Thermoplastic resin composition and molded article produced therefrom

Abstract

A thermoplastic resin composition of the present invention comprises: approximately 100 parts of a polycarbonate resin; approximately 20-40 parts of an aromatic vinyl-vinyl cyanide-based copolymer resin; approximately 3-15 parts by weight of a rubber-modified vinyl-based graft copolymer in which a monomer mixture comprising an aromatic vinyl-based monomer and an alkyl (meth)acrylic monomer is graft copolymerized onto a rubber polymer; approximately 0.7-3 parts by weight of an ethylene-methyl acrylate copolymer; approximately 20-50 parts of a glass fiber; approximately 10-40 parts by weight of a brominated epoxy resin; and approximately 0.5-3 parts by weight of an aromatic phosphate compound containing a resorcinol-derived unit. The thermoplastic resin composition has excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, property balance therebetween, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of these properties, and a molded article manufactured therefrom.

[0002]

[0003] Thermoplastic resin compositions have lower specific gravity than glass and metal, and superior physical properties such as formability and impact resistance, making them useful for electrical / electronic product housings, automotive interior / exterior materials, and architectural exterior materials. Among these thermoplastic resin compositions, thermoplastic resin compositions that mix aromatic vinyl-vinyl cyanide copolymer resins, such as acrylonitrile-butadiene-styrene (ABS) copolymer resin, with polycarbonate (PC) resin can improve processability and chemical resistance without reducing the impact resistance and heat resistance of polycarbonate resin, and can also reduce costs, and are therefore utilized for various purposes.

[0004] Driven by demand for eco-friendly vehicles, electric vehicle sales are on the rise, with sales projected to reach around 35 million units by 2030. As the electric vehicle market grows, electric vehicle factories are being established around the world, including in Europe, the Americas, and China. Battery manufacturers are also building factories near these plants to supply the batteries needed for these vehicles. Electric vehicle batteries are installed in electric vehicles in the form of cells, modules, and packs. This is driving demand for trays within battery production lines, which are used to assemble batteries into packs. Materials used for battery trays require high flame and heat resistance to prevent battery thermal runaway fires, as well as high impact resistance and rigidity to protect against damage during assembly and transportation.

[0005] Therefore, there is a need to develop a thermoplastic resin composition with excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of these properties.

[0006] The background technology of the present invention is disclosed in Korean Patent No. 10-1914875, etc.

[0007]

[0008] The purpose of the present invention is to provide a thermoplastic resin composition having excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of these physical properties.

[0009] Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below.

[0011]

[0012] 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 polycarbonate resin; about 20 to about 40 parts by weight of an aromatic vinyl-vinylcyanide copolymer resin; about 3 to about 15 parts by weight of a rubber-modified vinyl graft copolymer obtained by graft polymerizing a monomer mixture comprising an aromatic vinyl monomer and an alkyl (meth)acrylic monomer onto a rubber polymer; about 0.7 to about 3 parts by weight of an ethylene-methyl acrylate copolymer; about 20 to about 50 parts by weight of a glass fiber; about 10 to about 40 parts by weight of a brominated epoxy resin; and about 0.5 to about 3 parts by weight of an aromatic phosphate compound comprising a resorcinol-derived unit.

[0013] 2. In the above 1 specific example, the glass fiber may be surface-treated with an epoxy sizing agent.

[0014] 3. In the above 1 or 2 specific examples, the brominated epoxy resin may have a bromine content of about 20 to about 80 wt%.

[0015] 4. In the above 1 to 3 specific examples, the brominated epoxy resin may have a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of about 15,000 to about 25,000 g / mol.

[0016] 5. In the above 1 to 4 specific examples, the aromatic phosphate compound including the resorcinol-derived unit may include at least one of resorcinol-di(bis-2,6-dimethylphenyl)phosphate, resorcinol bis(diphenylphosphate), and resorcinol di[bis(2,4-ditertiarybutylphenyl)phosphate].

[0017] 6. In the above 1 to 5 specific examples, the weight ratio of the rubber-modified vinyl graft copolymer and the ethylene-methyl acrylate copolymer may be about 1:0.1 to about 1:0.7.

[0018] 7. In the above specific examples 1 to 6, the weight ratio of the brominated epoxy resin and the aromatic phosphate compound may be about 1:0.02 to about 1:0.25.

[0019] 8. In the above 1 to 7 specific examples, the thermoplastic resin composition may have a notched Izod impact strength of about 3.7 to about 20 kgf·cm / cm for a 1 / 8" thick specimen measured according to ASTM D256.

[0020] 9. In the above 1 to 8 specific examples, the thermoplastic resin composition may have an FDI (falling dart impact) impact strength of about 7 to about 20 J of a 3.2 mm thick specimen measured by dropping a 7 kg dart from a height of 1 m according to the DuPont drop measurement method.

[0021] 10. In the above 1 to 9 specific examples, the thermoplastic resin composition may have a tensile strength of about 1,000 to about 2,000 MPa of a 4 mm thick specimen measured under conditions of 5 mm / min according to ISO 527.

[0022] 11. In the above 1 to 10 specific examples, the thermoplastic resin composition may have a flame retardancy of V-1 or higher in a 1.5 mm thick injection molded specimen measured by the UL-94 vertical test method.

[0023] 12. In the above 1 to 11 specific examples, the thermoplastic resin composition may have a heat distortion temperature (HDT) of about 115 to about 160°C of a 6.4 mm thick specimen measured under conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

[0024] 13. In the above 1 to 12 specific examples, the thermoplastic resin composition may have a spiral flow length of about 200 to about 450 mm when measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 2 mm under conditions of a molding temperature of 240°C, a mold temperature of 60°C, an injection pressure of 1,000 MPa, and an injection speed of 60 mm / s.

[0025] 14. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a thermoplastic resin composition according to any one of 1 to 13.

[0026] 15. Another aspect of the present invention relates to a battery tray. The battery tray is formed from a thermoplastic resin composition according to any one of 1 to 13, and is characterized in that it is an injection-molded product having a size of about 100 to about 800 mm × about 100 to about 700 mm × about 100 to about 500 mm.

[0027]

[0028] The present invention has the effect of providing a thermoplastic resin composition having excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of these physical properties, and a molded article formed therefrom.

[0029]

[0030] Hereinafter, the present invention will be described in detail as follows.

[0031] A thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) an aromatic vinyl-vinyl cyanide copolymer resin; (C) a rubber-modified vinyl graft copolymer; (D) an ethylene-methyl acrylate copolymer; (E) glass fiber; (F) a brominated epoxy resin; and (G) an aromatic phosphate compound.

[0032] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0033]

[0034] (A) Polycarbonate resin

[0035] As a polycarbonate resin according to one specific example of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition can be used. For example, an aromatic polycarbonate resin produced by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic diester can be used.

[0036] In specific examples, the diphenols may include, but are not limited to, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, and specifically, 2,2-bis(4-hydroxyphenyl)propane, also called bisphenol-A, can be used.

[0037] In a specific example, the polycarbonate resin may be one having a branched chain, and for example, a branched polycarbonate resin may be used that is prepared by adding 0.05 to 2 mol% of a trivalent or higher polyfunctional compound, specifically, a compound having a trivalent or higher phenol group, to the total diphenols used in the polymerization.

[0038] In specific examples, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a difunctional carboxylic acid.

[0039] In a specific example, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 18,000 to about 50,000 g / mol, for example, about 20,000 to about 40,000 g / mol. Within this range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), etc.

[0040] In a specific example, the polycarbonate resin may have a melt flow index (MI) of about 5 to about 80 g / 10 min, measured under conditions of 300°C and a load of 1.2 kg, according to ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.

[0041]

[0042] (B) Aromatic vinyl-cyanide vinyl copolymer resin

[0043] An aromatic vinyl-vinyl cyanide copolymer resin according to one specific example of the present invention can be applied to a polycarbonate resin together with a rubber-modified vinyl graft copolymer, an ethylene-methyl acrylate copolymer, glass fiber, a brominated epoxy resin, and an aromatic phosphate compound to improve the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of a thermoplastic resin composition, and may be an aromatic vinyl-vinyl cyanide copolymer resin used in a typical thermoplastic resin composition. For example, the aromatic vinyl-vinyl cyanide copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer.

[0044] In a specific example, the aromatic vinyl-cyanide vinyl copolymer resin can be obtained by mixing an aromatic vinyl monomer and a cyanide vinyl monomer, and then polymerizing the mixture. The polymerization can be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization.

[0045] In specific examples, the aromatic vinyl monomer may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be about 60 to about 90 wt%, for example, about 65 to about 85 wt%, based on 100 wt% of the total aromatic vinyl-cyanide vinyl copolymer resin. Within this range, the thermoplastic resin composition may exhibit excellent impact resistance, fluidity, and appearance properties.

[0046] In specific examples, the vinyl cyanide monomer may include, but is not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. may be used. The content of the vinyl cyanide monomer may be about 10 to about 40 wt%, for example, about 15 to about 35 wt%, based on 100 wt% of the total aromatic vinyl-vinyl cyanide copolymer resin. Within this range, the thermoplastic resin composition may exhibit excellent impact resistance, fluidity, heat resistance, appearance characteristics, etc.

[0047] In a specific example, the aromatic vinyl-vinyl cyanide copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 300,000 g / mol, for example, about 15,000 to about 150,000 g / mol. Within this range, the thermoplastic resin composition may have excellent mechanical strength, moldability, etc.

[0048] In a specific example, the aromatic vinyl-vinyl cyanide copolymer resin may be included in an amount of about 20 to about 40 parts by weight, for example, about 25 to about 35 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the aromatic vinyl-vinyl cyanide copolymer resin is less than about 20 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the moldability of the thermoplastic resin composition may be reduced, and if it exceeds about 40 parts by weight, there is a concern that the impact resistance, rigidity, flame retardancy, heat resistance, moldability, etc. of the thermoplastic resin composition may be reduced.

[0049]

[0050] (C) Rubber-modified vinyl graft copolymer

[0051] According to one specific example of the present invention, a rubber-modified vinyl graft copolymer can be applied to a polycarbonate resin together with an aromatic vinyl-cyanide vinyl copolymer resin, an ethylene-methyl acrylate copolymer, glass fiber, a brominated epoxy resin, and an aromatic phosphate compound, thereby improving the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of a thermoplastic resin composition. A rubber-modified vinyl graft copolymer obtained by graft polymerizing a monomer mixture including an aromatic vinyl monomer and an alkyl (meth)acrylic monomer onto a rubber polymer can be used. For example, the rubber-modified vinyl graft copolymer can be obtained by graft polymerizing a monomer mixture including an aromatic vinyl monomer and an alkyl (meth)acrylic monomer and, if necessary, a monomer copolymerizable with the aromatic vinyl monomer onto a rubber polymer. The above polymerization can be performed by a known polymerization method such as emulsion polymerization or suspension polymerization. In addition, the rubber-modified vinyl graft copolymer can form a core (rubber polymer) - shell (copolymer of a monomer mixture) structure, but is not limited thereto.

[0052] In specific examples, examples of the rubber polymer include diene rubbers such as polybutadiene, poly(acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubber, isoprene rubber, alkyl (meth)acrylate rubbers having 2 to 10 carbon atoms, copolymers of alkyl (meth)acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymer (EPDM), etc. These may be used singly or in combination of two or more. For example, diene rubbers, (meth)acrylate rubbers, etc. may be used, and specifically, butadiene rubbers, butylacrylate rubbers, etc. may be used, but are not limited thereto.

[0053] In a specific example, the rubber polymer (rubber particles) may have an average particle size of about 0.05 to about 6 μm, for example, about 0.15 to about 4 μm, specifically, about 0.25 to about 3.5 μm. Within this range, the impact resistance, appearance properties, etc. of the thermoplastic resin composition may be excellent. Here, the average particle size (z-average) of the rubber polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulants generated during the polymerization of the rubber polymer, a solution of 0.5 g of the latex and 30 ml of distilled water is mixed and poured into a 1,000 ml flask, and the distilled water is filled to prepare a sample, and then 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubber polymer can be measured using a light scattering particle size analyzer (Malvern, nano-zs).

[0054] In a specific example, the content of the rubber polymer may be about 20 to about 80 wt%, for example, about 25 to about 70 wt%, based on 100 wt% of the total rubber-modified vinyl-based graft copolymer, and the content of the monomer mixture may be about 20 to about 80 wt%, for example, about 30 to about 75 wt%, based on 100 wt% of the total rubber-modified vinyl-based graft copolymer. Within this range, the thermoplastic resin composition may exhibit excellent impact resistance, heat resistance, moldability, appearance properties, and the like.

[0055] In a specific example, the aromatic vinyl monomer is one that can be graft copolymerized to the rubber polymer, and examples thereof include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be about 10 to about 90 wt%, for example, about 20 to about 80 wt%, based on 100 wt% of the monomer mixture. Within this range, the thermoplastic resin composition may exhibit excellent moldability, impact resistance, and the like.

[0056] In a specific example, the alkyl (meth)acrylic monomer is copolymerizable with the aromatic vinyl monomer, and examples thereof include methyl methacrylate, methyl acrylate, and ethyl acrylate. These may be used alone or in combination of two or more. For example, methyl methacrylate may be used. The content of the alkyl (meth)acrylic monomer may be about 10 to about 90 wt%, for example, about 20 to about 80 wt%, based on 100 wt% of the monomer mixture. Within this range, the thermoplastic resin composition may exhibit excellent moldability, impact resistance, and the like.

[0057] In specific examples, examples of monomers copolymerizable with the aromatic vinyl monomer include, but are not limited to, cyanide vinyl monomers, maleic anhydride, N-substituted maleimides, etc. When applying a monomer copolymerizable with the aromatic vinyl monomer, the content thereof may be about 50 wt% or less out of 100 wt% of the monomer mixture, but is not limited thereto.

[0058] In specific examples, examples of the rubber-modified vinyl graft copolymer include a copolymer (g-MBS) in which a styrene monomer, which is an aromatic vinyl compound, and methyl methacrylate, which is a copolymerizable monomer, are grafted onto a butadiene rubber polymer, and a copolymer (g-MABS) in which a styrene monomer, an acrylonitrile monomer, and methyl methacrylate are grafted onto a butadiene rubber polymer. For example, g-MBS and the like can be used.

[0059] In a specific example, the rubber-modified vinyl graft copolymer may be included in an amount of about 3 to about 15 parts by weight, for example, about 5 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the rubber-modified vinyl graft copolymer is less than about 3 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 15 parts by weight, there is a concern that the rigidity, flame retardancy, heat resistance, etc. of the thermoplastic resin composition may be reduced.

[0060]

[0061] (D) Ethylene-methyl acrylate copolymer

[0062] An ethylene-methyl acrylate copolymer according to one specific example of the present invention can be applied to a polycarbonate resin together with an aromatic vinyl-vinyl cyanide copolymer resin, a rubber-modified vinyl graft copolymer, glass fiber, a brominated epoxy resin, and an aromatic phosphate compound, thereby improving the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of a thermoplastic resin composition.

[0063] In a specific example, the ethylene-methyl acrylate copolymer can be prepared by polymerizing ethylene and methyl acrylate. For example, the ethylene-methyl acrylate copolymer can include about 50 to about 95 wt%, for example, about 70 to about 93 wt%, of ethylene repeating units and about 5 to about 50 wt%, for example, about 7 to about 30 wt%, of methyl acrylate repeating units. Within this range, the impact resistance, etc. of the thermoplastic resin composition can be excellent.

[0064] In specific examples, the ethylene-methyl acrylate copolymer may be in the form of a random, block, or multiblock copolymer, and may also be used in the form of a combination thereof.

[0065] In a specific example, the ethylene-methyl acrylate copolymer may have a melt flow index of about 0.01 to about 40 g / 10 min, for example, about 0.1 to about 10 g / 10 min, measured under conditions of 190°C and 2.16 kgf according to ASTM D1238.

[0066] In a specific example, the ethylene-methyl acrylate copolymer may be included in an amount of about 0.7 to about 3 parts by weight, for example, about 1 to about 2.5 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the ethylene-methyl acrylate copolymer is less than about 0.7 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 3 parts by weight, there is a concern that the flame retardancy, etc. of the thermoplastic resin composition may be reduced.

[0067] In a specific example, the weight ratio of the rubber-modified vinyl graft copolymer and the ethylene-methyl acrylate copolymer (rubber-modified vinyl graft copolymer: ethylene-methyl acrylate copolymer) may be about 1:0.1 to about 1:0.7, for example, about 1:0.1 to about 1:0.5, specifically about 1:0.14 to about 1:0.36. In the above range, the impact resistance, moldability, etc. of the thermoplastic resin composition may be more excellent.

[0068]

[0069] (E) Glass fiber

[0070] According to one specific example of the present invention, glass fiber can be applied to a polycarbonate resin together with an aromatic vinyl-cyanide vinyl copolymer resin, a rubber-modified vinyl graft copolymer, an ethylene-methyl acrylate copolymer, a brominated epoxy resin, and an aromatic phosphate compound, thereby improving the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of the thermoplastic resin composition.

[0071] In specific embodiments, the glass fibers may include circular cross-sectional glass fibers, flat-shaped glass fibers, combinations thereof, and the like.

[0072] In a specific example, the circular cross-section glass fiber may be a glass fiber having an average diameter of a circular cross-section measured using an optical microscope of about 5 to about 15 μm, for example, about 6 to about 14 μm. Within this range, the thermoplastic resin composition may have excellent rigidity, impact resistance, etc.

[0073] In a specific example, the flat glass fiber may have an aspect ratio of a cross-section measured by an optical microscope of about 1.5 to about 4, for example, about 2 to about 4, and a short diameter of about 6 to about 10 μm, for example, about 6 to about 9 μm. In this range, the thermoplastic resin composition may have excellent rigidity, impact resistance, etc.

[0074] In a specific example, the glass fibers may have an average length of about 1 to about 5 mm before extrusion, and an average length of about 100 to about 700 μm, for example, about 110 to about 690 μm, after extrusion (processing). Within this range, the thermoplastic resin composition may have excellent impact resistance, rigidity, appearance properties, etc.

[0075] In a specific example, the glass fiber may be surface-treated with an epoxy sizing agent to increase bonding strength with the constituent components. Examples of the epoxy sizing agent include, but are not limited to, epoxy resin, modified epoxy resin, hydrogenated modified epoxy resin, and combinations thereof.

[0076] In a specific example, the glass fiber surface-treated with the epoxy sizing agent may have a content of the epoxy sizing agent of about 0.1 to about 10 wt%, for example, about 0.1 to about 5 wt%, based on 100 wt% of the total glass fiber surface-treated with the epoxy sizing agent. Within this range, the impact resistance, rigidity, moldability, etc. of the thermoplastic resin composition may be excellent.

[0077] In a specific example, the glass fiber may be included in an amount of about 20 to about 50 parts by weight, for example, about 25 to about 40 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the glass fiber is less than about 20 parts by weight relative to about 100 parts by weight of the polycarbonate resin, there is a concern that the rigidity, moldability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 50 parts by weight, there is a concern that the impact resistance, flame retardancy, moldability, etc. of the thermoplastic resin composition may be reduced.

[0078]

[0079] (F) Brominated epoxy resin

[0080] According to one specific example of the present invention, a brominated epoxy resin can be applied to a polycarbonate resin together with an aromatic vinyl-vinyl cyanide copolymer resin, a rubber-modified vinyl graft copolymer, an ethylene-methyl acrylate copolymer, glass fiber, and an aromatic phosphate compound, thereby improving the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of a thermoplastic resin composition. A commercially available brominated epoxy resin used in a typical thermoplastic resin composition can be used.

[0081] In a specific example, the brominated epoxy resin may have a bromine content of about 20 to about 80 wt%, for example, about 30 to about 60 wt%, based on 100 wt% of the total brominated epoxy resin. Within this range, the thermoplastic resin composition may have excellent flame retardancy, heat resistance, and the like.

[0082] In a specific example, the brominated epoxy resin may have a weight average molecular weight (Mw) of about 15,000 to about 25,000 g / mol as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition may exhibit excellent flame retardancy, thermal stability, moldability, and the like.

[0083] In a specific example, the brominated epoxy resin may be included in an amount of about 10 to about 40 parts by weight, for example, about 15 to about 35 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the amount of the brominated epoxy resin is less than about 10 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the flame retardancy, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 40 parts by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

[0084]

[0085] (G) Aromatic phosphate compound

[0086] According to one specific example of the present invention, an aromatic phosphate compound can be applied to a polycarbonate resin together with an aromatic vinyl-vinyl cyanide copolymer resin, a rubber-modified vinyl graft copolymer, an ethylene-methyl acrylate copolymer, glass fiber, and a brominated epoxy resin, thereby improving the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the balance of these physical properties of a thermoplastic resin composition. An aromatic phosphate compound including a resorcinol-derived unit can be used.

[0087] In specific examples, the aromatic phosphate compound comprising the resorcinol-derived unit may include resorcinol-di(bis-2,6-dimethylphenyl)phosphate, resorcinol bis(diphenylphosphate), resorcinol di[bis(2,4-ditertiarybutylphenyl)phosphate], combinations thereof, and the like.

[0088] In a specific example, the aromatic phosphate compound may be included in an amount of about 0.5 to about 3 parts by weight, for example, about 1 to about 2.5 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the aromatic phosphate compound is less than about 0.5 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the flame retardancy, fluidity, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 3 parts by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

[0089] In a specific example, the weight ratio of the brominated epoxy resin and the aromatic phosphate compound (brominated epoxy resin: aromatic phosphate compound) may be from about 1:0.02 to about 1:0.25, for example from about 1:0.04 to about 1:0.11. In this range, the flame retardancy, fluidity, etc. of the thermoplastic resin composition may be more excellent.

[0090]

[0091] A thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additives include, but are not limited to, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, dyes, pigments, and mixtures thereof. When the additives are used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin.

[0092]

[0093] A thermoplastic resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 230 to about 300°C, for example, about 240 to about 290°C, using a conventional twin-screw extruder.

[0094] The thermoplastic resin composition may have a notched Izod impact strength of about 3.7 to about 20 kgf·cm / cm, for example, about 4 to about 15 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0095] In a specific example, the thermoplastic resin composition may have an FDI (falling dart impact) strength of about 7 to about 20 J, for example, about 7.5 to about 17 J, of a 3.2 mm thick specimen measured by dropping a 7 kg dart from a height of 1 m according to the DuPont drop measurement method.

[0096] In a specific example, the thermoplastic resin composition may have a tensile strength of about 1,000 to about 2,000 MPa, for example, about 1,040 to about 1,900 MPa, of a 4 mm thick specimen measured under conditions of 5 mm / min according to ISO 527.

[0097] In a specific example, the thermoplastic resin composition may have a flame retardancy of V-1 or higher in a 1.5 mm thick injection molded specimen measured by the UL-94 vertical test method.

[0098] In a specific example, the thermoplastic resin composition may have a heat deflection temperature (HDT) of about 115 to about 160°C, for example, about 118 to about 150°C, of ​​a 6.4 mm thick specimen measured under conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

[0099] In a specific example, the thermoplastic resin composition may have a spiral flow length of about 200 to about 450 mm, for example, about 220 to about 430 mm, measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 2 mm under conditions of a molding temperature of 240°C, a mold temperature of 60°C, an injection pressure of 1,000 MPa, and an injection speed of 60 mm / s.

[0100]

[0101] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention pertains.

[0102] In a specific example, the molded product has excellent impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of these properties, and is therefore useful as a battery tray, a battery pallet, a movable tray, and the like.

[0103] In a specific example, the battery tray may be an injection molded product having a size of about 100 to about 800 mm × about 100 to about 700 mm × about 100 to about 500 mm.

[0104]

[0105] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0106]

[0107] Example

[0108] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0109] (A) Polycarbonate resin

[0110] Bisphenol-A polycarbonate resin (manufacturer: Lotte Chemical, weight average molecular weight: approximately 25,000 g / mol) was used.

[0111] (B) Aromatic vinyl-cyanide vinyl copolymer resin

[0112] SAN resin (manufacturer: Lotte Chemical, weight average molecular weight: approximately 100,000 g / mol) manufactured by polymerizing 75 wt% styrene and 25 wt% acrylonitrile was used.

[0113] (C) Rubber-modified vinyl graft copolymer

[0114] (C1) A rubber-modified vinyl graft copolymer (g-MBS, manufacturer: Dow, product name: EXL 2616) manufactured by graft copolymerizing a monomer mixture containing styrene and methyl methacrylate onto butadiene rubber having an average particle size of 0.15 ㎛ was used.

[0115] (C2) A core-shell type graft copolymer (g-ABS, manufacturer: Lotte Chemical) manufactured by graft copolymerizing 58 wt% of butadiene rubber with an average particle size of 0.3 ㎛ and 42 wt% of styrene and acrylonitrile (weight ratio: 75 / 25) was used.

[0116] (D) Ethylene-methyl acrylate copolymer

[0117] Ethylene-methyl acrylate copolymer (EMA, manufacturer: DOW, product name: ELVALOY 1330AC) was used.

[0118] (E) Glass fiber

[0119] Glass fiber (manufacturer: Nittobo, product name: ECS-03T-187H, epoxy sizing agent applied) was used.

[0120] (F) Brominated epoxy resin

[0121] Brominated epoxy resin (Manufacturer: Woojin Polymer, Product Name: CXB-2000H) was used.

[0122] (G) Aromatic phosphate compound

[0123] (G1) Resorcinol-di(bis-2,6-dimethylphenyl)phosphate (Manufacturer: DAIHACHI, Product name: PX-200) was used.

[0124] (G2) Oligomeric bisphenol-A diphosphate (manufacturer: Yoke Chemical, product name: YOKE BDP) was used.

[0125]

[0126] Examples 1 to 13 and Comparative Examples 1 to 14

[0127] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at about 250°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 44 and a diameter of 45 mm. The manufactured pellets were dried at about 80°C for about 4 hours or more, and then injection-molded using a 6 oz injection molding machine (molding temperature: about 250°C, mold temperature: about 60°C) to produce specimens. The physical properties of the manufactured specimens were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0128]

[0129] Method of measuring physical properties

[0130] (1) Notched Izod impact strength (unit: kgf·cm / cm): The notched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0131] (2) FDI impact strength (unit: J): The FDI (falling dart impact) strength of a 3.2 mm thick specimen was measured by dropping a 7 kg dart from a height of 1 m according to the DuPont drop measurement method.

[0132] (3) Tensile strength (unit: MPa): The tensile strength of a 4 mm thick specimen was measured under conditions of 5 mm / min according to ISO 527.

[0133] (4) Flame retardancy: The flame retardancy of 1.5 mm thick injection molded specimens was measured using the UL-94 vertical test method.

[0134] (5) Heat deflection temperature (unit: ℃): According to ASTM D648, the heat deflection temperature (HDT) of a 6.4 mm thick specimen was measured under the conditions of 1.82 MPa and a heating rate of 120℃ / hr.

[0135] (6) Spiral flow length (unit: mm): The spiral flow length of the specimen was measured after injection molding in a spiral-shaped mold with a width of 15 mm and a thickness of 2 mm under the conditions of a molding temperature of 240°C, a mold temperature of 60°C, an injection pressure of 1,000 MPa, and an injection speed of 60 mm / s.

[0136]

[0137] Example 1234567(A) (parts by weight) 100100100100100100100(B) (parts by weight) 25303530303030(C1) (parts by weight) 77751077(C2) (parts by weight)-------(D) (parts by weight) 1.61.61.61.61.612.5(E) (parts by weight) 36363636363636(F) (parts by weight) 24242424242424(G1) (parts by weight) 1.61.61.61.61.61.61.6(G2) (parts by weight)-------Notched Izod impact strength (kgf·cm / cm) 7.56.75.06.07.55.86.2FDI impact strength (J)12.812.210.511.513.511.512.5Tensile strength (MPa)1,2501,2001,1001,1501,1001,1501,050FlammabilityV-0V-0V-1V-0V-1V-0V-1Heat distortion temperature (℃)140130120133125128123Spiral flow length (mm)320360400370300370385

[0138]

[0139] Example 8910111213(A) (parts by weight)100100100100100100(B) (parts by weight)303030303030(C1) (parts by weight)777777(C2) (parts by weight)------(D) (parts by weight)1.61.61.61.61.61.6(E) (parts by weight)254036363636(F) (parts by weight)242415352424(G1) (parts by weight)1.61.61.61.612.5(G2) (parts by weight)------Notched Izod impact strength (kgf·cm / cm)8.54.07.06.88.06.8FDI impact strength (J)14.08.011.39.512.311.2Tensile strength (MPa)1,0501,8001,1501,1501,2001,200FlammabilityV-0V-1V-1V-0V-1V-0Heat distortion temperature (℃)120145131132130126Spiral flow length (mm)400250320380350380

[0140]

[0141] Comparative Example 1234567(A) (parts by weight) 100100100100100100100(B) (parts by weight) 15453030303030(C1) (parts by weight) 77116-77(C2) (parts by weight) ----7--(D) (parts by weight) 1.61.61.61.61.60.54(E) (parts by weight) 36363636363636(F) (parts by weight) 24242424242424(G1) (parts by weight) 1.61.61.61.61.61.61.6(G2) (parts by weight)-------Notched Izod impact strength (kgf·cm / cm) 8.03.03.510.05.03.57.5FDI impact strength (J)13.06.54.016.06.06.013.0Tensile strength (MPa)1,2809501,2509001,2501,1801,000FlammabilityV-0V-2V-0FailV-1V-0FailHeat distortion temperature (℃)145110135110130130120Spiral flow length (mm)180490380270340365420

[0142]

[0143] Comparative Example 891011121314(A) (parts by weight)100100100100100100100(B) (parts by weight)3030303030303030(C1) (parts by weight)7777777(C2) (parts by weight)-------(D) (parts by weight)1.61.61.61.61.61.61.6(E) (parts by weight)15553636363636(F) (parts by weight)2424545242424(G1) (parts by weight)1.61.61.61.60.14-(G2) (parts by weight)------1.6Notch Izod impact strength (kgf·cm / cm)9.53.07.43.58.53.56.5FDI impact strength (J)14.54.011.56.013.010.510.5Tensile strength (MPa)8002,1001,1001,0501,2501,1001,200FlammabilityV-0FailV-2V-0V-2V-0V-2Heat distortion temperature (℃)115150130133133124126Spiral flow length (mm)480150315400360380380

[0144]

[0145] From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in impact resistance (notched Izod impact strength, FDI impact strength), rigidity (tensile strength), flame retardancy (flame retardancy), heat resistance (heat distortion temperature), and moldability (spiral flow length).

[0146] On the other hand, in the case of Comparative Example 1, where a small amount of aromatic vinyl-cyanide vinyl copolymer resin was applied, it can be seen that the moldability, etc. were reduced, and in the case of Comparative Example 2, where an excessive amount of aromatic vinyl-cyanide vinyl copolymer resin was applied, it can be seen that the impact resistance, rigidity, flame retardancy, heat resistance, moldability, etc. were reduced. In the case of Comparative Example 3, where a small amount of the rubber-modified vinyl-based graft copolymer of the present invention was applied, it can be seen that the impact resistance, etc. were reduced, and in the case of Comparative Example 4, where an excessive amount of the rubber-modified vinyl-based graft copolymer of the present invention was applied, it can be seen that the rigidity, flame retardancy, heat resistance, etc. were reduced, and in the case of Comparative Example 5, where g-ABS (C2) was applied instead of the rubber-modified vinyl-based graft copolymer of the present invention, it can be seen that the impact resistance, etc. were reduced. In the case of Comparative Example 6, where a small amount of ethylene-methyl acrylate copolymer was applied, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 7, where an excessive amount of ethylene-methyl acrylate copolymer was applied, it can be seen that flame retardancy, etc. were reduced. In the case of Comparative Example 8, where a small amount of glass fiber was applied, it can be seen that rigidity, moldability, etc. were reduced, and in the case of Comparative Example 9, where an excessive amount of glass fiber was applied, it can be seen that impact resistance, flame retardancy, moldability, etc. were reduced. In the case of Comparative Example 10, where a small amount of brominated epoxy resin was applied, it can be seen that flame retardancy, etc. were reduced, and in the case of Comparative Example 11, where an excessive amount of brominated epoxy resin was applied, it can be seen that impact resistance, etc. were reduced. In addition, in the case of Comparative Example 12, in which a small amount of the aromatic phosphate compound of the present invention was applied, it can be seen that the flame retardancy, etc. were reduced, and in the case of Comparative Example 13, in which an excessive amount of the aromatic phosphate compound of the present invention was applied, it can be seen that the impact resistance, etc. were reduced, and in the case of Comparative Example 14, in which oligomeric bisphenol-A diphosphate (G2) was applied instead of the aromatic phosphate compound of the present invention, it can be seen that the flame retardancy, etc. were reduced.

[0147]

[0148] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of polycarbonate resin; About 20 to about 40 parts by weight of an aromatic vinyl-cyanide vinyl copolymer resin; About 3 to about 15 parts by weight of a rubber-modified vinyl graft copolymer, wherein a monomer mixture comprising an aromatic vinyl monomer and an alkyl (meth)acrylic monomer is graft-polymerized onto a rubber polymer; About 0.7 to about 3 parts by weight of ethylene-methyl acrylate copolymer; About 20 to about 50 parts by weight of glass fiber; About 10 to about 40 parts by weight of a brominated epoxy resin; and A thermoplastic resin composition comprising about 0.5 to about 3 parts by weight of an aromatic phosphate compound comprising a resorcinol-derived unit.

2. A thermoplastic resin composition according to claim 1, characterized in that the glass fiber is surface-treated with an epoxy sizing agent.

3. A thermoplastic resin composition according to claim 1 or 2, wherein the brominated epoxy resin has a bromine content of about 20 to about 80 wt%.

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the brominated epoxy resin has a weight average molecular weight (Mw) of about 15,000 to about 25,000 g / mol as measured by gel permeation chromatography (GPC).

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the aromatic phosphate compound including the resorcinol-derived unit includes at least one of resorcinol-di(bis-2,6-dimethylphenyl)phosphate, resorcinol bis(diphenylphosphate), and resorcinol di[bis(2,4-ditertiarybutylphenyl)phosphate].

6. A thermoplastic resin composition according to any one of claims 1 to 5, characterized in that the weight ratio of the rubber-modified vinyl graft copolymer and the ethylene-methyl acrylate copolymer is about 1:0.1 to about 1:0.

7.

7. A thermoplastic resin composition according to any one of claims 1 to 6, characterized in that the weight ratio of the brominated epoxy resin and the aromatic phosphate compound is about 1:0.02 to about 1:0.

25.

8. A thermoplastic resin composition according to any one of claims 1 to 7, characterized in that the thermoplastic resin composition has a notched Izod impact strength of about 3.7 to about 20 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

9. A thermoplastic resin composition according to any one of claims 1 to 8, characterized in that the thermoplastic resin composition has an FDI (falling dart impact) impact strength of about 7 to about 20 J of a 3.2 mm thick specimen, measured by dropping a 7 kg dart from a height of 1 m according to the DuPont drop measurement method.

10. A thermoplastic resin composition according to any one of claims 1 to 9, characterized in that the thermoplastic resin composition has a tensile strength of about 1,000 to about 2,000 MPa of a 4 mm thick specimen measured under a condition of 5 mm / min according to ISO 527.

11. A thermoplastic resin composition according to any one of claims 1 to 10, characterized in that the thermoplastic resin composition has a flame retardancy of V-1 or higher in a 1.5 mm thick injection molded specimen measured by the UL-94 vertical test method.

12. A thermoplastic resin composition according to any one of claims 1 to 11, characterized in that the thermoplastic resin composition has a heat distortion temperature (HDT) of about 115 to about 160°C of a 6.4 mm thick specimen measured under the conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

13. A thermoplastic resin composition according to any one of claims 1 to 12, characterized in that the thermoplastic resin composition has a spiral flow length of about 200 to about 450 mm of a specimen measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 2 mm under the conditions of a molding temperature of 240°C, a mold temperature of 60°C, an injection pressure of 1,000 MPa, and an injection speed of 60 mm / s.

14. A molded product characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 13.

15. A battery tray formed from a thermoplastic resin composition according to any one of claims 1 to 13, characterized in that it is an injection-molded product having a size of about 100 to about 800 mm × about 100 to about 700 mm × about 100 to about 500 mm.