KR20200050064A - Thermoplastic resin composition having excellent impact resistance and fluidity and improved dimensional stability and heat aging property and molded article produced using the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition with excellent impact resistance and fluidity and improved dimensional stability and heat aging properties and a molded article manufactured by using the same, and more particularly to a thermoplastic resin composition and a molded article manufactured by using the same, wherein the composition comprises a predetermined content of polycarbonate resin, polyester resin, a core-shell copolymer having a butadiene-based rubbery polymer as a core, a core-shell copolymer having a silicon-based rubbery polymer as a core, and an isosorbide epoxy compound to have excellent impact strength and fluidity, improved dimensional stability and heat aging properties, and a low shrinkage rate, so that the composition can be suitable for manufacturing parts with a large surface area and various designs and prevent impact strength from declining in a hot and humid environment.

Description

The thermoplastic resin composition having excellent impact resistance and fluidity and improved dimensional stability and heat aging property and molded article produced using the same }

The present invention relates to a thermoplastic resin composition having excellent impact resistance and fluidity, improved dimensional stability and thermal aging characteristics, and a molded article manufactured using the same, more specifically, polycarbonate resin, polyester resin, butadiene-based rubber polymer By including a core-shell copolymer having a core, a core-shell copolymer having a silicone-based rubbery polymer as a core, and an isosorbide epoxy compound in a specific content, it has excellent impact strength and fluidity, and has dimensional stability and thermal aging characteristics. It relates to a thermoplastic resin composition capable of preventing a reduction in impact strength in a high-temperature and high-humidity environment, and improving molded products manufactured using the same, which is suitable for manufacturing parts having various surface earthquakes with improved low molding shrinkage and excellent fluidity.

Polybutylene terephthalate resin is excellent in mechanical properties, electrical properties, and chemical resistance, and has a high crystallization speed, so it has excellent molding processability, and has been spotlighted as a thermosetting resin for injection molding and a metal replacement agent. It is widely used in the field of electrical, electronic and electronic industries. However, since polybutylene terephthalate resin has a glass transition temperature of about 40 to 60 ° C, the heat deformation temperature is low, and the molding shrinkage rate is high due to the shrinkage stress caused by crystallization of the resin during injection molding, and the impact resistance at room temperature and low temperature is low. In the area where the size of the injection material was large and the impact resistance was required, many polyester / polycarbonate alloys were studied.

On the other hand, Japanese Patent Publication No. 52-121659 discloses a method of alloying with a polycarbonate resin to compensate for the impact resistance to improve it. However, the ester bond between the polybutylene terephthalate resin and the polycarbonate resin is vulnerable to hydrolysis, and when the resin product is exposed for a long time under hot water and high temperature and high humidity environments, molecular weight decrease due to cutting of the main chain occurs, such as impact resistance. It may cause deterioration of physical properties.

U.S. Patent Nos. 4,393,153, 4,180,494, 4,906,202, 4,034,013, and the like, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), methylmethacrylate-butadiene-styrene A method of improving impact resistance by adding coalescence (MBS) or the like has been proposed, but there is a disadvantage of increasing the molding shrinkage rate by not considering the particle size of the impact modifier. In addition, if only these are added without a compatibilizer, the phases of the polyester and the polycarbonate are unstable, and thus there is a problem in that there is a large variation in mechanical properties.

Under the above background, the present inventors were studying polyester / polycarbonate alloy alloy resins having excellent impact strength and fluidity and excellent dimensional stability and heat aging characteristics, while polyester / polycarbonate alloy resins, 2 The polyester / polycarbonate alloy resin prepared by mixing the composition of a core-shell structured butadiene-based impact modifier, silicone-based impact modifier, and isosorbide epoxy-based compound in an appropriate ratio while maintaining excellent impact strength and fluidity The present invention was completed by confirming that the stability and thermal aging characteristics were improved.

The present invention is intended to solve the problems of the prior art as described above, a core-shell copolymer having a polycarbonate resin, polyester resin, butadiene-based rubbery polymer as a core, and a core-shell copolymer having a silicone-based rubbery polymer as a core. By including a specific amount of coalescing and isosorbide epoxy compounds, it has excellent impact strength and fluidity, and has improved dimensional stability and thermal aging characteristics, and is suitable for manufacturing parts of various designs with a low surface area due to low molding shrinkage and excellent fluidity. And, it is a technical problem to provide a thermoplastic resin composition capable of preventing a drop in impact strength in a high temperature and high humidity environment and a molded article manufactured using the same.

In order to solve the above problems, the present invention is based on 100% by weight of the total composition, (a) 20 to 60% by weight of a polycarbonate resin; (b) 30 to 60% by weight of a polyester resin; (c-1) 1 to 20% by weight of a core-shell copolymer having a butadiene-based rubbery polymer as a core as a first impact modifier, and (c-2) a core having a silicone-based rubbery polymer as a core as a second impact modifier- It provides a thermoplastic resin composition, comprising 1 to 30% by weight of the shell copolymer.

According to another aspect of the present invention, a molded article manufactured using the thermoplastic resin composition is provided.

The thermoplastic resin composition according to the present invention includes a polycarbonate resin, a polyester resin, a core-shell structure butadiene-based, and a silicone-based impact modifier in an appropriate ratio, and at the same time includes an isosorbide epoxy compound, resulting in the final polyester / It has the effect of improving dimensional stability and thermal aging characteristics while maintaining excellent chemical resistance, impact strength, and fluidity of the polycarbonate alloy resin molded article.

Therefore, it can be easily applied to industries requiring the thermoplastic resin, for example, a mobile phone housing, a TV housing, a computer monitor housing, an automobile bumper, a wheel housing, a panel button part, an interior and exterior lighting lamp housing, and the like. .

Hereinafter, the present invention will be described in detail for each component.

1. Thermoplastic polymer composition

(a) Polycarbonate resin

The polycarbonate resin used in the composition of the present invention is not particularly limited as a thermoplastic aromatic polycarbonate resin, and may be used in general, but may be prepared by reacting a divalent phenol and phosgene in the presence of a molecular weight modifier and a catalyst or divalent It is preferable to prepare by using the ester interchange reaction of a carbonate precursor such as phenol and diphenyl carbonate. The divalent phenols are, for example, monomers of a polycarbonate resin having the structure of Formula 1 below.

[Formula 1]

In Formula 1, X is an alkylene group, a straight, branched or cyclic alkylene group having no functional group, sulfide, ether, sulfoxide, sulfone, ketone, one or more functional groups selected from the group consisting of naphthyl and isobutylphenyl Represents a straight, branched or cyclic alkylene group containing, preferably, X may be a straight, branched or cyclic alkylene group having 3 to 6 carbon atoms; R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, such as a straight, branched or 3 to 20 carbon atoms (preferably 3 to 6) cyclic alkyl group having 1 to 20 carbon atoms; n and m are independently an integer from 0 to 4.

Non-limiting examples of the divalent phenols are bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxy Phenyl)-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, 1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and the like. Among them, bisphenol A is representative.

The carbonate precursor is another monomer of the polycarbonate resin, it is preferable to use phosgene (carbonyl chloride). Non-limiting examples of carbonate precursors include carbonyl bromide, bis halo formate, diphenylcarbonate or dimethylcarbonate, and the like.

As the molecular weight modifier, a monofunctional compound similar to a monomer used for preparing a thermoplastic aromatic polycarbonate resin may be used. As a non-limiting example, derivatives thereof based on phenol (e.g., para-isopropylphenol, para-tert-butylphenol, para-cumylphenol, para-isooctylphenol, para-isononylphenol, etc.) Can be used, and other materials such as aliphatic alcohols can be used, and among these, para-tert-butylphenol (PTBP) is most preferably applied.

Examples of the aromatic polycarbonate resin produced by such a divalent phenol, carbonate precursor, and molecular weight modifier include, for example, linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin, and polyester carbonate resin. There is this.

In an exemplary embodiment of the present invention, as a thermoplastic aromatic polycarbonate resin, it is preferable to apply that having a viscosity average molecular weight (Mv) of 15,000 to 40,000 measured in a solution of methylene chloride at 25 ° C, and to apply 17,000 to 35,000. It is more preferable to do. When the viscosity average molecular weight is less than 15,000, mechanical properties such as impact strength and tensile strength may be deteriorated, and when it exceeds 40,000, problems may occur in the processing of the resin due to an increase in melt viscosity. In particular, from the viewpoint of excellent mechanical properties such as impact strength and tensile strength, the viscosity average molecular weight is more preferably 19,000 or more, and from the viewpoint of processability, the viscosity average molecular weight is more preferably 35,000 or less.

In one embodiment of the present invention, (a) polycarbonate resin, based on the total weight of the composition 100% by weight, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more or 45 It may be included by weight or more, 60% by weight or less, 58% by weight or less, 55% by weight or less, 53% by weight or less or 50% by weight or less, for example, 20% to 60% by weight, 25% to 55% by weight Weight%, 30% to 52% by weight, 40% to 50% by weight may be included. When the polycarbonate resin is included in the content range, excellent heat resistance and impact resistance, which are characteristics of the polycarbonate resin, may be exhibited.

(b) polyester resin

The polyester resin may be an aromatic polyester resin, preferably a resin condensed by melt polymerization from terephthalic acid or terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms. In this case, the alkyl means alkyl having 1 to 10 carbon atoms. Specific examples of such an aromatic polyester resin include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, or some of these resins It is possible to use an amorphous resin modified by mixing other monomers, and among them, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, and amorphous polyethylene terephthalate resin are used. good.

The polyester resin preferably has an intrinsic viscosity [η] of 0.85 0.8 to 1.52 ㎗ / g, more preferably 1.03 to 1.22 ㎗ / g. When the polyester resin has an intrinsic viscosity [η] in the above range, excellent mechanical properties and moldability can be secured.

According to one embodiment of the present invention, preferably, polybutylene terephthalate may be used in the polyester resin.

The polybutylene terephthalate is a polymer obtained by condensation polymerization of 1,4-butanediol and terephthalic acid or dimethyl terephthalate as a monomer by direct esterification or transesterification. In addition, to increase the impact strength of the resin, the polybutylene terephthalate is copolymerized with polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or aliphatic polyamide, or improved in impact It can also be used in the form of a modified polybutylene terephthalate blended with components.

In one embodiment of the present invention, (b) the polyester resin, based on 100% by weight of the total composition, 30% by weight or more, 32% by weight or more, 35% by weight or more or 38% by weight or more may be included, 60% by weight Or less, 55% by weight or less, 50% by weight or less, or 45% by weight or less may be included, for example, 30 to 60% by weight, 32 to 55% by weight, 35 to 50% by weight, 38 to 45% by weight. When the above-described polycarbonate resin and polyester resin are included in a content range defined in the present invention, excellent heat resistance and impact resistance, which are characteristics of the polycarbonate resin, are expressed, and excellent chemical resistance and fluidity can be secured.

(c) Impact modifier

The impact modifier according to the present invention is (c-1) a first impact modifier that is a core-shell copolymer having a butadiene-based rubbery polymer as a core and (c-2) a second impact that is a core-shell copolymer having a silicone-based rubbery polymer as a core. It includes a reinforcing agent, the content of the second impact modifier (c-2) is greater than the first impact modifier (c-1), according to the type and content of the impact modifier, fluidity, impact strength of the thermoplastic resin composition , Dimensional stability, thermal aging characteristics, etc. can all be improved.

In a specific example, the weight ratio (c-1: c-2) of the (c-1) first impact modifier and (c-2) second impact modifier is 1: 1.5 to 1: 4.5, preferably 1: 1.7 It may be 1 to 4, more preferably 1: 1.9 to 1: 3.5. Since the gap between the rubbery polymer cores in the matrix resin can be reduced in the above range, the processability, impact resistance, dimensional stability, and thermal aging characteristics of the thermoplastic resin composition can be further improved.

(c-1) First impact modifier

The first impact modifier according to one embodiment of the present invention is 40 to 99% by weight, for example, 50 to 90% by weight of a butadiene-based rubbery polymer core and 1 to 60% by weight, for example 10 to 50% by weight It may be a core-shell type impact modifier comprising a shell. In the above range, the heat aging characteristics, impact resistance, and the like of the thermoplastic resin composition may be excellent.

In one embodiment, the first impact modifier is prepared by graft polymerization of a shell component comprising styrene and acrylonitrile on the core (rubber polymer) to form a shell comprising a styrene repeating unit and an acrylonitrile repeating unit. It may be, the polymerization may be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization.

In one embodiment, the core of the first impact modifier may be a butadiene-based rubbery polymer (rubber) such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and combinations thereof. Further, the average particle size (D ₅₀ ) of the rubbery polymer may be 220 to 400 nm, for example, 250 to 350 μm. In the above range, the thermoplastic resin composition may have excellent impact resistance, processability, and thermal aging characteristics.

In one embodiment, the shell of the first impact modifier is 60 to 99% by weight, for example 70 to 95% by weight of styrene repeat units and 1 to 40% by weight, for example 5 to 30% by weight of acrylonitrile It may contain repeating units. In the above range, the impact resistance, processability, and appearance of the thermoplastic resin composition may be excellent.

In one embodiment, the first impact modifier may include 1% by weight or more, 2% by weight or more, or 3% by weight or more with respect to 100% by weight of the thermoplastic resin composition, 20% by weight or less, 15% by weight or less, 10% by weight It may be included below or 8% by weight, for example, 1 to 20% by weight, 1 to 15% by weight or 1 to 10% by weight. In the above range, the processability, thermal aging characteristics, impact resistance, and balance of physical properties of the thermoplastic resin composition may be excellent.

(c-2) Second impact modifier

The second impact modifier according to an embodiment of the present invention is 60 to 99% by weight, for example, 70 to 90% by weight of a silicone-based rubbery polymer core, and 1 to 40% by weight, for example 10 to 30% by weight It may be a core-shell type impact modifier comprising a shell. In the above range, the dimensional stability and processability of the thermoplastic resin composition may be excellent.

In one embodiment, the second impact modifier comprises a methyl methacrylate repeat unit and a methyl methacrylate repeat unit by graft polymerization of a shell component comprising methyl methacrylate and methyl acrylate on the core (rubber polymer). It can be prepared by forming a shell, the polymerization can be carried out by known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization.

In one embodiment, the core of the second impact modifier may have two or more unsaturated reactors. As an example, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diacetoxy methylvinylsilane, 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane, 2,4,6 , 8-tetramethyl tetravinyl cyclotetrasiloxane, α, ω-divinyl polydimethylsiloxane, vinyl-modified dimethylsiloxane, and mixtures thereof.

In addition, the average particle size (D ₅₀ ) of the rubbery polymer may be 100 to 180 nm, for example, 100 to 150 nm. In the above range, the dimensional stability, processability, and appearance of the thermoplastic resin composition may be excellent.

In one embodiment, the shell of the second impact modifier is 60 to 99.9% by weight, for example 70 to 99.5% by weight of methyl methacrylate repeating units and 0.1 to 40% by weight, for example 0.5 to 30% by weight It may include a methyl acrylate repeating unit. In the above range, the processability, appearance, and the like of the thermoplastic resin composition may be excellent.

In one embodiment, the second impact modifier may include 1 wt% or more, 2 wt% or more, 3 wt% or more, or 5 wt% or more with respect to 100 wt% of the thermoplastic resin composition, and 30 wt% or less, 25 wt% Or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less may be included, for example, 1 to 30% by weight, 3 to 20% by weight or 5 to 10% by weight. In the above range, the dimensional stability of the thermoplastic resin composition, processability, appearance and balance of these properties may be excellent.

(d) Isosorbide  Epoxy compounds

The isosorbide epoxy compound contained in the thermoplastic resin composition of the present invention may be derived from a natural raw material, and may be a compound represented by the following Chemical Formula 2 in one embodiment.

[Formula 2]

Here, n is an integer from 0 to 300.

The natural material-derived isosorbide epoxy compound represented by Chemical Formula 2 according to the present invention may be formed of a molecular structure in which two epoxy groups are bonded to an isosorbide skeleton.

In other words, by applying Isosorbide Formula 1 derived from carbohydrate-based natural raw materials as a basic skeleton, it replaces bisphenol A, which is derived from petroleum resources and is an environmental hormone, and can be applied to eco-friendly applications, food and human contact applications, etc. Can be.

In one embodiment, the content of the isosorbide epoxy compound, 100% by weight of the thermoplastic resin composition, may be included in 0.1 to 3% by weight, preferably 0.1% to 2% by weight, more preferably 0.2% by weight % To 1.5% by weight.

Thermoplastic resin composition according to an embodiment of the present invention, in addition to the above components, in the range that does not inhibit the effect of the present invention, flame retardants, antioxidants, lubricants, mold release agents, nucleating agents, antistatic agents, ultraviolet (UV) stabilizers, pigments, Additives such as dyes and combinations thereof may be further included. When using the additive, the content may be 20 wt% or less, for example, 0.1 to 10 wt%, based on 100 wt% of the thermoplastic resin composition, but is not limited thereto.

2. Molded product and its manufacturing method

The thermoplastic resin composition according to an embodiment of the present invention may be prepared by a known method. For example, after mixing the above-described components and additives of the present invention, it can be melt extruded in an extruder and produced in pellet form.

According to another embodiment of the present invention, there is provided a molded article manufactured using the thermoplastic resin composition of one embodiment of the present invention. The thermoplastic resin composition is a molded product in a field in which excellent dimensional stability and thermal aging characteristics as well as fluidity and impact strength are important, for example, automobile parts, mechanical parts, electrical and electronic parts, office equipment such as computers, miscellaneous goods, etc. It can be used for the purpose, in particular, it can be preferably applied to automotive interior and exterior products such as automobile bumper back beams, wheel covers, garnishes, crash pads, panels, lighting housings, and the like.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, these examples are only for understanding the present invention, and the scope of the present invention is not limited to these examples in any sense.

[ Example  And Comparative example ]

The components used in the examples and comparative examples are specifically as follows.

(a) polycarbonate

A polycarbonate thermoplastic resin (TRILOY 3030PJ, Samyang Co.) having a viscosity average molecular weight of 30,000 was used.

(b) polyester

A polybutylene terephthalate resin (TRILOY 1700S, Samyang Co.) having an intrinsic viscosity of 1.1 Pa / g was used.

(c) Impact modifier

(c-1) First impact modifier

As a rubbery polymer (core), 50% by weight of polybutadiene rubber having an average particle diameter of 340 nm is prepared by graft copolymerization of 50% by weight of styrene and acrylonitrile (styrene / acrylonitrile (weight ratio) = 75/25) as a shell component. A core-shell structured butadiene-based rubber-modified graft copolymer (g-ABS) was used.

(c-2) Second impact modifier

As a rubbery polymer (core), methyl methacrylate and methyl acrylate (methyl methacrylate / methyl acrylate (weight ratio) = 99) as a shell component in 70% by weight of rubber composed of dimethylsiloxane and butyl acrylate having an average particle diameter of 110 nm. / 1) A silicone-based rubber-modified graft copolymer having a core-shell structure prepared by graft copolymerization of 30% by weight was used.

(d) Isosorbide  Epoxy compounds

As a plant-derived raw material, an isosorbide-containing epoxy compound (isosorbide diglycidyl ether) was used.

Example  1 to 6 and Comparative example  1 to 5

Eco-friendly polycarbonate and polyester resin, impact modifier, and isosorbide epoxy compound are mixed and uniformly dispersed using a Henschel mixer with the components and contents shown in Table 1 below, followed by L / D = 48 and Φ = 25mm twin-screw melt mixing extruder. Extruded under conditions of a melting temperature of 260 ° C, a screw rotation speed of 300 rpm, a first vent pressure of about -600 mmHg, and a self-feeding rate of 30 kg / h. After the extruded strand was cooled in water, the pellets were prepared by cutting with a rotary cutter. After drying the pellets at 90 to 100 ° C. for 4 hours, injection molding was performed at a temperature of 250 to 270 ° C. to prepare specimens. .

Property evaluation

For each specimen prepared in the above Examples and Comparative Examples, characteristics were measured by the following method, and the results are shown in Table 2.

(1) Flow Index (MI)

After drying at 90 ° C. for 4 hours in a pellet state according to ASTM D1238, the amount of flowed for 10 minutes at 250 ° C. and 5 kg load was measured.

(2) IZOD  Impact properties

A specimen of 1/8 "thickness was prepared. Impact strength was measured according to ASTM D256.

(3) Heat aging  Test

The obtained impact specimen was heat treated at 300 ° C. for 120 hours in a hot air dryer, and evaluated as an impact strength retention rate according to ASTM D256.

(4) Molding shrinkage

According to ASTM D955, a shrinkage ratio in the flow direction was evaluated using a disc specimen having a diameter of 100 mm, and the unit is%.

As can be seen from Table 2, the resin composition according to the embodiment of the present invention exhibited a state in which all of the measured properties were excellently balanced. In the case of the thermal aging test, a retention rate of 75% or higher was observed in all compositions, and excellent IZOD impact strength characteristics of 60 or higher were exhibited. In addition, it maintains an MI flow index of 25 or more, and realizes excellent molding shrinkage at a level of 0.7 or less. On the other hand, in the case of the comparative composition, the fluidity, the IZOD impact strength, the thermal aging retention rate, and the molding shrinkage ratio showed unbalanced characteristics compared to the examples, which can significantly degrade various characteristics of the final product.

As can be seen from this, when the molded article is manufactured of the thermoplastic resin of the present invention, excellent characteristics such as dimensional stability and thermal aging stability can be realized while maintaining excellent impact resistance and flow characteristics.

Claims (7)

Based on 100% by weight of the total composition,
(a) 20 to 60% by weight of polycarbonate resin;
(b) 30 to 60% by weight of a polyester resin;
(c-1) 1 to 20% by weight of a core-shell copolymer having a butadiene-based rubbery polymer as a core as the first impact modifier; And
(c-2) As a second impact modifier, a thermoplastic resin composition comprising 1 to 30% by weight of a core-shell copolymer having a silicone-based rubbery polymer as a core. The thermoplastic resin composition according to claim 1, further comprising (d) 0.1 to 3% by weight of an isosorbide epoxy compound. The polyester resin according to claim 1, wherein the polyester resin is polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin or these resins. It is selected from the group consisting of an amorphous, modified polyester resin, thermoplastic resin composition. The average particle diameter (D50) of the butadiene-based rubber polymer of the (c-1) first impact modifier is 200 to 400 nm, and (c-2) the average particle diameter of the silicone-based rubber polymer of the second impact modifier (1). D50) is a thermoplastic resin composition of 100 to 180 nm. The thermoplastic resin composition according to claim 1, wherein the weight ratio (c-1: c-2) of the (c-1) first impact modifier and the (c-2) second impact modifier is 1: 1.5 to 1: 4.5. The thermoplastic resin composition according to claim 2, wherein the (d) isosorbide epoxy compound is a compound represented by Formula 2 below:
[Formula 2]

Here, n is an integer from 0 to 300. A molded article manufactured using the thermoplastic resin composition according to any one of claims 1 to 6.