Thermoplastic resin composition and molded article formed therefrom

Abstract

The thermoplastic resin composition of the present invention is characterized by comprising: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 2 to about 23 parts by weight of a rubber-modified polystyrene resin; about 2 to about 23 parts by weight of a polyolefin resin; about 1 to about 13 parts by weight of a saturated fatty acid bisamide; about 1 to about 13 parts by weight of a styrene-diene rubber-based polymer; and about 1 to about 13 parts by weight of an ethylene-a-olefin rubber-based polymer. The thermoplastic resin composition is excellent in chemical resistance, processability, impact resistance, rigidity, heat resistance, and the like.

Description

TECHNICAL FIELD

[0001] The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in chemical resistance, processability, impact resistance, rigidity, heat resistance, and the like, and a molded article formed therefrom. BACKGROUND

[0002] Rubber-modified aromatic vinyl-based copolymer resins such as acrylonitrile-butadiene-styrene copolymer resins (ABS resins) are excellent in mechanical physical properties, processability, appearance characteristics, and the like, and thus are widely used as interior / exterior materials for electric / electronic products, interior / exterior materials for automobiles, exterior materials for buildings, and the like.

[0003] Recently, with the trend of strengthening the chemical resistance of raw materials, a thermoplastic resin composition excellent in chemical resistance and processability (injection moldability) than conventional rubber-modified aromatic vinyl-based copolymer resins is required.

[0004] In order to improve the processability of rubber-modified aromatic vinyl-based copolymer resins, it is possible to attempt to reduce the content of cyano-based monomers, the ratio of rubber-modified vinyl-based graft copolymers, the molecular weight of resins, and the like, but at this time, the chemical resistance and the like can be reduced. Also, when a common olefin-based chemical resistance additive is used in order to improve the chemical resistance, the flowability, mechanical physical properties, and the like can be reduced.

[0005] Therefore, there is an urgent need to develop a thermoplastic resin composition excellent in chemical resistance, processability, impact resistance, rigidity, heat resistance, and balance of these physical properties, and the like, without such problems.

[0006] The background art of the present invention is disclosed in Korean Patent No. 10-0760457, and the like. SUMMARY

[0007] An object of the present invention is to provide a thermoplastic resin composition excellent in chemical resistance, processability, impact resistance, rigidity, heat resistance, and the like.

[0008] Another object of the present invention is to provide a molded article formed of the above-described thermoplastic resin composition.

[0009] The above and other objects of the present invention can be achieved by the present invention described below.

[0010] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is characterized by comprising: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 2 parts by weight to about 23 parts by weight of a rubber-modified polystyrene resin; about 2 parts by weight to about 23 parts by weight of a polyolefin resin; about 1 part by weight to about 13 parts by weight of a saturated fatty acid bisamide; about 1 part by weight to about 13 parts by weight of a styrene-butadiene rubber-based polymer; and about 1 part by weight to about 13 parts by weight of an ethylene-a-olefin rubber-based polymer.

[0011] 2. In the embodiment of the foregoing 1, the rubber-modified aromatic vinyl-based copolymer resin can include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

[0012] 3. In the embodiment of the foregoing 2, the rubber-modified vinyl-based graft copolymer can be a copolymer formed by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a cyano-based vinyl monomer in a rubber-based polymer.

[0013] 4. In the embodiments of the foregoing 1 to 3, the rubber-modified polystyrene resin can be a polymer of about 3% by weight to about 30% by weight of a rubber-based polymer and about 70% by weight to about 97% by weight of an aromatic vinyl-based monomer.

[0014] 5. In the embodiments of the foregoing 1 to 4, the polyolefin resin can include one or more of polypropylene, polyethylene, and a propylene-ethylene copolymer.

[0015] 6. In the embodiments of the foregoing 1 to 5, the saturated fatty acid bisamide can include one or more of methylene bis-stearamide, methylene bis-oleamide, ethylene bis-stearamide, ethylene bis-oleamide, hexamethylene bis-stearamide, and hexamethylene bis-oleamide.

[0016] 7. In the embodiments of the foregoing 1 to 6, the styrene-butadiene rubber-based polymer can be a polymer of a monomer mixture including about 25% by weight to about 45% by weight of styrene and about 55% by weight to about 75% by weight of butadiene.

[0017] 8. In the embodiments of the foregoing 1 to 7, the ethylene-a-olefin rubber-based polymer can be a polymer of a monomer mixture including about 25% by weight to about 55% by weight of ethylene and about 45% by weight to about 75% by weight of a-olefin.

[0018] 9. In the embodiments of the foregoing 1 to 8, the weight ratio of the rubber-modified polystyrene resin and the polyolefin resin can be about 1:0.2 to about 1:5.

[0019] 10. In the embodiments of the preceding 1 to 9, the weight ratio of the saturated fatty acid bisamide to the styrene-butadiene rubber-based polymer can be from about 1 :0.2 to about 1 :4.

[0020] 11. In the embodiments of the preceding 1 to 10, the weight ratio of the styrene-butadiene rubber-based polymer to the ethylene-a-olefin rubber-based polymer can be from about 1 :0.2 to about 1 :4.

[0021] 12. In the embodiments of the preceding 1 to 11, a test piece of the thermoplastic resin composition having a size of 200 mm x 50 mm x 2 mm is installed in a 1 / 4 elliptical jig (length of major axis: 120 mm, length of minor axis: 34 mm), 10 ml of olive oil or isopropyl alcohol is applied over the entire test piece, and the strain (ε) at which a crack occurs calculated according to the following Formula 1 after 24 hours can be from about 1.0% to about 1.4%.

[0022] [Formula 1]

[0023]

[0024] In the Formula 1, ε represents the strain at which a crack occurs, a is the length of the major axis of the elliptical jig (mm), b is the length of the minor axis of the elliptical jig (mm), t is the thickness of the test piece (mm), and x is the distance from the perpendicular intersection of the position at which a crack occurs and the major axis of the elliptical jig to the midpoint of the elliptical jig.

[0025] 13. In the embodiments of the preceding 1 to 12, the spiral flow length of a test piece of the thermoplastic resin composition measured after injection molding in a spiral mold having a width of 15 mm and a thickness of 1 mm under conditions of a molding temperature of 230°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s can be from about 210 mm to about 280 mm.

[0026] 14. In the embodiments of the preceding 1 to 13, the Charpy notched impact strength of a test piece having a thickness of 1 / 4" of the thermoplastic resin composition measured according to ASTM D256 can be from about 12 kgf-cm / cm to about 30 kgf-cm / cm, the tensile strength of a test piece having a thickness of 3.2 mm measured according to ASTM D638 at a condition of 50 mm / min can be from about 290 kgf / cm 2 to about 380 kgf / cm 2 , and the Vicat softening temperature measured according to ISO R306 at a load of 5 kg and a condition of 50°C / hr can be from about 79°C to about 92°C.

[0027] 15. Another aspect of the present application relates to a molded article. The molded article is characterized by being formed from the thermoplastic resin composition described in any one of the items 1 to 14.

[0028] The present application has an effect of providing a thermoplastic resin composition having excellent chemical resistance, processability, impact resistance, rigidity, heat resistance, etc., and a molded article formed therefrom. DETAILED DESCRIPTION

[0029] Hereinafter, the present application will be described in detail as follows.

[0030] The thermoplastic resin composition of the present application includes a rubber-modified aromatic vinyl-based copolymer resin (A); a rubber-modified polystyrene resin (B); a polyolefin resin (C); a saturated fatty acid bisamide (D); a styrene-butadiene rubber-based polymer (E); and an ethylene-a-olefin rubber-based polymer (F).

[0031] In the present specification, "a to b" indicating a numerical range is defined as "≥ a and ≤ b".

[0032] Rubber-modified aromatic vinyl-based copolymer resin (A)

[0033] The rubber-modified aromatic vinyl-based copolymer resin of one embodiment of the present application can include a rubber-modified vinyl-based graft copolymer (Al) and an aromatic vinyl-based copolymer resin (A2).

[0034] Rubber-modified vinyl-based graft copolymer (Al)

[0035] The rubber-modified vinyl-based graft copolymer of one embodiment of the present application can be a graft copolymer formed by graft-polymerizing a monomer mixture including an aromatic vinyl-based monomer and a cyano-based vinyl monomer in a rubber-based polymer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a monomer mixture including an aromatic vinyl-based monomer and a cyano-based vinyl monomer in a rubber-based polymer, and, if necessary, a monomer imparting processability and heat resistance can be further included in the monomer mixture to perform graft-polymerization. The polymerization can be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, etc. Also, the rubber-modified vinyl-based graft copolymer can form a core (rubber-based polymer)-shell (copolymer of the monomer mixture) structure, but is not limited thereto.

[0036] In specific examples, as the rubbery polymer, diene-based rubbers such as polybutadiene, poly(acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenation of the diene-based rubbers, isoprene rubber, (meth)acrylic alkyl ester rubbers having 2 to 10 carbon atoms, copolymers of (meth)acrylic alkyl esters having 2 to 10 carbon atoms and styrene, and terpolymers of ethylene-propylene-diene monomers (EPDM) can be exemplified. These substances can be used alone or in a mixture of two or more. For example, diene-based rubbers, (meth)acrylic ester rubbers, and the like can be used, and specifically, butadiene-based rubbers, butyl acrylate rubbers, and the like can be used.

[0037] In specific examples, the average particle size of the rubbery polymer (rubber particles) can be about 0.05 μm to about 6 μm, for example, about 0.15 μm to about 4 μm, and specifically, about 0.25 μm to about 3.5 μm. In the range, the thermoplastic resin composition can have excellent impact resistance and appearance properties, and the like. Among them, for the average particle size (z-average) of the rubbery polymer (rubber particles), measurement can be performed using a light scattering method in a latex state. Specifically, the rubbery polymer latex can be meshed to remove coagulum generated in the polymerization of the rubbery polymer, and a solution obtained by mixing 0.5 g of the latex and 30 ml of distilled water is injected into a 1,000 ml flask and filled with distilled water to prepare a sample, and then 10 ml of the sample is moved into a quartz cell, and the average particle size of the rubbery polymer is measured by a light scattering particle size analyzer (malvern company, nano-zs).

[0038] In specific examples, the content of the rubbery polymer can be about 20% by weight to about 80% by weight, for example, about 25% by weight to about 70% by weight, in 100% by weight of the total amount of the rubber-modified vinyl-based graft copolymer, and the content of the monomer mixture (including the aromatic vinyl-based monomer and the cyano-based vinyl-based monomer) can be about 20% by weight to about 80% by weight, for example, about 30% by weight to about 75% by weight, in 100% by weight of the total amount of the rubber-modified vinyl-based graft copolymer. In the range, the thermoplastic resin composition can have excellent impact resistance and appearance properties, and the like.

[0039] In an embodiment, the aromatic vinyl-based monomer can be graft copolymerized to the rubbery polymer, and styrene, a-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like can be exemplified. These substances can be used alone or two or more kinds thereof can be used in mixture. The content of the aromatic vinyl-based monomer can be about 10% by weight to about 90% by weight, for example, about 20% by weight to about 80% by weight, in 100% by weight of the monomer mixture. In the range, the thermoplastic resin composition can have excellent processability and impact resistance, and the like.

[0040] In an embodiment, the cyano-based vinyl monomer can be copolymerized with the aromatic vinyl-based monomer, and acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, a-chloroacrylonitrile, fumaronitrile, and the like can be exemplified. These substances can be used alone or two or more kinds thereof can be used in mixture. For example, acrylonitrile, methacrylonitrile, and the like can be used. The content of the cyano-based vinyl monomer can be about 10% by weight to about 90% by weight, for example, about 20% by weight to about 80% by weight, in 100% by weight of the monomer mixture. In the range, the thermoplastic resin composition can have excellent chemical resistance and mechanical properties, and the like.

[0041] In an embodiment, as the monomer for imparting processability and heat resistance, (meth)acrylic acid, (meth)acrylic acid alkyl ester having 1 to 10 carbon atoms, maleic anhydride, N-substituted maleimide, and the like can be exemplified, but are not limited thereto. In the case where the monomer for imparting processability and heat resistance is used, the content thereof can be about 60% by weight or less, for example, about 1% by weight to about 50% by weight, in 100% by weight of the monomer mixture. In the range, it is possible to impart processability and heat resistance to the thermoplastic resin composition without deteriorating other physical properties.

[0042] In an embodiment, as the rubber-modified vinyl graft copolymer, a copolymer (g-ABS) in which styrene monomers as aromatic vinyl-based compounds and acrylonitrile monomers as cyano-based vinyl compounds are grafted to a butadiene-based rubbery polymer, and the like can be exemplified.

[0043] In an embodiment, in 100% by weight of the total amount of the rubber-modified aromatic vinyl copolymer resin, about 10% by weight to about 50% by weight, for example, about 15% by weight to about 45% by weight of the rubber-modified vinyl graft copolymer can be included. In the range, the thermoplastic resin composition can have excellent impact resistance, flowability (molding processability), appearance properties, balance of these physical properties, and the like.

[0044] Aromatic vinyl-based copolymer resin (A2)

[0045] The aromatic vinyl-based copolymer resin of one embodiment of the present application can be an aromatic vinyl-based copolymer resin used in a common rubber-modified aromatic vinyl-based copolymer resin. For example, the aromatic vinyl-based copolymer resin can be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a cyano-based vinyl monomer.

[0046] In one embodiment, the aromatic vinyl-based copolymer resin can be obtained by polymerizing a mixture of an aromatic vinyl-based monomer and a cyano-based vinyl monomer, etc., after mixing them. The polymerization can be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, or the like.

[0047] In one embodiment, as the aromatic vinyl-based monomer, styrene, a-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, or the like can be used. These substances can be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer can be 60 to 90 wt%, for example, 65 to 85 wt% in 100 wt% of the total amount of the aromatic vinyl-based copolymer resin. In the range, the thermoplastic resin composition can have excellent impact resistance, flowability, and appearance properties, and the like.

[0048] In one embodiment, as the cyano-based vinyl monomer, acrylonitrile, methacrylonitrile, ethyl acrylonitrile, phenyl acrylonitrile, a-chloroacrylonitrile, fumaronitrile, or the like can be exemplified. These substances can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, or the like can be used. The content of the cyano-based vinyl monomer can be about 10 to about 40 wt%, for example, about 15 to about 35 wt% in 100 wt% of the total amount of the aromatic vinyl-based copolymer resin. In the range, the thermoplastic resin composition can have excellent impact resistance, flowability, heat resistance, and appearance properties, and the like.

[0049] In one embodiment, the aromatic vinyl-based copolymer resin can be a copolymer resin polymerized further including a monomer for imparting processability and heat resistance in the monomer mixture. As the monomer for imparting processability and heat resistance, (meth)acrylic acid, N-substituted maleimide, or the like can be exemplified, but is not limited thereto. When the monomer for imparting processability and heat resistance is used, the content thereof can be about 15 wt% or less, for example, about 0.1 to about 10 wt% in 100 wt% of the monomer mixture. In the range, the thermoplastic resin composition can be imparted with processability and heat resistance without reducing other physical properties.

[0050] In embodiments, the aromatic vinyl-based copolymer resin can have a weight average molecular weight (Mw) of about 10,000 g / mol to about 300,000 g / mol, for example, about 20,000 g / mol to about 200,000 g / mol, as measured by GPC (gel permeation chromatography). Within the range, the thermoplastic resin composition can have excellent mechanical strength and molding processability, etc.

[0051] In embodiments, the aromatic vinyl-based copolymer resin can be included in an amount of about 50% by weight to about 90% by weight, for example, about 55% by weight to about 85% by weight, in 100% by weight of the total amount of the rubber-modified aromatic vinyl-based copolymer resin. Within the range, the thermoplastic resin composition can have excellent impact resistance and flowability (molding processability), etc.

[0052] Rubber-modified polystyrene resin (B)

[0053] The rubber-modified polystyrene resin of an embodiment of the present application can improve impact resistance and rigidity, etc. of the thermoplastic resin composition, and can use a polymer prepared by polymerizing a rubbery polymer and an aromatic vinyl-based monomer, such as a common impact-resistant polystyrene (HIPS) resin.

[0054] In embodiments, as the rubbery polymer, a diene-based rubber such as polybutadiene, poly(acrylonitrile-butadiene), and saturated rubber obtained by hydrogenating the diene-based rubber, isoprene rubber, (meth)acrylic alkyl ester rubber having 2 to 10 carbon atoms, a copolymer of (meth)acrylic alkyl ester having 2 to 10 carbon atoms and styrene, a terpolymer of ethylene-propylene-diene monomer (EPDM), etc. can be exemplified. These substances can be used alone or two or more kinds can be used in mixture. For example, a diene-based rubber, a (meth)acrylic ester rubber, etc. can be used, and specifically, a butadiene-based rubber, a butyl acrylate rubber, etc. can be used.

[0055] In embodiments, the average particle size of the rubbery polymer (rubber particles) can be about 0.05 μm to about 6 μm, for example, can be about 0.15 μm to about 4 μm, and specifically can be about 0.25 μm to about 3.5 μm. In the range, the thermoplastic resin composition can have excellent impact resistance and appearance properties, etc. Among them, for the average particle size (z-average) of the rubbery polymer, measurement can be performed in a latex state using a light scattering method. Specifically, the rubbery polymer latex can be meshed, coagulum generated in the polymerization of the rubbery polymer is removed, and after a solution in which 0.5 g of the latex and 30 ml of distilled water are mixed is injected into a 1,000 ml flask and filled with distilled water to prepare a sample, 10 ml of the sample is moved into a quartz cell, and the average particle size of the rubbery polymer is measured by a light scattering particle size analyzer (malvern company, nano-zs).

[0056] In embodiments, the content of the rubbery polymer can be about 3% by weight to about 30% by weight, for example, can be about 5% by weight to about 20% by weight, in 100% by weight of the total amount of the rubber-modified polystyrene resin. In the range, the thermoplastic resin composition can have excellent impact resistance and appearance properties, etc.

[0057] In embodiments, as the aromatic vinyl monomer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. can be exemplified. These substances can be used alone, or two or more kinds can be used in mixture. The content of the aromatic vinyl monomer can be about 70% by weight to about 97% by weight, for example, can be about 80% by weight to about 95% by weight, in 100% by weight of the total amount of the rubber-modified polystyrene resin. In the range, the thermoplastic resin composition can have excellent molding processability, impact resistance, and appearance properties, etc.

[0058] In embodiments, the rubber-modified polystyrene resin, in order to impart properties such as chemical resistance, processability, heat resistance to the thermoplastic resin composition, after polymerization, a monomer such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, etc. can be additionally polymerized at the time of polymerization of the rubber-modified polystyrene resin. At this time, the amount of addition of the monomer can be about 40% by weight or less, relative to 100% by weight of the total amount of the rubber-modified polystyrene resin. In the range, it is possible to impart chemical resistance, processability, and heat resistance, etc. to the thermoplastic resin composition without lowering other physical properties.

[0059] In an embodiment, the rubber-modified polystyrene resin can be polymerized by thermal polymerization in the absence of an initiator, or in the presence of an initiator. As the initiator, one or more of a peroxide initiator such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, and the like, and an azo initiator such as azobisisobutyronitrile, and the like, can be exemplified. The rubber-modified polystyrene resin can be performed by a known polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization, and the like.

[0060] In an embodiment, about 2 parts by weight to about 23 parts by weight, for example, about 3 parts by weight to about 20 parts by weight, of the rubber-modified polystyrene resin can be included with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the rubber-modified polystyrene resin is less than about 2 parts by weight, the impact resistance and the like of the thermoplastic resin composition can be reduced, and when it exceeds about 23 parts by weight, the processability, heat resistance, rigidity, and the like of the thermoplastic resin composition can be reduced.

[0061] Polyolefin Resin (C)

[0062] The polyolefin resin of an embodiment of the present application can improve the chemical resistance, processability, and the like of the thermoplastic resin composition, and a common polyolefin resin can be used. For example, a polyethylene such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and the like; a polypropylene-based resin such as polypropylene, a propylene-ethylene copolymer, a propylene-1-butene copolymer, a mixture thereof, and the like; a polymer crosslinked from these substances; a mixture including polyisobutylene; a combination thereof; and the like can be used. Specifically, polypropylene, polyethylene, a propylene-ethylene copolymer, a combination thereof, and the like can be used.

[0063] In an embodiment, the melt-flow index of the polyolefin resin, measured according to ASTM D1238 at 230°C under a load of 2.16 kg, can be about 0.5 g / 10 min to about 50 g / 10 min, for example, about 1 g / 10 min to about 30 g / 10 min. In the range, the thermoplastic resin composition can have excellent chemical resistance, processability, and the like.

[0064] In an embodiment, about 2 parts by weight to about 23 parts by weight, for example, about 3 parts by weight to about 20 parts by weight, of the polyolefin resin can be included with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the polyolefin resin is less than about 2 parts by weight, the chemical resistance and the like of the thermoplastic resin composition can be reduced, and when it exceeds about 23 parts by weight, the impact resistance, heat resistance, rigidity, and the like of the thermoplastic resin composition can be reduced.

[0065] In an embodiment, the weight ratio (B:C) of the rubber-modified polystyrene resin (B) and the polyolefin resin (C) can be about 1 :0.2 to about 1 :5, for example, about 1 :0.25 to about 1 :4. In the range, the thermoplastic resin composition can have more excellent chemical resistance, impact resistance, heat resistance, rigidity, balance of these physical properties, and the like.

[0066] Saturated fatty acid bisamide (D)

[0067] The saturated fatty acid bisamide of an embodiment of the present application can be used together with a styrene-butadiene rubber-based polymer, an ethylene-a-olefin rubber-based polymer in the rubber-modified aromatic vinyl-based copolymer resin, the rubber-modified polystyrene resin, and the polyolefin resin to improve the chemical resistance, processability, impact resistance, rigidity, heat resistance, balance of these physical properties, and the like of the thermoplastic resin composition, and a common saturated fatty acid bisamide can be used.

[0068] In an embodiment, the saturated fatty acid bisamide can include methylene bis stearamide, methylene bis oleamide, ethylene bis stearamide, ethylene bis oleamide, hexamethylene bis stearamide, hexamethylene bis oleamide, combinations thereof, and the like.

[0069] In an embodiment, about 1 part by weight to about 13 parts by weight, for example, about 1 part by weight to about 10 parts by weight of the saturated fatty acid bisamide can be included with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the saturated fatty acid bisamide is less than about 1 part by weight, the processability of the thermoplastic resin composition and the like can be reduced, and when it exceeds about 13 parts by weight, the heat resistance of the thermoplastic resin composition and the like can be reduced.

[0070] Styrene-butadiene rubber-based polymer (E)

[0071] The styrene-butadiene rubber-based polymer of an embodiment of the present application can be used together with a saturated fatty acid bisamide, an ethylene-a-olefin rubber-based polymer, and the like in the rubber-modified aromatic vinyl-based copolymer resin, the rubber-modified polystyrene resin, and the polyolefin resin to improve the chemical resistance, processability, impact resistance, rigidity, heat resistance, balance of these physical properties, and the like of the thermoplastic resin composition.

[0072] In an embodiment, the styrene-butadiene rubbery polymer can be a polymer of a monomer mixture including about 25 to about 45 wt% of styrene and about 55 to about 75 wt% of butadiene, for example, about 25 to about 35 wt% of styrene and about 65 to about 75 wt% of butadiene. In the range, the thermoplastic resin composition can have excellent impact resistance and rigidity, etc.

[0073] In an embodiment, the melt-flow index of the styrene-butadiene rubbery polymer, measured according to ASTM D1238 at 200°C under a 5 kg load, can be about 1 to about 10 g / 10 min, for example, about 3 to about 8 g / 10 min. In the range, the thermoplastic resin composition can have excellent impact resistance and rigidity, etc.

[0074] In an embodiment, about 1 to about 13 parts by weight, for example, about 1 to about 10 parts by weight, of the styrene-butadiene rubbery polymer can be included with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the styrene-butadiene rubbery polymer is less than about 1 part by weight, the impact resistance of the thermoplastic resin composition can be reduced, and when it exceeds about 13 parts by weight, the processability, heat resistance, rigidity, etc. of the thermoplastic resin composition can be reduced.

[0075] In an embodiment, the weight ratio (D:E) of the saturated fatty acid bisamide (D) and the styrene-butadiene rubbery polymer (E) can be about 1:0.2 to about 1:4, for example, about 1:0.3 to about 1:3.4. In the range, the thermoplastic resin composition can have more excellent chemical resistance, impact resistance, heat resistance, rigidity, and balance of these physical properties, etc.

[0076] Ethylene-α-olefin rubbery polymer (F)

[0077] The ethylene-α-olefin rubbery polymer of an embodiment of the present application can be applied to the rubber-modified aromatic vinyl-based copolymer resin, rubber-modified polystyrene resin, and polyolefin resin, together with the saturated fatty acid bisamide, styrene-butadiene rubbery polymer, etc., to improve the chemical resistance, processability, impact resistance, rigidity, heat resistance, and balance of these physical properties, etc. of the thermoplastic resin composition.

[0078] In an embodiment, the ethylene-α-olefin rubbery polymer can be a polymer of a monomer mixture including about 25 to about 55 wt%, for example, about 30 to about 50 wt% of ethylene and about 45 to about 75 wt%, for example, about 50 to about 70 wt% of α-olefin. In the range, the thermoplastic resin composition can have excellent impact resistance and toughness, etc.

[0079] In an embodiment, as the ethylene-α-olefin rubbery polymer, one or more of ethylene-1-octene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-decene copolymer, ethylene-1-undecene copolymer, and ethylene-1-dodecene copolymer can be used.

[0080] In an embodiment, the specific gravity of the ethylene-α-olefin rubbery polymer, measured according to ASTM D792 method, can be about 0.85 to about 0.88, for example, about 0.86 to about 0.87, and the melt flow index of the ethylene-α-olefin rubbery polymer, measured according to ASTM D1238 at 190°C under a load of 2.16 kg, can be about 0.5 to about 5, for example, about 0.5 to about 2. In the range, the thermoplastic resin composition can have excellent impact resistance and toughness, etc.

[0081] In an embodiment, with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, about 1 to about 13 parts by weight, for example, about 1 to about 10 parts by weight of the ethylene-α-olefin rubbery polymer can be included. When the content of the ethylene-α-olefin rubbery polymer is less than about 1 part by weight, the impact resistance, etc. of the thermoplastic resin composition can be reduced, and when it exceeds about 13 parts by weight, the heat resistance, rigidity, etc. of the thermoplastic resin composition can be reduced.

[0082] In an embodiment, the weight ratio (E:F) of the styrene-butadiene rubbery polymer (E) and the ethylene-α-olefin rubbery polymer (F) can be about 1:0.2 to about 1:4, for example, about 1:0.3 to about 1:3.4. In the range, the thermoplastic resin composition can have more excellent chemical resistance, impact resistance, heat resistance, rigidity, and balance of these physical properties, etc.

[0083] The thermoplastic resin composition of an embodiment of the present application can further include an additive included in a general thermoplastic resin composition. As the additive, an organic / inorganic filler, an antioxidant, a flame retardant, an anti-dripping agent, a core agent, an antistatic agent, a stabilizer, a pigment, a dye, a mixture thereof, or the like can be exemplified, but is not limited thereto. In the case of using the additive, the content of the additive can be about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 10 parts by weight, with respect to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.

[0084] The thermoplastic resin composition of an embodiment of the present application can be in a pellet form by mixing the above-described components and melt-extruding using a general twin-screw extruder at about 180°C to about 280°C, for example, at about 200°C to about 260°C.

[0085] In an embodiment, after a test piece of the thermoplastic resin composition having a size of 200 mm x 50 mm x 2 mm is installed in a 1 / 4 elliptical jig (length of major axis: 120 mm, length of minor axis: 34 mm), 10 ml of olive oil or isopropyl alcohol is applied to the entire test piece, and after 24 hours, the strain (ε) at which a crack occurs calculated according to Formula 1 below can be about 1.0% to about 1.4%, for example, about 1.1% to about 1.38%.

[0086] [Formula 1]

[0087]

[0088] In the Formula 1, ε denotes the strain at which a crack occurs, a is the length of the major axis of the elliptical jig (mm), b is the length of the minor axis of the elliptical jig (mm), t is the thickness of the test piece (mm), and x is the distance from the perpendicular intersection of the position at which a crack occurs and the major axis of the elliptical jig to the midpoint of the elliptical jig.

[0089] In an embodiment, the spiral flow length of a test piece of the thermoplastic resin composition measured after injection molding in a spiral mold having a width of 15 mm and a thickness of 1 mm at a molding temperature of 230°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s can be about 210 mm to about 280 mm, for example, about 220 mm to about 280 mm.

[0090] In an embodiment, the Izod notched impact strength of a test piece of the thermoplastic resin composition having a thickness of 1 / 4" measured according to ASTM D256 can be about 12 kgf·cm / cm to about 30 kgf·cm / cm, for example, about 13 kgf·cm / cm to about 25 kgf·cm / cm.

[0091] In a specific example, the tensile strength of a test piece of the thermoplastic resin composition having a thickness of 3.2 mm measured according to ASTM D638 at a condition of 50 mm / min can be about 290 kgf / cm 2 to about 380 kgf / cm 2 , for example, can be about 300 kgf / cm 2 to about 380 kgf / cm 2 .

[0092] In a specific example, the Vicat softening temperature of the thermoplastic resin composition measured according to ISO R306 at a condition of 5 kg load, 50°C / hr can be about 79°C to about 92°C, for example, can be about 80°C to about 90°C.

[0093] The molded article of the present application is formed from the thermoplastic resin composition. The thermoplastic resin composition can be prepared in a pellet form, and the prepared pellets can be made into various molded articles (products) by various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding, etc. Such molding methods are well known to those skilled in the art to which the present application pertains. The molded article has excellent chemical resistance, processability, impact resistance, rigidity, heat resistance, balance of these physical properties, etc., and thus is advantageous for use as an inner or outer material for electrical and electronic products, a housing for household products, etc.

[0094] Hereinafter, the present application will be described more specifically by way of Examples, but these Examples are for illustrative purposes only and should not be construed as limiting the present application.

[0095] Example

[0096] Hereinafter, the specifications of each component used in the Examples and Comparative Examples are as follows.

[0097] Rubber-modified aromatic vinyl-based copolymer resin (A)

[0098] The following rubber-modified vinyl-based graft copolymer (Al) 25 wt% and aromatic vinyl-based copolymer resin (A2) 75 wt% were mixed to use.

[0099] Rubber-modified vinyl-based graft copolymer (Al)

[0100] A graft copolymer (g-ABS) of core-shell form prepared by grafting copolymerization of styrene and acrylonitrile (weight ratio: 75 / 25) 42 wt% in butadiene rubber 58 wt% having an average particle size of 0.3 μm was used.

[0101] Aromatic vinyl-based copolymer resin (A2)

[0102] A SAN resin (weight average molecular weight: 140,000 g / mol) prepared by polymerizing styrene 80% by weight and acrylonitrile 20% by weight was used.

[0103] Rubber-modified polystyrene resin (B)

[0104] An impact-resistant polystyrene (HIPS) resin (manufacturing company: Styrolution, product name: PS576H) was used.

[0105] Polyolefin resin (C)

[0106] A polypropylene resin (manufacturing company: Lotte Fine Chemical Co., Ltd., product name: B-311) having a melt flow index (MI) of 12 g / 10 min measured according to ASTM D1238 at 230°C under a load of 2.16 kg was used.

[0107] Saturated fatty acid bisamide (D)

[0108] Ethylene bis-stearamide (manufacturing company: Shin-Etsu Chemical Co., Ltd., product name: HI-LUB B-50) was used.

[0109] Styrene-butadiene rubbery polymer (E1) (SBR, manufacturing company: Kumho Petrochemical Co., Ltd., product name: KTR-201, styrene content: 31.5% by weight) was used.

[0110] Styrene-ethylene-butadiene-styrene copolymer (E2) (SEBS, manufacturing company: KRATON, product name: G1652) was used.

[0111] Ethylene-1-octene rubbery polymer (F1) (EOR, manufacturing company: DOW, product name: ENGAGE 8150) was used as an ethylene-α-olefin rubbery polymer.

[0112] Ethylene methyl acrylate copolymer (F2) (EMA, manufacturing company: Dupont, product name: Elvaloy AC1330) was used.

[0113] Examples 1 to 11 and Comparative Examples 1 to 12

[0114] The respective components were added in the amounts described in Tables 1, 2, 3 and 4 below, and pellets were prepared by extrusion at 230°C. A biaxial extruder having an L / D = 44 and a diameter of 45 mm was used for the extrusion, and the pellets thus prepared were dried at 80°C for 4 hours or more, and then injection-molded in a 6 oz injection molding machine (molding temperature: 230°C, mold temperature: 60°C) to prepare test pieces. The physical properties of the test pieces thus prepared were evaluated according to the following methods, and the results are shown in Tables 1, 2, 3 and 4 below.

[0115] Method for measuring physical properties

[0116] (1) Evaluation of chemical resistance: After a test piece having a size of 200 mm x 50 mm x 2 mm was mounted on a 1 / 4 elliptical jig (length of major axis: 120 mm, length of minor axis: 34 mm), 10 ml of olive oil or isopropyl alcohol was applied to the entire test piece, and after 24 hours, the strain at which a crack appeared (ε, unit: %) was calculated according to the following Formula 1.

[0117] [Formula 1]

[0118]

[0119] In the Formula 1, ε represents the strain at which a crack appeared, a is the length of the major axis of the elliptical jig (mm), b is the length of the minor axis of the elliptical jig (mm), t is the thickness of the test piece (mm), and x is the distance from the perpendicular intersection of the position at which a crack appeared and the major axis of the elliptical jig to the midpoint of the elliptical jig.

[0120] (2) Evaluation of processability: After injection molding was performed in a spiral mold having a width of 15 mm and a thickness of 1 mm at a molding temperature of 230°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s, the spiral flow length of the test piece (unit: mm) was measured.

[0121] (3) Evaluation of impact resistance: According to ASTM D256, the Izod notched impact strength of a test piece having a thickness of 1 / 4" (unit: kgf-cm / cm) was measured.

[0122] (4) Tensile strength (TS, unit: kgf / cm 2 ): According to ASTM D638, the tensile strength of a test piece having a thickness of 3.2 mm was measured at a rate of 50 mm / min.

[0123] (5) Vicat softening temperature (VST, unit: °C): According to ISO 306, the Vicat softening temperature was measured at a load of 5 kg and a rate of 50°C / hr.

[0124] [Table 1]

[0125]

[0126] [Table 2]

[0127]

[0128] [Table 3]

[0129]

[0130] [Table 4]

[0131]

[0132] From the above results, it is known that the chemical resistance, processability, impact resistance, and the like of the thermoplastic resin composition of the present application are all excellent.

[0133] On the contrary, when the content of the rubber-modified polystyrene resin used is less than the content range of the present application (Comparative Example 1), it is known that the impact resistance and the like decrease, and when the content of the rubber-modified polystyrene resin used exceeds the content range of the present application (Comparative Example 2), it is known that the processability, heat resistance, rigidity, and the like decrease. When the content of the polyolefin resin used is less than the content range of the present application (Comparative Example 3), it is known that the chemical resistance and the like decrease, and when the content of the polyolefin resin used exceeds the content range of the present application (Comparative Example 4), it is known that the impact resistance, heat resistance, rigidity, and the like decrease. When the content of the saturated fatty acid bisamide used is less than the content range of the present application (Comparative Example 5), it is known that the processability and the like decrease, and when the content of the saturated fatty acid bisamide used exceeds the content range of the present application (Comparative Example 6), it is known that the heat resistance and the like decrease. When the content of the styrene-butadiene rubber-based polymer used is less than the content range of the present application (Comparative Example 7), it is known that the impact resistance and the like decrease, and when the content of the styrene-butadiene rubber-based polymer used exceeds the content range of the present application (Comparative Example 8), it is known that the processability, heat resistance, rigidity, and the like decrease, and when SEBS (E2) is used in place of the styrene-butadiene rubber-based polymer (Comparative Example 9), it is known that the impact resistance and the like decrease. Furthermore, when the content of the ethylene-a-olefin rubber-based polymer used is less than the content range of the present application (Comparative Example 10), it is known that the impact resistance and the like decrease, and when the content of the ethylene-a-olefin rubber-based polymer used exceeds the content range of the present application (Comparative Example 11), it is known that the heat resistance, rigidity, and the like decrease, and when EMA (F2) is used in place of the ethylene-a-olefin rubber-based polymer (Comparative Example 12), it is known that the impact resistance and the like decrease.

[0134] The application has been described above in an embodiment-centered fashion. It should be understood that the application can be practiced in other embodiments that are not specifically described. Thus, the present embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the application is to be indicated by the appended claims, rather than the foregoing description, and all changes that come within the meaning and range of equivalents are intended to be embraced therein.

Claims

1. A thermoplastic resin composition, characterized by, comprises: 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 2 to 23 parts by weight of a rubber-modified polystyrene resin; 2 to 23 parts by weight of a polyolefin resin; 1 to 13 parts by weight of a saturated fatty acid bisamide; 1 to 13 parts by weight of a styrene-butadiene rubber-based polymer; and 1 to 13 parts by weight of an ethylene-a-olefin rubber-based polymer, the rubber-modified aromatic vinyl-based copolymer resin comprises 10 to 50% by weight of a rubber-modified vinyl-based graft copolymer and 50 to 90% by weight of an aromatic vinyl-based copolymer resin, the rubber-modified polystyrene resin is a polymer of 3 to 30% by weight of a rubber-based polymer and 70 to 97% by weight of an aromatic vinyl-based monomer, the polyolefin resin comprises one or more of polypropylene, polyethylene, and a propylene-ethylene copolymer, the saturated fatty acid bisamide comprises one or more of methylene bis-stearamide, methylene bis-oleamide, ethylene bis-stearamide, ethylene bis-oleamide, hexamethylene bis-stearamide, and hexamethylene bis-oleamide, the styrene-butadiene rubber-based polymer is a polymer of a monomer mixture comprising 25 to 45% by weight of styrene and 55 to 75% by weight of butadiene, the ethylene-a-olefin rubber-based polymer is a polymer of a monomer mixture comprising 25 to 55% by weight of ethylene and 45 to 75% by weight of an a-olefin.

2. The thermoplastic resin composition according to claim 1, wherein the rubber-modified vinyl-based graft copolymer is a copolymer obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl-based monomer and a cyanoated vinyl-based monomer in a rubber-based polymer.

3. The thermoplastic resin composition according to claim 1 or 2, wherein a weight ratio of the rubber-modified polystyrene resin to the polyolefin resin is 1:0.2 to 1:

5.

4. The thermoplastic resin composition according to claim 1 or 2, wherein a weight ratio of the saturated fatty acid bisamide to the styrene-butadiene rubber-based polymer is 1:0.2 to 1:

4.

5. The thermoplastic resin composition according to claim 1 or 2, wherein a weight ratio of the styrene-butadiene rubber-based polymer to the ethylene-a-olefin rubber-based polymer is 1:0.2 to 1:

4.

6. The thermoplastic resin composition according to claim 1 or 2, wherein a strain ε at which a crack occurs calculated according to the following Formula 1 after 24 hours after 10 ml of olive oil or isopropyl alcohol is applied to the entire test piece after a test piece of the thermoplastic resin composition having a size of 200 mm x 50 mm x 2 mm is installed in a 1 / 4 elliptical jig having a major axis length of 120 mm and a minor axis length of 34 mm is 1.0 to 1.4%, [Formula 1] In the formula 1, ε represents a strain at which a crack occurs, a is a length of a long axis of the elliptical jig, b is a length of a short axis of the elliptical jig, t is a thickness of a test piece, and x is a distance from a perpendicular intersection of a position at which a crack occurs and the long axis of the elliptical jig to a midpoint of the elliptical jig, wherein the a, the b, and the t have units of mm.

7. The thermoplastic resin composition according to claim 1 or 2, wherein The spiral flow length of a test piece of the thermoplastic resin composition measured after injection molding in a spiral mold having a width of 15 mm and a thickness of 1 mm under conditions of a molding temperature of 230°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s is 210 mm to 280 mm.

8. The thermoplastic resin composition according to claim 1 or 2, wherein The Izod notched impact strength of a 1 / 4" thick test piece of the thermoplastic resin composition measured according to ASTM D256 is 12 to 30 kgf-cm / cm, the tensile strength of a 3.2 mm thick test piece measured according to ASTM D638 at 50 mm / min is 290 kgf / cm 2 to 380 kgf / cm 2 and the Vicat softening temperature measured according to ISO R306 at 5 kg load, 50°C / hr is 79 to 90°C.

9. A molded article characterized by The thermoplastic resin composition according to any one of claims 1 to 8 is formed.

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