WO2013100349A1 - Flame-retardant thermoplastic resin composition and molded product comprising same - Google Patents

Description

Thermoplastic Resin Composition and Molded Articles Comprising the Same

A thermoplastic resin composition and a molded article including the same.

Recently, as materials such as electric wires or wire coating materials used in electric and electronic device parts, automobile device parts, chemical device parts, and the like, a resin having excellent flexibility, flame retardancy, wear resistance, mechanical strength, chemical resistance, and heat resistance is desired. In addition, there is a demand for a resin that can be easily recycled in consideration of environmental aspects.

Polyolefins, which are widely used as wire covering materials, have excellent flexibility and chemical resistance, but have disadvantages of poor flame retardancy, wear resistance, mechanical strength, and heat resistance.

On the other hand, polyphenylene ether widely used as a material for electric and electronic device parts and automotive device parts has excellent insulation, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability, but due to its high melt viscosity, poor workability, flexibility and resistance The disadvantage is poor chemicality.

Therefore, research is being conducted on resin compositions that are excellent in workability, flexibility, flame retardancy, wear resistance, heat resistance, mechanical strength and chemical resistance and can be easily recycled.

One embodiment provides a thermoplastic resin composition excellent in workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, mechanical strength and chemical resistance and easily recyclable.

Another embodiment provides a molded article including the thermoplastic resin composition.

According to one embodiment, a thermoplastic resin composition includes a base resin including (A) a polyarylene ether resin and a polyolefin resin, and (B) an air including (b-1) a styrene repeating unit and an olefin repeating unit. Include coalescing. At this time, the content of the polyolefin resin (W _OL ) and the content of the polyarylene ether resin (W _AR ) satisfies the relationship of W _AR ≤1.9 × W _OL , the aryl in the polyarylene ether resin The ratio of the content (wt%) of the styrene portion to the content (wt%) of the styrene portion in the copolymer is about 100: 20 to about 100: 55.

The thermoplastic resin composition according to another embodiment may include (A) a base resin including a polyarylene ether resin and a polyolefin resin, and (B) (b-2) a styrene repeat unit and an olefin repeat unit. And polar copolymers with grafted polar functional groups. In this case, the content (weight, W _OL ) of the polyolefin resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy a relational expression of W _AR ≤1.9 × W _OL , and the polar functional group is electronegative. And a bond between elements having a difference of about 0.5 to about 3.0, wherein the polar copolymer (b-2) is from about 0.1 part by weight to 100 parts by weight of the total repeating units including the polar functional group in the polar copolymer. It is grafted at about 7.0 parts by weight.

The polyolefin-based resin may have a melt index (MI) of about 0.1 g / 10 min to about 30 g / 10 min.

The polyolefin resin may have a melting point of about 80 ℃ to about 170 ℃.

The polyolefin resin may have a weighted average density of about 0.95 g / cm ³ or less.

Specifically, the polyolefin-based resin is a high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer ), Ultra-low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene ) And combinations thereof.

The copolymer comprising the (b-1) styrene repeating unit and the olefin repeating unit is styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene air Styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer (SIS) ), Styrene-ethylene copolymer (styrene-ethylene copolymer), styrene-ethylene-butadiene-styrene copolymer (styrene-ethylene-butadiene-styrene copolymer) and combinations thereof may be included.

The polar functional group is a substituted or unsubstituted C3 to C30 anhydride group, a substituted or unsubstituted C1 to C30 carboxyl group, a substituted or unsubstituted C2 to C30 ester group, a hydroxyl group, a substituted or unsubstituted C1 to C30 Alcohol group, amine group (NH ₂ ), substituted or unsubstituted C1 to C20 amino group (NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or mutually Different and each independently C1 to C10 alkyl group), substituted or unsubstituted C2 to C30 epoxy group, substituted or unsubstituted C1 to C30 ketone group, -SH, substituted or unsubstituted C1 to C30 thioalcohol group and these Can be selected from a combination of

The (b-2) polar copolymer is maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS), maleic hydride (maleic anhydride-grafted styrene-ethylene-butylene-styrene copolymer) Maleic Anhydride Grafted Styrene-Ethylene-Butadiene-Styrene Copolymer, Maleic Unhydride-Grafted Styrene-Ethylene-Styrene Copolymer, Maleic Unhydride-Graft Styrene-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-propylene-styrene copolymer, maleic hydride-grafted styrene-ethylene-octene-styrene copolymer, maleic hydride It may include one selected from the grafted x styrene-isoprene-styrene copolymer and combinations thereof.

In the thermoplastic resin composition, (A) the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% to about 90% by weight of the polyolefin resin relative to the total amount of the base resin %, And the (b-1) copolymer may be included in an amount of about 1 part by weight to about 40 parts by weight based on 100 parts by weight of the base resin.

In the thermoplastic resin composition, (A) the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% to about 90% by weight of the polyolefin resin relative to the total amount of the base resin %, And the (b-2) polar copolymer may be included in about 1 parts by weight to about 40 parts by weight based on 100 parts by weight of the base resin.

The thermoplastic resin composition may be grafted to about 0.001 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total repeating units contained in the thermoplastic resin composition.

In another embodiment, the thermoplastic resin composition is a (A) a base resin containing a polyarylene ether resin and a polyolefin resin, (b-1) a copolymer comprising a styrene repeat unit and an olefin repeat unit, And (b-2) a copolymer comprising a styrene repeating unit and an olefin repeating unit and having a polar functional group grafted thereon, a polymer containing a styrene repeating unit and a polar functional group grafted therein, an olefin repeating unit having a polarity Polar polymers selected from polymers grafted with functional groups and combinations thereof. At this time, the content of the polyolefin resin (weight, W _OL ) and the content of the polyarylene ether resin (weight, W _AR ) satisfies the relationship of W _AR ≤ 1.9 × W _OL , the polar functional group is And (b-2) the polar polymer comprises about 0.1 part by weight to about 100 parts by weight of the total repeating units of which the polar functional group is included in the polar polymer. It is grafted to 7.0 parts by weight.

The base resin (A) may include about 10 wt% to about 80 wt% of the polyarylene ether resin and about 20 wt% to about 90 wt% of the polyolefin resin with respect to the total amount of the base resin. The copolymer (b-1) may be included in an amount of about 1 parts by weight to about 40 parts by weight based on 100 parts by weight of the base resin, and (b-2) the polar polymer is about 1 part by weight based on 100 parts by weight of the base resin. It may be included in parts by weight to about 40 parts by weight.

The thermoplastic resin composition may further include an inorganic filler.

The inorganic fillers are magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate and potassium titanate. ), Magnesium silicate, aluminum oxide hydroxide, and combinations thereof.

The thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight of the inorganic filler based on 100 parts by weight of the thermoplastic resin composition not containing the inorganic filler.

The thermoplastic resin composition may further include a flame retardant.

The flame retardant is selected from phosphate compounds, phosphite compounds, phosphonate compounds, polysiloxanes, phosphazene compounds, phosphinate compounds, melamine compounds, and combinations thereof. It may include one.

The thermoplastic resin composition may include about 1 parts by weight to about 50 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin composition not containing the flame retardant.

Another embodiment provides a molded article including the thermoplastic resin composition.

The molded article may be an electric wire or an electric wire covering material.

The molded article may have an elongation of from about 50% to about 600% as measured by JASO D 618.

The molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 70 seconds.

The molded article may have a wear resistance of about 400 mm to about 3000 mm as measured by the ISO 6722 sandpaper abrasion test method.

The molded article may have a diameter change rate of about 15% or less after gasoline immersion as measured by ISO 6722.

By including a polyolefin resin and a polyarylene ether resin in a specific weight range, by including a specific copolymer, or a specific polar copolymer or a specific polar polymer, workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, mechanical Provided is a thermoplastic resin composition excellent in strength and chemical resistance and recyclable, and a molded article including the same.

1 is a cross-sectional view of a wire according to one embodiment.

2 is a cross-sectional view of a wire according to another embodiment.

3 is a cross-sectional view of a wire according to another embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (-F, -Cl, -Br or -I), hydroxy group, nitro group, Cyano group, amino group (NH ₂ , NH (R ¹⁰⁰ ) or N (R ¹⁰¹ ) (R ¹⁰² ), wherein R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² are the same or different from each other, and are each independently C1 to C10 alkyl groups) , Amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted haloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted At least one substituent selected from the group consisting of a substituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocycloalkyl group. It means substituted.

Unless stated otherwise in the present specification, "alkyl group" means a C1 to C30 alkyl group, specifically, a C1 to C20 alkyl group, and "cycloalkyl group" means a C3 to C30 cycloalkyl group, and specifically C3 To C20 cycloalkyl group, "heterocycloalkyl group" means C2 to C30 heterocycloalkyl group, specifically C2 to C20 heterocycloalkyl group, "alkylene group" means C1 to C30 alkylene group , Specifically, a C1 to C20 alkylene group, "alkoxy group" means a C1 to C30 alkoxy group, specifically a C1 to C20 alkoxy group, and a "cycloalkylene group" refers to a C3 to C30 cycloalkylene group It means, specifically, C3 to C20 cycloalkylene group, "heterocycloalkylene group" means C2 to C30 heterocycloalkylene group It means, specifically, C2 to C20 heterocycloalkylene group, "aryl group" means C6 to C30 aryl group, specifically C6 to C20 aryl group, "heteroaryl group" means C2 to C30 It means a heteroaryl group, specifically means a C2 to C18 heteroaryl group, "arylene" group means a C6 to C30 arylene group, specifically means a C6 to C20 arylene group, "heteroarylene group" Means a C2 to C30 heteroarylene group, specifically means a C2 to C20 heteroarylene group, "alkylaryl group" means a C7 to C30 alkylaryl group, specifically means a C7 to C20 alkylaryl group, "Halogen" means F, Cl, Br or I.

Also, unless stated otherwise in the present specification, a heterocycloalkyl group, a heterocycloalkylene group, a heteroaryl group, and a heteroarylene group each independently represent one or more heteroatoms of N, O, S, Si, or P in one ring. It contains three, and the rest means a cycloalkyl group, a cycloalkylene group, an aryl group, and an arylene group which are carbon.

Also, unless stated otherwise, "aliphatic" means C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C1 to C30 alkylene, C2 to C30 alkenylene, or C2 to C30 alkynylene Specifically, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkylene, C2 to C20 alkenylene, or C2 to C20 alkynylene, and "alicyclic" C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl, C3 to C30 cycloalkynyl, C3 to C30 cycloalkylene, C3 to C30 cycloalkenylene, or C3 to C30 cycloalkynylene, specifically C3 to C30 cycloalkynylene C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C3 to C20 cycloalkylene, C3 to C20 cycloalkenylene, or C3 to C20 cycloalkynylene, meaning "aromatic" 6 to C30 aryl, C2 to C30 heteroaryl, C6 to C30 arylene or C2 to C30 heteroarylene, specifically C6 to C16 aryl, C2 to C16 heteroaryl, C6 to C16 arylene or C2 to C16 Heteroarylene means.

Unless otherwise defined herein, “combination” generally means mixing or copolymerizing, in an alicyclic organic group and an aromatic organic group, at least two rings form a fused ring, or at least two rings are single Bond, -O-, -S-, -C (= O)-, -CH (OH)-, -S (= O)-, -S (= O) _2- , -Si (CH ₃ ) _2- ,-(CH ₂ ) _p- (where 1 ≤ p ≤ 2),-(CF ₂ ) _q- (where 1 ≤ _q ≤ 2), -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) (CF ₃ )-or -C (= 0) NH- means that they are connected to each other. Here, "copolymerization" means block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" means a block copolymer, random copolymer, graft copolymer or alternating copolymer.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

The thermoplastic resin composition according to one embodiment includes a base resin including (A) a polyarylene ether resin and a polyolefin resin, and (b-1) a copolymer including a styrene repeat unit and an olefin repeat unit. do. At this time, the content (weight, W _OL ) of the polyolefin resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy the relational formula of W _AR ≤1.9 × W _OL , and the polyarylene ether The ratio of the content of arylene moiety (% by weight) in the system resin to the content (% by weight) of styrene moiety in the copolymer is about 100: 20 to about 100: 55.

The thermoplastic resin composition according to another embodiment includes (A) a base resin including a polyarylene ether resin and a polyolefin resin, and (b-2) a styrene repeating unit and an olefin repeating unit, and a polar functional group Grafted polar copolymers. At this time, the content of the polyolefin resin (weight, W _OL ) and the content of the polyarylene ether resin (weight, W _AR ) satisfies the relationship of W _AR ≤ 1.9 × W _OL , the polar functional group is And (B1) the polar copolymer comprises about 0.1 parts by weight to about 100 parts by weight of the total repeating units of which the polar functional group is included in the polar copolymer. It is grafted to 7.0 parts by weight.

Polyarylene ether resins have excellent insulation, water resistance, dimensional stability, heat resistance, flame retardancy and mechanical strength, but poor meltability due to high melt viscosity, and poor flexibility and chemical resistance such as oil resistance. It has a strong smell and is yellow. Thereby, the polyarylene ether-based resin is difficult to be used alone to produce electric wires, for example, automotive electric wires.

Polyolefin resins are excellent in workability, flexibility and chemical resistance, and have low odor, but are poor in heat resistance, flame retardancy, and mechanical strength. As a result, the polyolefin-based resin is difficult to be used alone to produce electric wires, such as automotive electric wires.

The thermoplastic resin composition includes the polyarylene ether resin and the polyolefin resin, wherein the content of the polyolefin resin (W _OL ) and the content of the polyarylene ether resin (W _AR ) are W _AR ≦ 1.9. By including so as to satisfy the relation of x W _OL , the melt viscosity may be appropriately adjusted to have excellent workability, and may have excellent flexibility and chemical resistance, such as oil resistance. In addition, fillers, flame retardants and the like may be included in a sufficient amount to maintain the excellent level of insulation, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability. Specifically, the thermoplastic resin composition is a relational expression of the polyarylene ether-based resin and the polyolefin-based resin may include as to satisfy a relational expression of W _AR ≤1.2 × W _OL, more specifically, _AR W _OL ≤W Can be included to satisfy.

Specifically, the polyarylene ether resin may include a repeating unit represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ¹ is the same or different from each other, and each independently hydrogen, a halogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C2 to C30 aromatic organic group, or a substituted or unsubstituted C1 to C30 alkoxy group It may be specifically hydrogen, halogen, substituted or unsubstituted C1 to C10 aliphatic organic group, substituted or unsubstituted C2 to C10 aromatic organic group, or substituted or unsubstituted C1 to C10 alkoxy group, more specifically May be hydrogen, a halogen, a substituted or unsubstituted C1 to C5 aliphatic organic group, a substituted or unsubstituted C2 to C8 aromatic organic group, or a substituted or unsubstituted C1 to C6 alkoxy group.

n1 is the same or different in each repeating unit and is each independently an integer of 0 to 4.

When n1 is an integer of 2 or more, each of R ¹ may be the same or different from each other. In addition, R ¹ may be the same or different from each other in the repeating unit.

The polyarylene ether-based resin may include an arylene part in an amount of about 50% by weight to about 90% by weight with respect to the total weight of the polyarylene ether-based resin, and an electronegativity is 2.58 or more. It may include. In this case, it may have excellent workability, it is possible to effectively improve the heat resistance and flame retardance of the molded article manufactured using the thermoplastic resin composition comprising the same. Specifically, the polyarylene ether resin may include about 60% by weight to about 85% by weight, more specifically about 65% by weight to about 60% by weight, based on the total weight of the polyarylene ether resin. 75 wt%, more specifically, about 65 wt% to about 72 wt%.

Specifically, the polyarylene ether resin may be poly (1,4-phenylene ether), poly (1,3-phenylene ether), poly (1,2-phenylene ether), poly (2-methyl- 1,4-phenylene ether), poly (3-methyl-1,4-phenylene ether), poly (2-methyl-1,3-phenylene ether), poly (4-methyl-1,3-phenyl Lene ether), poly (5-methyl-1,3-phenylene ether), poly (6-methyl-1,3-phenylene ether), poly (3-methyl-1,2-phenylene ether), poly (4-methyl-1,2-phenylene ether), poly (5-methyl-1,2-phenylene ether), poly (6-methyl-1,2-phenylene ether), poly (2,6- Dimethyl-1,4-phenylene ether), poly (2,3-dimethyl-1,4-phenylene ether), poly (3,5-dimethyl-1,4-phenylene ether), poly (2,5 -Dimethyl-1,4-phenylene ether), poly (2,4-dimethyl-1,3-phenylene ether), poly (2,5-dimethyl-1,3-phenylene ether), poly (2, 6-dimethyl-1,3-phenylene ether), poly (4,5-dimethyl-1,3-phenylene ether), poly (4,6-dimethyl-1,3-phenylene ether), poly (5 , 6-di Thile-1,3-phenylene ether), poly (3,4-dimethyl-1,2-phenylene ether), poly (3,5-dimethyl-1,2-phenylene ether), poly (3,6 -Dimethyl-1,2-phenylene ether), poly (4,5-dimethyl-1,2-phenylene ether), poly (4,6-dimethyl-1,2-phenylene ether), poly (5, 6-dimethyl-1,2-phenylene ether) and combinations thereof, but is not limited thereto.

The polyarylene ether-based resin may have a weight average molecular weight (Mw) of about 10,000 μg / mol to about 1,000,000 μg / mol. When the weight average molecular weight (Mw) of the polyarylene ether-based resin is within the above range, processing is easy, and mechanical strength and heat resistance of the thermoplastic resin composition including the same may be effectively improved. Specifically, the polyarylene ether resin may have a weight average molecular weight (Mw) of about 40,000 μg / mol to about 300,000 μg / mol.

The polyarylene ether resin may have a number average molecular weight (Mn) of about 10,000 μg / mol to about 1,000,000 μg / mol. When the number average molecular weight (Mn) of the polyarylene ether-based resin is within the above range, processing is easy, and mechanical strength and heat resistance of a molded article manufactured using the thermoplastic resin composition including the same can be effectively improved. Specifically, the polyarylene ether resin may have a number average molecular weight (Mn) of about 15,000 μg / mol to about 300,000 μg / mol, more specifically about 15,000 μg / mol to about 30,000 μg / mol.

The polyarylene ether-based resin may have a polydispersity index (PDI) of about 1.2 to about 2.5. When the polydispersity index of the polyarylene ether resin is within the above range, processing is easy, and elongation and heat resistance of a molded article manufactured using the thermoplastic resin composition including the same may be effectively improved. Specifically, the polyarylene ether resin may have a polydispersity index (PDI) of about 1.3 kPa to about 1.8.

The polyolefin-based resin may have a melt index (MI) of about 0.1 g / 10 min to about 30 g / 10 min. When the melt index of the polyolefin resin is within the above range, it can be easily mixed with other resins and can effectively improve the mechanical strength of the thermoplastic resin composition comprising the same. Specifically, the polyolefin resin may have a melt index (MI) of about 0.1 g / 10 min to about 20 g / 10 min.

The polyolefin resin may have a melting point of about 80 ℃ to about 170 ℃. When the melting point of the polyolefin resin is within the above range, it is possible to effectively improve the heat resistance and mechanical strength of the thermoplastic resin composition comprising the same. Specifically, the polyolefin resin may have a melting point of about 95 ° C to about 135 ° C, more specifically about 105 ° C to about 125 ° C.

The polyolefin-based resin may have a weight average molecular weight (Mw) of about 10,000 μg / mol to about 1,000,000 μg / mol. When the weight average molecular weight (Mw) of the polyolefin resin is within the above range, the processing is easy, and the mechanical strength of the thermoplastic resin composition including the same may be effectively improved. Specifically, the polyolefin resin may have a weight average molecular weight (Mw) of about 40,000 kg / mol to about 300,000 kg / mol.

The polyolefin resins may be used alone or in combination of two or more, and may have a weighted average density of about 0.95 g / cm ³ or less. In this case, the flexibility and cold resistance of the thermoplastic resin composition including the same can be effectively improved. Specifically, the polyolefin-based resin may have a weight-weighted average density of about 0.94 g / cm ³ or less, more specifically about 0.91 g / cm ³ to 0.94 g / cm ³ . The weight-weighted average density means that the weight of each polyolefin is multiplied by each polyolefin density and averaged. When a single resin is used, the density of the resin is a weighted weight average density.

The polyolefin resin is a high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer (ethylene-octene copolymer), ultra low density Ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene and combinations thereof It may include one selected from, but is not limited thereto. Specifically, the polyolefin resin may be a linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer (ethylene-octene copolymer), ethylene-propylene copolymer (ethylene- propylene copolymer, ethylene-butene copolymer, and combinations thereof.

In the copolymer comprising the (b-1) styrene repeating unit and the olefin repeating unit, the styrene repeating unit is compatible with the polyarylene ether resin, the olefin repeating unit with the polyolefin resin By acting as a compatibilizer having compatibility, the polyarylene ether resin and the polyolefin resin can be uniformly dispersed.

Specifically, the (b-1) copolymer is a styrene-ethylene-butylene-styrene copolymer (styrene-ethylene-butylene-styrene copolymer, SEBS), styrene-butadiene-styrene copolymer (styrene-butadiene-styrene copolymer, SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene copolymer (styrene) -ethylene copolymer), styrene-ethylene-butadiene-styrene copolymer (styrene-ethylene-butadiene-styrene copolymer) may include one selected from, but combinations thereof, but is not limited thereto.

The (b-1) copolymer may include about 20 wt% to about 45 wt% of a styrene part based on the total weight of the (b-1) copolymer. In this case, compatibility with polyarylene ether resin and compatibility with polyolefin resin can be improved effectively. Specifically, the copolymer (b-1) may include about 30 wt% to about 40 wt% of the styrene portion based on the total weight of the copolymer.

In the thermoplastic resin composition, the ratio of the content (wt%) of the arylene portion in the polyarylene ether resin to the content (wt%) of the styrene portion in the copolymer is about 100: 20 to about 100: 55 Can be. In this case, the elongation, heat resistance, flame retardancy, and cold resistance of the thermoplastic resin composition can be effectively improved. Specifically, the ratio of the content of arylene portion (% by weight) in the polyarylene ether resin to the content (% by weight) of styrene part in the copolymer is about 100: 30 to about 100: 50, more specifically And from about 100: 35 to about 100: 45.

The (b-2) polar copolymer serves to help uniformly disperse the polyarylene ether-based resin and the polyolefin-based resin, and also includes a polar functional group to fill fillers, flame retardants, and other additives with the base resin. The affinity with and to help the filler, flame retardant and other additives to be uniformly dispersed in the base resin.

The polar copolymer (b-2) is about 0.1 parts by weight to 100 parts by weight of the total repeating units of the polar copolymer including a bond between elements having an electronegativity difference of about 0.5 kPa to about 3.0. It is grafted at about 7.0 parts by weight. In this case, the polyarylene ether resin and the polyolefin resin may be effectively and uniformly dispersed, and fillers, flame retardants and other additives may be effectively and uniformly dispersed in the base resin. Specifically, the polar copolymer (b-2) may be grafted at about 0.3 parts by weight to about 2.0 parts by weight based on 100 parts by weight of the total repeating units included in the polar copolymer.

The polar functional group is a substituted or unsubstituted C3 to C30 anhydride group, a substituted or unsubstituted C1 to C30 carboxyl group, a substituted or unsubstituted C2 to C30 ester group, a hydroxyl group, a substituted or unsubstituted C1 to C30 Alcohol group, amine group (NH ₂ ), substituted or unsubstituted C1 to C20 amino group (NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or mutually Different and each independently C1 to C10 alkyl group), substituted or unsubstituted C2 to C30 epoxy group, substituted or unsubstituted C1 to C30 ketone group, -SH, substituted or unsubstituted C1 to C30 thioalcohol group and these It may be selected from a combination of, specifically substituted or unsubstituted C3 to C20 unhydride group, substituted or unsubstituted C1 to C20 carboxyl group, substituted or unsubstituted C2 to C20 ester group, hydroxy group, substituted Or unsubstituted A C1 to C20 alcohol group, an amine group (NH ₂ ), a substituted or unsubstituted C1 to C10 amino group (NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are The same or different from each other, each independently a C1 to C5 alkyl group, a substituted or unsubstituted C2 to C20 epoxy group, a substituted or unsubstituted C1 to C20 ketone group, -SH, a substituted or unsubstituted C1 to C20 thioalcohol Groups and combinations thereof, and more particularly, substituted or unsubstituted C3 to C10 unhydride groups, substituted or unsubstituted C1 to C10 carboxyl groups, substituted or unsubstituted C2 to C10 ester groups, and hydrides. A hydroxyl group, a substituted or unsubstituted C1 to C10 alcohol group, an amine group (NH ₂ ), a substituted or unsubstituted C1 to C6 amino group (NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ^200, R ²⁰¹ and R ²⁰² are the same or different, each independently represent a C1 to C3 Or a substituted or unsubstituted C2 to C10 epoxy group, a substituted or unsubstituted C1 to C10 ketone group, -SH, a substituted or unsubstituted C1 to C10 thioalcohol group, and combinations thereof, but It is not limited.

Specifically, the (b-2) polar copolymer is maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS), maleic hydride-grafted styrene-ethylene-butadiene -Styrene copolymer, maleic hydride-grafted styrene-ethylene-styrene copolymer, maleic hydride-grafted styrene-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-propylene Styrene copolymer, maleic hydride-grafted styrene-ethylene-octene-styrene copolymer, maleic hydride-grafted styrene-isoprene-styrene copolymer, and combinations thereof. However, the present invention is not limited thereto.

The (b-2) polar copolymer may include about 10 wt% to about 50 wt% of the styrene repeating unit with respect to the total amount of repeating units included in the (b-2) polar copolymer. In this case, the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility with the resin, the filler, the flame retardant, etc. are improved, and the workability, flexibility, flame retardancy, and heat resistance of the thermoplastic resin composition including the same can be effectively improved. Can be. Specifically, the (b-2) polar copolymer may include about 15% to about 35% by weight of the styrene-based repeating unit based on the total amount of repeating units included in the (b-2) polar copolymer. .

In the thermoplastic resin composition, (A) the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% to about 90% by weight of the polyolefin resin relative to the total amount of the base resin %, And the (b-1) copolymer may be included in an amount of about 1 parts by weight to about 40 parts by weight based on 100 parts by weight of the base resin. When the content of the polyarylene ether resin, the polyolefin resin and the (b-1) copolymer is within the above range, the flexibility, heat resistance, voltage resistance, abrasion resistance, and flame resistance of the thermoplastic resin composition may be effectively improved. . Specifically, in the thermoplastic resin composition, the base resin is about 20% to about 55% by weight of the polyarylene ether resin and about 45% to about 80% by weight of the polyolefin resin based on the total amount of the base resin. %, And the copolymer may be included in about 5 parts by weight to about 30 parts by weight based on 100 parts by weight of the base resin.

In the thermoplastic resin composition, (A) the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% to about 90% by weight of the polyolefin resin relative to the total amount of the base resin %, And the (b-2) polar copolymer may be included in about 1 parts by weight to about 40 parts by weight based on 100 parts by weight of the base resin. When the content of the polyarylene ether resin, the polyolefin resin and the polar copolymer is within the above range, the flexibility, heat resistance, abrasion resistance and flame retardancy of the thermoplastic resin composition can be effectively improved. Specifically, in the thermoplastic resin composition, the base resin (A) may include about 20 wt% to about 55 wt% of the polyarylene ether resin and about 45 wt% of the polyolefin resin based on the total amount of the base resin. About 80% by weight, and the (b-2) polar copolymer may be included in an amount of about 5 parts by weight to about 30 parts by weight based on 100 parts by weight of the base resin.

The thermoplastic resin composition may be grafted to about 0.001 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total repeating units contained in the thermoplastic resin composition. In this case, the polyarylene ether resin and the polyolefin resin may be effectively and uniformly dispersed, and fillers, flame retardants, and other additives may be effectively and uniformly dispersed in the base resin. Specifically, the thermoplastic resin composition may be grafted to about 0.01 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total repeating units included in the thermoplastic resin composition.

According to another embodiment, a thermoplastic resin composition includes a base resin including (A) a polyarylene ether resin and a polyolefin resin, (B) (b-1) a styrene repeating unit, and an air containing an olefin repeating unit. (B-2) a copolymer comprising a styrene repeating unit and an olefin repeating unit and grafted with a polar functional group, a polymer containing a styrene repeating unit and a grafted polar functional group, and an olefin repeating unit And polar polymers selected from polymers grafted with polar functional groups and combinations thereof. At this time, the content of the polyolefin-based resin (W _OL ) and the content of the polyarylene ether-based resin (W _AR ) satisfies the relationship of W _AR ≤ 1.9 × W _OL , the polar functional group has a slight difference in electronegativity And (b-2) the polar polymer is grafted from about 0.1 parts by weight to about 7.0 parts by weight based on 100 parts by weight of the total repeating units included in the polar polymer. have.

Unless otherwise described below, descriptions of the polyarylene ether resin, the polyolefin resin, and the polar functional group are as described above.

The copolymer (b-1) includes a styrene repeating unit and an olefin repeating unit to uniformly disperse the polyarylene ether resin and the polyolefin resin, and the thermoplastic resin composition including the same has excellent physical properties. Can help you implement

Specifically, the (b-1) copolymer may be a styrene-ethylene-butylene-styrene copolymer (SEBS), a styrene-butadiene-styrene copolymer (SBS), a styrene-ethylene-propylene-styrene copolymer (SEPS), Styrene-isoprene-styrene copolymer (SIS), styrene-ethylene copolymer, styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-octene-styrene copolymer, and combinations thereof, It is not limited to this.

The (b-1) copolymer may include about 10% by weight to about 50% by weight of the styrene-based repeating unit based on the total amount of repeating units included in the (b-1) copolymer. In this case, the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility with the resin, the filler, the flame retardant, etc. are improved, and the workability, flexibility, flame retardancy, and heat resistance of the thermoplastic resin composition including the same can be effectively improved. Can be. Specifically, the (b-1) copolymer may include about 15 wt% to about 35 wt% of the styrene-based repeating unit based on the total amount of repeating units included in the (b-1) copolymer.

The (b-2) polar polymer serves to help uniformly disperse the polyarylene ether resin and the polyolefin resin, and also includes a polar functional group to fill fillers, flame retardants and other additives with the base resin. By increasing the affinity of the filler may help to uniformly disperse fillers, flame retardants and other additives in the base resin.

The polar polymer (b-2) may have a polar functional group including a bond between elements having an electronegativity difference of about 0.5 kPa to about 3.0, based on 100 parts by weight of the total repeating unit included in the polar polymer, and about 0.1 part by weight to about 7.0. It is grafted in parts by weight. In this case, the polyarylene ether resin and the polyolefin resin may be effectively and uniformly dispersed, and fillers, flame retardants and other additives may be effectively and uniformly dispersed in the base resin. Specifically, the polar polymer (B2) may be grafted at about 0.3 parts by weight to about 2.0 parts by weight based on 100 parts by weight of the total repeating units included in the polar polymer.

Specifically, the (b-2) polar polymer may be a maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS), a maleic hydride-grafted styrene-ethylene-butadiene- Styrene copolymer, maleic hydride-grafted styrene-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-propylene-styrene copolymer, maleic hydride-grafted styrene-isoprene- Styrene copolymer, maleic anhydride grafted styrene-ethylene copolymer, maleic unhydride-grafted styrene-ethylene-styrene copolymer, maleic unhydride-graft Styrene-ethylene-octene-styrene copolymer, maleic anhydride grafted polyphenyle ne ether), maleic anhydride grafted high impact polystyrene, maleic anhydride grafted low density polyethylene, maleic hydride-grafted low density polyethylene Ethylene-propylene copolymer, maleic hydride-grafted ethylene-butadiene copolymer, maleic hydride-grafted ethylene-octene copolymer, maleic hydride grafted polypropylene ), Maleic anhydride-grafted linear low density polyethylene (maleic anhydride grafted linear low density polyethylene), and combinations thereof, but is not limited thereto.

When the (b-2) polar polymer includes a styrene repeating unit and an olefin repeating unit, the styrene repeating unit may include about 10% by weight to about 50% by weight based on the total amount of repeating units included therein. And specifically, about 15% to about 35% by weight. In this case, the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility with the resin, the filler, the flame retardant, etc. are improved, and the workability, flexibility, flame retardancy, and heat resistance of the thermoplastic resin composition including the same can be effectively improved. Can be.

In the thermoplastic resin composition, (A) the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% to about 90% by weight of the polyolefin resin relative to the total amount of the base resin %, Wherein the (b-1) copolymer may be included in an amount of about 1 parts by weight to about 40 parts by weight based on 100 parts by weight of the base resin, and the (b-2) polar polymer may include 100 parts by weight of the base resin. It can be included from about 1 to about 40 parts by weight relative to parts by weight. When the content of the polyarylene ether resin, the polyolefin resin, the (b-1) copolymer and the (b-2) polar polymer is within the above range, the flexibility, heat resistance, abrasion resistance and flame resistance of the thermoplastic resin composition Can be effectively improved. Specifically, in the thermoplastic resin composition, the base resin (A) may include about 20 wt% to about 55 wt% of the polyarylene ether resin and about 45 wt% of the polyolefin resin based on the total amount of the base resin. About 80% by weight, the (b-1) copolymer may be included in an amount of about 5 parts by weight to about 30 parts by weight with respect to 100 parts by weight of the base resin, and the (b-2) polar polymer is About 5 parts by weight to about 30 parts by weight based on 100 parts by weight of the base resin may be included.

The thermoplastic resin composition may be grafted to about 0.001 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total repeating units contained in the thermoplastic resin composition. In this case, the polyarylene ether resin and the polyolefin resin may be effectively and uniformly dispersed, and fillers, flame retardants, and other additives may be effectively and uniformly dispersed in the base resin. Specifically, the thermoplastic resin composition may be grafted to about 0.01 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total repeating units included in the thermoplastic resin composition.

The thermoplastic resin composition may further include a filler, specifically, an inorganic filler.

The fillers or inorganic fillers may serve as flame retardants and reinforcing agents to improve flame retardancy and mechanical properties, such as wear resistance, of the thermoplastic resin composition comprising the same.

The inorganic filler may have a decomposition temperature of about 200 ° C. or more. If the decomposition temperature of the inorganic filler is within the above range, physical properties may not be impaired during melt mixing with the polymer. Specifically, the inorganic filler may have a decomposition temperature of about 200 ° C to about 900 ° C, more specifically about 250 ° C to about 350 ° C. The decomposition temperature of the inorganic filler is measured by heating in nitrogen or air using a Q5000 (manufactured by TA Instrument) equipment.

For example, the inorganic filler is magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate (potassium titanate), magnesium silicate (magnesium silicate), aluminum oxide hydroxide (aluminum oxide hydroxide), and combinations thereof, but is not limited thereto. Specifically, the inorganic filler may include one selected from magnesium oxide, magnesium hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate, magnesium silicate, and combinations thereof.

The thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight of the (inorganic) filler with respect to 100 parts by weight of the thermoplastic resin composition not containing the (inorganic) filler. When the filler is included in the above range, it is possible to effectively improve the flame retardancy and mechanical properties, such as wear resistance of the thermoplastic resin composition comprising the same. Specifically, the thermoplastic resin composition may contain about 10 parts by weight to about 100 parts by weight, more specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the thermoplastic resin composition not containing the filler. More specifically, it may include from about 10 parts by weight to about 40 parts by weight.

On the other hand, the thermoplastic resin composition may further include a flame retardant. The flame retardant may play a role of improving flame retardancy and heat resistance of the thermoplastic resin composition including the same.

The flame retardant is selected from phosphate compounds, phosphite compounds, phosphonate compounds, polysiloxanes, phosphazene compounds, phosphinate compounds, melamine compounds and combinations thereof It may include one, but is not limited thereto.

The thermoplastic resin composition may include about 1 parts by weight to about 50 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin composition not containing the flame retardant. When the content of the flame retardant is within the above range, it is possible to effectively improve the flame retardancy and heat resistance of the thermoplastic resin composition comprising the same. Specifically, the thermoplastic resin composition may contain about 1 parts by weight to about 40 parts by weight, more specifically about 3 parts by weight to about 30 parts by weight, based on 100 parts by weight of the thermoplastic resin composition not containing the flame retardant. More specifically, the content may be included in about 5 parts by weight to about 20 parts by weight.

When the thermoplastic resin composition includes both the filler and the flame retardant, the filler and the flame retardant may be included in a weight ratio of about 50: 1 Pa to about 1:10. When the content ratio of the filler and the flame retardant is within the above range, it is possible to effectively improve the flame retardancy, heat resistance, mechanical strength and elongation of the thermoplastic resin composition including the same. Specifically, the filler and the flame retardant may be included in a weight ratio of about 10: 1 kPa to about 1: 3.

The thermoplastic resin composition may have a limited oxygen index (LOI) of about 18 kPa to about 50. When the limit oxygen index of the thermoplastic resin composition is within the above range, the thermoplastic resin composition may have excellent flame resistance, heat resistance and mechanical strength. Specifically, the thermoplastic resin composition may have a limiting oxygen index (LOI) of about 21 kPa to about 35, more specifically about 21 kPa to about 28.

In addition to the components, the thermoplastic resin composition may include dyes, pigments, stabilizers, lubricants, etc., as necessary to improve injection moldability, physical property balance, dispersibility, and to prevent oxidation and to suppress the formation of die drool. Processing additives such as stearates, antibacterial agents, mold release agents, resin antioxidants, copper antioxidants, and halogen scavengers may be further appropriately included. In this case, the additives may be used alone or in combination of two or more thereof.

Thermoplastic resin composition according to one embodiment may be prepared by a known method for producing a resin composition. For example, after mixing each of the components and other additives simultaneously, they can be melt extruded in an extruder and made into pellets.

Thermoplastic resin composition according to one embodiment does not include a separate crosslinking (crosslinking) can be easily recycled and does not use a halogen-based flame retardant is environmentally friendly. In addition, the thermoplastic resin composition includes the polyolefin-based resin and the polyarylene ether-based resin in a specific weight range, and includes a specific copolymer, thereby providing workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, insulation, and mechanical strength. And chemical resistance can be effectively improved.

Another embodiment manufactures a molded article including the thermoplastic resin composition. The molded article may be manufactured by various methods such as injection molding, blow molding, extrusion, and thermoforming using the thermoplastic resin composition.

The molded article may be a wire or a wire covering material, which may be used in various fields such as power lines, communication lines, automotive wires, electronic device wires, nuclear power wires, and wind power wires.

As an example, a cross-sectional view of a wire according to one embodiment is shown in FIG. 1.

Referring to FIG. 1, the wire 1 comprises a conductor 2 and a sheathing material 4 surrounding the conductor. At this time, the conductor 2, the coating material 4 or a combination thereof may include the thermoplastic resin composition.

The conductor 2 may be one strand or may include two or more strands. When the conductor 2 has several strands, the coating member 4 may be formed to surround each strand, or the coating member 4 may be formed to surround several strands at once.

As an example, a cross-sectional view of a wire according to another embodiment is shown in FIG. 2.

Referring to FIG. 2, the electric wire 10 surrounds the conductor 11, the covering material 13 surrounding the conductor 11, the insulator 15 surrounding the covering material 13, and the insulator 15. It includes a sheath (17). In this case, the conductor 11, the covering 13, the insulator 15, the sheath 17, or a combination thereof may include the thermoplastic resin composition.

The conductor 11 may be one strand or may include two or more strands. When the conductor 11 has several strands, the covering 13, the insulator 15, the sheath 17, or a combination thereof are formed to surround each strand, or the covering 13 is formed so as to surround several strands at once. The insulator 15, the sheath 17, or a combination thereof may be formed, but is not limited thereto.

As an example, a cross-sectional view of a wire according to another embodiment is shown in FIG. 3.

Referring to FIG. 3, the electric wire 20 surrounds the conductor 21, the covering member 23 surrounding the conductor 21, the insulator 25 surrounding the covering member 23, and the insulator 25. Shield 27, and a sheath 29 surrounding the shield 27. In this case, the conductor 21, the cover material 23, the insulator 25, the shield 27, the sheath 29, or a combination thereof may include the thermoplastic resin composition.

The conductor 21 may be one strand or may include two or more strands. When the conductor 21 has several strands, the coating member 23, the insulator 25, the shield 27, the sheath 29, or a combination thereof are formed to surround each strand, or the strands are surrounded at one time. The covering 23, the insulator 25, the shield 27, the sheath 29, or a combination thereof may be formed, but is not limited thereto.

1 to 3 only show examples of the structure of the wire according to the embodiment, and the structure of the wire according to the embodiment is not limited thereto.

Unless stated otherwise herein, information about wires, conductors, sheaths, insulators, shields, and sheaths is as generally known in the art.

The molded article may have an elongation of from about 50% to about 600% as measured by JASO D 618. When the elongation of the molded article is within the above range, it can be effectively elongated without being broken when pulled through various spaces, and can have excellent compatibility, flexibility and cold resistance. Specifically, the molded article may have an elongation of about 110% to about 600%, more specifically about 120% to about 400%, more specifically about 150% to about 400% as measured by JASO D 618. The JASO D 618 is a 2008 version.

The molded article may have an elongation after aging for about 240 hours at a temperature of about 150 ° C. may be about 60% or more relative to the elongation before aging, which can be obtained by calculating the following Equation 1. In this case, the molded article can maintain excellent durability even when used for a long time in a high temperature environment. Specifically, the molded article has an elongation after the molded article aged at a temperature of about 150 ° C. for about 240 hours, about 60% to about 130%, more specifically about 60% to about elongation before the aging. May be 100%.

[Equation 1]

(Elongation after aging / Elongation before aging) × 100 (%)

The molded article may have a time from extinguishing to igniting, as measured by ISO 6722, within about 70 seconds, such as from about 1 second to about 70 seconds. When the time from the ignition to extinguishing the molded article is within the above range, the molded article may have excellent flame retardancy. Specifically, the molded article has a time from ignition to extinguishment as measured by ISO 6722 within about 50 seconds, such as about 1 second to about 50 seconds, more specifically about 1 second to about 40 seconds, more specifically About 1 second to about 20 seconds, more specifically about 1 second to about 15 seconds. The ISO 6722 is the August 1, 2006 version.

The molded article may have a tensile strength of about 5 MPa to about 60 MPa as measured by ASTM D638. When the tensile strength of the molded article is within the above range, the molded article has excellent mechanical strength and can be effectively applied to various applications. Specifically, the molded article may have a tensile strength of about 10 MPa to about 40 MPa, more specifically about 15 MPa to about 35 MPa as measured by ASTM D638.

The molded article may have a wear resistance of about 400 mm to about 3000 mm as measured by the ISO 6722 sandpaper abrasion test method. When the wear resistance of the molded article is within the above range, the molded article may have appropriately balanced strength and flexibility. Specifically, the molded article may have a wear resistance of about 600 mm to about 2500 mm as measured by the ISO 6722 sandpaper abrasion test method. The ISO 6722 is the August 1, 2006 version.

The molded article may have a diameter change rate of about 15% or less after gasoline immersion as measured by ISO 6722. When the diameter change rate after the gasoline immersion of the molded product is within the above range, the molded article may have excellent oil resistance, flexibility and cold resistance. Specifically, the molded article may have a diameter change rate of about 0.01% to about 10.0% after gasoline immersion as measured by ISO 6722. The ISO 6722 is the August 1, 2006 version.

The molded article may have an abnormality in the lead when the cold resistance evaluation according to ISO 6722, and may pass the withstand voltage test. The ISO 6722 is the August 1, 2006 version.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.

Each component used for manufacture of a thermoplastic resin composition is as follows.

(A1) polyarylene ether resin

Polyphenylene ether (PPE): LXR-035C (manufactured by Blue Star), content of phenylene moiety 87% by weight

(A2) polyolefin resin

Linear low density polyethylene (LLDPE): LLDPE 9730 (manufactured by Hanwha Chemical), density 0.92 g / cm ³ , melting point 112 ° C

(b-2-1) polar copolymers

Maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS): Tuftec M1913 (manufactured by Asahi Kasei Chemicals), maleic hydride The graft ratio of 0.5 parts by weight relative to the total 100 parts by weight of the repeating units contained in the styrene-ethylene-butylene-styrene copolymer, the styrene repeating unit content is the total amount of repeating units included in the styrene-ethylene-butylene-styrene copolymer 30 wt% against

(b-1) copolymer

(b-1-1) Styrene-ethylene-butylene-styrene copolymer (SEBS): Kraton G1651 (manufactured by Kraton Polymers), and the styrene repeating unit content is styrene-ethylene-butylene- 22% by weight, based on the total amount of repeating units contained in the styrene copolymer

(b-1-2) Styrene-butadiene-styrene copolymer (SBS): Kraton D1102 (manufactured by Kraton Polymers), the styrene repeating unit content is a repeating unit included in the styrene-butadiene-styrene copolymer 28 wt% based on the total amount

(b-2-2) polar polymers

Maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS): Tuftec M1913 (manufactured by Asahi Kasei Chemicals), maleic hydride The graft ratio of 0.5 parts by weight relative to the total 100 parts by weight of the repeating units contained in the styrene-ethylene-butylene-styrene copolymer, the styrene repeating unit content is the total amount of repeating units included in the styrene-ethylene-butylene-styrene copolymer 30 wt% against

(b-2-3) Polar polymer

Maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS): The graft ratio of maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer (styrene-ethylene-butyl) 8.0 parts by weight based on 100 parts by weight of the total repeating units contained in the styrene-styrene copolymer, and styrene repeating unit content is 30% by weight based on the total amount of the repeating units included in the styrene-ethylene-butylene-styrene copolymer.

(b-1) copolymer

(b-1-3) Styrene-ethylene-butylene-styrene copolymer (SEBS): Kraton G1643 (manufactured by Kraton Polymer), content of styrene portion 20% by weight

(b-1-4) Styrene-ethylene-butylene-styrene copolymer (SEBS): Kraton D1102 (manufactured by Kraton Polymer), content of styrene portion 30% by weight

(b-1-5) Styrene-ethylene-butylene-styrene copolymer (SEBS): Tuftec H1051 (manufactured by Asahi Kasei), content of styrene portion 45% by weight

(b-1-6) Styrene-ethylene-butylene-styrene copolymer (SEBS): Kraton G1657 (manufactured by Kraton Polymer), content of styrene portion 15% by weight

(b-1-7) Styrene-ethylene-butylene-styrene copolymer (SEBS): Kraton A1535 (manufactured by Kraton Polymer), content of styrene portion 60% by weight

(D-1) Filler

Magnesium hydroxide (Mg (OH) ₂ ): MAGNIFIN ^® -5A (manufactured by Albemarle)

(D-2) inorganic filler

Magnesium hydroxide (Mg (OH) ₂ ): MAGNIFIN ^® H-5 IV (manufactured by Albemarle), decomposition temperature 320 ° C

The decomposition temperature was measured using a Q5000 (manufactured by TA Instrument) equipment.

(E) flame retardant

Exolit OP 1240 (manufactured by Clarit)

Examples 1 to 7 and Comparative Examples 1 to 3: Preparation of the thermoplastic resin composition

The thermoplastic resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1 using the above-mentioned components. In addition, the thermoplastic resin compositions of Examples 8 to 11 and Comparative Examples 4 to 7 were prepared with the compositions shown in Table 2 below.

As the manufacturing method, each component was mixed by the composition shown in following Table 1, and it mixed in the usual mixer. Then, the barrel temperature (barrel temperature) was set to about 250 ° C. and put into a twin screw extruder SHJ35 (manufactured by NJFY) having L / D = 44 and Φ = 35 mm. The mixture was prepared into a resin composition in pellet form through an extruder.

Moreover, each component was mixed by the composition shown in following Table 2, and it mixed in the usual mixer. Then, the barrel temperature (barrel temperature) was set to about 260 ° C. and put into a twin screw extruder SHJ35 (manufactured by NJFY) having L / D = 44 and Φ = 35 mm. The mixture was prepared into a resin composition in pellet form through an extruder.

Table 1 Example Comparative example One 2 3 4 5 6 7 One 2 3 Base resin (A1) weight% 40 40 40 44 40 40 10 40 40 85 (A2) 60 60 60 56 60 60 90 60 60 15 (b-1) Arylene part: styrene part ratio (weight ratio) (b-1-3) 87:20 Parts by weight relative to 100 parts by weight of the base resin 15 - - - - - - - - - (b-1-4) 87:30 - 15 - 24 22 7 15 - - 15 (b-1-5) 87:45 - - 15 - - - - - - - (b-1-6) 87:15 - - - - - - - 15 - - (b-1-7) 87:60 - - - - - - - - 15 - (D-1) 21 21 21 23 13 36 50 21 21 10 (E) 13 13 13 15 13 6 5 13 13 30

TABLE 2 Example Comparative example 8 9 10 11 4 5 6 Base resin (A1) PPE weight% 60 50 50 50 95 50 50 (A2) LLDPE 40 50 50 50 15 50 50 (b-2-1) Tuftec M1913 Parts by weight relative to 100 parts by weight of the base resin 20 20 20 (b-1) (b-1-1) 20 20 (b-1-2) 20 (b-2-2) Tuftec M1913 10 10 (b-2-3) Cheil Industries Polymers 20 (D-2) MAGNIFIN ^® H-5 IV 30 30 30 30 30 30 30

Test Example 1: Elongation Evaluation

The thermoplastic resin compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were each set to a barrel temperature of about 240 ° C. and fed into a single screw extruder (manufactured by Vikas engineering Works) having L / D = 28 and Φ = 30 mm. The thermoplastic resin composition was prepared in the form of a wire through an extruder. At this time, a wire rod of 0.5 SQ was used.

For each specimen prepared above, elongation was measured according to the JASO D 618 elongation measuring method. The higher the value, the better the elongation.

The results are shown in Tables 3 and 4 below.

Test Example 2: Flame Retardancy Evaluation

For each specimen prepared in Test Example 1, the flame retardancy was evaluated by measuring the time taken before ignition after ignition according to the ISO 6722 flame retardant test method. The smaller the value, the faster the fire extinguisher is.

The results are shown in Tables 3 and 4 below.

Test Example 3 Evaluation of Heat Resistance and Voltage Resistance

Each of the specimens of Examples 1 to 7 and Comparative Examples 1 to 3 of the specimens prepared in Test Example 1 was aged at a temperature of about 150 ° C. for about 240 hours, and then a voltage of about 8 kV for about 1 minute. Was added to evaluate the heat resistance and voltage resistance according to whether or not the specimen was destroyed. At this time, each specimen is immersed in a water-filled water bath, and if there is no current leakage, it is marked as "pass" because the specimen is not destroyed, and if there is a current leakage, it is considered as "fail". Display.

The results are shown in Table 3 below.

Test Example 4: Cold Resistance Evaluation

Among the specimens prepared in Test Example 1, each of the specimens of Examples 1 to 7 and Comparative Examples 1 to 3 was evaluated for cold resistance according to the ISO 6722 cold resistance (low temperature characteristics) evaluation method. At this time, if there is no abnormality in the conductor and there is no current leakage and there is no abnormality in the breakdown voltage, the specimen is not broken and is marked as "pass". It is marked as "fail" because it is destroyed.

The results are shown in Table 3 below.

Test Example 5: Evaluation of Wear Resistance

For each specimen prepared in Test Example 1, wear resistance was evaluated according to the ISO 6722 sandpaper abrasion test method. The larger the value, the better the wear resistance.

The results are shown in Tables 3 and 4 below.

Test Example 6: Oil Resistance Evaluation

For each specimen prepared in Test Example 1, after immersion in gasoline according to the ISO 6722 oil resistance test method, the rate of change of the diameter of the specimen was measured. The smaller the rate of change of the diameter of the specimen, the better the oil resistance.

The results are shown in Tables 3 and 4 below.

Test Example 7: Evaluation of Tensile Strength

Among the specimens prepared in Test Example 1, for each of the specimens of Examples 8 to 11 and Comparative Examples 4 to 6, the tensile strength was measured according to the ASTM D 638 tensile strength measurement method. The larger the value, the better the tensile strength.

The results are shown in Table 4 below.

Test Example 8: Evaluation of physical property retention after heating

Of the specimens prepared in Test Example 1, each of the specimens of Examples 8 to 11 and Comparative Examples 4 to 6 after aging (240) for 240 hours at a temperature of about 150 ℃ to measure the elongation before aging The physical property retention after heating was evaluated by calculating the ratio of elongation after aging to Equation 1 below. The larger the value, the better the property retention after heating.

The results are shown in Table 4 below.

[Equation 1]

(Elongation after aging / Elongation before aging) × 100 (%)

TABLE 3 Example Comparative example One 2 3 4 5 6 7 One 2 3 % Elongation 220 210 190 170 200 150 250 200 110 110 Flame retardant (seconds) 10 7 3 5 9 12 13 120 21 One Heat resistance and voltage resistance pass pass pass pass pass pass pass pass fail pass Cold resistance pass pass pass pass pass pass pass fail fail fail Wear resistance 1200 1100 1000 1300 900 1500 450 1000 1200 2000 Oil resistance 5 6 7 9 6 4 3 8 7 21

Table 4 Example Comparative example 8 9 10 11 4 5 6 % Elongation 270 220 250 250 50 90 190 Flame retardant (seconds) 20 50 40 40 10 70 100 Tensile Strength (MPa) 27 23 22 22 30 25 20 Abrasion Resistance (mm) 2500 2000 1900 1800 3000 2000 1000 Physical property retention rate after heating (%) 80 65 70 70 70 45 45 Oil resistance (%) 7 5 5 4 20 8 8

As shown in Table 3, it can be seen that the case of using the thermoplastic resin composition of Examples 1 to 7 is excellent in cold resistance than the case of using the thermoplastic resin composition of Comparative Examples 1 to 3. When the thermoplastic resin compositions of Examples 1 to 7 were used, the flame retardancy was superior to that of the thermoplastic resin compositions of Comparative Examples 1 and 2, and the elongation was superior to that when the thermoplastic resin compositions of Comparative Examples 2 and 3 were used. It can be confirmed that heat resistance and withstand voltage resistance are superior to the case where the thermoplastic resin composition of Example 2 is used, and oil resistance is superior to the case where the thermoplastic resin composition of Comparative Example 3 is used.

Therefore, it can be seen that the thermoplastic resin compositions of Examples 1 to 7 have excellent cold resistance and at the same time have excellent elongation, flame retardancy, heat resistance and voltage resistance, abrasion resistance, and oil resistance.

As shown in Table 4, when the thermoplastic resin compositions of Examples 8 to 11 were used, the elongation and oil resistance were superior to those of the thermoplastic resin compositions of Comparative Examples 4 to 6, and the thermoplastic resin compositions of Comparative Examples 5 and 6 were used. It can be seen that the flame retardancy and the retention of physical properties after heating are superior to the case of using, and the tensile strength and the wear resistance are superior to the case of using the thermoplastic resin composition of Comparative Example 6.

Therefore, when the thermoplastic resin compositions of Examples 8 to 11 are used, it can be confirmed that all of the elongation, flame retardancy, tensile strength, wear resistance, physical property retention after heating, and oil resistance are excellent.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

[Description of the code]

71, 10, 20: wires, 2, 11, 21: conductors,

4, 13, 23: covering material, 15, 25: insulator,

17, 29: sheath, 27: shield

Claims (20)

(A) a base resin containing a polyarylene ether resin and a polyolefin resin, and (B) (b-1) A copolymer comprising a styrene repeating unit and an olefin repeating unit, (b-2) A polarity containing at least one of a styrene repeating unit and an olefin repeating unit and having a polar functional group grafted thereon Copolymers, or combinations thereof Including, The content of the polyolefin-based resin (W _OL ) and the content of the polyarylene ether-based resin (W _AR ) satisfies the relationship of W _AR ≤ 1.9 × W _OL , The ratio of the content (wt%) of the arylene portion in the polyarylene ether resin and the content (wt%) of the styrene portion in the copolymer is 100: 20 to 100: 55. The method of claim 1, The polar functional group includes a bond between elements having an electronegativity difference of 0.5 kPa to 3.0, The (b-2) polar copolymer is a thermoplastic resin composition in which the polar functional group is grafted to 0.1 parts by weight to 7.0 parts by weight based on 100 parts by weight of the total repeating units included in the polar copolymer. The method of claim 1, The polyolefin resin is a thermoplastic resin composition having a melt index (melt index, MI) of 0.1 g / 10min to 30 g / 10min. The method of claim 1, The polyolefin resin is a thermoplastic resin composition having a melting point (melting point) of 80 ℃ to 170 ℃. The method of claim 1, The polyolefin resin is a thermoplastic resin composition having a weight-weighted average density of 0.95 g / cm ³ or less. The method of claim 1, The polyolefin-based resin is a high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer (ethylene-octene copolymer), ultra Ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene and their A thermoplastic resin composition comprising one selected from the combination. The method of claim 1, The (b-1) copolymer is a styrene-ethylene-butylene-styrene copolymer (styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), Styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene copolymer ), A styrene-ethylene-butadiene-styrene copolymer (styrene-ethylene-butadiene-styrene copolymer) and a thermoplastic resin composition comprising one selected from a combination thereof. The method of claim 1, The polar functional group is a substituted or unsubstituted C3 to C30 anhydride group, a substituted or unsubstituted C1 to C30 carboxyl group, a substituted or unsubstituted C2 to C30 ester group, a hydroxyl group, a substituted or unsubstituted C1 to C30 Alcohol group, amine group (NH ₂ ), substituted or unsubstituted C1 to C20 amino group (NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or mutually Different and each independently C1 to C10 alkyl group), substituted or unsubstituted C2 to C30 epoxy group, substituted or unsubstituted C1 to C30 ketone group, -SH, substituted or unsubstituted C1 to C30 thioalcohol group and these The thermoplastic resin composition is selected from the combination of. The method of claim 1, The (b-2) polar copolymer is a maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS), maleic hydride (maleic anhydride-grafted styrene-ethylene-butylene-styrene copolymer) Maleic Anhydride Grafted Styrene-Ethylene-Butadiene-Styrene Copolymer, Maleic Unhydride-Grafted Styrene-Ethylene-Styrene Copolymer, Maleic Unhydride-Graft Styrene-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-propylene-styrene copolymer, maleic hydride-grafted styrene-ethylene-octene-styrene copolymer, maleic hydride Thermoplastic resin composition comprising one selected from grafted styrene-isoprene-styrene copolymers and combinations thereof. The method of claim 1 The base resin includes 10 wt% to 80 wt% of the polyarylene ether resin and 20 wt% to 90 wt% of the polyolefin resin, based on the total amount of the base resin, The (b-1) copolymer or the (b-2) polar copolymer is included in an amount of 1 to 40 parts by weight based on 100 parts by weight of the base resin. The method of claim 1 The thermoplastic resin composition is a thermoplastic resin composition in which the polar functional group is grafted to 0.001 parts by weight to 0.5 parts by weight based on 100 parts by weight of the total repeating units included in the thermoplastic resin composition. The method of claim 1, The thermoplastic resin composition further comprises an inorganic filler. The method of claim 12, The inorganic filler is magnesium oxide (magnesium oxide), magnesium hydroxide (magnesium hydroxide), aluminum hydroxide (aluminium hydroxide), calcium hydroxide (calcium hydroxide), hydromagnesite (hydromagnesite), calcium carbonate (calcium carbonate), potassium titanate (potassium titanate) ), Magnesium silicate (magnesium silicate), aluminum oxide hydroxide (aluminum oxide hydroxide) and a thermoplastic resin composition comprising one selected from them. The method of claim 12, The thermoplastic resin composition comprises the inorganic filler in an amount of 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin composition not containing the inorganic filler. The method of claim 1, The thermoplastic resin composition further comprises a flame retardant. The method of claim 15, The flame retardant is selected from phosphate compounds, phosphite compounds, phosphonate compounds, polysiloxanes, phosphazene compounds, phosphinate compounds, melamine compounds, and combinations thereof. It will comprise one thermoplastic resin composition. The method of claim 15, The thermoplastic resin composition comprises the flame retardant in an amount of 1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin composition not containing the flame retardant. The method of claim 1, (A) a base resin containing a polyarylene ether resin and a polyolefin resin, and (B) (b-1) A copolymer comprising a styrene repeating unit and an olefin repeating unit, and (b-2) A polar air containing a styrene repeating unit and an olefin repeating unit and to which a polar functional group is grafted A polar polymer selected from a combination, a polymer containing a styrene repeat unit and grafted with a polar functional group, a polymer containing an olefin repeat unit and grafted with a polar functional group, and a combination thereof, The polar functional group includes a bond between elements having an electronegativity difference of 0.5 kPa to 3.0, The (b-2) polar polymer is a thermoplastic resin composition in which the polar functional group is grafted at 0.1 to 7.0 parts by weight based on 100 parts by weight of the total repeating units included in the polar polymer. The method of claim 1, The base resin (A) comprises 10 wt% to 80 wt% of the polyarylene ether resin and 20 wt% to 90 wt% of the polyolefin resin, based on the total amount of the base resin, The copolymer (b-1) is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the base resin, and the (b-2) polar polymer is included in an amount of 1 to 40 parts by weight based on 100 parts by weight of the base resin. Phosphorus thermoplastic resin composition. 20. An electric wire or electric wire coating material molded article comprising the thermoplastic resin composition according to any one of claims 1 to 19, wherein the molded article satisfies at least one of the following; Elongation between 50% and 600% as measured by JASO D 618; -Time to extinguish after ignition, as measured by ISO 6722, within 70 seconds; Abrasion resistance of 400 mm to 3000 mm as measured by the ISO 6722 sandpaper abrasion test method; -The rate of change of diameter after gasoline dipping is less than 15% as measured by ISO 6722.

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