KR20130077468A - Thermoplastic resin composition and article including same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to enable users to recycle the composition, and to offer excellent workability, flexibility, heat resistance, voltage resistance, mechanical strength, and chemical resistance. CONSTITUTION: A thermoplastic resin composition contains a base resin including a polyaryleneether resin and a polyolefin resin, and a phosphate flame retardant having the thermal decomposition temperature greater than 230°C. The content of the polyolefin resin (weight, W_OL) and the content of the polyaryleneether resin (weight, W_AR) satisfy relative formula: W_AR<=1.9×W_OL. The polyolefin resin has the melt index of 0.1-30 g/10min, the melting point of 80-170°C, and the weighted value average density of 0.95 g/cm^3. A molded produce contains the thermoplastic resin composition, and the molded product is a wire (1) or a wire coating (4).

Description

Thermoplastic resin composition and molded article containing same {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE INCLUDING 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 resins that are excellent in workability, flexibility, flame retardancy, abrasion resistance, heat resistance, mechanical strength and chemical resistance and can be easily recycled.

One embodiment provides a thermoplastic resin composition that is excellent in workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, mechanical strength, and chemical resistance, can smoothly form an appearance, and can be easily recycled.

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

The thermoplastic resin composition according to one embodiment includes a base resin including a polyarylene ether resin and a polyolefin resin, and a phosphorous flame retardant having a thermal decomposition temperature of about 230 ° C. or more. 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 formula of W _AR ≤1.9 × W _OL .

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

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 It may include one selected from a combination.

The phosphorus flame retardant may include about 5 atomic% or more of phosphorus based on the total amount of atoms included in the phosphorus flame retardant.

The phosphorus flame retardant may include one selected from phosphate compounds, phosphite compounds, phosphonate compounds, phosphazene compounds, phosphinate compounds, and combinations thereof. Can be.

Specifically, the phosphorus-based flame retardant is triphenyl phosphate (TPP), ammonium polyphosphate (phase II), melamine phosphate (melamine phosphate), resorcinol-di (bis-2, 6-dimethylphenyl) phosphate (resorcinol-di (bis-2,6-dimethylphenyl) phosphate (RDP), bisphenol A diphenyl phosphate (BDP), cyclo phosphazene, diethyl phosphite It may include one selected from diethyl phosphinate ammonium salt, Exolit OP930, Clariant and combinations thereof.

The base resin 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 based on the total amount of the base resin. The flame retardant may be included in about 1 part by weight to about 50 parts by weight based on 100 parts by weight of the base resin.

When the phosphorus flame retardant is a mixture of two or more kinds and includes triphenyl phosphate (TPP), the triphenyl phosphate may be included in an amount of about 20 parts by weight or less based on 100 parts by weight of the base resin.

The thermoplastic resin composition may further include a compatibilizer.

The compatibilizer is styrene-ethylene-butylene-styrene copolymer (SEBS), maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (maleic anhydride grafted styrene -ethylene-butylene-styrene copolymer (MA-SEBS), high impact polystyrene (HIPS), ethylene vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), 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-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-butadiene-styrene Maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted linear low density polyethylene), maleic anhydride grafted low density polyethylene, and combinations thereof.

The thermoplastic resin composition may include about 1 parts by weight to about 40 parts by weight of the compatibilizer with respect to 100 parts by weight of the thermoplastic resin composition not including the compatibilizer.

The thermoplastic resin composition may further include a filler.

The filler is magnesium oxide (magnesium oxide), magnesium hydroxide (magnesium hydroxide), aluminum hydroxide (aluminium hydroxide), calcium hydroxide (calcium hydroxide), hydromagnesite (Mg ₅ (CO ₃ ) ₄ (OH) ₂ , hydromagnesite), carbonic acid It may include one selected from calcium carbonate, 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 filler based on 100 parts by weight of the thermoplastic resin composition not containing the filler.

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 a time from ignition to digestion as measured by JASO D 618 within about 20 seconds.

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 tensile strength of about 5 MPa to about 60 MPa as measured by ASTM D 638.

By including polyolefin resin and polyarylene ether resin in specific weight range and including specific phosphorus flame retardant, it has excellent workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, elongation, mechanical strength, chemical resistance and appearance characteristics. Provided are a thermoplastic resin composition 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 "copolymerization" means block copolymer, random copolymer, graft copolymer or alternating copolymer.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

The thermoplastic resin composition according to one embodiment includes a base resin including a polyarylene ether resin and a polyolefin resin, and a phosphorous flame retardant having a thermal decomposition temperature of about 230 ° C. or more. 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 formula of W _AR ≤1.9 × W _OL . The pyrolysis temperature of the phosphorus-based flame retardant is measured by thermogravimetric analysis (2 wt% weight loss) using TGA / DSC1 (manufactured by Metttler Toledo).

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, a flame retardant, a filler and the like may be included in a sufficient amount to maintain an 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 resin can be included to satisfy the relationship 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 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, the 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 based on the total weight of the polyarylene ether-based resin, can do. 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-based resin has an arylene part of about 60% by weight to about 85% by weight, more specifically 65% by weight to about 75% by weight, based on the total weight of the polyarylene ether-based resin. Wt%, more specifically, 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-based resin is within the above range, it is easy to process, and the elongation and heat resistance of the molded article produced using the thermoplastic resin composition can 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.

The phosphorus-based flame retardant may play a role of improving flame retardancy and heat resistance of the thermoplastic resin composition including the same.

The phosphorus flame retardant has a pyrolysis temperature of about 230 ° C. or more. When the pyrolysis temperature of the phosphorus-based flame retardant is within the above range, it is not decomposed even when processing the thermoplastic resin composition including the same, thereby effectively improving the flame resistance, heat resistance, mechanical strength and elongation of the thermoplastic resin composition including the same. Specifically, the phosphorus flame retardant may have a pyrolysis temperature of about 250 ° C. or more.

The phosphorus flame retardant may include about 5 atomic% or more of phosphorus based on the total amount of atoms included in the phosphorus flame retardant. When the phosphorus content of the phosphorus-based flame retardant is within the above range, it is possible to effectively improve the flame retardancy, it is possible to effectively improve the elongation of the molded article manufactured using the thermoplastic resin composition comprising the same. Specifically, the phosphorus-based flame retardant may include phosphorus in an amount of about 5 kPa to about 30 kPa, more specifically, about 7 kPa to about 30 kPa, based on the total amount of atoms included in the phosphorus flame retardant.

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

Specifically, the phosphorus-based flame retardant is triphenyl phosphate (TPP), ammonium polyphosphate (phase II), melamine phosphate (melamine phosphate), resorcinol-di (bis-2, 6-dimethylphenyl) phosphate (resorcinol-di (bis-2,6-dimethylphenyl) phosphate (RDP), bisphenol A diphenyl phosphate (BDP), cyclo phosphazene, diethyl phosphite Nate ammonium salt (diethyl phosphinate ammonium salt, Exolit OP930, Clariant) and a combination thereof may be included, but is not limited thereto.

In the thermoplastic resin composition, the base resin includes about 10 wt% to about 80 wt% of the polyarylene ether resin and about 20 wt% to about 90 wt% of the polyolefin resin based on the total amount of the base resin. The phosphorus-based flame retardant may be included in an amount of about 1 part by weight to about 50 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 phosphorus flame retardant is within the range, it is possible to effectively improve the flexibility, heat resistance, wear resistance, flame retardancy, elongation, mechanical strength and appearance characteristics of the thermoplastic resin composition. . 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. %, Wherein the phosphorus-based flame retardant is about 5 parts by weight to about 50 parts by weight, more specifically about 5 parts by weight to about 40 parts by weight, more specifically about 5 parts by weight based on 100 parts by weight of the base resin To about 30 parts by weight may be included.

The phosphorus flame retardant may be used alone or in a mixture of two or more thereof.

When the phosphorus flame retardant is a mixture of two or more kinds and includes triphenyl phosphate (TPP), the triphenyl phosphate may be included in about 20 parts by weight or less based on 100 parts by weight of the base resin. In this case, the elongation and flame retardancy of the molded article manufactured using the thermoplastic resin composition including the same can be effectively improved. Specifically, when the phosphorus flame retardant is a mixture of two or more kinds and includes triphenyl phosphate (TPP), the triphenyl phosphate may be included in an amount of about 5 parts by weight to about 15 parts by weight based on 100 parts by weight of the base resin.

On the other hand, the thermoplastic resin composition may further comprise a non-phosphorous flame retardant.

When the thermoplastic resin composition further includes a non-phosphorus-based flame retardant, elongation, heat resistance, and wear resistance of a molded article manufactured using the thermoplastic resin composition including the same may be improved.

Specifically, the non-phosphorus flame retardant may include one selected from polysiloxane, melamine compound, and a combination thereof, but is not limited thereto.

The thermoplastic resin composition may include about 5 parts by weight to about 30 parts by weight of the non-phosphorous flame retardant based on 100 parts by weight of the thermoplastic resin composition not including the non-phosphorous flame retardant. When the content of the non-phosphorus-based flame retardant is within the above range, the elongation, heat resistance, and flame retardancy of the molded article manufactured using the thermoplastic resin composition including the same may be effectively improved. Specifically, the thermoplastic resin composition may include about 10 parts by weight to about 20 parts by weight of the non-phosphorous flame retardant based on 100 parts by weight of the thermoplastic resin composition not containing the non-phosphorous flame retardant.

The thermoplastic resin composition may further include a compatibilizer. The compatibilizer may serve to help the polyarylene ether-based resin and the polyolefin-based resin to be uniformly dispersed, and also to help the resin to be uniformly dispersed in a flame retardant, a filler, and the like. It may be.

For example, the compatibilizer is a compound containing both a functional group and the polyolefin resin-friendly functional group and the polyarylene ether resin, so that the polyarylene ether resin and the polyolefin resin can be uniformly dispersed. Can play a role in helping In one example, the polyolefin resin is used as the base resin, the polyarylene ether resin may be dispersed in the polyolefin resin.

When the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility of the flame retardant, filler, etc. with the resin is improved, processability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance of the thermoplastic resin composition comprising the same Mechanical strength and chemical resistance can be improved.

Specifically, the compatibilizer is styrene-ethylene-butylene-styrene copolymer (SEBS), maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (maleic) anhydride grafted styrene-ethylene-butylene-styrene copolymer (MA-SEBS), high impact polystyrene (HIPS), ethylene vinyl acetate copolymer (EVA), ethylene-methylacrylate copolymer ( ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), styrene-butadiene-styrene copolymer (styrene-butadiene-styrene copolymer, SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer (styrene-isoprene- styrene copolymer (SIS), styrene-ethylene copolymer, styrene-ethylene-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene- Maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer, maleic anhydride grafted polypropylene, maleic anhydride-grafted linear low density polyethylene (maleic anhydride) grafted linear low density polyethylene), maleic anhydride grafted low density polyethylene, and combinations thereof, but is not limited thereto.

The thermoplastic resin composition may include about 1 parts by weight to about 40 parts by weight of the compatibilizer with respect to 100 parts by weight of the thermoplastic resin composition not including the compatibilizer. When the compatibilizer is included in the above range, it is possible to effectively improve the mechanical strength, heat resistance and processability of the thermoplastic resin composition including the same, and can effectively improve the appearance characteristics of the molded article manufactured using the thermoplastic resin composition. . Specifically, the thermoplastic resin composition may contain about 1 parts by weight to about 20 parts by weight, more specifically about 1 parts by weight to about 10 parts by weight, based on 100 parts by weight of the thermoplastic resin composition not including the compatibilizer. It can be included as a wealth.

The thermoplastic resin composition may further include a filler.

The filler may play a role as a flame retardant and a reinforcing agent, thereby improving flame retardancy and mechanical properties, such as wear resistance, of the thermoplastic resin composition including the same.

For example, the filler may be magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg ₅ (CO ₃ ) ₄ (OH) ₂ , hydromagnesite ), Calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide, and combinations thereof, but is not limited thereto. It is not.

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

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 above components, the thermoplastic resin composition according to an embodiment may include dyes, pigments, and the like as necessary to improve injection moldability, physical property balance, dispersibility, and to prevent oxidation and to suppress the formation of die drool. Additives such as stabilizers, lubricants, processing aids such as stearates, antibacterial agents, mold release agents, resin antioxidants, copper antioxidants, halogen scavengers and the like may also be appropriately included. At this time, the additives may be used singly or in combination of two or more.

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.

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 resin composition according to the embodiment includes the polyolefin-based resin and the polyarylene ether-based resin in a specific weight range and includes the phosphorus-based flame retardant, so that workability, flexibility, flame retardancy, abrasion resistance, heat resistance, voltage resistance, insulation, Elongation, mechanical strength, chemical resistance, water resistance, dimensional stability and appearance properties 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 wires, and wind 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 a time from ignition to digestion as measured by JASO D 618 within about 20 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 may have a time from extinguishing after ignition as measured by JASO D 618 to about 1 second to about 20 seconds, more specifically, about 1 second to about 15 seconds. The JASO D 618 is a 2008 version.

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 a tensile strength of about 5 MPa to about 60 MPa as measured by ASTM D 638. 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 D 638.

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.

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.

(A) polyarylene ether-based resin

(A-1) polyphenylene ether (PPE): LXR-035C (manufactured by Blue Star), number average molecular weight (Mn) 15,000 g / mol, polydispersity index (PDI) 1.31

(A-2) polyphenylene ether (PPE): PX100L (manufactured by Mitsubishi Engineering Plastics), number average molecular weight (Mn) 30,000 g / mol, polydispersity index (PDI) 1.74

(B) polyolefin resin

Linear low density polyethylene (LLDPE): LLDPE 9730 (manufactured by Hanwha Chemical), density 0.92 g / cm ³

(C) phosphorus flame retardant

(C-1) Exolit AP 760 (manufactured by Clariant), pyrolysis temperature 250 ° C, phosphorus content 20 atom%

(C-2) Exolit OP 930 (manufactured by Clariant), pyrolysis temperature 300 ° C, phosphorus content 23 k atomic%

(C-3) Exolit AP 742 (manufactured by Clariant), pyrolysis temperature 200 ° C, phosphorus content 22 k atomic%

(C-4) Antiblaze V6 (manufactured by Albemarle), pyrolysis temperature 200 ° C, phosphorus content 10

The pyrolysis temperature of each phosphorus-based flame retardant was measured using a TGA / DSC1 (manufactured by Mettler Toledo) equipment.

Example  1 to 7 and Comparative example  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.

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.

Example Comparative example One 2 3 4 5 6 7 One 2 3 Base resin (A) (A-1) weight% 47 47 47 47 - 25 10 47 47 85 (A-2) - - - - 47 - - - - - (B) 53 53 53 53 53 75 90 53 53 15 (C) (C-1) Base Resin 100
Parts by weight to parts by weight 25 - 10 50 25 25 50 - - 5 (C-2) - 25 - - - - - - - - (C-3) - - - - - - - 25 - - (C-4) - - - - - - - - 25 -

Test Example  1: flame retardancy evaluation

The thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were each set to a barrel temperature of about 240 ° C. and fed into a single screw extruder 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, flame retardancy was evaluated by measuring the time from ignition to digestion according to the JASO D 618 Flame Retardant Test Method. The smaller the value, the faster the fire extinguisher is.

The results are shown in Table 2 below.

Test Example  2: Elongation  evaluation

For each specimen prepared in Test Example 1, the 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 Table 2 below.

Test Example  3: tensile strength evaluation

For each specimen prepared in Test Example 1, the tensile strength was measured according to the ASTM D 638 mm tensile strength measurement method. The larger the value, the better the tensile strength.

The results are shown in Table 2 below.

Test Example  4: appearance evaluation

For each of the wire specimens prepared in Test Example 1, six wires were randomly selected for each 100 m from the 1.0 km long wire, and the average number was obtained by counting the number of protrusions. The smaller the value, the better the appearance.

The results are shown in Table 2 below.

Test Example  5: wear resistance evaluation

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 Table 2 below.

Test Example  6: oil resistance evaluation

Each of the specimens prepared in Test Example 1 was immersed in gasoline according to the ISO 6722 oil resistance test method, and the change rate of the specimen diameter was measured. The smaller the rate of change of the diameter of the specimen, the better the oil resistance.

The results are shown in Table 2 below.

Example Comparative example One 2 3 4 5 6 7 One 2 3 Flammability
(second) 5 3 18 One 6 15 One 25 40 One Elongation (%) 250 255 260 220 280 310 320 120 140 100 Tensile Strength (MPa) 29.4 29.4 31.4 25.5 26.5 23.5 21.0 16.7 17.6 63.2 Exterior 0 0 One 3 0 0 2 15 10 14 Wear resistance 1100 1100 1500 900 1200 600 400 1000 1100 1700 Oil resistance 6 5 6 9 7 3 One 7 5 21

As shown in Table 2, it can be seen that the case of using the thermoplastic resin composition of Examples 1 to 7 is excellent in elongation, tensile strength and appearance characteristics compared to the case of using the thermoplastic resin composition of Comparative Examples 1 to 3. In addition, the case where the thermoplastic resin compositions of Examples 1 to 7 were used was superior to the case of using the thermoplastic resin compositions of Comparative Examples 1 and 2, and the oil resistance was superior to that of the thermoplastic resin compositions of Comparative Example 3. You can check it.

Therefore, in the case of using the thermoplastic resin composition of Examples 1 to 7, it can be confirmed that it has excellent appearance characteristics and at the same time excellent flame resistance, elongation, tensile strength, wear resistance and oil resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

1, 10, 20: wires, 2, 11, 21: conductors,
4, 13, 23: covering material, 15, 25: insulator,
17, 29: sheath, 27: shield

Claims (21)

A base resin comprising a polyarylene ether resin and a polyolefin resin, and
Phosphorus flame retardant with pyrolysis temperature of 230 ℃ or higher
Lt; / RTI &gt;
The content (weight, W _OL ) of the polyolefin-based resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy a relationship of W _AR ≤1.9 × W _OL .
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 phosphorus flame retardant is a thermoplastic resin composition containing 5 atomic% or more phosphorus relative to the total amount of atoms contained in the phosphorus flame retardant.
The method of claim 1,
The phosphorus flame retardant includes a phosphate compound, a phosphite compound, a phosphonate compound, a phosphonate compound, a phosphazene compound, a phosphinate compound, and a combination thereof. The thermoplastic resin composition.
The method of claim 1,
The phosphorus flame retardant is triphenyl phosphate (TPP), ammonium polyphosphate (phase II), melamine phosphate (melamine phosphate), resorcinol-di (bis-2,6-dimethyl Phenyl) phosphate (resorcinol-di (bis-2,6-dimethylphenyl) phosphate (RDP), bisphenol A diphenyl phosphate (BDP), cyclo phosphazene, diethyl phosphinate ammonium salt ( A thermoplastic resin composition comprising one selected from diethyl phosphinate ammonium salt, Exolit OP930, Clariant) and a combination 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 phosphorus-based flame retardant is a thermoplastic resin composition containing 1 to 50 parts by weight based on 100 parts by weight of the base resin.
10. The method of claim 9,
When the phosphorus-based flame retardant is a mixture of two or more kinds and includes triphenyl phosphate (TPP), the triphenyl phosphate is included in 20 parts by weight or less based on 100 parts by weight of the base resin.
The method of claim 1,
The thermoplastic resin composition further comprises a compatibilizer.
The method of claim 11,
The compatibilizer is styrene-ethylene-butylene-styrene copolymer (SEBS), maleic hydride-grafted styrene-ethylene-butylene-styrene copolymer (maleic anhydride grafted styrene -ethylene-butylene-styrene copolymer (MA-SEBS), high impact polystyrene (HIPS), ethylene vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), 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-butadiene-styrene copolymer, maleic hydride-grafted styrene-ethylene-butadiene-styrene Maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted linear low density polyethylene), maleic anhydride-grafted low density polyethylene, and a combination thereof.
The method of claim 11,
The thermoplastic resin composition comprises 1 to 40 parts by weight of the compatibilizer with respect to 100 parts by weight of the thermoplastic resin composition not containing the compatibilizer.
The method of claim 1,
The thermoplastic resin composition further comprises a filler.
15. The method of claim 14,
The filler is magnesium oxide (magnesium oxide), magnesium hydroxide (magnesium hydroxide), aluminum hydroxide (aluminium hydroxide), calcium hydroxide (calcium hydroxide), hydromagnesite (Mg ₅ (CO ₃ ) ₄ (OH) ₂ , hydromagnesite), carbonic acid A thermoplastic resin composition comprising one selected from calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide, and combinations thereof.
15. The method of claim 14,
The thermoplastic resin composition includes the 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 filler.
A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 16.
18. The method of claim 17,
The molded article is an electric wire or a wire covering material.
18. The method of claim 17,
The molded article is a molded article having a time from ignition to digestion is within 20 seconds as measured by JASO D 618.
18. The method of claim 17,
The molded article is a molded article having an elongation of 50% to 600% as measured by JASO D 618.
18. The method of claim 17,
The molded article is a molded article having a tensile strength of 5 MPa to 60 MPa as measured by ASTM D 638.

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