a single melt filtration system or through a multiple melt filtration system.

The melt-filtered mixture may be directly coated on the conductor or passed through a die head and pelletized by either strand pelletization or underwater pelletization, then melted again, Can be coated on the conductor in any suitable manner, such as by coating. For example, a coating extruder equipped with a screw, crosshead, breaker plate, dispenser, nipple and die may be used.

The conductors may comprise a single strand or a plurality of strands. The plurality of strands may be bundled, twisted or braided to form a conductor. Additionally, the conductors may have various shapes, such as circular or elliptical. The conductor may be any type of conductor used to transmit signals.

Signals transmitted through the conductors include optical, electrical, and electromagnetic. Glass fibers are an example of optical conductors. Suitable electrical conductors can include, but are not limited to, copper, aluminum, lead, and alloys comprising one or more of these materials.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

[Example]

The following polyethylene resins, polyolefin elastomers, maleic anhydride grafted modified polyolefin resins, antioxidants, antioxidants, flame retardants, auxiliary flame retardants, TMPTMA, and other additives used in the following Examples and Comparative Examples are as follows.

1) Polyethylene resin

PE1: Mr. Hippo (HPC), HIVOREX 2700J

PE2: LG Chem, Lucene SP980

2) Polyolefin elastomer

POE1: JP (JPE), EEA 1150

POE2: DuPont, Elvax 40L

POE3: DuPont, Elvax 150

POE4: Hanhwa, EVA-1155

3) Modified polyolefin-based resin grafted with maleic anhydride

Modified PO1: DuPont, Fusabond 100D

Modified PO2: DuPont, Fusabond 250D

4) Antioxidants

Primary antioxidants: CIBA-Specialty, Irganox-1010

Secondary Antioxidants: Ciba Specialty, Irganox-PS-802

5) Antioxidants

Antioxidant 1: Ciba Specialty, Irganox-MD 1024

Antioxidant 2: Chitec, Deox MD-1012

6) Flame retardant

Albemale, Magnefine H5A

7) Secondary flame retardant

U.S. BORAX, ZB-2335

8) Trimethylol trimethacrylate (TMPTMA)

Sartomer, SR-350 < RTI ID = 0.0 >

9) Other additives

Danseok Industry, ZN-ST

The resin compositions for wires of Examples 1 to 5 and Comparative Examples 1 to 12 were prepared by melt mixing the constituents described in Tables 1 and 2 by a compound extruder and applied to conductors each having a cross section of 0.5 mm 2, .

Component (Physical Properties) Example Comparative Example One 2 3 One 2 3 4 5 6 7 8 PE1 (F *: 8500, Tg: -25 ° C, C *: 55%) 35 50 25 35 35 35 35 35 35 PE2 (F *: 5000, Tg: -35 ° C, C *: 40%) 35 35 POE1 (F *: 78, Tg: -32 ° C, C *: 30%, Co *: 15% 50 40 55 50 50 50 50 POE2 (F *: 28, Tg: -48 deg. C, C *: 13%, Co *: 40% 50 POE3 (F *: 47, Tg: -40 ° C, C *: 23%, Co *: 30% 50 POE4 (F *: 240, Tg: -10 ° C, C *: 58%, Co *: 5% 50 50 Denatured PO1 (F *: 8000, Tg: -10 ° C, C *: 52%) 15 10 20 15 15 15 15 15 15 15 Denatured PO2 (F *: 1000, Tg: -25 ° C, C *: 10%) 15 Primary antioxidant 2 2 2 2 2 2 2 2 2 2 2 Secondary antioxidant 2 2 2 2 2 2 2 2 2 2 2 Antioxidant 1 (Mw: 550) One One One One One One One One One One One Flame retardant 145 145 145 145 145 145 145 145 145 155 185 Auxiliary Flame Retardant 10 10 10 10 10 10 10 10 10 TMPTMA 3 3 3 3 3 3 3 3 3 3 3 Other additives 4 4 4 4 4 4 4 4 4 4 4

F *: flexural modulus (kgf / cm 2); C *: crystallinity; Co *: Copolymer content ratio

Component (Physical Properties) Example Comparative Example 4 5 9 10 11 12 PE1 (F *: 8500, Tg: -25 ° C, C *: 55%) 35 35 35 35 35 35 POE1 (F *: 78, Tg: -32 ° C, C *: 30%, Co *: 15% 50 50 50 50 50 50 Denatured PO1 (F *: 8000, Tg: -10 ° C, C *: 52%) 15 15 15 15 15 15 Primary antioxidant 2.5 3 0.3 3 3 2 Secondary antioxidant 1.5 One 2.5 0 3 2 Antioxidant 1 (Mw: 550) One One One One 0 Antioxidant 2 (Mw: 200) One Flame retardant 145 145 145 145 145 145 Auxiliary Flame Retardant 10 10 10 10 10 10 TMPTMA 3 3 3 3 3 3 Other additives 4 4 4 4 4 4

F *: flexural modulus (kgf / cm 2); C *: crystallinity; Co *: Copolymer content ratio

Methods for evaluating the abrasion resistance, cold resistance, heat resistance, flame retardancy, and flexibility of the resin composition prepared in Examples and Comparative Examples and the wires produced therefrom are as follows.

1) Abrasion resistance evaluation

The abrasion resistance of the resin composition for wires was evaluated using a needle measurement method according to ISO 6722. Specifically, after a specimen was prepared from the resin composition prepared in each of the examples and the comparative examples, a load of 7 ± 0.05 N was applied to a needle having a diameter of 0.45 mm on the specimen at room temperature (23 ° C) The test piece was abraded by exercise and the number of reciprocating movements at the time of the insulation breakdown due to abrasion of the test piece was recorded and the average value was obtained by repeating this 4 times. The sample was moved horizontally by 100 mm for each measurement and rotated 90 ° clockwise. It was judged that the abrasion resistance was excellent when the average number of reciprocating motions was 300 or more.

2) Cold resistance evaluation

The cold resistance of the wire made from the resin composition for wire was evaluated according to ISO 6722. Specifically, weights were weighed at one end of each wire prepared in each of the examples and the comparative examples, and allowed to stand for 4 hours in an oven set at -40 DEG C, and then subjected to a bending test , And after standing at room temperature (23 ± 5 ° C), the appearance inspection of the wire inscribed on the metal sheet and the application of a voltage of 1 kV were carried out to judge whether or not insulation breakdown occurred.

3) Evaluation of heat resistance

The heat resistance of the wire made from the resin composition for wires was evaluated according to ISO 6722. Specifically, the wires prepared in each of the examples and the comparative examples were allowed to stand in an oven set at a prescribed temperature for 240 hours, taken out of the oven and allowed to stand at room temperature (23 ± 5 ° C) for 16 hours, C for 4 hours and then subjected to a bending test by winding at a prescribed number of revolutions / times, and a voltage was applied to the electric wire to record an applied voltage at which insulation breakdown occurred. Further, after the heat treatment, some samples were stretched at a predetermined speed to record elongation at break of the wire. When the applied voltage is 1 kV or more and the elongation percentage is 100% or more, it is judged that the heat resistance is excellent.

4) Flexibility evaluation

The flexibility of the wire made from the resin composition for wire was evaluated according to ISO 6722. More specifically, a force was applied to the other end by pulling the end of the electric wire with a force of 10 N by placing a wire on a predetermined drum. And when the force applied to the other end is 18N or less, flexibility is judged to be excellent.

5) Evaluation of flame retardancy

The flame retardancy of the electric wire produced from the resin composition for wire was evaluated according to IEC 60332-1. Specifically, the specimen wire was vertically suspended in a chamber free of drafts and sparked for 60 seconds. It was judged that the flame retardancy was excellent when the combustion length of the electric wire after the application of the flame was 550 mm or less.

The evaluation results of flexibility, heat resistance, cold resistance, abrasion resistance, flame retardancy, and appearance of the resin compositions for electric wires or wires prepared according to Examples 1 to 5 and Comparative Examples 1 to 12 shown in Tables 1 and 2 are shown in Table 3 4 < / RTI >

Evaluation items standard Example Comparative Example One 2 3 One 2 3 4 5 6 7 8 flexibility 18N or less 15.5 17.6 13.4 10.2 20.4 9.3 12.3 25.4 14.3 15.4 18.3 Heat resistance Applied voltage at insulation breakdown 1kV or more 10 10 10 10 8 10 10 8 9 10 0.3 Elongation rate 100%
More than 210 180 240 230 126 235 231 124 164 200 fracture Cold resistance Is insulation destroyed when 1 kV is applied? Pass Pass Pass Pass Fail Pass Pass Fail Pass Pass Fail Abrasion resistance More than 300 times 623 700 413 226 540 120 239 950 95 600 280 Flammability 550 mm or less 210 240 230 210 280 150 220 240 230 Fire 110 Exterior Visual observation Good Good Good Good Good Good Good Good Good Good Good

As shown in Table 3, the resin composition for wires or the wires made therefrom according to Examples 1 to 3 according to the present invention had excellent effects satisfying the requirements of excellent flexibility, heat resistance, cold resistance, abrasion resistance and flame retardancy according to ISO 6722 .

On the other hand, in Comparative Example 1, the coefficient of bending elasticity of the polyethylene resin of the constituent components was low, and it was confirmed that the flexibility of the wire was excellent but the abrasion resistance was decreased.

Comparative Example 2 showed that the flexural elastic modulus of the polyolefin elastomer was high, the content ratio of the copolymer was low, and the glass transition temperature was high, thereby lowering the flexibility and cold resistance of the wire, even though the coefficient of bending elasticity of the polyethylene resin was low.

In Comparative Example 3, it was confirmed that the polyolefin elastomer in the composition had a low flexural modulus and crystallinity, a high copolymer content ratio and a high glass transition temperature,

In Comparative Example 4, it was confirmed that the flexibility of the wire was improved due to the high copolymer content ratio of the polyolefin elastomer among the constituent components, but the abrasion resistance was deteriorated,

In Comparative Example 5, it was confirmed that the polyolefin elastomer of the composition had a high flexural modulus and glass transition temperature and a low copolymer content ratio, thereby improving the abrasion resistance of the wire but decreasing the flexibility and cold resistance.

In Comparative Example 6, the modified polyolefin-based resin grafted with maleic anhydride was found to have poor flexural modulus and crystallinity, thereby improving flexibility but lowering abrasion resistance.

In Comparative Example 7, it was confirmed that the flame retardancy was deteriorated due to the absence of the auxiliary flame retardant,

In Comparative Example 8, the flame retardant content was high and the flame retardancy was excellent, but it was confirmed that the other properties such as flexibility, heat resistance, cold resistance and abrasion resistance were all lowered.

Evaluation items standard Example Comparative Example 4 5 9 10 11 12 flexibility 18N or less 15.4 15.6 15.4 15.2 15.4 15.3 Heat resistance
Applied voltage at insulation breakdown 1kV or more 10 10 0.7 0.3 0.1 0.8 Elongation rate over 100% 220 170 60 fracture fracture 85 Cold resistance Is insulation destroyed when 1 kV is applied? Pass Pass Pass Pass Pass Pass Abrasion resistance More than 300 times 612 690 590 610 640 620 Flammability 550 mm or less 215 230 230 210 280 250 Exterior Visual observation Good Good Good Good Good Good

As shown in Table 4, the resin compositions for wires according to Examples 4 and 5 according to the present invention or wires produced therefrom had excellent effects satisfying excellent flexibility, heat resistance, cold resistance, abrasion resistance and flame retardancy in accordance with ISO 6722 .

On the other hand, in Comparative Example 9, it was confirmed that the content of the primary antioxidant was small and the heat resistance was degraded.

In Comparative Example 10, it was confirmed that the content of the secondary antioxidant was small and the heat resistance was lowered,

In Comparative Example 11, although the content of the antioxidant was large, the antioxidant content was small and the heat resistance was low.

It was confirmed that the molecular weight of the antioxidant was low in Comparative Example 12 and the heat resistance was lowered.

While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. . It is therefore to be understood that the modified embodiments are included in the technical scope of the present invention if they basically include elements of the claims of the present invention.

Claims (20)

A mixture of a polyethylene resin, a polyolefin elastomer resin and a maleic anhydride-grafted modified polyolefin resin is contained as a base resin, the content of the polyethylene resin is 10 to 50 parts by weight based on 100 parts by weight of the base resin, the content of the polyolefin elastomer Wherein the content of the resin is 20 to 80 parts by weight, the content of the modified polyolefin resin to which the maleic anhydride is grafted is 10 to 30 parts by weight,
Wherein the polyethylene resin and the polyolefin elastomer resin have a glass transition temperature of -50 to -15 占 폚, the maleic anhydride-grafted modified polyolefin resin has a glass transition temperature of -20 to 0 占 폚,
Wherein the crystallinity of the polyethylene resin, the polyolefin elastomer resin and the modified polyolefin resin grafted with maleic anhydride is 15 to 80%, respectively. The method according to claim 1,
Wherein the polyethylene resin has a flexural modulus (5% flexural modulus measured according to ASTM D790) of 6,000 to 14,000 kgf / cm2 and a flexural modulus (2% flexural modulus measured according to ASTM D790) of the polyolefin elastomeric resin, Is 20 to 400 kgf / cm < 2 >, and the modulus of bending elastic modulus (5% flexural modulus measured according to ASTM D790) of the maleic anhydride grafted modified polyolefin resin is 4,000 to 14,000 kgf / / RTI > 3. The method of claim 2,
Wherein the polyethylene resin has a flexural modulus (5% flexural modulus measured according to ASTM D790) of 8,000 to 13,000 kgf / cm2 and a flexural modulus (2% flexural modulus measured according to ASTM D790) of the polyolefin elastomeric resin, Is 40 to 200 kgf / cm 2, and the modulus of flexural modulus (5% flexural modulus measured according to ASTM D790) of the maleic anhydride grafted modified polyolefin resin is 6,000 to 13,000 kgf / cm 2. / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the polyethylene resin and the polyolefin elastomer resin have a glass transition temperature of -70 to 0 占 폚 and the maleic anhydride grafted modified polyolefin resin has a glass transition temperature of -30 to 10 占 폚 Composition. delete delete The method according to claim 1,
Wherein the crystallinity of the polyethylene resin, the polyolefin elastomer resin and the modified polyolefin resin grafted with maleic anhydride is 20 to 60%, respectively. 4. The method according to any one of claims 1 to 3,
Wherein the content of the copolymer in the polyolefin elastomer resin is 5 to 40% by weight based on the total weight of the polyolefin elastomer resin. 9. The method of claim 8,
Wherein the content of the copolymer in the polyolefin elastomer resin is 10 to 25% by weight based on the total weight of the polyolefin elastomer resin. 9. The method of claim 8,
Wherein the copolymer is ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylate, ethylene butyl acrylate, ethylene butene, ethylene-octene copolymer or a combination thereof. 4. The method according to any one of claims 1 to 3,
Wherein the content of maleic acid in the maleic anhydride-grafted modified polyolefin-based resin is 0.3 to 10% by weight based on the total weight of the grafted maleic anhydride-modified polyolefin-based resin . 4. The method according to any one of claims 1 to 3,
0.5 to 4 parts by weight of the primary antioxidant, 0.5 to 4 parts by weight of the secondary antioxidant and 0.3 to 4 parts by weight of the antioxidant, based on 100 parts by weight of the base resin, wherein the molecular weight of the antioxidant is 200 To 700 g / mol. ≪ / RTI > 13. The method of claim 12,
Wherein the content of the first antioxidant is 1 to 3 parts by weight, the content of the second antioxidant is 1 to 3 parts by weight, the amount of the antioxidant is 0.5 to 3 parts by weight based on 100 parts by weight of the base resin, And the molecular weight of the anti-oxidizing agent is 300 to 600 g / mol. 4. The method according to any one of claims 1 to 3,
Wherein the resin composition further comprises 100 to 180 parts by weight of a flame retardant and 5 to 40 parts by weight of an auxiliary flame retardant based on 100 parts by weight of the base resin. 15. The method of claim 14,
Wherein the content of the auxiliary flame retardant is 10 to 30 parts by weight based on 100 parts by weight of the base resin. 15. The method of claim 14,
Characterized in that the flame retardant is a metal hydroxide-based inorganic flame retardant that is not surface-treated or surface-treated with a silane-based, amine-based, stearic acid, or fatty acid, and the auxiliary flame retardant is melamine cyanurate, zinc borate, tin-based flame retardant, By weight based on the total weight of the resin composition. 4. The method according to any one of claims 1 to 3,
Wherein the additive further comprises at least one additive selected from a lubricant, a crosslinking additive, a reinforcing agent, a releasing agent, a UV absorber, a stabilizer, a pigment, a dye, a colorant, an antistatic agent, a foaming agent and a metal deactivator, Is 3 to 10 parts by weight based on the weight of the resin composition. 18. The method of claim 17,
And a tri-methacrylic acid-based material as a crosslinking assistant. Conductor; And
An electric wire comprising an insulating coating made from a resin composition for electric wire according to any one of claims 1 to 3 and coated on the conductor. 20. The automotive cable of claim 19,