KR20250081029A - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention is characterized by including: 100 parts by weight of a polycarbonate resin; 20 to 40 parts by weight of an aromatic vinyl-cyanide vinyl copolymer resin; 3 to 15 parts by weight of a rubber-modified vinyl graft copolymer obtained by graft polymerizing a monomer mixture containing an aromatic vinyl monomer and an alkyl (meth)acrylic monomer onto a rubbery polymer; 0.7 to 3 parts by weight of an ethylene-methyl acrylate copolymer; 20 to 50 parts by weight of a glass fiber; 10 to 40 parts by weight of a brominated epoxy resin; and 0.5 to 3 parts by weight of an aromatic phosphate compound containing a resorcinol-derived unit. The thermoplastic resin composition is excellent in impact resistance, rigidity, flame retardancy, heat resistance, moldability, and a balance of their physical properties.

Description

Thermoplastic resin composition and molded article produced therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

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 physical properties, and a molded article manufactured therefrom.

Thermoplastic resin compositions have lower specific gravity than glass and metal, and have excellent physical properties such as formability and impact resistance, and are therefore useful for housings of electrical/electronic products, interior/exterior materials of automobiles, and exterior materials for buildings. Among these thermoplastic resin compositions, a thermoplastic resin composition in which an aromatic vinyl-vinyl cyanide copolymer resin, such as an acrylonitrile-butadiene-styrene (ABS) copolymer resin, is mixed with a polycarbonate (PC) resin can improve processability and chemical resistance without lowering the impact resistance, heat resistance, etc. of the polycarbonate resin, and can also reduce costs, and thus is utilized for various purposes.

Due to the demand for eco-friendly products, electric vehicle sales are on the rise, and it is expected that electric vehicle sales will reach approximately 35 million units in 2030. As the electric vehicle market grows, electric vehicle factories are being established all over the world, including in Europe, the Americas, and China, and battery manufacturers are also building factories near electric vehicle factories to supply batteries for electric vehicles. Electric vehicle batteries are installed in electric vehicles in the form of cells → modules → packs, and the demand for trays in battery production lines for assembling batteries into packs is increasing. Materials used for battery trays require high flame resistance and heat resistance to prevent battery thermal runaway fires, and high impact resistance and rigidity to protect against damage during assembly and movement.

Therefore, there is a need to develop a thermoplastic resin composition that has excellent impact resistance, rigidity, flame retardancy, heat resistance, formability, and a balance of these properties.

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

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.

Another object of the present invention is to provide a molded product formed from the thermoplastic resin composition.

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

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is characterized by comprising: 100 parts by weight of a polycarbonate resin; 20 to 40 parts by weight of an aromatic vinyl-cyanide vinyl copolymer resin; 3 to 15 parts by weight of a rubber-modified vinyl graft copolymer obtained by graft polymerizing a monomer mixture containing an aromatic vinyl monomer and an alkyl (meth)acrylic monomer onto a rubbery polymer; 0.7 to 3 parts by weight of an ethylene-methyl acrylate copolymer; 20 to 50 parts by weight of a glass fiber; 10 to 40 parts by weight of a brominated epoxy resin; and 0.5 to 3 parts by weight of an aromatic phosphate compound containing a resorcinol-derived unit.

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

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

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

5. In the above specific examples 1 to 4, 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].

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

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

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

9. In the above 1 to 8 specific examples, the thermoplastic resin composition may have an FDI (falling dart impact) impact strength of 7 to 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. In the above specific examples 1 to 9, the thermoplastic resin composition may have a tensile strength of 1,000 to 2,000 MPa of a 4 mm thick specimen measured under a condition of 5 mm/min according to ISO 527.

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.

12. In the above specific examples 1 to 11, the thermoplastic resin composition may have a heat distortion temperature (HDT) of 115 to 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.

13. In the above specific examples 1 to 12, the thermoplastic resin composition may have a spiral flow length of 200 to 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. 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.

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 100 to 800 mm × 100 to 700 mm × 100 to 500 mm.

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.

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

A thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) an aromatic vinyl-cyanide vinyl 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.

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

(A) Polycarbonate resin

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 diphenols (aromatic diol compounds) with a precursor such as phosgene, halogen formate, or carbonic diester can be used.

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, called bisphenol-A, can be used.

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 for polymerization.

In specific examples, the polycarbonate resin can be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin can be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor, for example, a difunctional carboxylic acid.

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

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

(B) Aromatic vinyl-cyanide vinyl copolymer resin

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 like 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.

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.

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

In specific examples, the cyanide vinyl 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 cyanide vinyl monomer may be 10 to 40 wt%, for example, 15 to 35 wt%, based on 100 wt% of the total aromatic vinyl-cyanide vinyl copolymer resin. In this range, the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, appearance characteristics, etc.

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

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

(C) Rubber-modified vinyl graft copolymer

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, to improve the impact resistance, rigidity, flame retardancy, heat resistance, moldability, and the like of a thermoplastic resin composition in terms of their physical property balance. The rubber-modified vinyl graft copolymer can be used, in which a monomer mixture including an aromatic vinyl monomer and an alkyl (meth)acrylic monomer is graft-polymerized onto a rubber polymer. 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.

In specific examples, the rubber polymer may include diene rubbers such as polybutadiene, poly(acrylonitrile-butadiene), and saturated rubbers obtained by adding hydrogen to 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 applied 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.

In a specific example, the rubber polymer (rubber particles) may have an average particle size of 0.05 to 6 ㎛, for example, 0.15 to 4 ㎛, specifically, 0.25 to 3.5 ㎛. In the above 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) can 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, 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).

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

In a specific example, the aromatic vinyl monomer is one which can be graft copolymerized to the rubber polymer, and examples thereof include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-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 10 to 90 wt%, for example, 20 to 80 wt%, based on 100 wt% of the monomer mixture. In this range, the moldability, impact resistance, and the like of the thermoplastic resin composition may be excellent.

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 10 to 90 wt%, for example, 20 to 80 wt%, based on 100 wt% of the monomer mixture. In this range, the moldability, impact resistance, and the like of the thermoplastic resin composition may be excellent.

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 50 wt% or less out of 100 wt% of the monomer mixture, but is not limited thereto.

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 thereof, are grafted onto a butadiene-based rubber polymer, and a copolymer (g-MABS) in which a styrene monomer, an acrylonitrile monomer, and methyl methacrylate are grafted onto a butadiene-based rubber polymer. For example, g-MBS and the like can be used.

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

(D) Ethylene-methyl acrylate copolymer

According to one specific example of the present invention, an ethylene-methyl acrylate copolymer can be applied to a polycarbonate resin together with an aromatic vinyl-cyanide vinyl 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, etc. of a thermoplastic resin composition.

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 contain 50 to 95 wt%, for example, 70 to 93 wt%, of ethylene repeating units and 5 to 50 wt%, for example, 7 to 30 wt%, of methyl acrylate repeating units. In the above range, the impact resistance, etc. of the thermoplastic resin composition can be excellent.

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.

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

In a specific example, the ethylene-methyl acrylate copolymer may be included in an amount of 0.7 to 3 parts by weight, for example, 1 to 2.5 parts by weight, relative to 100 parts by weight of the polycarbonate resin. If the content of the ethylene-methyl acrylate copolymer is less than 0.7 parts by weight relative to 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 3 parts by weight, there is a concern that the flame retardancy, etc. of the thermoplastic resin composition may be reduced.

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 1:0.1 to 1:0.7, for example, 1:0.1 to 1:0.5, and specifically 1:0.14 to 1:0.36. In the above range, the impact resistance, moldability, etc. of the thermoplastic resin composition may be more excellent.

(E) Glass fiber

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, etc. of a thermoplastic resin composition.

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

In a specific example, the circular cross-section glass fiber may be a glass fiber having an average diameter of a circular cross-section of 5 to 15 ㎛, for example, 6 to 14 ㎛, as measured by an optical microscope. In the above range, the rigidity, impact resistance, etc. of the thermoplastic resin composition may be excellent.

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

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

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

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

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

(F) Brominated epoxy resin

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-cyanide vinyl 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.

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

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

In a specific example, the brominated epoxy resin may be included in an amount of 10 to 40 parts by weight, for example, 15 to 35 parts by weight, relative to 100 parts by weight of the polycarbonate resin. If the content of the brominated epoxy resin is less than 10 parts by weight relative to 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 40 parts by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

(G) Aromatic phosphate compound

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-cyanide vinyl 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.

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.

In a specific example, the aromatic phosphate compound may be included in an amount of 0.5 to 3 parts by weight, for example, 1 to 2.5 parts by weight, relative to 100 parts by weight of the polycarbonate resin. If the content of the aromatic phosphate compound is less than 0.5 parts by weight relative to 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 3 parts by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

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 1:0.02 to 1:0.25, for example, 1:0.04 to 1:0.11. In this range, the flame retardancy, fluidity, etc. of the thermoplastic resin composition may be more excellent.

The thermoplastic resin composition according to one specific example 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-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, dyes, pigments, and mixtures thereof. When the additives are used, the content thereof may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the polycarbonate resin.

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 230 to 300°C, for example, 240 to 290°C, using a conventional twin-screw extruder.

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

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

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

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.

In a specific example, the thermoplastic resin composition may have a heat distortion temperature (HDT) of 115 to 160°C, for example, 118 to 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.

In a specific example, the thermoplastic resin composition may be injection-molded 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, and the spiral flow length of the specimen measured may be 200 to 450 mm, for example, 220 to 430 mm.

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 belongs.

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

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

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

Example

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

(A) Polycarbonate resin

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

(B) Aromatic vinyl-cyanide vinyl copolymer resin

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

(C) Rubber-modified vinyl graft copolymer

(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.

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

(D) Ethylene-methyl acrylate copolymer

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

(E) Glass fiber

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

(F) Brominated epoxy resin

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

(G) Aromatic phosphate compound

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

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

Examples 1 to 11 and Comparative Examples 1 to 12

The above-described components were added in the contents as shown in Tables 1, 2, 3, and 4 below, and then extruded at about 250°C to manufacture pellets. The extrusion was performed using a twin-screw extruder with L/D=44 and a diameter of 45 mm, and 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 manufacture specimens. The physical properties of the manufactured specimens were evaluated by the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

Method of measuring physical properties

(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.

(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.

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

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

(5) Heat distortion temperature (unit: ℃): According to ASTM D648, the heat distortion 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.

(6) Spiral flow length (unit: mm): The spiral flow length of the specimen was measured after injection molding in a spiral 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.

Example 1 2 3 4 5 6 7 (A) (weight) 100 100 100 100 100 100 100 (B) (Weight) 25 30 35 30 30 30 30 (C1) (weight) 7 7 7 5 10 7 7 (C2) (weight) - - - - - - - (D) (weight) 1.6 1.6 1.6 1.6 1.6 1 2.5 (E) (weight) 36 36 36 36 36 36 36 (F) (Weight) 24 24 24 24 24 24 24 (G1) (Weight) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 (G2) (Weight) - - - - - - - Notched Izod impact strength (kgf cm/cm) 7.5 6.7 5.0 6.0 7.5 5.8 6.2 FDI impact strength (J) 12.8 12.2 10.5 11.5 13.5 11.5 12.5 Tensile strength (MPa) 1,250 1,200 1,100 1,150 1,100 1,150 1,050 Flame retardancy V-0 V-0 V-1 V-0 V-1 V-0 V-1 Heat deflection temperature (℃) 140 130 120 133 125 128 123 Spiral flow length (mm) 320 360 400 370 300 370 385

Example 8 9 10 11 12 13 (A) (weight) 100 100 100 100 100 100 (B) (Weight) 30 30 30 30 30 30 (C1) (weight) 7 7 7 7 7 7 (C2) (weight) - - - - - - (D) (weight) 1.6 1.6 1.6 1.6 1.6 1.6 (E) (weight) 25 40 36 36 36 36 (F) (Weight) 24 24 15 35 24 24 (G1) (Weight) 1.6 1.6 1.6 1.6 1 2.5 (G2) (Weight) - - - - - - Notched Izod impact strength (kgf cm/cm) 8.5 4.0 7.0 6.8 8.0 6.8 FDI impact strength (J) 14.0 8.0 11.3 9.5 12.3 11.2 Tensile strength (MPa) 1,050 1,800 1,150 1,150 1,200 1,200 Flame retardancy V-0 V-1 V-1 V-0 V-1 V-0 Heat deflection temperature (℃) 120 145 131 132 130 126 Spiral flow length (mm) 400 250 320 380 350 380

Comparative example 1 2 3 4 5 6 7 (A) (weight) 100 100 100 100 100 100 100 (B) (Weight) 15 45 30 30 30 30 30 (C1) (weight) 7 7 1 16 - 7 7 (C2) (weight) - - - - 7 - - (D) (weight) 1.6 1.6 1.6 1.6 1.6 0.5 4 (E) (weight) 36 36 36 36 36 36 36 (F) (Weight) 24 24 24 24 24 24 24 (G1) (Weight) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 (G2) (Weight) - - - - - - - Notched Izod impact strength (kgf cm/cm) 8.0 3.0 3.5 10.0 5.0 3.5 7.5 FDI impact strength (J) 13.0 6.5 4.0 16.0 6.0 6.0 13.0 Tensile strength (MPa) 1,280 950 1,250 900 1,250 1,180 1,000 Flame retardancy V-0 V-2 V-0 Fail V-1 V-0 Fail Heat deflection temperature (℃) 145 110 135 110 130 130 120 Spiral flow length (mm) 180 490 380 270 340 365 420

Comparative example 8 9 10 11 12 13 14 (A) (weight) 100 100 100 100 100 100 100 (B) (Weight) 30 30 30 30 30 30 30 (C1) (weight) 7 7 7 7 7 7 7 (C2) (weight) - - - - - - - (D) (weight) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 (E) (weight) 15 55 36 36 36 36 36 (F) (Weight) 24 24 5 45 24 24 24 (G1) (Weight) 1.6 1.6 1.6 1.6 0.1 4 - (G2) (Weight) - - - - - - 1.6 Notched Izod impact strength (kgf cm/cm) 9.5 3.0 7.4 3.5 8.5 3.5 6.5 FDI impact strength (J) 14.5 4.0 11.5 6.0 13.0 10.5 10.5 Tensile strength (MPa) 800 2,100 1,100 1,050 1,250 1,100 1,200 Flame retardancy V-0 Fail V-2 V-0 V-2 V-0 V-2 Heat deflection temperature (℃) 115 150 130 133 133 124 126 Spiral flow length (mm) 480 150 315 400 360 380 380

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).

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 could be seen that the moldability, etc. were deteriorated, and in the case of Comparative Example 2 where an excessive amount of aromatic vinyl-cyanide vinyl copolymer resin was applied, it could be seen that impact resistance, rigidity, flame retardancy, heat resistance, moldability, etc. were deteriorated. 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 could be seen that impact resistance, etc. were deteriorated, 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 could be seen that rigidity, flame retardancy, heat resistance, etc. were deteriorated, 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 could be seen that impact resistance, etc. were deteriorated. 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 deteriorated, 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 deteriorated. In the case of Comparative Example 8 where a small amount of glass fiber was applied, it can be seen that rigidity, formability, etc. were deteriorated, 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, formability, etc. were deteriorated. 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 deteriorated, 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 deteriorated. In addition, in the case of Comparative Example 12, where a small amount of the aromatic phosphate compound of the present invention was applied, it can be seen that flame retardancy, etc. were reduced, and in the case of Comparative Example 13, where an excessive amount of the aromatic phosphate compound of the present invention was applied, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 14, where oligomeric bisphenol-A diphosphate (G2) was applied instead of the aromatic phosphate compound of the present invention, it can be seen that flame retardancy, etc. were reduced.

The present invention has been described with reference to embodiments. Those skilled in the art will understand that the present invention can be implemented in modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated by the claims, not the foregoing description, and all differences within the scope equivalent thereto should be interpreted as being included in the present invention.

Claims (15)

100 parts by weight of polycarbonate resin;
20 to 40 parts by weight of aromatic vinyl-cyanide vinyl copolymer resin;
3 to 15 parts by weight of a rubber-modified vinyl graft copolymer, wherein a monomer mixture containing an aromatic vinyl monomer and an alkyl (meth)acrylic monomer is graft-polymerized onto a rubber polymer;
0.7 to 3 parts by weight of ethylene-methyl acrylate copolymer;
20 to 50 parts by weight of glass fiber;
10 to 40 parts by weight of brominated epoxy resin; and
A thermoplastic resin composition comprising 0.5 to 3 parts by weight of an aromatic phosphate compound containing a resorcinol-derived unit.
A thermoplastic resin composition, characterized in that in claim 1, the glass fiber is surface-treated with an epoxy sizing agent.
A thermoplastic resin composition according to claim 1, wherein the brominated epoxy resin has a bromine content of 20 to 80 wt%.
A thermoplastic resin composition in claim 1, wherein the brominated epoxy resin has a weight average molecular weight (Mw) of 15,000 to 25,000 g/mol as measured by gel permeation chromatography (GPC).
A thermoplastic resin composition, characterized in that in claim 1, 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].
A thermoplastic resin composition, characterized in that in claim 1, the weight ratio of the rubber-modified vinyl graft copolymer and the ethylene-methyl acrylate copolymer is 1:0.1 to 1:0.7.
A thermoplastic resin composition, characterized in that in claim 1, the weight ratio of the brominated epoxy resin and the aromatic phosphate compound is 1:0.02 to 1:0.25.
In claim 1, the thermoplastic resin composition is characterized in that the notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 is 3.7 to 20 kgf·cm/cm.
In the first paragraph, the thermoplastic resin composition is characterized in that the FDI (falling dart impact) impact strength 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, is 7 to 20 J.
In the first paragraph, the thermoplastic resin composition is a thermoplastic resin composition characterized in that the tensile strength of a 4 mm thick specimen measured under the condition of 5 mm/min according to ISO 527 is 1,000 to 2,000 MPa.
In claim 1, the thermoplastic resin composition is characterized in that the flame retardancy of a 1.5 mm thick injection molded specimen measured by the UL-94 vertical test method is V-1 or higher.
In the first paragraph, the thermoplastic resin composition is a thermoplastic resin composition characterized in that the heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under the conditions of 1.82 MPa and a heating rate of 120°C/hr is 115 to 160°C according to ASTM D648.
In claim 1, the thermoplastic resin composition is characterized in that the spiral flow length of a specimen measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 2 mm is 200 to 450 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.
A molded product characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 13.
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 100 to 800 mm × 100 to 700 mm × 100 to 500 mm.