KR101466276B1 - Thermoplastic resin composition and article including same - Google Patents

Abstract

A base resin comprising a polyarylene ether-based resin and a polyolefin-based resin, and a first flame retardant having a molecular weight of at least about 1000 g / mol, a second flame retardant having an octanol-water partition coefficient (log Kow) of about 5 or less, (W _OL ) of the polyolefin resin and a content (weight, W _AR ) of the polyarylene ether resin satisfy W _AR ≤1.9 × W _And a molded article comprising the thermoplastic resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition and a molded article including the thermoplastic resin composition.

To a thermoplastic resin composition and a molded article containing the same.

BACKGROUND ART [0002] Resins having excellent flexibility, flame retardancy, abrasion resistance, mechanical strength, chemical resistance, and heat resistance are required as materials for electric wires and wire covering materials used in electric and electronic parts, automobile parts, and chemical equipment parts. In addition, a resin that exhibits environmentally friendly properties and can be easily recycled in consideration of environmental aspects is required.

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

On the other hand, polyphenylene ether, which is widely used as a material for parts for electric and electronic devices and automobile devices, has excellent insulating properties, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability, but has a poor melt processability, There is a disadvantage that chemical resistance is poor.

Therefore, studies are being made on resins which are excellent in processability, flexibility, flame retardancy, abrasion resistance, heat resistance, mechanical strength and chemical resistance, and which are excellent in environmentally friendly properties and can be easily recycled.
On the other hand, prior art documents related to the present invention include Japanese Patent Laid-Open Publication No. 2008-524829, Japanese Laid-Open Patent Publication No. 1999-189686, and Korean Laid-Open Patent Publication No. 2007-0117410.

One embodiment provides a thermoplastic resin composition excellent in processability, flexibility, flame retardancy, abrasion resistance, heat resistance, pressure resistance, mechanical strength and chemical resistance, excellent in environment-friendly properties and easily recyclable.

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

The thermoplastic resin composition according to one embodiment comprises a base resin comprising a polyarylene ether-based resin and a polyolefin-based resin, and a first flame retardant having a molecular weight of at least about 1000 g / mol, an octanol-water partition coefficient log Kow), and a combination thereof. At this time, the content (weight, W _OL ) of the polyolefin-based resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy a relation 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-based resin may have a melting point of about 80 캜 to about 170 캜.

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

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

The first flame retardant having a molecular weight of 1000 g / mol or more may include one selected from ammonium polyphosphate (APP), melamine polyphosphate (MPP), and combinations thereof.

The second flame retardant having an octanol-water partition coefficient (log Kow) of less than 5 is resorcinol bis (diphenyl phosphate) (RDP), resorcinol bis Di-2,6-dimethylphenyl) phosphate, ammonium phosphinate, melamine phosphinate, triphenyl phosphate, and combinations thereof. And may include one selected.

In the thermoplastic resin composition, the base resin includes about 10 wt% to about 80 wt% of the polyarylene ether-based resin and about 20 wt% to about 90 wt% of the polyolefin-based resin based on the total amount of the base resin And the 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.

The thermoplastic resin composition may further comprise a compatibilizing agent.

The compatibilizing agent may be a styrene-ethylene-butylene-styrene copolymer (SEBS), a maleic anhydride grafted styrene-maleic anhydride grafted styrene copolymer (HIPS), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (MAE-SEBS) acrylate copolymer (EMA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-butyl acrylate copolymer (EBA), a styrene-butadiene-styrene copolymer butadiene-styrene copolymer (SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer SIS), a styrene-ethylene copolymer, a styrene-ethylene-butadiene-styrene copolymer, a maleic anhydride-grafted styrene-ethylene-butadiene-styrene But are not limited to, 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 contain about 1 part by weight to about 40 parts by weight of the compatibilizing agent per 100 parts by weight of the thermoplastic resin composition not containing the compatibilizer.

The thermoplastic resin composition may further include a filler.

The filler may be selected from the group consisting of magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate, , Magnesium silicate, aluminum oxide hydroxide, and combinations thereof. ≪ RTI ID = 0.0 >

The thermoplastic resin composition may include about 1 part 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 comprising the thermoplastic resin composition.

The molded article may be wire or wire covering material.

The time required for the molded article to be extinguished after being ignited and measured in accordance with JAS D 618 may be within about 20 seconds.

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

The molded article may have a tensile strength of from about 5 MPa to about 60 MPa as measured by ASTM D 638.

It is excellent in processability, flexibility, flame retardancy, abrasion resistance, heat resistance, dielectric strength, elongation, mechanical strength, chemical resistance, and environment-friendly characteristics by including a polyolefin resin and a polyarylene ether resin in a specific weight range and containing a specific flame retardant. And a molded article including the thermoplastic resin composition.

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, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one of the functional groups of the present invention is substituted with at least one substituent selected from halogen (-F, -Cl, -Br, or -I), a hydroxyl group, a nitro group, a cyano group, an 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, being each independently selected from C1 to C10 alkyl group) , A substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted 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 Substituted "

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

Also, unless otherwise specified herein, the heterocycloalkyl, heterocycloalkylene, heteroaryl and heteroarylene groups are each independently selected from the group consisting of N, O, S, Si or P heteroatoms in one ring in one Means a cycloalkyl group, cycloalkylene group, aryl group and arylene group which contain 3 carbon atoms and the remainder carbon.

"Aliphatic" as used herein, unless otherwise specified, refers to a C 1 to C 30 alkyl, a C 2 to C 30 alkenyl, a C 2 to C 30 alkynyl, a C 1 to C 30 alkylene, a C 2 to C 30 alkenylene, or a C 2 to C 30 alkynylene Means a C1 to C20 alkyl, a C2 to C20 alkenyl, a C2 to C20 alkynyl, a C1 to C20 alkylene, a C2 to C20 alkenylene or a C2 to C20 alkynylene, and the term "alicyclic" Means a C3 to C30 cycloalkyl, a C3 to C30 cycloalkenyl, a C3 to C30 cycloalkynyl, a C3 to C30 cycloalkylene, a C3 to C30 cycloalkenylene, or a 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, and "aromatic & C6 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 < / RTI >

Unless defined otherwise herein, the term "combination" generally means mixing or copolymerization, and in the case of alicyclic organic groups and aromatic organic groups, two or more rings may form a fused ring, or two or more rings may be single bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) -, -S (= O) 2 -, -Si (CH 3) 2 - _{, - (CH 2) p -} ( _{wherein, 1≤p≤2), - (CF 2} ) q - ( _{wherein, 1≤q≤2), -C (CH 3} ) 2 -, -C (CF 3) Means that they are connected to each other by a functional group of -C (O) ₂ -, -C (CH ₃ ) (CF ₃ ) - or -C (= O) NH-. Herein, "copolymerization" means block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" 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 comprises a base resin comprising a polyarylene ether-based resin and a polyolefin-based resin, and a first flame retardant having a molecular weight of at least about 1000 g / mol, an octanol-water partition coefficient log Kow), and a combination thereof. At this time, the content (weight, W _OL ) of the polyolefin-based resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy a relation of W _AR ≤1.9 × W _OL . The octanol-water partition coefficient (log Kow) is determined by HPLC column method using Model 510 HPLC pumps (Waters).

The polyarylene ether-based resin is excellent in insulation, water resistance, dimensional stability, heat resistance, flame retardancy and mechanical strength, but it has poor processability due to high melt viscosity, and has poor flexibility and chemical resistance such as oil resistance It has strong odor and shows yellow color. As a result, the polyarylene ether-based resin is difficult to be used solely for producing electric wires, for example, electric wires for automobiles.

The polyolefin-based resin has excellent processability, flexibility and chemical resistance, and has a poor smell, but is poor in heat resistance, flame retardancy and mechanical strength. As a result, the polyolefin-based resin is difficult to be used solely for producing electric wires, for example, electric wires for automobiles.

Wherein the thermoplastic resin composition comprises the polyarylene ether resin and the polyolefin resin, wherein the content (W _OL ) of the polyolefin resin and the content (W _AR ) of the polyarylene ether resin satisfy W _AR ? X W _OL , it is possible to control the melt viscosity appropriately to have excellent workability and to have excellent flexibility and chemical resistance, for example, oil resistance. In addition, a flame retardant, a filler, etc. can be contained in a sufficient amount, and insulation, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability can be maintained at a good level. 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 satisfied.

Specifically, the polyarylene ether resin may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ are the same or different and each independently represents hydrogen, halogen, substituted or unsubstituted C1 to C30 aliphatic organic groups, substituted or unsubstituted C2 to C30 aromatic organic groups, or substituted or unsubstituted C1 to C30 alkoxy groups , And specifically may be hydrogen, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, substituted or unsubstituted C2 to C10 aromatic organic groups, or substituted or unsubstituted C1 to C10 alkoxy groups, and more specifically May be hydrogen, halogen, substituted or unsubstituted C1 to C5 aliphatic organic groups, substituted or unsubstituted C2 to C8 aromatic organic groups, or substituted or unsubstituted C1 to C6 alkoxy groups.

n1 is the same as or different from each other in each repeating unit, and is independently an integer of 0 to 4;

When n1 is an integer of 2 or more, the R < ¹ > s may be the same or different from each other. The R ¹ may be the same as or different from each other in each 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, excellent workability can be obtained, and heat resistance and flame retardancy of the molded article produced using the thermoplastic resin composition containing the thermoplastic resin composition can be effectively improved. Specifically, the polyarylene ether-based resin may have an arylene moiety in an amount of about 60 wt% to about 85 wt%, more specifically, about 65 wt% to about 75 wt%, based on the total weight of the polyarylene ether- By weight, more specifically from 65% by weight to about 72% by weight.

Specifically, the polyarylene ether resin may be a poly (1,4-phenylene ether), a poly (1,3-phenylene ether), a poly (1,2-phenylene ether) 1,4-phenylene ether), poly (3-methyl-1,4-phenylene ether), poly (2-methyl- Phenylene ether), poly (3-methyl-1, 2-phenylene ether), poly Poly (6-methyl-1,2-phenylene ether), poly (5-methyl-1,2-phenylene ether) Dimethyl-1,4-phenylene ether), poly (2,3-dimethyl-1,4-phenylene ether), poly (3,5- (2,4-dimethyl-1,3-phenylene ether), poly (2,5-dimethyl-1,3-phenylene ether) (4,5-dimethyl-1,3-phenylene ether), poly (4,6-dimethyl-1,3-phenylene ether), poly , 6-di (3,4-dimethyl-1,2-phenylene ether), poly (3,5-dimethyl-1,2-phenylene ether), poly Dimethyl-1,2-phenylene ether), poly (4,5-dimethyl-1,2-phenylene ether), poly (4,6- 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 g / mol to about 1,000,000 g / mol. When the weight average molecular weight (Mw) of the polyarylene ether-based resin is within the above range, it is easy to work and the mechanical strength and heat resistance of the thermoplastic resin composition containing the polyarylene ether-based resin can be effectively improved. Specifically, the polyarylene ether resin may have a weight average molecular weight (Mw) of about 40,000 g / mol to about 300,000 g / mol.

The polyarylene ether based resin may have a number average molecular weight (Mn) of about 10,000 g / mol to about 1,000,000 g / mol. When the number average molecular weight (Mn) of the polyarylene ether-based resin is within the above range, it is easy to work and the mechanical strength and heat resistance of the molded article produced using the thermoplastic resin composition can be effectively improved. Specifically, the polyarylene ether-based resin may have a number average molecular weight (Mn) of about 15,000 g / mol to about 300,000 g / mol, more specifically about 15,000 g / mol to about 30,000 g / 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-based resin may have a polydispersity index (PDI) of about 1.3 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 as measured by ASTM D1238 (190 캜, 2.16 kg). When the melt index of the polyolefin-based resin is within the above range, it can be easily mixed with other resins and the mechanical strength of the thermoplastic resin composition containing the same can be effectively improved. Specifically, the polyolefin-based resin may have a melt index (MI) of about 0.1 g / 10 min to about 20 g / 10 min.

The polyolefin-based resin may have a melting point of about 80 캜 to about 170 캜. When the melting point of the polyolefin resin is within the above range, the heat resistance and mechanical strength of the thermoplastic resin composition containing the polyolefin resin can be effectively improved. Specifically, the polyolefin-based resin may have a melting point of about 95 캜 to about 135 캜, more specifically about 105 캜 to about 125 캜.

The polyolefin-based resin may have a weight average molecular weight (Mw) of from about 10,000 g / mol to about 1,000,000 g / mol. When the weight average molecular weight (Mw) of the polyolefin-based resin is within the above range, it is easy to work and the mechanical strength of the thermoplastic resin composition containing the polyolefin-based resin can be effectively improved. Specifically, the polyolefin-based resin may have a weight average molecular weight (Mw) of about 40,000 g / mol to about 300,000 g / mol.

The polyolefin-based resin may be used singly 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 containing the thermoplastic resin composition can be effectively improved. Specifically, the polyolefin-based resin may have a 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 weighted average density means that the weight of each polyolefin is multiplied by the respective polyolefin density and averaged. When a single resin is used, the density of the resin is a weighted average density.

The polyolefin resin may be a high density polyethylene (HDPE), a linear low density polyethylene (LLDPE), a low density polyethylene (LDPE), an ethylene-octene copolymer, But are not limited to, polyethylene, ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene, But it is not limited thereto. Specifically, the polyolefin-based resin may be selected from linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer, ethylene- propylene copolymer, an ethylene-butene copolymer, and a combination thereof.

The first flame retardant having a molecular weight of about 1000 g / mol or more, for example, about 1000 g / mol to about 200,000 g / mol can improve the flame retardancy and heat resistance of the thermoplastic resin composition containing the same . In addition, since the first flame retardant having a molecular weight of about 1000 g / mol or more is not penetrated into the cell membrane, there is no risk of bioconcentration and thus it can be used environmentally.

Specifically, the first flame retardant having a molecular weight of about 1000 g / mol or more may include one selected from ammonium polyphosphate (APP), melamine polyphosphate (MPP), and combinations thereof. However, But is not limited thereto.

The second flame retardant having an octanol-water partition coefficient (log Kow) of about 5 or less can improve the flame retardancy and heat resistance of the thermoplastic resin composition containing the same. In addition, the second flame retardant having an octanol-water partition coefficient (log Kow) of about 5 or less has a molecular weight of less than about 1000 g / mol, and is soluble in water due to affinity with water, It can be used eco-friendly.

Specifically, the second flame retardant having an octanol-water partition coefficient (log Kow) of about 5 or less is resorcinol bis (diphenyl phosphate) (RDP), resorcinol bis Di-2,6-dimethylphenyl) phosphate, ammonium phosphinate, melamine phosphinate, triphenyl phosphate and And combinations thereof. However, the present invention is not limited thereto. 　

In the thermoplastic resin composition, the base resin includes about 10 wt% to about 80 wt% of the polyarylene ether-based resin and about 20 wt% to about 90 wt% of the polyolefin-based resin based on the total amount of the base resin Wherein the flame retardant comprises a first flame retardant having a molecular weight of at least about 1000 g / mol, a second flame retardant having an octanol-water partition coefficient (log Kow) of about 5 or less, And 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 flame retarder is within the above range, the flexibility, heat resistance, abrasion resistance, flame retardancy, elongation, mechanical strength and environment friendliness of the thermoplastic resin composition can be effectively improved. Specifically, in the thermoplastic resin composition, the base resin comprises about 20% by weight to about 55% by weight of the polyarylene ether-based resin and about 45% by weight to about 80% by weight of the polyolefin- %, And the flame retardant may be included in an amount of about 5 parts by weight to about 50 parts by weight, more specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the base resin.

The thermoplastic resin composition may further comprise a compatibilizing agent. The compatibilizer can serve to help the polyarylene ether-based resin and the polyolefin-based resin to be uniformly dispersed, and also to help disperse the resin uniformly with the flame retardant, the filler, etc. It is possible.

For example, the compatibilizing agent is a compound containing both a functional group closely related to the polyarylene ether resin and a functional group closely related to the polyolefin resin, wherein the polyarylene ether resin and the polyolefin resin are uniformly dispersed It can play a role of helping. In one example, the polyolefin-based resin is used as a base resin, and the polyarylene ether-based resin can be dispersed in the polyolefin-based resin.

When the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility of the flame retardant, filler and the like with the resin are improved, the processability, flexibility, flame retardancy, abrasion resistance, heat resistance, , Mechanical strength and chemical resistance can be improved.

Specifically, the compatibilizing agent may be a styrene-ethylene-butylene-styrene copolymer (SEBS), a maleic anhydride-grafted styrene-ethylene-butylene-styrene copolymer 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- butadiene-styrene copolymer (SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene- styrene copolymer, SIS, a styrene-ethylene copolymer, a styrene-ethylene-butadiene-styrene copolymer, a maleic anhydride-grafted styrene- Butadiene-styrene copolymers, maleic anhydride grafted polypropylene, maleic anhydride-grafted linear low density polyethylene (maleic anhydride-grafted styrene-butadiene- but are not limited to, grafted low density polyethylene, maleic anhydride grafted low density polyethylene, and combinations thereof.

The thermoplastic resin composition may contain about 1 part by weight to about 40 parts by weight of the compatibilizing agent per 100 parts by weight of the thermoplastic resin composition not containing the compatibilizer. When the compatibilizing agent is contained within the above range, the mechanical strength, heat resistance and processability of the thermoplastic resin composition containing the compatibilizing agent can be effectively improved. Specifically, the thermoplastic resin composition contains about 1 to about 20 parts by weight, more specifically about 1 to about 10 parts by weight, of the compatibilizing agent per 100 parts by weight of the thermoplastic resin composition not containing the compatibilizing agent .

The thermoplastic resin composition may further include a filler.

The filler acts as a flame retardant and a reinforcing agent, so that the flame retardancy and mechanical properties, such as abrasion resistance, of the thermoplastic resin composition containing the filler can be improved.

For example, the filler may be selected from the group consisting of magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate but are not limited to, potassium titanate, magnesium silicate, aluminum oxide hydroxide, and combinations thereof.

The thermoplastic resin composition may include about 1 part 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 contained within the above range, flame retardancy and mechanical properties, such as abrasion resistance, of the thermoplastic resin composition containing the filler can be effectively improved. Specifically, the thermoplastic resin composition contains about 10 parts by weight to about 100 parts by weight, more specifically about 10 parts by weight to about 50 parts by weight, of the filler relative to 100 parts by weight of the thermoplastic resin composition not containing the filler can do.

When the thermoplastic resin composition contains both the filler and the flame retardant, the filler and the flame retardant may be contained in a weight ratio of about 50: 1 to about 1:10. When the content ratio of the filler and the flame retardant is within the above range, the flame retardancy, heat resistance, mechanical strength and elongation of the thermoplastic resin composition containing the filler and the flame retardant can be effectively improved. Specifically, the filler and the flame retardant may be contained in a weight ratio of about 10: 1 to about 1: 3.

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

The thermoplastic resin composition according to one embodiment may further contain, in addition to the above-mentioned components, a dye, a pigment, an antioxidant, an antioxidant, an antioxidant, an antioxidant, and the like in order to improve injection moldability, physical property balance, dispersibility, An additive such as a stabilizer, a lubricant, a processing aid such as stearate, an antibacterial agent, a releasing agent, a resin antioxidant, a copper antioxidant, and a halogen scavenger may be suitably added. At this time, the additives may be used singly or in combination of two or more.

The thermoplastic resin composition according to one embodiment can be produced by a known method for producing a resin composition. For example, after the respective components and other additives are mixed at the same time, they may be melt-extruded in an extruder and produced in the form of pellets.

The resin composition according to one embodiment can be easily recycled because it does not include any crosslinking and is environmentally friendly without using a halogen-based flame retardant. In addition, the resin composition according to one embodiment includes the polyolefin resin and the polyarylene ether resin in a specific weight range and includes the specific flame retardant to provide a resin composition having excellent processability, flexibility, flame retardancy, abrasion resistance, heat resistance, Mechanical strength, chemical resistance, water resistance, dimensional stability and environmental friendliness.

Another embodiment provides a molded article comprising the thermoplastic resin composition. The molded article can be produced 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 an electric wire covering material and may be used in various fields such as a power line, a communication line, an automobile wire, an electric wire for an electronic device, an electric wire for nuclear power, and a wire for wind power.

For example, a cross-sectional view of a wire according to one embodiment is shown in Fig.

Referring to Fig. 1, the electric wire 1 comprises a conductor 2 and a covering 4 surrounding the conductor. At this time, the conductor (2), the covering material (4), or a combination thereof may include the thermoplastic resin composition.

The conductor (2) may be a single strand or may include two or more strands. When the conductors 2 are in multiple strands, the covering material 4 may be formed to surround each strand, or the covering material 4 may be formed so as 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, the electric wire 10 includes a conductor 11, a cover 13 surrounding the conductor 11, an insulator 15 surrounding the cover 13, and an insulator 15 surrounding the insulator 15 And a sheath (17). At this time, the conductor 11, the covering material 13, the insulator 15, the sheath 17, or a combination thereof may include the thermoplastic resin composition.

The conductor 11 may be a single strand or may include two or more strands. In the case where the conductors 11 are of multiple strands, the cover 13, the insulator 15, the sheath 17, or a combination thereof may be formed to surround each strand, or the sheath 13, An insulator 15, a sheath 17, or a combination thereof, but is not limited thereto.

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

3, the electric wire 20 includes a conductor 21, a covering material 23 surrounding the conductor 21, an insulator 25 surrounding the covering material 23, a conductor 23 surrounding the insulator 25, A shield 27 and a sheath 29 surrounding the shield 27. [ At this time, the conductor 21, the covering 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. If the conductors 21 are of multiple strands, the cover 23, the insulator 25, the shield 27, the sheath 29, or a combination thereof may be formed to surround each strand, The covering material 23, the insulator 25, the shield 27, the sheath 29, or a combination thereof, but is not limited thereto.

1 to 3 are merely examples of the structure of the wire according to one embodiment, and the structure of the wire according to one embodiment is not limited thereto.

Unless otherwise specified herein, the contents of wires, conductors, coverings, insulators, shields, and sheath are as generally known in the art.

The time required for the molded article to be extinguished after being ignited and measured in accordance with JAS D 618 may be within about 20 seconds. When the time taken for the molded article to be extinguished after being ignited is within the above range, the molded article may have excellent flame retardancy. Specifically, the molded article may have a time from ignition to extinguishment in the measurement according to JASO D 618 of 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 a elongation of 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 stretched effectively without being broken when pulled through various spaces, and can have excellent compatibility, flexibility and cold resistance. Specifically, the molded article may have a elongation of from about 110% to about 600%, more specifically from about 120% to about 400%, more specifically from 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 from 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 uses. 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 an abrasion resistance of about 400 mm to about 3000 mm as measured by the ISO 6722 sandpaper abrasion test method. When the abrasion resistance of the molded article is within the above range, the molded article can have an appropriately balanced strength and flexibility. More specifically, the molded article may have an abrasion resistance of about 600 mm to about 2500 mm as measured by the ISO 6722 sandpaper abrasion test method. 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 when measured according to ISO 6722. When the rate of change in diameter of the molded article after gasoline immersion 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 when measured according to ISO 6722. 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. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

The respective components used in the production of the thermoplastic resin composition are as follows.

(A) a polyarylene ether resin

(A-1) Polyphenylene ether (PPE): LXR-035C (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) a polyolefin resin

Linear low density polyethylene (linear low density polyethylene, LLDPE) : LLDPE 9730 ( Hanwha Chemical Co., Ltd.), density 0.92 g / cm ³

(C) Flame retardant

(C-1) FR CROS 484 (manufactured by Budenheim), a molecular weight of 1000 to 200,000 g / mol (1000 g / mol or more)

, A molecular weight of 575 g / mol (less than 1000 g / mol), a molecular weight of less than 1000 g / mol (C-2) CR-733S (manufactured by Daihachi Chemical)

, A molecular weight of 693 g / mol (less than 1000 g / mol), a molecular weight of less than 1000 g / mol (C-3) CR-741 (manufactured by Daihachi Chemical)

The octanol-water partition coefficient column (log Kow) of each of the flame retardants was measured using Modle 510 HPLC pumps (Waters).

Example  1 to 7, Comparative Example  1 and Comparative Example  2: Preparation of thermoplastic resin composition

Using the above-mentioned components, the thermoplastic resin compositions according to Examples 1 to 7, Comparative Example 1 and Comparative Example 2 were prepared with the compositions shown in Table 1 below.

As the production method thereof, the respective components were mixed in the composition shown in Table 1 below and mixed in a usual mixer. Then, the extruder was fed to a twin-screw extruder SHJ35 (manufactured by NJFY) having a barrel temperature of about 250 DEG C and L / D = 44 and? = 35 mm. The mixture was made into a resin composition in the form of a pellet through an extruder.

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

Test Example  1: Eco-friendliness evaluation

The thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were respectively fed to a uniaxial extruder having a barrel temperature of 240 ° C and L / D = 28 and Φ = 30 mm. The thermoplastic resin composition was extruded through an extruder to prepare a wire-shaped specimen. At this time, a wire of 0.5SQ was used.

For each specimen, the environmental friendliness was evaluated by the OECD 305 method. The evaluation criteria of environment friendliness are as follows.

<Evaluation criteria for eco-friendliness>

Good: Bioconcentration factor (BCF) <500

Poor: Bioconcentration factor (BCF) ≥ 500

Test Example  2: Evaluation of flammability

For each of the specimens prepared in Test Example 1, the flame retardancy was evaluated by measuring the time taken until ignition and extinguishing according to the JASO D 618 flame retardancy test method. The smaller the value, the faster the digestion and the better the flame retardancy.

The results are shown in Table 2 below.

Test Example  3: Elongation  evaluation

The elongation of each of the specimens prepared in Test Example 1 was measured according to JASO D 618 elongation measurement method. The larger the number, the better the elongation.

The results are shown in Table 2 below.

Test Example  4: Evaluation of tensile strength

The tensile strength of each of the specimens prepared in Test Example 1 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 2 below.

Example Comparative Example One 2 3 4 5 6 7 One 2 Eco-friendly Good Good Good Good Good Good Good Bad Good Flammability
(second) 10 12 15 6 13 18 18 10 One Elongation (%) 250 255 260 220 240 310 350 260 100 Tensile Strength (MPa) 29.4 29.4 31.4 25.5 32.3 23.5 21.1 31.4 40.3

As shown in Table 2, the use of the thermoplastic resin compositions of Examples 1 to 7 is superior to the case of using the thermoplastic resin composition of Comparative Example 1, and in the case of using the thermoplastic resin composition of Comparative Example 2 It can be confirmed that the elongation is excellent.

Therefore, when the thermoplastic resin compositions of Examples 1 to 7 are used, it can be confirmed that they have excellent flame retardance, elongation and tensile strength while having excellent environmental friendliness.

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 (19)

A base resin comprising a polyarylene ether-based resin and a polyolefin-based resin, and
A flame retardant comprising a first flame retardant having a molecular weight of at least 1000 g / mol, a second flame retardant having an octanol-water partition coefficient (log Kow) of 5 or less,
Lt; / RTI &gt;
Wherein the content (weight, W _OL ) of the polyolefin-based resin and the content (weight, W _AR ) of the polyarylene ether-based resin satisfy a relation of W _AR? W _OL ,
Wherein the base resin comprises 20 to 55% by weight of the polyarylene ether-based resin and 45 to 80% by weight of the polyolefin-based resin based on the total amount of the base resin.
The method according to claim 1,
Wherein the polyolefin-based resin has a melt index (MI) of 0.1 g / 10 min to 30 g / 10 min as measured by ASTM D1238 (190 캜, 2.16 kg).
The method according to claim 1,
Wherein the polyolefin-based resin has a melting point of 80 ° C to 170 ° C.
The method according to claim 1,
Wherein the polyolefin-based resin has a weighted average density of about 0.95 g / cm &lt; ³ &gt; or less.
The method according to claim 1,
The polyolefin-based resin may be selected from the group consisting of high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer, But are not limited to, low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene, Wherein the thermoplastic resin composition comprises one selected from the group consisting of a combination of a thermoplastic resin and a thermoplastic resin.
The method according to claim 1,
Wherein the first flame retardant having a molecular weight of 1000 g / mol or more comprises one selected from the group consisting of ammonium polyphosphate (APP), melamine polyphosphate (MPP), and combinations thereof.
The method according to claim 1,
The second flame retardant having an octanol-water partition coefficient (log Kow) of less than 5 is resorcinol bis (diphenyl phosphate) (RDP), resorcinol bis Di-2,6-dimethylphenyl) phosphate, ammonium phosphinate, melamine phosphinate, triphenyl phosphate, and combinations thereof. Wherein the thermoplastic resin composition comprises a thermoplastic resin composition.
The method according to claim 1,
Wherein the base resin comprises 20 to 55% by weight of the polyarylene ether-based resin and 45 to 80% by weight of the polyolefin-based resin with respect to the total amount of the base resin,
Wherein the flame retardant is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the base resin.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises a compatibilizing agent.
10. The method of claim 9,
The compatibilizing agent may be a styrene-ethylene-butylene-styrene copolymer (SEBS), a maleic anhydride grafted styrene-maleic anhydride grafted styrene copolymer (HIPS), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (MAE-SEBS) acrylate copolymer (EMA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-butyl acrylate copolymer (EBA), a styrene-butadiene-styrene copolymer butadiene-styrene copolymer (SBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isoprene-styrene copolymer SIS), a styrene-ethylene copolymer, a styrene-ethylene-butadiene-styrene copolymer, a maleic anhydride-grafted styrene-ethylene-butadiene-styrene But are not limited to, 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. &lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
10. The method of claim 9,
Wherein the thermoplastic resin composition contains 1 to 40 parts by weight of the compatibilizing agent per 100 parts by weight of the thermoplastic resin composition not containing the compatibilizing agent.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises a filler.
13. The method of claim 12,
The filler may be selected from the group consisting of magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite, calcium carbonate, potassium titanate, , Magnesium silicate, aluminum oxide hydroxide, and combinations thereof. &Lt; Desc / Clms Page number 13 &gt;
13. The method of claim 12,
Wherein the thermoplastic resin composition contains 1 to 100 parts by weight of the filler per 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 14.
16. The method of claim 15,
Wherein the molded article is a wire or wire covering material.
16. The method of claim 15,
Wherein the molded article has a time of 20 seconds or less after ignition and extinguishing under measurement according to JASO D 618.
16. The method of claim 15,
Wherein the molded article has a elongation of 50% to 600% as measured by JASO D 618.
16. The method of claim 15,
Wherein the molded article has a tensile strength of 5 MPa to 60 MPa as measured by ASTM D 638.

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