WO2013100414A1 - Thermoplastic resin composition and molded product including same - Google Patents

Thermoplastic resin composition and molded product including same Download PDF

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Publication number
WO2013100414A1
WO2013100414A1 PCT/KR2012/010240 KR2012010240W WO2013100414A1 WO 2013100414 A1 WO2013100414 A1 WO 2013100414A1 KR 2012010240 W KR2012010240 W KR 2012010240W WO 2013100414 A1 WO2013100414 A1 WO 2013100414A1
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WIPO (PCT)
Prior art keywords
styrene
resin composition
ethylene
thermoplastic resin
weight
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PCT/KR2012/010240
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French (fr)
Korean (ko)
Inventor
장도훈
조진경
홍창민
김두영
Original Assignee
제일모직 주식회사
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Priority claimed from KR1020110144827A external-priority patent/KR20130076298A/en
Priority claimed from KR1020110146192A external-priority patent/KR101466277B1/en
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Publication of WO2013100414A1 publication Critical patent/WO2013100414A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/427—Polyethers

Definitions

  • thermoplastic resin composition and a molded article including the same.
  • 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.
  • 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.
  • thermoplastic resin composition that is excellent in workability, flexibility, flame retardancy, wear resistance, mechanical strength, chemical resistance, and heat resistance, and can be easily recycled.
  • thermoplastic resin composition having excellent processability, flexibility, flame retardancy, abrasion resistance, heat resistance, voltage resistance, mechanical strength, and chemical resistance, which can form a smooth appearance and can be easily recycled.
  • Another embodiment provides a molded article including the thermoplastic resin composition.
  • thermoplastic resin composition comprising a polyarylene ether-based resin and a polyolefin-based resin having a weight weighted average density of about 0.95 g / cm 3 or less.
  • the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression 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 ° C to about 170 ° C.
  • the polyolefin-based resin is a high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer ), Ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene And combinations thereof.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • Ultra low density polyethylene medium density polyethylene
  • ethylene-propylene copolymer ethylene-butene copolymer
  • the thermoplastic resin composition may include about 20 wt% to about 65 wt% of the polyarylene ether resin, and about 35 wt% to about 80 wt% of the polyarylene ether resin based on the total amount of the thermoplastic resin composition. It may include.
  • 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-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 (S
  • the thermoplastic resin composition may include about 1 part by weight to about 40 parts by weight of the compatibilizer based on 100 parts by weight of the thermoplastic resin composition not including the compatibilizer.
  • thermoplastic resin composition may further include a filler.
  • the filler is magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 , hydromagnesite ), Calcium carbonate, potassium titanate, magnesium silicate, and combinations thereof.
  • the thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight, more specifically about 1 part by weight to about 80 parts by weight based on 100 parts by weight of the thermoplastic resin composition not including the filler. .
  • thermoplastic resin composition may further include a phosphorous flame retardant, a non-phosphorous flame retardant, or a combination thereof.
  • the thermoplastic resin composition 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.
  • a base resin including a polyarylene ether resin and a polyolefin resin
  • a phosphorous flame retardant having a thermal decomposition temperature of about 230 ° C. or more.
  • the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression of W AR ⁇ 1.9 ⁇ W OL .
  • the thermoplastic resin composition may include about 1 part by weight to about 50 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin composition not including the flame retardant.
  • 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-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.
  • 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.
  • 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 extinguishment as measured by ISO 6722 within about 70 seconds.
  • 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 a diameter change rate of about 15% or less after gasoline immersion as measured by ISO 6722.
  • 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.
  • It includes a specific polyolefin resin, and includes a polyolefin resin and a polyarylene ether resin in a specific weight range, and is excellent in workability, flexibility, flame retardancy, abrasion resistance, mechanical strength, chemical resistance and heat resistance and can be recycled thermoplastic resin. It provides a composition and a molded article comprising the same.
  • a polyolefin resin and a polyarylene ether resin in a specific weight range and by including a specific phosphorus flame retardant, workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, elongation, mechanical strength, chemical resistance and appearance characteristics It provides an excellent and recyclable thermoplastic resin composition and a molded article comprising the same.
  • FIG. 1 is a cross-sectional view of a wire according to one embodiment.
  • FIG. 2 is a cross-sectional view of a wire according to another embodiment.
  • FIG 3 is a cross-sectional view of a wire according to another embodiment.
  • 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
  • alkyl group means a C1 to C30 alkyl group, specifically, a C1 to C20 alkyl group
  • 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
  • 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.
  • 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 cycloalken
  • copolymerization means block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization
  • copolymer means a block copolymer, random copolymer, graft copolymer or alternating copolymer.
  • the thermoplastic resin composition includes a polyarylene ether resin and a polyolefin resin having a weight weighted average density of about 0.95 g / cm 3 or less.
  • the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression of W AR ⁇ 1.9 ⁇ W OL .
  • the thermoplastic resin composition may include a phosphorous flame retardant, a non-phosphorous flame retardant, or a combination thereof.
  • the thermoplastic resin composition may include a base resin including the polyarylene ether resin and the polyolefin resin, and a phosphorous flame retardant having a thermal decomposition temperature of about 230 ° C. or more.
  • the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression 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
  • the melt viscosity may be appropriately adjusted to have excellent workability, and may have excellent flexibility and chemical resistance, such as oil resistance.
  • a sufficient amount of fillers, flame retardants and the like may be included to maintain excellent insulation, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability.
  • the thermoplastic resin composition may include the polyarylene ether-based resin and the polyolefin-based resin so as to satisfy a relation of W AR ⁇ 1.2 ⁇ W OL , and more specifically, a relation of W AR ⁇ W OL . Can be included to satisfy.
  • the polyarylene ether resin may include a repeating unit represented by Formula 1 below.
  • 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.
  • each of R 1 may be the same or different from each other.
  • R 1 may be the same or different from each other in the repeating unit.
  • the polyarylene ether resin may include an arylene part in an amount of about 50 wt% to about 90 wt% with respect to the total weight of the polyarylene ether resin, and have an electronegativity of 2.58 or more. 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.
  • 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%.
  • 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- Phenylene 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(,
  • the polyarylene ether-based resin may have a weight average molecular weight of about 10,000 g / mol to about 1,000,000 g / mol.
  • the weight average molecular weight 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 can be effectively improved.
  • the polyarylene ether resin may have a weight average molecular weight of about 40,000 kg / mol to about 300,000 kg / mol.
  • the polyarylene ether resin may have a number average molecular weight (Mn) of about 10,000 ⁇ g / mol to about 1,000,000 ⁇ g / mol.
  • Mn number average molecular weight
  • the polyarylene ether 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.
  • PDI polydispersity index
  • the polyarylene ether resin may have a polydispersity index (PDI) of about 1.3 kPa to about 1.8.
  • the said olefin resin can be used individually or in mixture of 2 or more types, and has a weight 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.
  • 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-based resin may have a melt index (MI) of about 0.1 g / 10 min to about 30 g / 10 min.
  • MI melt index
  • 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.
  • 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 °C to about 170 °C. 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 of about 10,000 g / mol to about 1,000,000 g / mol.
  • the weight average molecular weight of the polyolefin-based resin is in the above range, the processing is easy, it is possible to effectively improve the mechanical strength of the thermoplastic resin composition comprising the same.
  • the polyolefin-based resin may have a weight average molecular weight of about 40,000 kg / mol to about 300,000 kg / mol.
  • 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, but is not limited thereto.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • 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, but is not limited thereto.
  • 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.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • ethylene-octene copolymer ethylene-octene copolymer
  • ethylene-propylene copolymer ethylene- propylene copolymer
  • ethylene-butene copolymer ethylene-butene copolymer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • TPP triphenyl phosphate
  • phase II ammonium polyphosphate
  • melamine phosphate melamine phosphate
  • resorcinol-di bis-2, 6-dimethylphenyl
  • RDP resorcinol-di (bis-2,6
  • the thermoplastic resin composition may include about 20 wt% to about 65 wt% of the polyarylene ether resin, and about 35 wt% to about 80 wt% of the polyarylene ether resin, based on the total amount of the thermoplastic resin composition. It may include. When the content of the polyarylene ether resin and the polyolefin resin is within the above range, the flexibility, heat resistance, wear resistance, oil resistance and flame resistance of the thermoplastic resin composition can be effectively improved. Specifically, the thermoplastic resin composition may include about 30 wt% to about 55 wt% of the polyarylene ether resin, and about 45 wt% to about 70 wt% of the polyarylene ether resin, based on the total amount of the thermoplastic resin composition. It may be included in weight percent.
  • the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% by weight to the polyolefin resin based on the total amount of the base resin About 90% by weight, and 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoplastic resin composition may further comprise a non-phosphorous flame retardant.
  • 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.
  • 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.
  • 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 when the filler or the flame retardant is included, the resin may be uniformly dispersed in the flame retardant, the filler, and the like. It can also play a role in helping.
  • 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
  • the polyolefin resin is used as the base resin, the polyarylene ether resin may be dispersed in the polyolefin resin.
  • the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility with the resin, the filler, the flame retardant, etc. are improved, processability, flexibility, flame retardancy, abrasion resistance, heat resistance, and voltage resistance of the thermoplastic resin composition including the same are improved. Mechanical strength and chemical resistance can be improved.
  • 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 (S
  • the thermoplastic resin composition may include about 1 part by weight to about 40 parts by weight of the compatibilizer based on 100 parts by weight of the thermoplastic resin composition not including the compatibilizer.
  • 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.
  • 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.
  • thermoplastic resin composition including the thermoplastic resin composition or the phosphorus-based flame retardant may further include a filler.
  • the filler may act as a flame retardant and a reinforcing agent to improve the flame retardancy and mechanical properties, such as wear resistance, of the thermoplastic resin composition including the foil.
  • the filler may be an inorganic filler, for example, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (CO) 3 ) minerals selected from 4 (OH) 2 , hydromagnesite, calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide and combinations thereof It may include, but is not limited thereto.
  • inorganic filler for example, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (CO) 3 ) minerals selected from 4 (OH) 2 , hydromagnesite, calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide and combinations thereof It may include, but is not limited thereto.
  • the inorganic material may optionally be surface-treated with one selected from vinylsilane, aminosilane, stearic acid, oleic acid, fatty acid, polymer, phenylsilane, urethane, epoxy, derivatives thereof, and combinations thereof, but is not limited thereto.
  • the polymer is one selected from polyethylene, polystyrene, poly (butyl acrylate), poly (methyl methacrylate), poly (dodecyl methacrylate), poly (octadecyl methacrylate) and combinations thereof It may include, but is not limited thereto.
  • the thermoplastic resin composition may include about 1 parts by weight to about 80 parts by weight of the filler based on 100 parts by weight of the thermoplastic resin composition not containing the filler.
  • the thermoplastic resin composition may include about 5 parts by weight to about 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition not containing the filler.
  • the thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight based on 100 parts by weight of the thermoplastic resin composition not including the filler.
  • 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.
  • 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.
  • the flame retardant may play a role of improving the flame retardancy and heat resistance of the thermoplastic resin composition comprising a whip.
  • the filler and the flame retardant may be included in a weight ratio of about 50: 1 to about 1:10.
  • the content ratio of the filler and the flame retardant is within the range, it is possible to effectively improve the flame retardancy, heat resistance, mechanical strength and elongation of the thermoplastic resin composition comprising the same.
  • 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 to about 50.
  • LOI limited oxygen index
  • the thermoplastic resin composition may have excellent flame resistance, heat resistance and mechanical strength.
  • 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.
  • 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. In this case, the additives may be used alone or in combination of two or more thereof.
  • thermoplastic resin composition may be prepared by a known method for preparing a thermoplastic resin composition. For example, after mixing each of the components and other additives simultaneously, they can be melt extruded in an extruder and made into pellets.
  • Thermoplastic resin composition according to one embodiment does not include a separate crosslinking (crosslinking) can be easily recycled and does not use a halogen-based flame retardant is environmentally friendly.
  • the thermoplastic resin composition according to one embodiment includes a specific polyolefin-based resin, and includes the polyolefin-based resin and the polyarylene ether-based resin in a specific weight range, so that workability, flexibility, flame retardancy, wear resistance, heat resistance, Withstand voltage, insulation, mechanical strength, chemical resistance, water resistance and dimensional stability can be effectively improved.
  • thermoplastic resin composition 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, wires for electronic devices, wires for nuclear power generation, wires for wind power generation, and the like.
  • FIG. 1 a cross-sectional view of a wire according to one embodiment is shown in FIG. 1.
  • the wire 1 comprises a conductor 2 and a sheathing material 4 surrounding the conductor.
  • 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.
  • 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.
  • FIG. 2 a cross-sectional view of a wire according to another embodiment is shown in 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).
  • 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.
  • 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.
  • FIG. 3 a cross-sectional view of a wire according to another embodiment is shown in 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.
  • 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.
  • 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.
  • the molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 70 seconds. When the time from the ignition to extinguishing the molded article is within the above range, the molded article may have excellent flame retardancy. Specifically, the molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 50 seconds, for example, about 1 second to about 50 seconds, more specifically about 1 second to about 20 seconds.
  • the ISO 6722 is the August 1, 2006 version.
  • the molded article may have a time to extinguish after ignition as measured by JASO D 618 within about 20 seconds.
  • the time from the ignition to extinguishing the molded article is within the above range, the molded article may have excellent flame retardancy.
  • 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 a diameter change rate of about 15% or less after gasoline immersion as measured by ISO 6722.
  • 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.
  • the molded article may have a diameter change rate of about 0.01% to about 10.0% after dipping gasoline as measured by ISO 6722.
  • the ISO 6722 is the August 1, 2006 version.
  • the molded article may have an elongation of from about 50% to about 600% as measured by JASO D 618.
  • 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.
  • 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.
  • the wear resistance of the molded article is within the above range, the molded article may have appropriately balanced strength and flexibility.
  • 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 an abnormality in the lead when the cold resistance evaluation according to ISO 6722, and may pass the withstand voltage test.
  • the ISO 6722 is the August 1, 2006 version.
  • thermoplastic resin composition Each component used for manufacture of a thermoplastic resin composition is as follows.
  • Linear low density polyethylene LLDPE 9730 (manufactured by Hanwha Chemical), density 0.92 g / cm 3
  • LDPE Low density polyethylene
  • Ethylene-octene copolymer (ethylene-octene copolymer, Mitsui Chemicals Co., Ltd.): density 0.9 g / cm 3
  • High density polyethylene (HDPE, made by Samsung Total): Density 0.96 g / cm 3
  • Styrene-ethylene-butylene-styrene copolymer (styrene-ethylene-butylene-styrene copolymer, SEBS): Kraton G 1651 (manufactured by Shell)
  • Magnesium hydroxide (Mg (OH) 2 ) Magnesium hydroxide (Magnifin H5, product made by Albemarle)
  • the pyrolysis temperature of each of the flame retardants was measured using a TGA / DSC1 (Mettler Toledo) equipment.
  • thermoplastic resin compositions according to Examples 1 to 14 and Comparative Examples 1 to 7 were prepared using the above-mentioned components in the compositions shown in Tables 1 and 2 below.
  • 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.
  • Test Example 1 The specimens of Examples 1 to 7 and Comparative Examples 1 to 4 prepared in Test Example 1 were evaluated for wear resistance according to the ISO 6722 sandpaper abrasion test method. The larger the value, the better the wear resistance.
  • Example 1 The specimens of Examples 1 to 7 and Comparative Examples 1 to 4 prepared in Test Example 1 were evaluated for cold resistance according to the ISO 6722 cold resistance (low temperature characteristic) evaluation method. At this time, if there is no abnormality in the conductor and there is no current leakage, there is no abnormality in the withstand voltage, so the specimen is not broken, and it is marked as "pass” . If there is an abnormality in the conductor or there is a current leakage, the specimen is destroyed. It is marked as "fail”.
  • Test Example 1 The specimens of Examples 8 to 14 and Comparative Examples 5 to 7 prepared in Test Example 1 were evaluated for wear resistance according to the ISO 6722 sandpaper abrasion test method. The larger the value, the better the wear resistance.
  • Example Comparative example 8 9 10 11 12 13 14 5 6 7 Flame retardant (seconds) 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
  • thermoplastic resin composition of Examples 1 to 7 is excellent in physical properties such as elongation, oil resistance, cold resistance, etc. when using the thermoplastic resin composition of Comparative Examples 1 to 4.
  • thermoplastic resin composition of Examples 8 to 14 is superior to the elongation, tensile strength and appearance characteristics compared to the case of using the thermoplastic resin composition of Comparative Examples 5 to 7.
  • thermoplastic resin composition of Examples 8-14 was used compared with the case of using the thermoplastic resin compositions of Comparative Examples 5 and 6 was excellent in flame retardancy, and it was excellent in oil resistance compared with the case where the thermoplastic resin composition of Comparative Example 7 was used. You can check it.
  • thermoplastic resin composition of Examples 8 to 14 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.

Abstract

Provided are a thermoplastic resin composition and a molded product including the same, the thermoplastic resin composition containing a poly arylene ether-based resin and a polyolefin-based resin having a weighted average density of 0.95 g/cm3 or less, wherein the contents of the polyolefin-based resin (weight, WOL) and the contents of the poly arylene ether-based resin (weight, WAR) satisfy the interaction formula of WAR ≤ 1.9×WOL.

Description

열가소성 수지 조성물 및 이를 포함하는 성형품Thermoplastic Resin Composition and Molded Articles Comprising the Same
열가소성 수지 조성물 및 이를 포함하는 성형품에 관한 것이다.A thermoplastic resin composition and a molded article including the same.
최근 전기전자 기기 부품, 자동차 기기 부품, 또는 화학 기기 부품 등에 사용되는 전선 또는 전선 피복재 등의 재료로서, 유연성, 난연성, 내마모성, 기계적 강도, 내화학성 및 내열성이 우수한 수지가 요구되고 있다. 　또한, 환경적인 측면을 고려하여 용이하게 재활용할 수 있는 수지가 요구되고 있다.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.
전선 피복재로 널리 사용되고 있는 폴리올레핀은 유연성 및 내화학성이 우수하나, 난연성, 내마모성, 기계적 강도 및 내열성이 열악한 단점이 있다.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.
한편, 전기전자 기기 부품 및 자동차 기기 부품의 재료로 널리 사용되고 있는 폴리페닐렌에테르는 절연성, 난연성, 기계적 강도, 내열성, 내수성 및 치수안정성이 우수하나, 용융 점도가 높아 가공성이 열악하고, 유연성 및 내화학성이 열악한 단점이 있다.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.
따라서, 가공성, 유연성, 난연성, 내마모성, 내열성, 기계적 강도, 내화학성 및 내열성이 우수하며, 용이하게 재활용할 수 있는 수지에 대한 연구가 진행되고 있다.Therefore, research is being conducted on resins that are excellent in workability, flexibility, flame retardancy, wear resistance, heat resistance, mechanical strength, chemical resistance, and heat resistance and can be easily recycled.
일 구현예는 가공성, 유연성, 난연성, 내마모성, 기계적 강도, 내화학성 및 내열성이 우수하며, 용이하게 재활용할 수 있는 열가소성 수지 조성물을 제공한다.One embodiment provides a thermoplastic resin composition that is excellent in workability, flexibility, flame retardancy, wear resistance, mechanical strength, chemical resistance, and heat resistance, and can be easily recycled.
다른 일 구현예는 가공성, 유연성, 난연성, 내마모성, 내열성, 내전압성, 기계적 강도 및 내화학성이 우수하며, 외관을 매끄럽게 형성할 수 있고 용이하게 재활용할 수 있는 열가소성 수지 조성물을 제공한다.Another embodiment provides a thermoplastic resin composition having excellent processability, flexibility, flame retardancy, abrasion resistance, heat resistance, voltage resistance, mechanical strength, and chemical resistance, which can form a smooth appearance and can be easily recycled.
다른 일 구현예는 상기 열가소성 수지 조성물을 포함하는 성형품을 제공한다. Another embodiment provides a molded article including the thermoplastic resin composition.
일 구현예는 폴리아릴렌에테르계 수지 및 약 0.95　g/cm3　이하의 중량가중평균밀도를 가지는 폴리올레핀계 수지를 포함하는 열가소성 수지 조성물을 제공한다. 　이때, 상기 폴리올레핀계 수지의 함량(중량, WOL)과 상기 폴리아릴렌에테르계 수지의 함량(중량, WAR)은 WAR ≤ 1.9×WOL의 관계식을 만족한다. 상기 폴리올레핀계 수지는 약 0.1 g/10min 내지 약 30 g/10min의 용융지수(melt index, MI)를 가질 수 있다.One embodiment provides a thermoplastic resin composition comprising a polyarylene ether-based resin and a polyolefin-based resin having a weight weighted average density of about 0.95 g / cm 3 or less. In this case, the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression 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.
상기 폴리올레핀계 수지는, 약 80℃ 내지 약 170℃의 녹는점(melting point)을 가질 수 있다.The polyolefin-based resin may have a melting point of about 80 ° C to about 170 ° C.
구체적으로는 상기 폴리올레핀계 수지는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 저밀도 폴리에틸렌(low density polyethylene, LDPE), 에틸렌-옥텐 공중합체(ethylene-octene copolymer), 초저밀도 폴리에틸렌(ultra low density polyethylene), 중밀도 폴리에틸렌(medium density polyethylene), 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-부텐 공중합체(ethylene-butene copolymer), 폴리프로필렌(polypropylene)　및 이들의 조합에서 선택되는 하나를 포함할 수 있다.Specifically, the polyolefin-based resin is a high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer ), Ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene And combinations thereof.
상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 20 중량% 내지 약 65 중량%로 포함할 수 있고, 상기 폴리올레핀계 수지를 약 35　중량% 내지 약 80 중량%로 포함할 수 있다.The thermoplastic resin composition may include about 20 wt% to about 65 wt% of the polyarylene ether resin, and about 35 wt% to about 80 wt% of the polyarylene ether resin based on the total amount of the thermoplastic resin composition. It may include.
상기 열가소성 수지 조성물은 상용화제를 더 포함할 수 있다.The thermoplastic resin composition may further include a compatibilizer.
구체적으로는 상기 상용화제는 스티렌-에틸렌-부틸렌-스티렌 공중합체(styrene-ethylene-butylene-styrene copolymer, SEBS), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부틸렌-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS), 내충격성 폴리스티렌(high impact polystyrene, HIPS), 에틸렌-아세트산비닐 공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌-메틸아크릴레이트 공중합체(ethylene-methyl acrylate copolymer, EMA), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethyl acrylate copolymer, EEA), 에틸렌-부틸아크릴레이트 공중합체(ethylene-butyl acrylate copolymer, EBA), 스티렌-부타디엔-스티렌 공중합체(styrene-butadiene-styrene copolymer, SBS), 스티렌-에틸렌-프로필렌-스티렌 공중합체(styrene-ethylene-propylene-styrene copolymer, SEPS), 스티렌-이소프렌-스티렌 공중합체(styrene-isoprene-styrene copolymer, SIS), 스티렌-에틸렌 공중합체(styrene-ethylene copolymer), 스티렌-에틸렌-부타디엔-스티렌 공중합체(styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부타디엔-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 폴리프로필렌(maleic anhydride grafted polypropylene), 말레익 언하이드라이드-그래프트된 선형 저밀도 폴리에틸렌(maleic anhydride grafted linear low density polyethylene), 말레익 언하이드라이드-그래프트된 저밀도 폴리에틸렌(maleic anhydride grafted low density polyethylene)　및 이들의 조합에서 선택되는 하나를 포함할 수 있다.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 polypropylene (maleic anhydride) grafted linear low density polyethylene, maleic anhydride grafted low density polyethylene, and combinations thereof.
상기 열가소성 수지 조성물은 상기 상용화제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 상용화제를 약 1 중량부 내지 약 40 중량부로 포함할 수 있다.The thermoplastic resin composition may include about 1 part by weight to about 40 parts by weight of the compatibilizer based on 100 parts by weight of the thermoplastic resin composition not including the compatibilizer.
상기 열가소성 수지 조성물은 충진제를 더 포함할 수 있다.The thermoplastic resin composition may further include a filler.
구체적으로는 상기 충진제는 산화 마그네슘(magnesium oxide), 수산화 마그네슘(magnesium hydroxide), 수산화 알루미늄(aluminium　hydroxide), 수산화 칼슘(calcium　hydroxide), 하이드로 마그네사이트(Mg5(CO3)4(OH)2, hydromagnesite), 탄산칼슘(calcium　carbonate), 티탄산칼륨(potassium titanate), 규산마그네슘(magnesium silicate)　및 이들의 조합에서 선택되는 무기물을 포함할 수 있다.Specifically, the filler is magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 , hydromagnesite ), Calcium carbonate, potassium titanate, magnesium silicate, and combinations thereof.
상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 약 1　중량부 내지 약 100 중량부, 더 구체적으로는 약 1 중량부 내지 약 80　중량부로 포함할 수 있다.The thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight, more specifically about 1 part by weight to about 80 parts by weight based on 100 parts by weight of the thermoplastic resin composition not including the filler. .
상기 열가소성 수지 조성물은 인계 난연제, 비인계 난연제, 또는 이들의 조합을 더 포함할 수 있다.The thermoplastic resin composition may further include a phosphorous flame retardant, a non-phosphorous flame retardant, or a combination thereof.
일 구현예에 따른 열가소성 수지 조성물은 폴리아릴렌에테르계 수지 및 폴리올레핀계 수지를 포함하는 베이스 수지, 그리고 약 230℃ 이상의 열분해 온도를 가지는 인계 난연제를 포함한다. 　이때, 상기 폴리올레핀계 수지의 함량(중량, WOL)과 상기 폴리아릴렌에테르계 수지의 함량(중량, WAR)은 WAR ≤ 1.9×WOL의 관계식을 만족한다.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-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression of W AR ≤ 1.9 × W OL .
상기 열가소성 수지 조성물은 상기 난연제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 난연제를 약 1 중량부 내지 약 50 중량부로 포함할 수 있다.The thermoplastic resin composition may include about 1 part by weight to about 50 parts by weight of the flame retardant based on 100 parts by weight of the thermoplastic resin composition not including the flame retardant.
상기 인계 난연제는 상기 인계 난연제에 포함되는 원자 총량에 대하여 인을 약 5 원자% 이상으로 포함할 수 있다.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.
구체적으로는 상기 인계 난연제는 트리페닐포스페이트(triphenyl phosphate, TPP), 암모늄 폴리포스페이트(phase II)(ammonium polyphosphate(phase II)), 멜라민 포스페이트(melamine phosphate), 레조시놀-디(비스-2,6-디메틸페닐) 포스페이트(resorcinol-di(bis-2,6-dimethylphenyl) phosphate, RDP), 비스페놀 A 디페닐 포스페이트(bisphenol A diphenyl phosphate, BDP), 사이클로 포스파젠(cyclo phosphazene), 디에틸 포스피네이트 암모늄염(diethyl phosphinate ammonium salt, Exolit OP930, Clariant) 및 이들의 조합에서 선택되는 하나를 포함할 수 있다.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.
상기 베이스 수지는 상기 베이스 수지 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 10 중량% 내지 약 80 중량% 및 상기 폴리올레핀계 수지를 약 20 중량% 내지 약 90 중량%로 포함할 수 있고, 상기 인계 난연제는 상기 베이스 수지 100 중량부에 대하여 약 1 중량부 내지 약 50 중량부로 포함될 수 있다.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.
상기 인계 난연제가 2종 이상의 혼합물이고 트리페닐포스페이트(triphenyl phosphate, TPP)를 포함하는 경우, 상기 트리페닐포스페이트는 상기 베이스 수지 100 중량부에 대하여 약 20 중량부 이하로 포함될 수 있다.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.
다른 일 구현예는 상기 열가소성 수지 조성물을 포함하는 성형품을 제공한다.Another embodiment provides a molded article including the thermoplastic resin composition.
상기 성형품은 전선 또는 전선 피복재일 수 있다.The molded article may be an electric wire or an electric wire covering material.
상기 성형품은 ISO 6722에 의해 측정시 점화 후 소화되기까지의 시간이 약 70초 이내일 수 있다.The molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 70 seconds.
상기 성형품은 JASO D 618에 의해 측정시 점화 후 소화되기까지의 시간이 약 20초 이내일 수 있다.The molded article may have a time from ignition to digestion as measured by JASO D 618 within about 20 seconds.
상기 성형품은 ISO 6722에 의해 측정시 가솔린(gasoline) 침지 후 직경 변화율이 약 15% 이하일 수 있다.The molded article may have a diameter change rate of about 15% or less after gasoline immersion as measured by ISO 6722.
상기 성형품은 JASO D 618에 의해 측정시 신율이 약 50% 내지 약 600%일 수 있다.The molded article may have an elongation of from about 50% to about 600% as measured by JASO D 618.
상기 성형품은 ASTM D 638에 의해 측정시 인장 강도가 약 5 MPa　내지 약 60 MPa일 수 있다.The molded article may have a tensile strength of about 5 MPa to about 60 MPa as measured by ASTM D 638.
특정한 폴리올레핀계 수지를 포함하며, 폴리올레핀계 수지와 폴리아릴렌에테르계 수지를 특정 중량 범위로 포함함으로써, 가공성, 유연성, 난연성, 내마모성, 기계적 강도, 내화학성 및 내열성이 우수하며 재활용할 수 있는 열가소성 수지 조성물 및 이를 포함하는 성형품을 제공한다. 또한, 폴리올레핀계 수지와 폴리아릴렌에테르계 수지를 특정 중량 범위로 포함하고 특정한 인계 난연제를 포함함으로써, 가공성, 유연성, 난연성, 내마모성, 내열성, 내전압성, 신율, 기계적 강도, 내화학성 및 외관 특성이 우수하며 재활용할 수 있는 열가소성 수지 조성물 및 이를 포함하는 성형품을 제공한다.It includes a specific polyolefin resin, and includes a polyolefin resin and a polyarylene ether resin in a specific weight range, and is excellent in workability, flexibility, flame retardancy, abrasion resistance, mechanical strength, chemical resistance and heat resistance and can be recycled thermoplastic resin. It provides a composition and a molded article comprising the same. In addition, by including a polyolefin resin and a polyarylene ether resin in a specific weight range and by including a specific phosphorus flame retardant, workability, flexibility, flame retardancy, wear resistance, heat resistance, voltage resistance, elongation, mechanical strength, chemical resistance and appearance characteristics It provides an excellent and recyclable thermoplastic resin composition and a molded article comprising the same.
도 1은 일 구현예에 따른 전선의 횡단면도이다.　1 is a cross-sectional view of a wire according to one embodiment.
도 2는 다른 일 구현예에 따른 전선의 횡단면도이다.2 is a cross-sectional view of a wire according to another embodiment.
도 3은 또 다른 일 구현예에 따른 전선의 횡단면도이다.3 is a cross-sectional view of a wire according to another embodiment.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 　다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다.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.
본 명세서에서 특별한 언급이 없는 한, "치환" 내지 "치환된"이란, 본 발명의 작용기 중의 하나 이상의 수소가 할로겐(-F, -Cl, -Br 또는 -I), 하이드록시기, 니트로기, 시아노기, 아미노기(NH2, NH(R100) 또는 N(R101)(R102)이고, 여기서 R100, R101　및 R102는 동일하거나 서로 상이하며, 각각 독립적으로 C1 내지 C10 알킬기임), 아미디노기, 하이드라진기, 하이드라존기, 카르복실기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 할로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 지환족 유기기, 치환 또는 비치환된 아릴기, 치환 또는 비치환된 알케닐기, 치환 또는 비치환된 알키닐기, 치환 또는 비치환된 헤테로아릴기, 및 치환 또는 비치환된 헤테로사이클로알킬기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환된 것을 의미한다.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.
본 명세서에서 특별한 언급이 없는 한, "알킬기"란 C1 내지 C30 알킬기를 의미하고, 구체적으로는 C1 내지 C20 알킬기를 의미하며, "사이클로알킬기"란 C3 내지 C30 사이클로알킬기를 의미하고, 구체적으로는 C3 내지 C20 사이클로알킬기를 의미하며, "헤테로사이클로알킬기"란 C2 내지 C30 헤테로사이클로알킬기를 의미하고, 구체적으로는 C2 내지 C20 헤테로사이클로알킬기를 의미하며, "알킬렌기"란 C1 내지 C30 알킬렌기를 의미하고, 구체적으로는 C1 내지 C20 알킬렌기를 의미하며, "알콕시기"란 C1 내지 C30 알콕시기를 의미하고, 구체적으로는 C1 내지 C20 알콕시기를 의미하며, "사이클로알킬렌기"란 C3 내지 C30 사이클로알킬렌기를 의미하고, 구체적으로는 C3 내지 C20 사이클로알킬렌기를 의미하며, "헤테로사이클로알킬렌기"란 C2 내지 C30 헤테로사이클로알킬렌기를 의미하고, 구체적으로는 C2 내지 C20 헤테로사이클로알킬렌기를 의미하며, "아릴기"란 C6 내지 C30 아릴기를 의미하고, 구체적으로는 C6 내지 C20 아릴기를 의미하며, "헤테로아릴기"란 C2 내지 C30 헤테로아릴기를 의미하고, 구체적으로는 C2 내지 C18 헤테로아릴기를 의미하며, "아릴렌"기란 C6 내지 C30 아릴렌기를 의미하고, 구체적으로는 C6 내지 C20 아릴렌기를 의미하며, "헤테로아릴렌기"란 C2 내지 C30 헤테로아릴렌기를 의미하고, 구체적으로는 C2 내지 C20 헤테로아릴렌기를 의미하며, "알킬아릴기"란 C7 내지 C30 알킬아릴기를 의미하고, 구체적으로는 C7 내지 C20 알킬아릴기를 의미하며, "할로겐"이란 F, Cl, Br 또는 I를 의미한다.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.
또한 본 명세서에서 특별한 언급이 없는 한, 헤테로사이클로알킬기, 헤테로사이클로알킬렌기, 헤테로아릴기 및 헤테로아릴렌기는 각각 독립적으로 N, O, S, Si 또는 P의 헤테로 원자를 하나의 고리 내에 1개 내지 3개 함유하고, 나머지는 탄소인 사이클로알킬기, 사이클로알킬렌기, 아릴기 및 아릴렌기를 의미한다.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.
또한 본 명세서에서 특별한 언급이 없는 한, "지방족"이란 C1 내지 C30 알킬, C2 내지 C30 알케닐, C2 내지 C30 알키닐, C1 내지 C30 알킬렌, C2 내지 C30 알케닐렌, 또는 C2 내지 C30 알키닐렌을 의미하고, 구체적으로는 C1 내지 C20 알킬, C2 내지 C20 알케닐, C2 내지 C20 알키닐, C1 내지 C20 알킬렌, C2 내지 C20 알케닐렌, 또는 C2 내지 C20 알키닐렌을 의미하고, "지환족"이란 C3 내지 C30 사이클로알킬, C3 내지 C30 사이클로알케닐, C3 내지 C30 사이클로알키닐, C3 내지 C30 사이클로알킬렌, C3 내지 C30 사이클로알케닐렌, 또는 C3 내지 C30 사이클로알키닐렌을 의미하고, 구체적으로는 C3 내지 C20 사이클로알킬, C3 내지 C20 사이클로알케닐, C3 내지 C20 사이클로알키닐, C3 내지 C20 사이클로알킬렌, C3 내지 C20 사이클로알케닐렌, 또는 C3 내지 C20 사이클로알키닐렌을 의미하고, "방향족"이란 C6 내지 C30 아릴, C2 내지 C30 헤테로아릴, C6 내지 C30 아릴렌 또는 C2 내지 C30 헤테로아릴렌을 의미하고, 구체적으로는 C6 내지 C16 아릴, C2 내지 C16 헤테로아릴, C6 내지 C16 아릴렌 또는 C2 내지 C16 헤테로아릴렌을 의미한다.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.
본 명세서에서 별도의 정의가 없는 한, "조합"이란 일반적으로는 혼합 또는 공중합을 의미하며, 지환족 유기기 및 방향족 유기기에서는 2개 이상의 고리가 융합고리를 형성하거나, 2개 이상의 고리가 단일결합, O, S, C(=O), CH(OH), S(=O), S(=O)2, Si(CH3)2, (CH2)p(여기서, 1 ≤ p ≤ 2), (CF2)q(여기서, 1 ≤ q ≤ 2), C(CH3)2, C(CF3)2, C(CH3)(CF3) 또는 C(=O)NH의 작용기에 의해 서로 연결되어 있는 것을 의미한다. 　여기서, "공중합"이란 블록 공중합, 랜덤 공중합, 그래프트 공중합 또는 교호 공중합을 의미하고, "공중합체"란 블록 공중합체, 랜덤 공중합체, 그래프트 공중합체 또는 교호 공중합체를 의미한다.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 (= 0), CH (OH), S (= 0), S (= 0) 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 (═O) NH It means that they are connected to each other by. Here, "copolymerization" means block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" means a block copolymer, random copolymer, graft copolymer or alternating copolymer.
또한 본 명세서에서 "＊"는 동일하거나 상이한 원자 또는 화학식과 연결되는 부분을 의미한다.In addition, in this specification, "*" means the part connected with the same or different atom or formula.
일 구현예에 따른 열가소성 수지 조성물은 폴리아릴렌에테르계 수지 및 약 0.95　g/cm3　이하의 중량가중평균밀도를 가지는 폴리올레핀계 수지를 포함한다. 　이때, 상기 폴리올레핀계 수지의 함량(중량, WOL)과 상기 폴리아릴렌에테르계 수지의 함량(중량, WAR)은 WAR ≤ 1.9×WOL의 관계식을 만족한다. The thermoplastic resin composition according to one embodiment includes a polyarylene ether resin and a polyolefin resin having a weight weighted average density of about 0.95 g / cm 3 or less. In this case, the content (weight, W OL ) of the polyolefin-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression of W AR ≤ 1.9 × W OL .
상기 열 가소성 수지 조성물은 인계 난연제, 비인계 난연제, 또는 이들의 조합을 포함할 수 있다.The thermoplastic resin composition may include a phosphorous flame retardant, a non-phosphorous flame retardant, or a combination thereof.
상기 열가소성 수지 조성물은 상기 폴리아릴렌에테르계 수지 및 상기 폴리올레핀계 수지를 포함하는 베이스 수지, 그리고 약 230℃ 이상의 열분해 온도를 가지는 인계 난연제를 포함할 수 있다. 이때, 상기 폴리올레핀계 수지의 함량(중량, WOL)과 상기 폴리아릴렌에테르계 수지의 함량(중량, WAR)은 WAR ≤ 1.9×WOL의 관계식을 만족한다. 　상기 인계 난연제의 열분해 온도는 TGA/DSC1(Metttler Toledo사제)　장비를 사용하여 열중량 분석법(2 중량% 무게 감량)으로 측정한다.The thermoplastic resin composition may include a base resin including the polyarylene ether resin and the 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-based resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy a relational expression 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).
폴리아릴렌에테르계 수지는 절연성, 내수성(water resistance), 치수 안정성, 내열성, 난연성 및 기계적 강도가 우수하나, 용융 점도가 높아 가공성이 열악하고, 유연성 및 내화학성, 예컨대 내유성(oil resistance)이 열악하며 강한 냄새가 있고 황색을 나타낸다. 　이에 의해, 상기 폴리아릴렌에테르계 수지는 전선, 예컨대 자동차용 전선을 제조하기 위해 단독으로 사용되기 어렵다. 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.
폴리올레핀계 수지는 가공성, 유연성 및 내화학성이 우수하고 냄새도 약하나, 내열성, 난연성 및 기계적 강도가 열악하다. 　이에 의해, 상기 폴리올레핀계 수지는 전선, 예컨대 자동차용 전선을 제조하기 위해 단독으로 사용되기 어렵다. 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.
상기 열가소성 수지 조성물은 상기 폴리아릴렌에테르계 수지와 상기 폴리올레핀계 수지를 포함하며, 상기 폴리올레핀계 수지의 함량(WOL)과 상기 폴리아릴렌에테르계 수지의 함량(WAR)이 WAR ≤ 1.9×WOL의 관계식을 만족하도록 포함함으로써, 용융 점도를 적절히 조절하여 우수한 가공성을 가질 수 있고, 우수한 유연성 및 내화학성, 예컨대 내유성을 가질 수 있다. 　또한, 충분한 양의 충진제, 난연제 등을 포함할 수 있어 절연성, 난연성, 기계적 강도, 내열성, 내수성 및 치수 안정성도 우수한 수준으로 유지할 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 폴리아릴렌에테르계 수지와 상기 폴리올레핀계 수지를 WAR ≤ 1.2×WOL의 관계식을 만족하도록 포함할 수 있고, 더욱 구체적으로는 WAR ≤ WOL의 관계식을 만족하도록 포함할 수 있다.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 sufficient amount of fillers, flame retardants and the like may be included to maintain excellent insulation, flame retardancy, mechanical strength, heat resistance, water resistance and dimensional stability. Specifically, the thermoplastic resin composition may include the polyarylene ether-based resin and the polyolefin-based resin so as to satisfy a relation of W AR ≤ 1.2 × W OL , and more specifically, a relation of W AR ≤ W OL . Can be included to satisfy.
구체적으로는 상기 폴리아릴렌에테르계 수지는 하기 화학식 1로 표시되는 반복단위를 포함할 수 있다.Specifically, the polyarylene ether resin may include a repeating unit represented by Formula 1 below.
[화학식 1][Formula 1]
Figure PCTKR2012010240-appb-I000001
Figure PCTKR2012010240-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
R1은 동일하거나 서로 상이하며 각각 독립적으로 수소, 할로겐, 치환 또는 비치환된 C1 내지 C30 지방족 유기기, 치환 또는 비치환된 C2 내지 C30 방향족 유기기, 또는 치환 또는 비치환된 C1 내지 C30 알콕시기이고, 구체적으로는 수소, 할로겐, 치환 또는 비치환된 C1 내지 C10 지방족 유기기, 치환 또는 비치환된 C2 내지 C10 방향족 유기기, 또는 치환 또는 비치환된 C1 내지 C10 알콕시기일 수 있고, 더욱 구체적으로는 수소, 할로겐, 치환 또는 비치환된 C1 내지 C5 지방족 유기기, 치환 또는 비치환된 C2 내지 C8 방향족 유기기, 또는 치환 또는 비치환된 C1 내지 C6 알콕시기일 수 있다.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.
n1은 각각의 반복단위에서 동일하거나 서로 상이하며 각각 독립적으로 0 내지 4의 정수이다.n1 is the same or different in each repeating unit and is each independently an integer of 0 to 4.
n1이 2 이상의 정수인 경우, 상기 R1은 각각 동일하거나 서로 상이할 수 있다. 　또한 상기 R1은 각각의 반복단위에서 동일하거나 서로 상이할 수 있다.When n1 is an integer of 2 or more, each of R 1 may be the same or different from each other. In addition, R 1 may be the same or different from each other in the repeating unit.
상기 폴리아릴렌에테르계 수지는 아릴렌 부분(arylene part)이 상기 폴리아릴렌에테르계 수지 전체 중량에 대하여 약 50　중량% 내지 약 90　중량%로 포함될 수 있고, 전기음성도가 2.58 이상의 원자를 포함할 수 있다. 　이 경우, 우수한 가공성을 가질 수 있고, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 내열성 및 난연성을 효과적으로 개선할 수 있다. 　구체적으로는 상기 폴리아릴렌에테르계 수지는 아릴렌 부분(arylene part)이 상기 폴리아릴렌에테르계 수지 전체 중량에 대하여 약 60　중량% 내지 약 85　중량%, 더욱 구체적으로는 65　중량% 내지 약 75　중량%, 보다 구체적으로는 65　중량% 내지 약 72　중량%로 포함될 수 있다.The polyarylene ether resin may include an arylene part in an amount of about 50 wt% to about 90 wt% with respect to the total weight of the polyarylene ether resin, and have an electronegativity of 2.58 or more. 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%.
더욱 구체적으로는 상기 폴리아릴렌에테르계 수지는 폴리(1,4-페닐렌에테르), 폴리(1,3-페닐렌에테르), 폴리(1,2-페닐렌에테르), 폴리(2-메틸-1,4-페닐렌에테르), 폴리(3-메틸-1,4-페닐렌에테르), 폴리(2-메틸-1,3-페닐렌에테르), 폴리(4-메틸-1,3-페닐렌에테르), 폴리(5-메틸-1,3-페닐렌에테르), 폴리(6-메틸-1,3-페닐렌에테르), 폴리(3-메틸-1,2-페닐렌에테르), 폴리(4-메틸-1,2-페닐렌에테르), 폴리(5-메틸-1,2-페닐렌에테르), 폴리(6-메틸-1,2-페닐렌에테르), 폴리(2,6-디메틸-1,4-페닐렌에테르), 폴리(2,3-디메틸-1,4-페닐렌에테르), 폴리(3,5-디메틸-1,4-페닐렌에테르), 폴리(2,5-디메틸-1,4-페닐렌에테르), 폴리(2,4-디메틸-1,3-페닐렌에테르), 폴리(2,5-디메틸-1,3-페닐렌에테르), 폴리(2,6-디메틸-1,3-페닐렌에테르), 폴리(4,5-디메틸-1,3-페닐렌에테르), 폴리(4,6-디메틸-1,3-페닐렌에테르), 폴리(5,6-디메틸-1,3-페닐렌에테르), 폴리(3,4-디메틸-1,2-페닐렌에테르), 폴리(3,5-디메틸-1,2-페닐렌에테르), 폴리(3,6-디메틸-1,2-페닐렌에테르), 폴리(4,5-디메틸-1,2-페닐렌에테르), 폴리(4,6-디메틸-1,2-페닐렌에테르), 폴리(5,6-디메틸-1,2-페닐렌에테르)　및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.More 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- Phenylene 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-dimethyl-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 a combination thereof may be included, but is not limited thereto.
상기 폴리아릴렌에테르계 수지는 약 10,000 g/mol 내지 약 1,000,000 g/mol의 중량평균 분자량을 가질 수 있다. 　상기 폴리아릴렌에테르계 수지의 중량평균 분자량이 상기 범위 내인 경우, 가공이 용이하고, 이를 포함하는 열가소성 수지 조성물의 기계적 강도 및 내열성을 효과적으로 개선할 수 있다.　　구체적으로는 상기 폴리아릴렌에테르계 수지는 약 40,000　g/mol 내지 약 300,000　g/mol의 중량평균 분자량을 가질 수 있다.The polyarylene ether-based resin may have a weight average molecular weight of about 10,000 g / mol to about 1,000,000 g / mol. When the weight average molecular weight 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 can be effectively improved. Specifically, the polyarylene ether resin may have a weight average molecular weight of about 40,000 kg / mol to about 300,000 kg / mol.
상기 폴리아릴렌에테르계 수지는 약 10,000　g/mol 내지 약 1,000,000　g/mol의 수평균 분자량(Mn)을 가질 수 있다. 　상기 폴리아릴렌에테르계 수지의 수평균 분자량(Mn)이 상기 범위 내인 경우, 가공이 용이하고, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 기계적 강도 및 내열성을 효과적으로 개선할 수 있다.　　구체적으로는 상기 폴리아릴렌에테르계 수지는 약 15,000　g/mol 내지 약 300,000　g/mol, 더욱 구체적으로는 약 15,000　g/mol 내지 약 30,000　g/mol의 수평균 분자량(Mn)을 가질 수 있다.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.
상기 폴리아릴렌에테르계 수지는 약 1.2 내지 약 2.5의 다분산 지수(polydispersity index, PDI)를 가질 수 있다. 　상기 폴리아릴렌에테르계 수지의 다분산 지수가 상기 범위 내인 경우, 가공이 용이하고, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 신율 및 내열성을 효과적으로 개선할 수 있다.　　구체적으로는 상기 폴리아릴렌에테르계 수지는 약 1.3　내지 약 1.8의 다분산 지수(PDI)를 가질 수 있다.The polyarylene ether-based resin may have a polydispersity index (PDI) of about 1.2 to about 2.5. When the polydispersity index of the polyarylene ether resin is within the above range, processing is easy, and elongation and heat resistance of a molded article manufactured using the thermoplastic resin composition including the same may be effectively improved. Specifically, the polyarylene ether resin may have a polydispersity index (PDI) of about 1.3 kPa to about 1.8.
상기 올레핀계 수지는 단독으로, 또는 2종 이상을 혼합하여 사용할 수 있고, 약 0.95　g/cm3　이하의 중량가중평균밀도를 갖는다. 　이 경우, 이를 포함하는 열가소성 수지 조성물의 유연성 및 내한성을 효과적으로 개선할　수 있다. 　구체적으로는 상기 폴리올레핀계 수지는 약 0.94　g/cm3　이하, 더욱 구체적으로는 약 0.91　g/cm3　내지 0.94　g/cm3의 중량가중평균밀도를 가질 수 있다.　　중량가중평균밀도는 각 폴리올레핀의 중량을 각 폴리올레핀 밀도에 곱하여 평균을 낸 것을 의미한다. 　단독 수지를 사용한 경우에는 그 수지의 밀도가 중량가중평균밀도가 된다. The said olefin resin can be used individually or in mixture of 2 or more types, and has a weight 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.
상기 폴리올레핀계 수지는 약 0.1 g/10min 내지 약 30 g/10min의 용융지수(melt index, MI)를 가질 수 있다. 　상기 폴리올레핀계 수지의 용융지수가 상기 범위 내인 경우, 다른 수지와 용이하게 혼합할 수 있고 이를 포함하는 열가소성 수지 조성물의 기계적 강도를 효과적으로 개선할 수 있다. 　구체적으로는 상기 폴리올레핀계 수지는 약 0.1 g/10min 내지 약 20 g/10min의 용융지수(MI)를 가질 수 있다.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.
상기 폴리올레핀계 수지는 약 80℃ 내지 약 170℃의 녹는점(melting point)을 가질 수 있다. 　상기 폴리올레핀계 수지의 녹는점이 상기 범위 내인 경우, 이를 포함하는 열가소성 수지 조성물의 내열성 및 기계적 강도를 효과적으로 개선할 수 있다. 　구체적으로는 상기 폴리올레핀계 수지는 약 95℃ 내지 약 135℃, 더욱 구체적으로는 약 105℃ 내지 약 125℃의 녹는점을 가질 수 있다.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.
상기 폴리올레핀계 수지는 약 10,000 g/mol 내지 약 1,000,000 g/mol의 중량평균 분자량을 가질 수 있다. 　상기 폴리올레핀계 수지의 중량평균 분자량이 상기 범위 내인 경우, 가공이 용이하고, 이를 포함하는 열가소성 수지 조성물의 기계적 강도를 효과적으로 개선할 수 있다. 　구체적으로는 상기 폴리올레핀계 수지는 약 40,000　g/mol 내지 약 300,000　g/mol의 중량평균 분자량을 가질 수 있다.The polyolefin-based resin may have a weight average molecular weight of about 10,000 g / mol to about 1,000,000 g / mol. When the weight average molecular weight of the polyolefin-based resin is in the above range, the processing is easy, it is possible to effectively improve the mechanical strength of the thermoplastic resin composition comprising the same. Specifically, the polyolefin-based resin may have a weight average molecular weight of about 40,000 kg / mol to about 300,000 kg / mol.
상기 폴리올레핀계 수지는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 저밀도 폴리에틸렌(low density polyethylene, LDPE), 에틸렌-옥텐 공중합체(ethylene-octene copolymer), 초저밀도 폴리에틸렌(ultra low density polyethylene), 중밀도 폴리에틸렌(medium density polyethylene), 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-부텐 공중합체(ethylene-butene copolymer), 폴리프로필렌(polypropylene)　및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다. 　구체적으로는 상기 폴리올레핀계 수지는 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 저밀도 폴리에틸렌(low density polyethylene, LDPE), 에틸렌-옥텐 공중합체(ethylene-octene copolymer), 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-부텐 공중합체(ethylene-butene copolymer)　및 이들의 조합에서 선택되는 하나를 포함할 수 있다.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, 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.
상기 인계 난연제는 이를 포함하는 열가소성 수지 조성물의 난연성 및 내열성을 개선하는 역할을 수행할 수 있다.The phosphorus-based flame retardant may play a role of improving flame retardancy and heat resistance of the thermoplastic resin composition including the same.
상기 인계 난연제는 약 230℃ 이상의 열분해 온도를 가진다. 　상기 인계 난연제의 열분해 온도가 상기 범위 내인 경우, 이를 포함하는 열가소성 수지 조성물의 가공 시에도 분해되지 않아 이를 포함하는 열가소성 수지 조성물의 난연성, 내열성, 기계적 강도 및 신율을 효과적으로 개선할 수 있다. 　구체적으로는 상기 인계 난연제는 약 250℃ 이상의　열분해 온도를 가질 수 있다.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.
상기 인계 난연제는 상기 인계 난연제에 포함되는 원자 총량에 대하여 인을 약 5 원자% 이상으로 포함할 수 있다. 　상기 인계 난연제의 인 함량이 상기 범위 내인 경우, 난연성을 효과적으로 개선할 수 있고, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 신율을 효과적으로 개선할 수 있다. 　구체적으로는 상기 인계 난연제는 상기 인계 난연제에 포함되는 원자 총량에 대하여 인을 약 5　원자% 내지 약 30　원자%, 더욱 구체적으로는 약 7　원자% 내지 약 30　원자%로 포함할 수 있다.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.
상기 인계 난연제는 포스페이트(phosphate) 화합물, 포스파이트(phosphite) 화합물, 포스포네이트(phosphonate) 화합물, 포스파젠(phosphazene) 화합물, 포스피네이트(phosphinate) 화합물　및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.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.
구체적으로는 상기 인계 난연제는 트리페닐포스페이트(triphenyl phosphate, TPP), 암모늄 폴리포스페이트(phase II)(ammonium polyphosphate(phase II)), 멜라민 포스페이트(melamine phosphate), 레조시놀-디(비스-2,6-디메틸페닐) 포스페이트(resorcinol-di(bis-2,6-dimethylphenyl) phosphate, RDP), 비스페놀 A 디페닐 포스페이트(bisphenol A diphenyl phosphate, BDP), 사이클로 포스파젠(cyclo phosphazene), 디에틸 포스피네이트 암모늄염(diethyl phosphinate ammonium salt, Exolit OP930, Clariant)　및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.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.
상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 20 중량% 내지 약 65　중량%로 포함할 수 있고, 상기 폴리올레핀계 수지를 약 35　중량% 내지 약 80 중량%로 포함할 수 있다. 　상기 폴리아릴렌에테르계 수지 및 상기 폴리올레핀계 수지의 함량이 상기 범위 내인 경우, 상기 열가소성 수지 조성물의 유연성, 내열성, 내마모성, 내유성　및 난연성을 효과적으로 개선할 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 30 중량% 내지 약 55 중량%로 포함할 수 있고, 상기 폴리올레핀계 수지를 약 45 중량% 내지 약 70 중량%로 포함할 수 있다.The thermoplastic resin composition may include about 20 wt% to about 65 wt% of the polyarylene ether resin, and about 35 wt% to about 80 wt% of the polyarylene ether resin, based on the total amount of the thermoplastic resin composition. It may include. When the content of the polyarylene ether resin and the polyolefin resin is within the above range, the flexibility, heat resistance, wear resistance, oil resistance and flame resistance of the thermoplastic resin composition can be effectively improved. Specifically, the thermoplastic resin composition may include about 30 wt% to about 55 wt% of the polyarylene ether resin, and about 45 wt% to about 70 wt% of the polyarylene ether resin, based on the total amount of the thermoplastic resin composition. It may be included in weight percent.
상기 인계 난연제를 포함하는 상기 열가소성 수지 조성물에서, 상기 베이스 수지는 상기 베이스 수지 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 10 중량% 내지 약 80 중량% 및 상기 폴리올레핀계 수지를 약 20 중량% 내지 약 90 중량%로 포함할 수 있으며, 상기 인계 난연제는 상기 베이스 수지 100 중량부에 대하여 약 1 중량부 내지 약 50 중량부로 포함될 수 있다. 　상기 폴리아릴렌에테르계 수지, 상기 폴리올레핀계 수지 및 상기 인계 난연제의 함량이 상기 범위 내인 경우, 상기 열가소성 수지 조성물의 유연성, 내열성, 내마모성, 난연성, 신율, 기계적 강도 및 외관 특성을 효과적으로 개선할　수 있다. 　구체적으로는 상기 열가소성 수지 조성물에서, 상기 베이스 수지는 상기 베이스 수지 총량에 대하여 상기 폴리아릴렌에테르계 수지를 약 20 중량% 내지 약 55 중량% 및 상기 폴리올레핀계 수지를 약 45 중량% 내지 약 80 중량%로 포함할 수 있으며, 상기 인계 난연제는 상기 베이스 수지 100 중량부에 대하여 약 5　중량부 내지 약 50　중량부, 더욱 구체적으로는 약 5　중량부 내지 약 40　중량부, 보다 구체적으로는 약 5　중량부 내지 약 30　중량부로 포함될 수 있다.In the thermoplastic resin composition comprising the phosphorus-based flame retardant, the base resin is about 10% to about 80% by weight of the polyarylene ether resin and about 20% by weight to the polyolefin resin based on the total amount of the base resin About 90% by weight, and 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.
상기 인계 난연제는 단독으로 또는 2종 이상의 혼합물로 사용할 수 있다.The phosphorus flame retardant may be used alone or in a mixture of two or more thereof.
상기 인계 난연제가 2종 이상의 혼합물이고 트리페닐포스페이트(TPP)를 포함하는 경우, 상기 트리페닐포스페이트는 상기 베이스 수지 100 중량부에 대하여 약 20 중량부 이하로 포함될 수 있다. 　이 경우, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 신율 및 난연성을 효과적으로 개선할　수 있다. 　구체적으로는 상기 인계 난연제가 2종 이상의 혼합물이고 트리페닐포스페이트(TPP)를 포함하는 경우, 상기 트리페닐포스페이트는 상기 베이스 수지 100 중량부에 대하여 약 5　중량부 내지 약 15　중량부로 포함될 수 있다.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.
한편, 상기 열가소성 수지 조성물은 비인계 난연제를 더 포함할 수 있다.On the other hand, the thermoplastic resin composition may further comprise a non-phosphorous flame retardant.
상기 열가소성 수지 조성물이 비인계 난연제를 더 포함하는 경우, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 신율, 내열성 및 내마모성 개선할　수 있다.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.
구체적으로는 상기 비인계 난연제는 폴리실록산, 멜라민 화합물　및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.Specifically, the non-phosphorus flame retardant may include one selected from polysiloxane, melamine compound, and a combination thereof, but is not limited thereto.
상기 열가소성 수지 조성물은 상기 비인계 난연제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 비인계 난연제를 약 5　중량부 내지 약 30　중량부로 포함할 수 있다. 　상기 비인계 난연제의 함량이 상기 범위 내인 경우, 이를 포함하는 열가소성 수지 조성물을 사용하여 제조한 성형품의 신율, 내열성 및 난연성을 효과적으로 개선할　수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 비인계 난연제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 비인계 난연제를 약 10　중량부 내지 약 20　중량부로 포함할 수 있다.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.
상기 열가소성 수지 조성물은 상용화제를 더 포함할 수 있다. 　상용화제는 상기 폴리아릴렌에테르계 수지와 상기 폴리올레핀계 수지가 균일하게 분산될 수 있게 도와주는 역할을 수행할 수 있으며, 또한 충진제, 또는 난연제가 포함된 경우 난연제, 충진제 등과 수지가 균일하게 분산될 수 있게 도와주는 역할을 수행할 수도 있다.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 when the filler or the flame retardant is included, the resin may be uniformly dispersed in the flame retardant, the filler, and the like. It can also play a role in helping.
예컨대, 상기 상용화제는 상기 폴리아릴렌에테르계 수지와 친한 작용기 및 상기 폴리올레핀계 수지와 친한 작용기를 모두 포함하는 화합물로서, 상기 폴리아릴렌에테르계 수지와 상기 폴리올레핀계 수지가 균일하게 분산될 수 있게 도와주는 역할을 수행할 수 있다. 　일 예에서, 상기 폴리올레핀계 수지가 베이스 수지로 사용되어, 상기 폴리아릴렌에테르계 수지가 상기 폴리올레핀계 수지에 분산될 수 있다.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.
상기 폴리아릴렌에테르계 수지와 상기 폴리올레핀계 수지의 상용성, 그리고 상기 수지와 충진제, 난연제 등과의 상용성이 개선되면, 이를 포함하는 열가소성 수지 조성물의 가공성, 유연성, 난연성, 내마모성, 내열성, 내전압성, 기계적 강도 및 내화학성이 개선될 수 있다.When the compatibility of the polyarylene ether resin and the polyolefin resin and the compatibility with the resin, the filler, the flame retardant, etc. are improved, processability, flexibility, flame retardancy, abrasion resistance, heat resistance, and voltage resistance of the thermoplastic resin composition including the same are improved. Mechanical strength and chemical resistance can be improved.
구체적으로는 상기 상용화제는 스티렌-에틸렌-부틸렌-스티렌 공중합체(styrene-ethylene-butylene-styrene copolymer, SEBS), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부틸렌-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS), 내충격성 폴리스티렌(high impact polystyrene, HIPS), 에틸렌-아세트산비닐 공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌-메틸아크릴레이트 공중합체(ethylene-methyl acrylate copolymer, EMA), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethyl acrylate copolymer, EEA), 에틸렌-부틸아크릴레이트 공중합체(ethylene-butyl acrylate copolymer, EBA), 스티렌-부타디엔-스티렌 공중합체(styrene-butadiene-styrene copolymer, SBS), 스티렌-에틸렌-프로필렌-스티렌 공중합체(styrene-ethylene-propylene-styrene copolymer, SEPS), 스티렌-이소프렌-스티렌 공중합체(styrene-isoprene-styrene copolymer, SIS), 스티렌-에틸렌 공중합체(styrene-ethylene copolymer), 스티렌-에틸렌-부타디엔-스티렌 공중합체(styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부타디엔-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 폴리프로필렌(maleic anhydride grafted polypropylene), 말레익 언하이드라이드-그래프트된 선형 저밀도 폴리에틸렌(maleic anhydride grafted linear low density polyethylene), 말레익 언하이드라이드-그래프트된 저밀도 폴리에틸렌(maleic anhydride grafted low density polyethylene) 및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.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 polypropylene (maleic anhydride) grafted linear low density polyethylene), maleic anhydride grafted low density polyethylene, and combinations thereof, but is not limited thereto.
상기　열가소성 수지 조성물은 상기 상용화제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 상용화제를 약 1 중량부 내지 약 40 중량부로 포함할 수 있다. 　상기 상용화제를 상기 범위 내로 포함하는 경우, 이를 포함하는 열가소성 수지 조성물의 기계적 강도, 내열성 및 가공성을 효과적으로 개선할 수 있고, 상기 열가소성 수지 조성물을 사용하여 제조한 성형품의 외관 특성을 효과적으로 개선할 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 상용화제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 상용화제를 약 1　중량부 내지 약 20　중량부, 더욱 구체적으로는 약 1　중량부 내지 약 10　중량부로 포함할 수 있다.The thermoplastic resin composition may include about 1 part by weight to about 40 parts by weight of the compatibilizer based on 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.
상기 열가소성 수지 조성물 또는 상기 인계 난연제를 포함하는 상기 열가소성 수지 조성물은 충진제를 더 포함할 수 있다. 　상기 충진제는 난연제 및 보강제로서의　역할을 수행하여,　이를 포함하는 열가소성 수지 조성물의 난연성 및 기계적 물성, 예컨대 내마모성을 개선할 수 있다.The thermoplastic resin composition including the thermoplastic resin composition or the phosphorus-based flame retardant may further include a filler. The filler may act as a flame retardant and a reinforcing agent to improve the flame retardancy and mechanical properties, such as wear resistance, of the thermoplastic resin composition including the foil.
구체적으로는 상기 충진제는 무기 충진제일 수 있고, 예를 들어 산화 마그네슘(magnesium oxide), 수산화 마그네슘(magnesium hydroxide), 수산화 알루미늄(aluminium　hydroxide), 수산화 칼슘(calcium　hydroxide), 하이드로 마그네사이트(Mg5(CO3)4(OH)2, hydromagnesite), 탄산칼슘(calcium　carbonate), 티탄산칼륨(potassium titanate), 규산마그네슘(magnesium silicate),　 알루미늄 옥사이드 하이드록사이드(aluminum oxide hydroxide) 및 이들의 조합에서 선택되는 무기물을 포함할 수 있으나, 이에 한정되는 것은 아니다.Specifically, the filler may be an inorganic filler, for example, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (CO) 3 ) minerals selected from 4 (OH) 2 , hydromagnesite, calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide and combinations thereof It may include, but is not limited thereto.
상기 무기물은 선택적으로 비닐실란, 아미노실란, 스테아린산, 올레산, 지방산, 폴리머, 페닐실란, 우레탄, 에폭시,　이들의 유도체 및 이들의 조합에서 선택되는 하나로 표면처리되어 있을 수 있으나, 이에 한정되는 것은 아니다. 　이때, 상기 폴리머는 폴리에틸렌, 폴리스티렌, 폴리(부틸 아크릴레이트), 폴리(메틸 메타크릴레이트), 폴리(도데실 메타크릴레이트), 폴리(옥타데실 메타크릴레이트) 및 이들의 조합에서 선택되는 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.The inorganic material may optionally be surface-treated with one selected from vinylsilane, aminosilane, stearic acid, oleic acid, fatty acid, polymer, phenylsilane, urethane, epoxy, derivatives thereof, and combinations thereof, but is not limited thereto. In this case, the polymer is one selected from polyethylene, polystyrene, poly (butyl acrylate), poly (methyl methacrylate), poly (dodecyl methacrylate), poly (octadecyl methacrylate) and combinations thereof It may include, but is not limited thereto.
상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 약 1　중량부 내지 약 80　중량부로 포함할 수 있다. 　상기 충진제의 함량이 상기 범위 내인 경우, 이를 포함하는 열가소성 수지 조성물의 내열성, 내마모성, 고온압력 특성 및 내유성을 효과적으로 개선할 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 약 5　중량부 내지 약 40　중량부로 포함할 수 있다.The thermoplastic resin composition may include about 1 parts by weight to about 80 parts by weight of the filler based on 100 parts by weight of the thermoplastic resin composition not containing the filler. When the content of the filler is in the above range, it is possible to effectively improve the heat resistance, wear resistance, high temperature pressure characteristics and oil resistance of the thermoplastic resin composition comprising the same. Specifically, the thermoplastic resin composition may include about 5 parts by weight to about 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition not containing the filler.
상기 열가소성 수지 조성물이 인계 난연제를 더 포함하는 경우, 상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 약 1　중량부 내지 약 100　중량부로 포함할 수 있다. 　상기 충진제를 상기 범위 내로 포함하는 경우, 이를 포함하는 열가소성 수지 조성물의 난연성 및 기계적 물성, 예컨대 내마모성을 효과적으로 개선할 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 약 10　중량부 내지 약 100　중량부, 더욱 구체적으로는 약 10　중량부 내지 약 50　중량부로 포함할 수 있다.When the thermoplastic resin composition further includes a phosphorus-based flame retardant, the thermoplastic resin composition may include about 1 parts by weight to about 100 parts by weight based on 100 parts by weight of the thermoplastic resin composition not including 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.
한편, 상기 열가소성 수지 조성물이 난연제를 더 포함할 경우, 상기 난연제는　이를 포함하는 열가소성 수지 조성물의 난연성 및 내열성을 개선하는 역할을 수행할 수 있다.On the other hand, when the thermoplastic resin composition further comprises a flame retardant, the flame retardant may play a role of improving the flame retardancy and heat resistance of the thermoplastic resin composition comprising a whip.
상기 열가소성 수지 조성물이 상기 충진제와 상기 난연제를 모두 포함하는 경우, 상기 충진제와 상기 난연제는 약 50:1 내지 약 1:10의 중량비로 포함될 수 있다. 　상기 충진제와 상기 난연제의 함량비가 상기 범위 내인 경우, 이를 포함하는 열가소성　수지 조성물의 난연성, 내열성, 기계적 강도 및 신율을 효과적으로 개선할 수 있다. 　구체적으로는 상기 충진제와 상기 난연제는 약 10:1　내지 약 1:3의 중량비로 포함될 수 있다.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 to about 1:10. When the content ratio of the filler and the flame retardant is within the range, it is possible to effectively improve the flame retardancy, heat resistance, mechanical strength and elongation of the thermoplastic resin composition comprising 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.
상기 열가소성 수지 조성물은 약 18 내지 약 50의 한계산소지수(limited oxygen index, LOI)를 가질 수 있다. 　상기 열가소성 수지 조성물의 한계산소지수가 상기 범위 내인 경우, 상기 열가소성 수지 조성물은 우수한 난연성, 내열성 및 기계적 강도를 가질 수 있다. 　구체적으로는 상기 열가소성 수지 조성물은 약 21　내지 약 35, 더욱 구체적으로는 약 21　내지 약 28의 한계산소지수(LOI)를 가질 수 있다.The thermoplastic resin composition may have a limited oxygen index (LOI) of about 18 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.
일 구현예에 따른 열가소성 수지 조성물은 상기 구성성분 외에도 사출 성형성, 물성 밸런스, 분산성 등을 개선하고, 산화를 방지하며 다이 드룰(die drool)의 형성을 억제하기 위해 필요에 따라 염료, 안료, 안정제, 윤활제, 스테아레이트와 같은 가공조제, 항균제, 이형제, 수지 산화 방지제, 구리 산화 방지제, 할로겐 스케빈져(halogen scavenger) 등의 첨가제를 적절히 더 포함할 수도 있다. 　이때, 상기 첨가제는 단독으로, 또는 2종 이상 혼합하여 사용될 수 있다.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. In this case, the additives may be used alone or in combination of two or more thereof.
일 구현예에 따른 열가소성 수지 조성물은 열가소성 수지 조성물을 제조하는 공지의 방법으로 제조할 수 있다. 　예를 들면, 상기 각각의 구성성분과 기타 첨가제들을 동시에 혼합한 후에, 압출기 내에서 용융 압출하고 펠렛 형태로 제조할 수 있다.The thermoplastic resin composition according to one embodiment may be prepared by a known method for preparing a thermoplastic 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.
일 구현예에 따른 열가소성 수지 조성물은 별도의 가교 결합(crosslinking)을 포함하지 않아 용이하게 재활용할 수 있으며 할로겐계 난연제를 사용하지 않아 환경 친화적이다. 　또한 일 구현예에 따른 열가소성 수지 조성물은 특정한 폴리올레핀계 수지를 포함하며, 상기 폴리올레1핀계 수지와 상기 폴리아릴렌에테르계 수지를 특정 중량 범위로 포함함으로써, 가공성, 유연성, 난연성, 내마모성, 내열성, 내전압성, 절연성, 기계적 강도, 내화학성, 내수성 및 치수 안정성을 효과적으로 개선할 수 있다.Thermoplastic resin composition according to one embodiment does not include a separate crosslinking (crosslinking) can be easily recycled and does not use a halogen-based flame retardant is environmentally friendly. In addition, the thermoplastic resin composition according to one embodiment includes a specific polyolefin-based resin, and includes the polyolefin-based resin and the polyarylene ether-based resin in a specific weight range, so that workability, flexibility, flame retardancy, wear resistance, heat resistance, Withstand voltage, insulation, mechanical strength, chemical resistance, water resistance and dimensional stability can be effectively improved.
다른 일 구현예는 상기 열가소성 수지 조성물을 포함하는 성형품을 제조한다. 　상기 성형품은 상기 열가소성 수지 조성물을 사용하여 사출성형, 블로우 성형, 압출, 열 성형 등 다양한 방법으로 제조할 수 있다.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.
상기 성형품은 전선 또는 전선 피복재일 수 있으며, 이는 전력선, 통신선, 자동차용 전선, 전자 기기용 전선, 원자력 발전에 사용 가능한 전선, 풍력 발전에 사용 가능한 전선 등 다양한 분야에 사용될 수 있다.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, wires for electronic devices, wires for nuclear power generation, wires for wind power generation, and the like.
일 예로, 일 구현예에 따른 전선의 횡단면도를 도 1에 나타낸다.As an example, a cross-sectional view of a wire according to one embodiment is shown in FIG. 1.
도 1을 참고하면, 전선(1)은 전도체(2) 및 상기 전도체를 둘러싸고 있는 피복재(4)를 포함한다. 　이때, 상기 전도체(2), 피복재(4) 또는 이들의 조합은 상기 열가소성 수지 조성물을 포함할 수 있다.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.
상기 전도체(2)는 한 가닥일 수도 있고, 2 이상의 여러 가닥을 포함할 수도 있다. 　상기 전도체(2)가 여러 가닥인 경우, 각각의 가닥을 둘러싸도록 피복재(4)를 형성하거나, 여러 가닥을 한번에 둘러싸도록 피복재(4)를 형성할 수 있다.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.
일 예로, 다른 일 구현예에 따른 전선의 횡단면도를 도 2에 나타낸다.As an example, a cross-sectional view of a wire according to another embodiment is shown in FIG. 2.
도 2를 참고하면, 전선(10)은 전도체(11), 상기 전도체(11)를 둘러싸고 있는 피복재(13), 상기 피복재(13)를 둘러싸고 있는 절연체(15), 그리고 상기 절연체(15)를 둘러싸고 있는 시스(sheath, 17)를 포함한다. 　이때, 상기 전도체(11), 피복재(13), 절연체(15), 시스(17) 또는 이들의 조합은 상기 열가소성 수지 조성물을 포함할 수 있다.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.
상기 전도체(11)는 한 가닥일 수도 있고, 2 이상의 여러 가닥을 포함할 수도 있다. 　상기 전도체(11)가 여러 가닥인 경우, 각각의 가닥을 둘러싸도록 피복재(13), 절연체(15), 시스(17) 또는 이들의 조합을 형성하거나, 여러 가닥을 한번에 둘러싸도록 피복재(13), 절연체(15), 시스(17) 또는 이들의 조합을 형성할 수 있으나, 이에 한정되는 것은 아니다.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.
일 예로, 또 다른 일 구현예에 따른 전선의 횡단면도를 도 3에 나타낸다.As an example, a cross-sectional view of a wire according to another embodiment is shown in FIG. 3.
도 3을 참고하면, 전선(20)은 전도체(21), 상기 전도체(21)를 둘러싸고 있는 피복재(23), 상기 피복재(23)를 둘러싸고 있는 절연체(25), 상기 절연체(25)를 둘러싸고 있는 차폐체(27), 그리고 상기 차폐체(27)를 둘러싸고 있는 시스(sheath, 29)를 포함한다. 　이때, 상기 전도체(21), 피복재(23), 절연체(25), 차폐체(27), 시스(29) 또는 이들의 조합은 상기 열가소성 수지 조성물을 포함할 수 있다.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.
상기 전도체(21)는 한 가닥일 수도 있고, 2 이상의 여러 가닥을 포함할 수도 있다. 　상기 전도체(21)가 여러 가닥인 경우, 각각의 가닥을 둘러싸도록 피복재(23), 절연체(25), 차폐체(27), 시스(29) 또는 이들의 조합을 형성하거나, 여러 가닥을 한번에 둘러싸도록 피복재(23), 절연체(25), 차폐체(27), 시스(29) 또는 이들의 조합을 형성할 수 있으나, 이에 한정되는 것은 아니다.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.
도 1 내지 도 3은 일 구현예에 따른 전선의 구조의 일 예들을 나타낸 것일 뿐이며, 일 구현예에 따른 전선의 구조가 이들에 한정되는 것은 아니다.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.
본 명세서에서 달리 설명하지 않는 한, 전선, 전도체, 피복재, 절연체, 차폐체 및 시스에 대한 내용은 당업계에 일반적으로 알려진 바와 같다.Unless stated otherwise herein, information about wires, conductors, sheaths, insulators, shields, and sheaths is as generally known in the art.
상기 성형품은 ISO 6722에 의해 측정시 점화 후 소화되기까지의 시간이 약 70초 이내일 수 있다. 　상기 성형품의 점화 후 소화되기까지의 시간이 상기 범위 내인 경우, 상기 성형품은 우수한 난연성을 가질 수 있다. 　구체적으로는 상기 성형품은 ISO 6722에 의해 측정시 점화 후 소화되기까지의 시간이 약 50초　이내, 예컨대 약 1초 내지 약 50초, 더욱 구체적으로는 약 1초 내지 약 20초일 수 있다. 　상기 ISO 6722는 2006년 8월 1일 버전이다.The molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 70 seconds. When the time from the ignition to extinguishing the molded article is within the above range, the molded article may have excellent flame retardancy. Specifically, the molded article may have a time from ignition to extinguishment as measured by ISO 6722 within about 50 seconds, for example, about 1 second to about 50 seconds, more specifically about 1 second to about 20 seconds. The ISO 6722 is the August 1, 2006 version.
일부 실시예에서, 상기 성형품은 JASO D 618에 의해 측정시 점화 후 소화되기까지의 시간이 약 20초 이내일 수 있다. 　상기 성형품의 점화 후 소화되기까지의 시간이 상기 범위 내인 경우, 상기 성형품은 우수한 난연성을 가질 수 있다. 　구체적으로는 상기 성형품은 JASO D 618에 의해 측정시 점화 후 소화되기까지의 시간이 약 1초 내지 약 20초, 더욱 구체적으로는 약 1초 내지 약 15초일 수 있다. 　상기 JASO D 618은 2008년 버전이다.In some embodiments, the molded article may have a time to extinguish after ignition 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.
상기 성형품은 ISO 6722에 의해 측정시 가솔린(gasoline) 침지 후 직경 변화율이 약 15% 이하일 수 있다. 　상기 성형품의 가솔린 침지 후 직경 변화율이 상기 범위 내인 경우, 상기 성형품은 우수한 내유성, 유연성 및 내한성을 가질 수 있다. 　구체적으로는 상기 성형품은 ISO 6722에 의해 측정시 가솔린 침지 후 직경 변화율이 약 0.01% 내지 약 10.0%일 수 있다. 　상기 ISO 6722는 2006년 8월 1일 버전이다.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 dipping gasoline as measured by ISO 6722. The ISO 6722 is the August 1, 2006 version.
상기 성형품은 JASO D 618에 의해 측정시 신율이 약 50% 내지 약 600%일 수 있다. 　상기 성형품의 신율이 상기 범위 내인 경우, 다양한 공간을 통해서 잡아당겨질 때 끊어지지 않고 효과적으로 신장될 수 있고, 우수한 상용성, 유연성 및 내한성을 가질 수 있다. 　구체적으로는 상기 성형품은 JASO D 618에 의해 측정시 신율이 약 110% 내지 약 600%, 더욱 구체적으로는 약 120% 내지 약 400%, 보다 구체적으로는 약 150% 내지 약 400%일 수 있다. 　상기 JASO D 618은 2008년 버전이다.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.
상기 성형품은 ASTM D 638에 의해 측정시 인장 강도가 약 5 MPa　내지 약 60 MPa일 수 있다. 　상기 성형품의 인장 강도가 상기 범위 내인 경우, 상기 성형품은 우수한 기계적 강도를 가져 다양한 용도에 효과적으로 적용될 수 있다. 　구체적으로는 상기 성형품은 ASTM D 638에 의해 측정시 인장 강도가 약 10 MPa　내지 약 40 MPa, 더욱 구체적으로는 약 15 MPa　내지 약 35 MPa일 수 있다.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.
상기 성형품은 ISO 6722 사포마모 시험 방법에 의해 측정시 내마모성이 약 400 mm　내지 약 3000 mm일 수 있다. 　상기 성형품의 내마모성이 상기 범위 내인 경우, 상기 성형품은 적절하게 균형을 이룬 강도와 유연성을 가질 수 있다. 　구체적으로는 상기 성형품은 ISO 6722 사포마모 시험 방법에 의해 측정시 내마모성이 약 600 mm　내지 약 2500 mm일 수 있다. 　상기 ISO 6722는 2006년 8월 1일 버전이다.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.
상기 성형품은 ISO 6722에 의해 내한성 평가시 도선에 이상이 없으며, 내전압 시험을 통과하는 것일 수 있다. 　상기 ISO 6722는 2006년 8월 1일 버전이다.The molded article may have an abnormality in the lead when the cold resistance evaluation according to ISO 6722, and may pass the withstand voltage test. The ISO 6722 is the August 1, 2006 version.
실시예EXAMPLE
이하에서 본 발명을 실시예　및 비교예를 통하여 보다 상세하게 설명하고자 하나, 하기의 실시예　및 비교예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것은 아니다.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.
열가소성 수지 조성물의 제조에 사용되는 각 구성성분은 다음과 같다.Each component used for manufacture of a thermoplastic resin composition is as follows.
(A) 폴리아릴렌에테르계 수지(A) polyarylene ether-based resin
(A-1) 폴리페닐렌에테르(polyphenylene ether, PPE): LXR-035C(Blue Star사제) 수평균 분자량(Mn) 15,000 g/mol, 다분산 지수(PDI) 1.31(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) 폴리페닐렌에테르(polyphenylene ether, PPE): PX100L(Mitsubishi Engineering Plastics사제), 수평균 분자량(Mn) 30,000 g/mol, 다분산 지수(PDI) 1.74(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) 폴리올레핀계 수지(B) polyolefin resin
선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE): LLDPE 9730 (한화석유화학사제), 밀도 0.92 g/cm3 Linear low density polyethylene (LLDPE): LLDPE 9730 (manufactured by Hanwha Chemical), density 0.92 g / cm 3
저밀도 폴리에틸렌(low density polyethylene, LDPE, 삼성토탈사제): 밀도 0.92 g/cm3 Low density polyethylene (LDPE, made by Samsung Total): Density 0.92 g / cm 3
에틸렌-옥텐 공중합체(ethylene-octene copolymer, 미쯔이케미칼사제): 밀도 0.9 g/cm3 Ethylene-octene copolymer (ethylene-octene copolymer, Mitsui Chemicals Co., Ltd.): density 0.9 g / cm 3
고밀도 폴리에틸렌(high density polyethylene, HDPE, 삼성토탈사제): 밀도 0.96 g/cm3 High density polyethylene (HDPE, made by Samsung Total): Density 0.96 g / cm 3
(C) 상용화제(C) compatibilizer
스티렌-에틸렌-부틸렌-스티렌 공중합체(styrene-ethylene-butylene-styrene copolymer, SEBS): Kraton G 1651(Shell사제)Styrene-ethylene-butylene-styrene copolymer (styrene-ethylene-butylene-styrene copolymer, SEBS): Kraton G 1651 (manufactured by Shell)
(D) 충진제(D) filler
수산화마그네슘(Mg(OH)2)(Magnifin H5, Albemarle사제)Magnesium hydroxide (Mg (OH) 2 ) (Magnifin H5, product made by Albemarle)
(E) 난연제(E) flame retardant
(E-1) 인계 에스테르 난연제(CR-733s, Daihachi사제)(E-1) Phosphorus ester flame retardant (CR-733s, Daihachi Co., Ltd.)
(E-2) Exolit AP 760(Clariant사제), 열분해 온도 250℃, 인 함량 20　원자%(E-2) Exolit AP 760 (manufactured by Clariant), pyrolysis temperature 250 ° C, phosphorus content 20 atom%
(E-3) Exolit OP 930(Clariant사제), 열분해 온도 300℃, 인 함량 23　원자%(E-3) Exolit OP 930 (manufactured by Clariant), pyrolysis temperature 300 deg.
(E-4) Exolit AP 742(Clariant사제), 열분해 온도 200℃, 인 함량 22　원자%(E-4) Exolit AP 742 (manufactured by Clariant), pyrolysis temperature 200 ° C, phosphorus content 22 k atomic%
(E-5) Antiblaze V6(Albemarle사제), 열분해 온도 200℃, 인 함량 10　원자%(E-5) Antiblaze V6 (manufactured by Albemarle), pyrolysis temperature 200 ° C, phosphorus content 10
상기 각각의 난연제의 열분해 온도는 TGA/DSC1(Mettler Toledo사제) 장비를 사용하여 측정한 값이다.The pyrolysis temperature of each of the flame retardants was measured using a TGA / DSC1 (Mettler Toledo) equipment.
실시예 1 내지 7 및 비교예 1 내지 4: 열가소성 수지 조성물의 제조Examples 1 to 7 and Comparative Examples 1 to 4: Preparation of the thermoplastic resin composition
상기 언급된 구성성분들을 이용하여 하기 표 1 및 표 2에 나타낸 조성으로 각 실시예 1 내지 14 및 비교예 1 내지 7에 따른　열가소성 수지 조성물을 제조하였다. 　The thermoplastic resin compositions according to Examples 1 to 14 and Comparative Examples 1 to 7 were prepared using the above-mentioned components in the compositions shown in Tables 1 and 2 below.
그 제조 방법으로는, 하기 표 1 및 표 2에 나타낸 조성으로 각 성분을 혼합하여 통상의 혼합기에서 혼합하였다. 　그 다음, 바렐 온도(barrel temperature)를 약 250℃로 설정하고 L/D=44, Φ= 35㎜인 이축 압출기 SHJ35(NJFY社제)에 투입하였다. 　상기 혼합물을 압출기를 통하여 펠렛 형태의 열가소성 수지 조성물로 제조하였다.As the manufacturing method, each component was mixed by the composition shown in following Table 1 and Table 2, 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 made into a thermoplastic resin composition in pellet form through an extruder.
표 1
실시예 비교예
1 2 3 4 5 6 7 1 2 3 4
(A-1) PPE 40중량부 40중량부 40중량부 30중량부 20중량부 49중량부 40중량부 40중량부 60중량부 70중량부 80중량부
(B) LLDPE 50중량부 - - 60중량부 70중량부 50중량부 30중량부 - 30중량부 20중량부 10중량부
LDPE - 50중량부 - - - - - - - - -
에틸렌-옥텐 공중합체 - - 50중량부 - - - - - - - -
HDPE - - - - - - 20중량부 50중량부 - - -
(C) SEBS 10중량부 10중량부 10중량부 10중량부 10중량부 1중량부 10중량부 10중량부 10중량부 10중량부 10중량부
(D) Mg(OH)2 20중량부 20중량부 20중량부 20중량부 50중량부 10중량부 20중량부 20중량부 20중량부 20중량부 20중량부
(E) (E-1)인계에스테르 난연제 15중량부 15중량부 15중량부 20중량부 20중량부 10중량부 15중량부 15중량부 15중량부 15중량부 15중량부
Table 1
Example Comparative example
One 2 3 4 5 6 7 One 2 3 4
(A-1) PPE 40 parts by weight 40 parts by weight 40 parts by weight 30 parts by weight 20 parts by weight 49 parts by weight 40 parts by weight 40 parts by weight 60 parts by weight 70 parts by weight 80 parts by weight
(B) LLDPE 50 parts by weight - - 60 parts by weight 70 parts by weight 50 parts by weight 30 parts by weight - 30 parts by weight 20 parts by weight 10 parts by weight
LDPE - 50 parts by weight - - - - - - - - -
Ethylene-Octene Copolymer - - 50 parts by weight - - - - - - - -
HDPE - - - - - - 20 parts by weight 50 parts by weight - - -
(C) SEBS 10 parts by weight 10 parts by weight 10 parts by weight 10 parts by weight 10 parts by weight 1 part by weight 10 parts by weight 10 parts by weight 10 parts by weight 10 parts by weight 10 parts by weight
(D) Mg (OH) 2 20 parts by weight 20 parts by weight 20 parts by weight 20 parts by weight 50 parts by weight 10 parts by weight 20 parts by weight 20 parts by weight 20 parts by weight 20 parts by weight 20 parts by weight
(E) (E-1) Phosphorus ester flame retardant 15 parts by weight 15 parts by weight 15 parts by weight 20 parts by weight 20 parts by weight 10 parts by weight 15 parts by weight 15 parts by weight 15 parts by weight 15 parts by weight 15 parts by weight
표 2
　 실시예 비교예
8 9 10 11 12 13 14 5 6 7
베이스 수지 (A) (A-1) 중량% 47 47 47 47 - 25 10 47 47 85
(A-2) - - - - 47 - - - - -
(B)LLDPE 53 53 53 53 53 75 90 53 53 15
(E) (E-2) 베이스 수지 100 중량부에 대한 중량부 25 - 10 50 25 25 50 - - 5
(E-3) - 25 - - - - - - - -
(E-4) - - - - - - - 25 - -
(E-5) - - - - - - - - 25 -
TABLE 2
Example Comparative example
8 9 10 11 12 13 14 5 6 7
Base resin (A) (A-1) weight% 47 47 47 47 - 25 10 47 47 85
(A-2) - - - - 47 - - - - -
(B) LLDPE 53 53 53 53 53 75 90 53 53 15
(E) (E-2) Parts by weight relative to 100 parts by weight of the base resin 25 - 10 50 25 25 50 - - 5
(E-3) - 25 - - - - - - - -
(E-4) - - - - - - - 25 - -
(E-5) - - - - - - - - 25 -
시험예 1: 난연성 평가Test Example 1: Flame Retardancy Evaluation
실시예 1 내지 14 및 비교예 1 내지 7의 열가소성 수지 조성물을 각각 바렐 온도를 약 240℃로 설정하고 L/D=28, Φ= 30㎜인 일축 압출기(Vikas engineering Works사제)에 투입하였다. 　상기 열가소성 수지 조성물을 압출기를 통하여 전선 형태의 시편을 제조하였다. 　이때, 0.5SQ의 선재를 사용하였다. The thermoplastic resin compositions of Examples 1 to 14 and Comparative Examples 1 to 7 were each set to a barrel temperature of about 240 ° C. and fed into a single screw extruder (manufactured by Vikas engineering Works) having L / D = 28 and Φ = 30 mm. The thermoplastic resin composition was prepared in the form of a wire through an extruder. At this time, a wire rod of 0.5 SQ was used.
실시예 1 내지 실시예 7 및 비교예 1 내지 비교예 4의 시편에 대하여, ISO 6722 난연 시험 방법에 따라 점화 후 소화되기까지 걸리는 시간을 측정하여 난연성을 평가하였다. 　수치가 작을수록 빨리 소화되어 난연성이 우수한 것이다.그 결과를 하기 표 3에 나타낸다.For the specimens of Examples 1 to 7 and Comparative Examples 1 to 4, the flame retardancy was evaluated by measuring the time taken for extinguishing after ignition according to the ISO 6722 flame retardant test method. The smaller the value, the more quickly it is digested and excellent in flame retardancy. The results are shown in Table 3 below.
실시예 8 내지 실시예 14과 비교예 5 내지 비교예 7의 시편에 대하여, JASO D 618 난연 시험 방법에 따라 점화 후 소화되기까지 걸리는 시간을 측정하여 난연성을 평가하였다. 　수치가 작을수록 빨리 소화되어 난연성이 우수한 것이다.With respect to the specimens of Examples 8 to 14 and Comparative Examples 5 to 7, the flame retardancy was evaluated by measuring the time taken to ignite after ignition according to the JASO D 618 flame retardant test method. The smaller the value, the faster the fire extinguisher is.
그 결과를 하기 표 4에 나타낸다.The results are shown in Table 4 below.
시험예 2: 신율 평가Test Example 2: Elongation Evaluation
상기 시험예 1에서 제조한 각각의 시편에 대하여, JASO D 618 신율 측정 방법에 따라 신율을 측정하였다. 　수치가 클수록 신율이 우수한 것이다.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.
그 결과를 하기 표 3 및 표 4에 나타낸다.The results are shown in Tables 3 and 4 below.
시험예 3: 내마모성 평가Test Example 3: Abrasion Resistance Evaluation
상기 시험예 1에서 제조한 실시예 1 내지 실시예 7 및 비교예 1 내지 비교예 4의 시편에 대하여, ISO 6722 사포마모(sandpaper abrasion) 시험 방법에 따라 내마모성을 평가하였다. 　수치가 클수록 내마모성이 우수한 것이다.The specimens of Examples 1 to 7 and Comparative Examples 1 to 4 prepared in Test Example 1 were evaluated for wear resistance according to the ISO 6722 sandpaper abrasion test method. The larger the value, the better the wear resistance.
그 결과를 하기 표 3에 나타낸다.The results are shown in Table 3 below.
시험예 4: 내유성 평가Test Example 4: Oil Resistance Evaluation
상기 시험예 1에서 제조한 각각의 시편에 대하여, ISO 6722 내유성 시험 방법에 따라 가솔린에 침지시킨 후, 시편의 직경 변화율을 측정하였다. 　시편의 직경 변화율이 작을수록 내유성이 우수한 것이다.For each specimen prepared in Test Example 1, after immersion in gasoline according to the ISO 6722 oil resistance test method, the rate of change of the diameter of the specimen was measured. The smaller the rate of change of the diameter of the specimen, the better the oil resistance.
그 결과를 하기 표 3 및 표 4에 나타낸다.The results are shown in Tables 3 and 4 below.
시험예 5: 내열성 및 내전압성 평가Test Example 5: Evaluation of heat resistance and voltage resistance
상기 시험예 1에서 제조한 실시예 1 내지 실시예 7 및 비교예 1 내지 비교예 4의 시편을 약 150℃의 온도에서 240시간 동안 에이징(aging)한 후, 1분 동안 8kV의 전압을 가하여 시편의 파괴 여부에 따라 내열성 및 내전압성을 평가하였다. 　이때, 각각의 시편을 각각 물이 채워진 수조에 담근 후, 전류 누설(leakage)이 없으면 시편이 파괴되지 않은 것으로 보아 "pass"로 표시하고, 전류 누설이 있으면 시편이 파괴된 것으로 보아 "fail"로 표시한다. After the specimens of Examples 1 to 7 and Comparative Examples 1 to 4 prepared in Test Example 1 were aged at a temperature of about 150 ° C. for 240 hours, a sample was applied by applying a voltage of 8 kV for 1 minute. The heat resistance and voltage resistance were evaluated according to the destruction of At this time, each specimen is immersed in a water-filled water bath, and if there is no current leakage, it is marked as "pass" because the specimen is not destroyed, and if there is a current leakage, it is considered as "fail". Display.
그 결과를 하기 표 3에 나타낸다. The results are shown in Table 3 below.
시험예 6: 내한성 평가Test Example 6: Cold Resistance Evaluation
상기 시험예 1에서 제조한 실시예 1 내지 실시예 7 및 비교예 1 내지 비교예 4의 시편을 ISO 6722 내한성(저온 특성) 평가 방법에 따라 내한성을 평가하였다. 　이때, 도선에 이상이 없고 전류 누설(leakage)이 없어 내전압에 이상이 없으면 시편이 파괴되지 않은 것으로 보아 "pass"로 표시하고, 도선에 이상이 있거나 전류 누설이 있어 내전압에 이상이 있으면　시편이 파괴된 것으로 보아 "fail"로 표시한다. The specimens of Examples 1 to 7 and Comparative Examples 1 to 4 prepared in Test Example 1 were evaluated for cold resistance according to the ISO 6722 cold resistance (low temperature characteristic) evaluation method. At this time, if there is no abnormality in the conductor and there is no current leakage, there is no abnormality in the withstand voltage, so the specimen is not broken, and it is marked as "pass" .If there is an abnormality in the conductor or there is a current leakage, the specimen is destroyed. It is marked as "fail".
그 결과를 하기 표 3에 나타낸다. The results are shown in Table 3 below.
시험예 7: 외관 평가Test Example 7: Appearance Evaluation
상기 시험예 1에서 제조한 실시예 8 내지 실시예 14 및 비교예 5 내지 비교예 7의 전선 시편에 대하여 길이 1.0km의 전선에서 임의로 100 m씩 6개를 선택한 후, 돌기의 개수를 세어 평균을 구하였다. 　수치가 작을수록 외관이 우수한 것이다.With respect to the wire specimens of Examples 8 to 14 and Comparative Examples 5 to 7 prepared in Test Example 1, six randomly selected 100 m wires of 1.0 km in length were counted, and the average number of protrusions was counted. Obtained. The smaller the value, the better the appearance.
그 결과를 하기 표 4에 나타낸다.The results are shown in Table 4 below.
시험예 8: 내마모성 평가Test Example 8: Wear Resistance Evaluation
상기 시험예 1에서 제조한 실시예 8 내지 실시예 14 및 비교예 5 내지 비교예 7의 시편에 대하여, ISO 6722 사포마모(sandpaper abrasion) 시험 방법에 따라 내마모성을 평가하였다. 　수치가 클수록 내마모성이 우수한 것이다.The specimens of Examples 8 to 14 and Comparative Examples 5 to 7 prepared in Test Example 1 were evaluated for wear resistance according to the ISO 6722 sandpaper abrasion test method. The larger the value, the better the wear resistance.
그 결과를 하기 표 4에 나타낸다.The results are shown in Table 4 below.
표 3
　 실시예 비교예
1 2 3 4 5 6 7 1 2 3 4
난연성 연소 시간 (초) 10 11 30 3 1 5 21 20 5 3 1
신율 (%) 280 170 480 350 560 240 280 120 100 80 70
내마모성 (mm) 1000 700 500 500 400 1300 1400 1800 1300 1500 1700
내유성 직경 변화율(%) 3 3 2 2 1 4 3 3 10 15 20
내열성 및 내전압성 pass pass pass pass pass pass pass pass pass pass pass
내한성 pass pass pass pass pass pass pass fail fail fail fail
TABLE 3
Example Comparative example
One 2 3 4 5 6 7 One 2 3 4
Flame retardant Burning time (sec) 10 11 30 3 One 5 21 20 5 3 One
Elongation (%) 280 170 480 350 560 240 280 120 100 80 70
Wear resistance (mm) 1000 700 500 500 400 1300 1400 1800 1300 1500 1700
Oil resistance Diameter change rate (%) 3 3 2 2 One 4 3 3 10 15 20
Heat resistance and voltage resistance pass pass pass pass pass pass pass pass pass pass pass
Cold resistance pass pass pass pass pass pass pass fail fail fail fail
표 4
　 실시예 비교예
8 9 10 11 12 13 14 5 6 7
난연성(초) 5 3 18 1 6 15 1 25 40 1
신율(%) 250 255 260 220 280 310 320 120 140 100
인장 강도(MPa) 29.4 29.4 31.4 25.5 26.5 23.5 21.0 16.7 17.6 63.2
외관 0 0 1 3 0 0 2 15 10 14
내마모성 1100 1100 1500 900 1200 600 400 1000 1100 1700
내유성 6 5 6 9 7 3 1 7 5 21
Table 4
Example Comparative example
8 9 10 11 12 13 14 5 6 7
Flame retardant (seconds) 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
상기 표 3에 나타난 바에 따르면, 실시예 1 내지 7의 열가소성 수지 조성물을 사용한 경우가 비교예 1 내지 4의 열가소성 수지 조성물을 사용한 경우에 비해 신율, 내유성, 내한성 등의 물성이 우수함을 확인할 수 있다.As shown in Table 3, it can be seen that the case of using the thermoplastic resin composition of Examples 1 to 7 is excellent in physical properties such as elongation, oil resistance, cold resistance, etc. when using the thermoplastic resin composition of Comparative Examples 1 to 4.
상기 표 4에 나타난 바에 따르면, 실시예 8 내지 14의 열가소성 수지 조성물을 사용한 경우가 비교예 5 내지 7의 열가소성 수지 조성물을 사용한 경우에 비해 신율, 인장 강도 및 외관 특성이 우수함을 확인할 수 있다. 　또한, 실시예 8 내지 14의 열가소성 수지 조성물을 사용한 경우가 비교예 5 및 6의 열가소성 수지 조성물을 사용한 경우에 비해 난연성이 우수하고, 비교예 7의 열가소성 수지 조성물을 사용한 경우에 비해 내유성이 우수함을 확인할 수 있다.As shown in Table 4, it can be seen that the use of the thermoplastic resin composition of Examples 8 to 14 is superior to the elongation, tensile strength and appearance characteristics compared to the case of using the thermoplastic resin composition of Comparative Examples 5 to 7. In addition, the case where the thermoplastic resin composition of Examples 8-14 was used compared with the case of using the thermoplastic resin compositions of Comparative Examples 5 and 6 was excellent in flame retardancy, and it was excellent in oil resistance compared with the case where the thermoplastic resin composition of Comparative Example 7 was used. You can check it.
따라서, 실시예 8 내지 14의 열가소성 수지 조성물을 사용한 경우, 우수한 외관 특성을 가지면서 동시에 우수한 난연성, 신율, 인장 강도, 내마모성 및 내유성을 가짐을 확인할 수 있다.Therefore, in the case of using the thermoplastic resin composition of Examples 8 to 14, 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.
이상을 통해 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명 및 첨부한 도면의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.　　　Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.
[부호의 설명][Description of the code]
1, 10, 20: 전선, 2, 11, 21: 전도체,1, 10, 20: wires, 2, 11, 21: conductors,
4, 13, 23: 피복재, 15, 25: 절연체,4, 13, 23: covering material, 15, 25: insulator,
17, 29: 시스, 27: 차폐체17, 29: sheath, 27: shield

Claims (20)

  1. 폴리아릴렌에테르계 수지 및Polyarylene ether resin and
    0.95　g/cm3　이하의 중량가중평균밀도를 가지는 폴리올레핀계 수지Polyolefin resin having a weight-weighted average density of 0.95 g / cm 3 or less
    를 포함하고,Including,
    상기 폴리올레핀계 수지의 함량(중량, WOL)과 상기 폴리아릴렌에테르계 수지의 함량(중량, WAR)은 WAR ≤ 1.9×WOL의 관계식을 만족하는 것인 열가소성 수지 조성물.　The content (weight, W OL ) of the polyolefin resin and the content (weight, W AR ) of the polyarylene ether-based resin satisfy the relational expression of W AR ≤ 1.9 × W OL .
  2. 제1항에 있어서, The method of claim 1,
    상기 폴리올레핀계 수지는 0.1 g/10min 내지 30 g/10min의 용융지수(melt index, MI)를 가지는 것인 열가소성 수지 조성물.　The polyolefin resin is a thermoplastic resin composition having a melt index (melt index, MI) of 0.1 g / 10min to 30 g / 10min.
  3. 제1항에 있어서, The method of claim 1,
    상기 폴리올레핀계 수지는 80℃ 내지 170℃의 녹는점(melting point)을 가지는 것인 열가소성 수지 조성물.　The polyolefin resin is a thermoplastic resin composition having a melting point (melting point) of 80 ℃ to 170 ℃.
  4. 제1항에 있어서, The method of claim 1,
    상기 폴리올레핀계 수지는 고밀도 폴리에틸렌(high density polyethylene, HDPE), 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE), 저밀도 폴리에틸렌(low density polyethylene, LDPE), 에틸렌-옥텐 공중합체(ethylene-octene copolymer), 초저밀도 폴리에틸렌(ultra low density polyethylene), 중밀도 폴리에틸렌(medium density polyethylene), 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-부텐 공중합체(ethylene-butene copolymer), 폴리프로필렌(polypropylene)　및 이들의 조합에서 선택되는 하나를 포함하는 것인 열가소성 수지 조성물.　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.
  5. 제1항에 있어서, The method of claim 1,
    상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 총량에 대하여 상기 폴리아릴렌에테르계 수지를 20 중량% 내지 65　중량%로 포함하고, 상기 폴리올레핀계 수지를 35　중량% 내지 80 중량%로 포함하는 것인 열가소성 수지 조성물.　The thermoplastic resin composition comprises 20 wt% to 65 wt% of the polyarylene ether resin and 35 wt% to 80 wt% of the polyolefin resin based on the total amount of the thermoplastic resin composition. Composition.
  6. 제1항에 있어서, The method of claim 1,
    상기 열가소성 수지 조성물은 스티렌-에틸렌-부틸렌-스티렌 공중합체(styrene-ethylene-butylene-styrene copolymer, SEBS), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부틸렌-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS), 내충격성 폴리스티렌(high impact polystyrene, HIPS), 에틸렌-아세트산비닐 공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌-메틸아크릴레이트 공중합체(ethylene-methyl acrylate copolymer, EMA), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethyl acrylate copolymer, EEA), 에틸렌-부틸아크릴레이트 공중합체(ethylene-butyl acrylate copolymer, EBA), 스티렌-부타디엔-스티렌 공중합체(styrene-butadiene-styrene copolymer, SBS), 스티렌-에틸렌-프로필렌-스티렌 공중합체(styrene-ethylene-propylene-styrene copolymer, SEPS), 스티렌-이소프렌-스티렌 공중합체(styrene-isoprene-styrene copolymer, SIS), 스티렌-에틸렌 공중합체(styrene-ethylene copolymer), 스티렌-에틸렌-부타디엔-스티렌 공중합체(styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부타디엔-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 폴리프로필렌(maleic anhydride grafted polypropylene), 말레익 언하이드라이드-그래프트된 선형 저밀도 폴리에틸렌(maleic anhydride grafted linear low density polyethylene), 말레익 언하이드라이드-그래프트된 저밀도 폴리에틸렌(maleic anhydride grafted low density polyethylene)　및 이들의 조합에서 선택되는 상용화제를 더 포함하는 것인 열가소성 수지 조성물.　The thermoplastic resin composition is a 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 (styrene-isoprene-st yrene 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 polypropylene, maleic anhydride-grafted linear low density polyethylene (maleic anhydride) and a compatibilizer selected from grafted linear low density polyethylene, maleic anhydride grafted low density polyethylene, and combinations thereof.
  7. 제6항에 있어서, The method of claim 6,
    상기 열가소성 수지 조성물은 상기 상용화제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 상용화제를 1 중량부 내지 40 중량부로 포함하는 것인 열가소성 수지 조성물.　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.
  8. 제1항에 있어서, The method of claim 1,
    상기 열가소성 수지 조성물은 산화 마그네슘(magnesium oxide), 수산화 마그네슘(magnesium hydroxide), 수산화 알루미늄(aluminium　hydroxide), 수산화 칼슘(calcium　hydroxide), 하이드로 마그네사이트(Mg5(CO3)4(OH)2, hydromagnesite), 탄산칼슘(calcium　carbonate), 티탄산칼륨(potassium titanate), 규산마그네슘(magnesium silicate)　및 이들의 조합에서 선택되는 충진제를 더 포함하는 것인 열가소성 수지 조성물.　The thermoplastic resin composition 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) And a filler selected from calcium carbonate, potassium titanate, magnesium silicate and combinations thereof.
  9. 제8항에 있어서, The method of claim 8,
    상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 1 중량부 내지 80 중량부로 포함하는 것인 열가소성 수지 조성물.　The thermoplastic resin composition comprises 1 part by weight to 80 parts by weight of the filler relative to 100 parts by weight of the thermoplastic resin composition not containing the filler.
  10. 제1항에 있어서, The method of claim 1,
    상기 열가소성 수지 조성물은 230℃ 이상의 열분해 온도를 가지는 인계 난연제, 비인계 난연제, 또는 이들의 조합을 더 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition further comprises a phosphorous flame retardant, a non-phosphorous flame retardant, or a combination thereof having a pyrolysis temperature of 230 ° C. or higher.
  11. 제10항에 있어서, The method of claim 10,
    상기 인계 난연제는 상기 인계 난연제에 포함되는 원자 총량에 대하여 인을 5 원자% 이상으로 포함하는 것인 열가소성 수지 조성물.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.
  12. 제10항에 있어서,The method of claim 10,
    상기 인계 난연제는 포스페이트(phosphate) 화합물, 포스파이트(phosphite) 화합물, 포스포네이트(phosphonate) 화합물, 포스파젠(phosphazene) 화합물, 포스피네이트(phosphinate) 화합물　및 이들의 조합에서 선택되는 하나를 포함하고, 상기 비인계 난연제는 폴리실록산, 멜라민 화합물 또는 이들의 조합을 포함하는 것인 열가소성 수지 조성물.　The phosphorus flame retardant includes one selected from phosphate compounds, phosphite compounds, phosphonate compounds, phosphazene compounds, phosphinate compounds, and combinations thereof. , The non-phosphorous flame retardant is a thermoplastic resin composition comprising a polysiloxane, melamine compound or a combination thereof.
  13. 제10항에 있어서,The method of claim 10,
    상기 열가소성 수지 조성물은, 상기 폴리아릴렌에테르계 수지를 10 중량% 내지 80 중량% 및 상기 폴리올레핀계 수지를 20 중량% 내지 90 중량%로 포함하고,The thermoplastic resin composition includes 10 wt% to 80 wt% of the polyarylene ether resin and 20 wt% to 90 wt% of the polyolefin resin,
    상기 폴리아릴렌에테르계 수지 및 폴리올레핀계 수지 100 중량부에 대하여, 상기 인계 난연제는 1 중량부 내지 50　중량부로 포함되는 것인 열가소성 수지 조성물.　To about 100 parts by weight of the polyarylene ether resin and polyolefin resin, the phosphorus-based flame retardant is 1 to 50 parts by weight of a thermoplastic resin composition.
  14. 제10항에 있어서, The method of claim 10,
    상기 열가소성 수지 조성물은 스티렌-에틸렌-부틸렌-스티렌 공중합체(styrene-ethylene-butylene-styrene copolymer, SEBS), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부틸렌-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer, MA-SEBS), 내충격성 폴리스티렌(high impact polystyrene, HIPS), 에틸렌-아세트산비닐 공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌-메틸아크릴레이트 공중합체(ethylene-methyl acrylate copolymer, EMA), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethyl acrylate copolymer, EEA), 에틸렌-부틸아크릴레이트 공중합체(ethylene-butyl acrylate copolymer, EBA), 스티렌-부타디엔-스티렌 공중합체(styrene-butadiene-styrene copolymer, SBS), 스티렌-에틸렌-프로필렌-스티렌 공중합체(styrene-ethylene-propylene-styrene copolymer, SEPS), 스티렌-이소프렌-스티렌 공중합체(styrene-isoprene-styrene copolymer, SIS), 스티렌-에틸렌 공중합체(styrene-ethylene copolymer), 스티렌-에틸렌-부타디엔-스티렌 공중합체(styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 스티렌-에틸렌-부타디엔-스티렌 공중합체(maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer), 말레익 언하이드라이드-그래프트된 폴리프로필렌(maleic anhydride grafted polypropylene), 말레익 언하이드라이드-그래프트된 선형 저밀도 폴리에틸렌(maleic anhydride grafted linear low density polyethylene), 말레익 언하이드라이드-그래프트된 저밀도 폴리에틸렌(maleic anhydride grafted low density polyethylene) 및 이들의 조합에서 선택되는 상용화제를 더 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition is a 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 (styrene-isoprene-st yrene 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 polypropylene, maleic anhydride-grafted linear low density polyethylene (maleic anhydride) and a compatibilizer selected from grafted linear low density polyethylene, maleic anhydride grafted low density polyethylene, and combinations thereof.
  15. 제14항에 있어서, The method of claim 14,
    상기 열가소성 수지 조성물은 상기 상용화제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 상용화제를 1　중량부 내지 40　중량부로 포함하는 것인 열가소성 수지 조성물.　The thermoplastic resin composition comprises the compatibilizer in an amount of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition not containing the compatibilizer.
  16. 제10항에 있어서, The method of claim 10,
    상기 열가소성 수지 조성물은 산화 마그네슘(magnesium oxide), 수산화 마그네슘(magnesium hydroxide), 수산화 알루미늄(aluminium　hydroxide), 수산화 칼슘(calcium　hydroxide), 하이드로 마그네사이트(Mg5(CO3)4(OH)2, hydromagnesite), 탄산칼슘(calcium　carbonate), 티탄산칼륨(potassium titanate), 규산마그네슘(magnesium silicate), 알루미늄 옥사이드 하이드록사이드(aluminum oxide hydroxide)　및 이들의 조합에서 선택되는 충진제를 더 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition 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) And a filler selected from calcium carbonate, potassium titanate, magnesium silicate, aluminum oxide hydroxide, and combinations thereof.
  17. 제16항에 있어서, The method of claim 16,
    상기 열가소성 수지 조성물은 상기 충진제를 포함하지 않은 열가소성 수지 조성물 100 중량부에 대하여, 상기 충진제를 1　중량부 내지 100　중량부로 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition comprises 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.
  18. 제1항 내지 제17항 중 어느 한 항에 따른 열가소성 수지 조성물을 포함하는 성형품.　A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 17.
  19. 제18항에 있어서,The method of claim 18,
    상기 성형품은 전선 또는 전선 피복재인 것인 성형품.　The molded article is an electric wire or a wire covering material.
  20. 제18항에 있어서,The method of claim 18,
    상기 성형품은, 하기 요건들 중 하나 이상을 만족하는 것인 성형품:The molded article meets one or more of the following requirements:
    ISO 6722에 의해 측정시 점화 후 소화되기까지의 시간이 70초 이내임;Time to extinguish after ignition, as measured by ISO 6722, within 70 seconds;
    JASO D 618에 의해 측정시 점화 후 소화되기까지의 시간이 20초 이내임;Time to digest after ignition is less than 20 seconds as measured by JASO D 618;
    ISO 6722에 의해 측정시 가솔린(gasoline) 침지 후 직경 변화율이 15% 이하임;Diameter change after gasoline dipping is less than 15% as measured by ISO 6722;
    JASO D 618에 의해 측정시 신율이 50% 내지 600%임;Elongation between 50% and 600% as measured by JASO D 618;
    ASTM D 638에 의해 측정시 인장 강도가 5 MPa　내지 60 MPa임.Tensile strength of 5 MPa to 60 MPa measured by ASTM D 638.
PCT/KR2012/010240 2011-12-28 2012-11-29 Thermoplastic resin composition and molded product including same WO2013100414A1 (en)

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