Thermoplastic resin composition, method for preparing same, and molded article

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition comprising 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C), the base resin comprises 79 to 86% by weight of a non-graft copolymer (A) comprising an alkyl (meth) acrylate, an alkyl-substituted styrene-based compound, and a vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B), said graft copolymer (B) comprising a graft copolymer (b-1) selected from the group consisting of graft copolymers obtained by grafting alkyl (meth) acrylates, aromatic vinyl compounds, and vinyl cyanides onto conjugated diene rubbers having an average particle size of 200 to 500 nm and one or more of the group consisting of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm, a method for preparing the thermoplastic resin composition, and a molded article comprising the thermoplastic resin composition. According to the present invention, the present invention has the effect of providing a thermoplastic resin composition which has excellent mechanical properties, heat resistance, chemical resistance, and sunscreen properties, has high blackness, and can be applied to an uncoated molded article due to a uniform injection appearance; also provided are a method for preparing the thermoplastic resin composition and a molded article comprising the thermoplastic resin composition.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10 - 2023 - 0146275, filed on October 30, 2023, and Korean Patent Application No. 10 - 2024 - 0117467, refiled on August 30, 2024, with the Korean Intellectual Property Office, and based on the priority of the above patents, their disclosures are incorporated herein by reference. Technical Field

[0003] The present invention relates to a thermoplastic resin, a method for preparing the same, and a molded article containing the same, and more particularly, to a thermoplastic resin composition having excellent mechanical properties, heat resistance, chemical resistance, and sunscreen resistance, having a high blackness, and being applicable to an unpainted molded article by achieving a uniform injection appearance, a method for preparing the same, and a molded article containing the same. Background Art

[0004] Recently, automobile manufacturers have made various attempts to omit the painting process of automobile parts in order to achieve environmental friendliness and cost reduction. That is, research is being conducted on unpainted automobile parts. In order to produce unpainted automobile parts, excellent appearance quality and automobile reliability evaluation must be satisfied.

[0005] Resin compositions based on PMMA resin, such as acrylate - styrene - acrylonitrile resin (hereinafter referred to as "ASA resin") / polymethyl methacrylate resin (hereinafter referred to as "PMMA resin") alloy and acrylonitrile - butadiene - styrene resin (hereinafter referred to as "ABS resin") / PMMA resin alloy, can achieve a high level of blackness, but are difficult to apply to products due to limitations in achieving reliable quality.

[0006] In particular, in order to achieve the high heat resistance, chemical resistance, and sunscreen resistance required for interior automotive parts, materials obtained by adding a heat - resistant resin to a PMMA - resin - based resin composition have been developed. However, due to poor compatibility between the resins, the desired appearance quality and uniform physical properties cannot be obtained, and the heat resistance and chemical resistance are also insufficient.

[0007] Therefore, there is a need to develop a material having excellent heat resistance, chemical resistance, and appearance quality and being applicable to an unpainted molded article.

[0008] [Prior Art Documents]

[0009] [Patent Documents]

[0010] KR 10 - 0417066B1 Summary of the Invention

[0011] Technical problem

[0012] Therefore, the present invention is made in view of the above problems, and an object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance, having a high blackness, and being applicable to unpainted molded articles by achieving a uniform injection appearance.

[0013] Another object of the present invention is to provide a method for preparing a thermoplastic resin composition.

[0014] Still another object of the present invention is to provide a molded article containing the thermoplastic resin composition.

[0015] The above objects and other objects can be achieved by the present invention described below.

[0016] Technical solution

[0017] I) According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C), wherein the base resin comprises 79 to 86% by weight of a non-grafted copolymer (A) comprising an alkyl (meth)acrylate, an alkyl-substituted styrenic compound, and a vinyl cyanide, and 14 to 21% by weight of a copolymer (B) comprising a rubber component, an aromatic vinyl compound, and a vinyl cyanide. wherein the brightness value (L value) of the thermoplastic resin composition measured by a color difference meter in a manner excluding the specular reflection component (SCE) for a square disk-shaped injection specimen according to the CIE1976 L*a*b* color system is 1.5 or less; and the heat distortion temperature of the thermoplastic resin composition measured at 1.8 MPa according to ISO 75 / Be is 85°C or higher.

[0018] II) According to I), the rubber component may be a conjugated diene rubber, an alkyl acrylate rubber, or a mixture thereof.

[0019] III) According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C), wherein the base resin comprises 79 to 86% by weight of a non-grafted copolymer (A) containing (meth)acrylic acid alkyl ester, alkyl-substituted styrene compounds, and vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B), and the graft copolymer (B) comprises one or more selected from the group consisting of a graft copolymer (b-1) obtained by grafting (meth)acrylic acid alkyl ester, aromatic vinyl compound, and vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an acrylic acid alkyl ester rubber having an average particle size of 50 to 400 nm.

[0020] IV) According to I) to III), based on its total weight, the non-grafted copolymer (A) may preferably comprise 30 to 60% by weight of (meth)acrylic acid alkyl ester, 20 to 50% by weight of alkyl-substituted styrene compounds, and 5 to 35% by weight of vinyl cyanide.

[0021] V) According to I) to IV), based on its total weight, the graft copolymer (b-1) may preferably comprise 35 to 65% by weight of conjugated diene rubber, 20 to 50% by weight of (meth)acrylic acid alkyl ester, 1 to 30% by weight of aromatic vinyl compound, and 1 to 20% by weight of vinyl cyanide.

[0022] VI) According to I) to V), based on its total weight, the graft copolymer (b-2) may preferably comprise 30 to 70% by weight of acrylic acid alkyl ester rubber, 10 to 55% by weight of aromatic vinyl compound, and 1 to 30% by weight of vinyl cyanide.

[0023] VII) According to I) to VI), the melt flow rate of the thermoplastic polyester elastomer (C) measured according to ASTM D1238 at a temperature of 230 °C and a load of 2.16 kg may preferably be 0.5 to 10 g / 10 min.

[0024] VIII) According to I) to VII), the thermoplastic polyester elastomer (C) may preferably be an elastomer comprising an aromatic dicarboxylic acid or its ester derivative; an aliphatic diol; and a polyalkylene oxide.

[0025] IX) According to I) to VIII), the aromatic dicarboxylic acid may preferably include one or more selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0026] X) According to I) to IX), the aliphatic diol may preferably include one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, and 1,4 - cyclohexanedimethanol.

[0027] XI) According to I) to X), the polyalkylene oxide may preferably contain one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide - added polymers of polypropylene glycol, and copolymers of ethylene oxide and tetrahydrofuran.

[0028] XII) According to I) to XI), based on 100 parts by weight of the base resin, the thermoplastic resin composition may preferably contain 0.1 to 5 parts by weight of a dye, a pigment, or a mixture thereof.

[0029] XIII) According to I) to XII), the sunscreen - resistant property of the thermoplastic resin composition may preferably be grade 3 or higher in terms of gray scale.

[0030] XIV) According to I) to XIII), the heat distortion temperature of the thermoplastic resin composition measured on an injection specimen with a thickness of 4 mm at 1.8 MPa according to ISO 75 / Be may preferably be 85°C or higher.

[0031] XV) According to still another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising kneading and extruding 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C) at 190 to 280°C and 100 to 800 rpm. The base resin contains 79 to 86 wt% of a non - graft copolymer (A) comprising (meth)acrylic acid alkyl ester, alkyl - substituted styrene compounds, and vinyl cyanide, and 14 to 21 wt% of a graft copolymer (B). The graft copolymer (B) contains one or more selected from the group consisting of a graft copolymer (b - 1) obtained by grafting (meth)acrylic acid alkyl ester, aromatic vinyl compound, and vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an acrylate - aromatic vinyl compound - vinyl cyanide graft copolymer (b - 2) containing an acrylate rubber having an average particle size of 50 to 400 nm.

[0032] XVI) According to still another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition according to any one of I) to XIV).

[0033] Advantageous Effects

[0034] According to the present invention, the present invention has the following effects: providing a thermoplastic resin composition having excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance, having a high blackness, and being applicable to an unpainted molded article by achieving a uniform injection appearance, a method for manufacturing the same, and a molded article including the same.

[0035] In particular, a molded article including the thermoplastic resin composition of the present invention has a painted-level color and a uniform appearance quality when unpainted, and thus can provide a molded article having a quality higher than that required by the market as an automotive interior part, and has the advantages of environmental friendliness and reduced process costs. Detailed Description of the Invention

[0036] Hereinafter, the thermoplastic resin composition of the present invention, a method for preparing the same, and a molded article including the same will be described in detail.

[0037] The inventors have confirmed that when a base resin and a predetermined content of a thermoplastic polyester elastomer (C) are included, and the base resin includes: a non-grafted copolymer containing an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide; a graft copolymer obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto a conjugated diene rubber having a predetermined average particle size; and one or more graft copolymers among an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer containing an alkyl acrylate rubber having a predetermined average particle size, the mechanical properties are excellent, and the heat resistance, chemical resistance, sunscreen lotion resistance, blackness, gloss, and appearance quality are improved. Based on these findings, the inventors have conducted further research to complete the present invention.

[0038] The thermoplastic resin composition of the present invention is described in detail as follows.

[0039] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C). The base resin comprises: 79 to 86% by weight of a non-grafted copolymer (A) containing an alkyl (meth)acrylate, an alkyl-substituted styrenic compound, and a vinyl cyanide, and 14 to 21% by weight of a copolymer (B) containing a rubber component, an aromatic vinyl compound, and a vinyl cyanide. In this case, the brightness value (L value) of the thermoplastic resin composition measured by a color difference meter in accordance with the CIE1976 L*a*b* color system excluding the specular reflection component (SCE) for a square disk-shaped injection specimen is 1.5 or less; and the heat distortion temperature of the thermoplastic resin composition measured in accordance with ISO 75 / Be at 1.8 MPa is 85°C or higher. In this case, it can have excellent mechanical properties, heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to those of a painted product due to its uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0040] Furthermore, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C). The base resin comprises: 79 to 86% by weight of a non-grafted copolymer (A) containing an alkyl (meth)acrylate, an alkyl-substituted styrenic compound, and a vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B). The graft copolymer (B) contains at least one selected from the group consisting of a graft copolymer (b-1) obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto a conjugated diene rubber having an average particle diameter of 200 to 500 nm and an acrylate-alkyl acrylate rubber-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm. In this case, it can have excellent mechanical properties, heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to those of a painted product due to its uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0041] Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.

[0042] Non-grafted copolymer (A)

[0043] For example, based on 100% by weight of the base resin, the content of the non-grafted copolymer (A) can be 79 to 86% by weight, preferably 80 to 85% by weight, more preferably 80 to 82% by weight. Within this range, it can have excellent heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to that of a painted product due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0044] In the present invention, "non-grafted" means that grafting is not performed, and more specifically, graft polymerization is not performed under rubber.

[0045] For example, the non-grafted copolymer (A) can contain an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide. In this case, it can have excellent heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to that of a painted product due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0046] Based on its total weight, the non-grafted copolymer (A) can preferably contain 30 to 60% by weight of an alkyl (meth)acrylate, 20 to 50% by weight of an alkyl-substituted styrene compound, and 5 to 35% by weight of a vinyl cyanide, more preferably 35 to 55% by weight of an alkyl (meth)acrylate, 25 to 45% by weight of an alkyl-substituted styrene compound, and 10 to 30% by weight of a vinyl cyanide, still more preferably 40 to 50% by weight of an alkyl (meth)acrylate, 30 to 40% by weight of an alkyl-substituted styrene compound, and 15 to 25% by weight of a vinyl cyanide, still more preferably 43 to 48% by weight of an alkyl (meth)acrylate, 33 to 38% by weight of an alkyl-substituted styrene compound, and 17 to 22% by weight of a vinyl cyanide. Within this range, the compatibility with the copolymer (B) to be described later can be excellent, it can have excellent light transmittance, gloss, heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to that of a painted product due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0047] The non-grafted copolymer (A) can preferably be a methyl methacrylate-α-methylstyrene-acrylonitrile copolymer. In this case, it can have excellent light transmittance, heat resistance, chemical resistance, and sunscreen milk resistance, can exhibit high blackness, and can achieve a color and appearance similar to that of a painted product due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0048] For example, the weight-average molecular weight of the non-grafted copolymer (A) can be from 50,000 to 200,000 g / mol, preferably from 70,000 to 150,000 g / mol, and more preferably from 80,000 to 120,000 g / mol. Within this range, excellent mechanical strengths such as impact strength and injection moldability can be achieved.

[0049] In the present invention, unless otherwise defined, the weight-average molecular weight can be measured using a gel permeation chromatograph (GPC, Waters Breeze). As a specific example, the weight-average molecular weight can be measured by using tetrahydrofuran (THF) as the eluent passing through the gel permeation chromatograph (GPC, Waters Breeze). In this case, the weight-average molecular weight is obtained as a value relative to a polystyrene (PS) standard sample. As a specific example, the weight-average molecular weight can be measured under the following conditions: solvent: THF, column temperature: 40.0 °C, flow rate 0.3 mL / minute, sample concentration: 20 mg / ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35 °C, data processing: Agilent ChemStation S / W, and test method (Mn, Mw and PDI): OECD TG 118.

[0050] For example, the glass transition temperature of the non-grafted polymer (A) according to ASTM D3418 can be 110 °C or higher, preferably 115 °C or higher, and more preferably from 115 to 150 °C. In this case, the heat resistance can be improved.

[0051] In the present invention, the glass transition temperature can be measured using a differential scanning calorimeter (TA Instruments Q100 DSC) at a heating rate of 10 °C / minute according to ASTM D3418.

[0052] For example, the melt flow index of the non-grafted polymer (A) measured at 220 °C and a load of 10 Kg according to ASTM D1238 can be 8 g / 10 minutes or higher, preferably 10 g / 10 minutes or higher, and more preferably from 10 to 20 g / 10 minutes. Within this range, excellent processability can be achieved.

[0053] For example, the refractive index of the non-grafted polymer (A) measured at room temperature using an Abbe refractometer according to ASTM D542 may be from 1.52 to 1.55, preferably from 1.53 to 1.54. Within this range, it can have excellent light transmittance and glossiness, and can have excellent heat resistance and weather resistance.

[0054] In the present invention, the room temperature may be any point within the range of 23 ± 3°C.

[0055] For example, the non-grafted polymer (A) can be prepared by including the following steps: Step i) supplying a reaction mixture containing 30 to 60% by weight of an alkyl (meth)acrylate, 20 to 50% by weight of an alkyl-substituted styrenic compound, 5 to 35% by weight of a vinyl cyanide, a solvent, and a polyfunctional organic peroxide initiator to a polymerization apparatus, and performing bulk polymerization to obtain a polymer reaction solution; and Step ii) supplying the polymer reaction solution of Step i) to a flash tank, and separating the polymer by evaporating unreacted monomers and the solvent.

[0056] The bulk polymerization of Step i) can preferably be carried out in a reactor at 100 to 130°C for a residence time of 6 to 8 hours, more preferably at 110 to 120°C for a residence time of 7 to 8 hours.

[0057] The polymerization apparatus used in the polymerization reaction is not particularly limited, but a continuous polymerization apparatus having two or more stirred tank reactors connected in series is preferred. At this time, the reactor is not particularly limited, but the first reactor is preferably a stirred tank reactor having a heat exchanger attached to the front end of the reactor, and the second reactor or subsequent reactors are preferably evaporation stirred tank reactors including a stirred tank, a storage tank, a condenser, and a pressure regulating plate.

[0058] For example, the solvent may be toluene, methyl ethyl ketone, or a mixture thereof, preferably toluene. In this case, the viscosity can be easily controlled, and a decrease in the polymerization conversion rate can be suppressed.

[0059] For example, the polyfunctional organic peroxide initiator may include one or more selected from the group consisting of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, and 1,1-bis(tert-butylperoxy)-2-methylcyclohexane. In this case, excellent productivity can be achieved, and heat discoloration can be reduced.

[0060] For example, based on the total amount of 100 parts by weight of the alkyl-substituted styrenic compound, alkyl (meth)acrylate, and vinyl cyanide, the content of the organic peroxide initiator may be from 0.05 to 0.3 parts by weight. Within this range, the polymerization conversion rate and molecular weight can be increased.

[0061] Step ii) can be carried out in a conventional evaporation tank through conventional evaporation and separation processes. For example, the polymer reaction solution polymerized and discharged in the continuous polymerization equipment is introduced into a first evaporation tank equipped with a heat exchanger maintaining a temperature of 100 to 200 °C and a vacuum pressure of 500 to 650 Torr, and then the reaction solution flowing out of the first evaporation tank is introduced into a second evaporation tank equipped with a heat exchanger maintaining a temperature of 200 to 250 °C and a vacuum pressure of 20 to 30 Torr or less. Then, the unreacted monomers and solvents are evaporated and condensed again to be reintroduced as raw materials, and the polymer can be processed into pellets while passing through a transfer pump and an extruder.

[0062] For example, the non-grafted copolymer (A) can be prepared by solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, preferably bulk polymerization. In the present invention, the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization methods commonly used in the field to which the present invention pertains can be used without particular limitation.

[0063] In the present invention, a polymer containing a certain compound means a polymer obtained by polymerizing the compound, and the units in the polymer are derived from the compound.

[0064] In the present invention, the (meth)acrylic acid alkyl ester may include acrylic acid alkyl ester and methacrylic acid alkyl ester.

[0065] In the present invention, for example, the acrylic acid alkyl ester may be an acrylic acid alkyl ester containing an alkyl group having 1 to 15 carbon atoms. Preferably, the acrylic acid alkyl ester may include one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and lauryl acrylate, more preferably an acrylic acid alkyl ester containing a linear alkyl group having 1 to 4 or 8 carbon atoms, still more preferably n-butyl acrylate or 2-ethylhexyl acrylate.

[0066] In the present invention, for example, the methacrylic acid alkyl ester may be a methacrylic acid alkyl ester containing an alkyl group having 1 to 15 carbon atoms. Preferably, the methacrylic acid alkyl ester may include one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate, more preferably containing a linear alkyl group having 1 to 4 carbon atoms, still more preferably methyl methacrylate.

[0067] In the present invention, for example, the alkyl-substituted styrene compound may include one or more selected from the group consisting of α-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, and 2,4-dimethylstyrene, and is preferably α-methylstyrene. In this case, excellent heat resistance can be achieved.

[0068] In the present invention, for example, the vinyl cyanide may contain one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, and is preferably acrylonitrile.

[0069] (B) Copolymer containing a rubber component, an aromatic vinyl compound, and a vinyl cyanide

[0070] For example, based on 100% by weight of the base resin, the content of the copolymer (B) may be 14 to 21% by weight, preferably 15 to 20% by weight, and more preferably 18 to 20% by weight. Within this range, excellent mechanical properties, heat resistance, chemical resistance, and sunscreen resistance can be achieved.

[0071] For example, the rubber component may be a conjugated diene rubber, an alkyl acrylate rubber, or a mixture thereof. In this case, excellent mechanical properties, heat resistance, chemical resistance, and sunscreen resistance can be achieved.

[0072] The aromatic vinyl compound and the vinyl cyanide may be of the same types as those included in the non-grafted copolymer (A) of the present invention within a certain range.

[0073] The copolymer (B) may preferably be a copolymer containing an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide; a copolymer containing a conjugated diene rubber, an (alkyl) acrylate, an aromatic vinyl compound, and a vinyl cyanide; or a mixture thereof, and more preferably a mixture of a copolymer containing an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide and a copolymer containing a conjugated diene rubber, an (alkyl) acrylate, an aromatic vinyl compound, and a vinyl cyanide, specifically a mixture of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and alkyl acrylate-styrene-acrylonitrile copolymer. In this case, excellent mechanical properties, heat resistance, chemical resistance, and sunscreen resistance can be achieved.

[0074] More preferably, the geopolymer (B) may include one or more selected from the group consisting of a graft copolymer (b-1) obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an acrylate-alkyl aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an acrylate rubber having an average particle size of 50 to 400 nm. Even more preferably, the graft copolymer (b-1) and the graft copolymer (b-2) are included simultaneously. In this case, excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance can be achieved.

[0075] When the graft copolymer (b-1) and the graft copolymer (b-2) are included, the weight ratio of the graft copolymer (b-1) to the graft copolymer (b-2) may be from 9:1 to 1:9, preferably from 7:3 to 5:5. Within this range, excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance can be achieved.

[0076] Graft copolymer (b-1) obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm

[0077] For example, based on its total weight, the graft copolymer (b-1) may contain 35 to 65% by weight of a conjugated diene rubber, 20 to 50% by weight of an alkyl (meth)acrylate, 1 to 30% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide. Preferably, it contains 40 to 60% by weight of a conjugated diene rubber, 25 to 45% by weight of an alkyl (meth)acrylate, 1 to 25% by weight of an aromatic vinyl compound, and 1 to 15% by weight of a vinyl cyanide. More preferably, it contains 45 to 55% by weight of a conjugated diene rubber, 30 to 40% by weight of an alkyl (meth)acrylate, 5 to 20% by weight of an aromatic vinyl compound, and 1 to 10% by weight of a vinyl cyanide. Even more preferably, it contains 47 to 52% by weight of a conjugated diene rubber, 33 to 38% by weight of an alkyl (meth)acrylate, 10 to 15% by weight of an aromatic vinyl compound, and 1 to 5% by weight of a vinyl cyanide. Within this range, excellent mechanical properties, light transmittance, gloss, and colorability can be achieved.

[0078] The average particle size of the conjugated diene rubber may preferably be 200 to 450 nm, more preferably 250 to 400 nm, even more preferably 250 to 350 nm, and even more preferably 270 to 320 nm. Within this range, excellent mechanical properties, light transmittance, gloss, and colorability can be achieved.

[0079] In the present invention, the average particle size is measured by dynamic light scattering method. Specifically, the average particle size is the intensity value measured in Gaussian mode using a Nicomp 380 particle size analyzer (manufacturer: PSS). As a specific example, a sample is prepared by diluting 0.1 g of latex (total solid content: 35 to 50 wt%) 1000 to 5000 times with water. Then, the average particle size of the sample is measured in the measurement mode of dynamic light scattering method / intensity 300 kHz / intensity-weight high-speed analysis using an automatically diluted flow cell. At this time, the set values are as follows: temperature: 23 °C, measurement wavelength: 632.8 nm, channel width: 10 μsec.

[0080] For example, conjugated diene rubber can be prepared by the following method: Add 0.2 to 4 parts by weight of an emulsifier, 0.02 to 1.5 parts by weight of a polymerization initiator, 0.5 part by weight of an electrolyte, 0.1 to 0.5 part by weight of a molecular weight regulator, and 90 to 130 parts by weight of deionized water to 100 parts by weight of a conjugated diene compound, and then carry out emulsion polymerization at 65 to 85 °C for 25 to 50 hours.

[0081] For example, the gel content of conjugated diene rubber can be 50 to 99 wt%, preferably 60 to 99 wt%, more preferably 70 to 95 wt%, still more preferably 80 to 95 wt%. Within this range, a graft copolymer can be effectively formed outside the rubber particles, and thus excellent mechanical properties, light transmittance, gloss, colorability, and processability can be obtained.

[0082] In the present invention, when measuring the gel content, 1 g of the graft copolymer is added to 30 mL of acetone, and then stirred at room temperature for 12 hours. Then, centrifugation is carried out to separate the insoluble matter insoluble in acetone, and then dried for 12 hours. Then, the weight of the insoluble matter is measured, and the gel content is calculated by the following Equation 1. As a specific measurement example, when measuring the gel content, 1 g of the graft copolymer is added to 30 mL of acetone, and then stirred at 210 rpm and room temperature for 12 hours using a gyratory shaker (equipment name: Lab companion SKC-6075). Then, centrifugation is carried out at 0 °C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co., Ltd.) to separate the insoluble matter insoluble in acetone, and then dried for 12 hours by forced circulation in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C. Then, the weight of the insoluble matter is measured, and the gel content is calculated by the following Equation 1.

[0083] [Equation 1]

[0084] Gel content (wt%) = [weight of insoluble matter (gel) (g) / weight of sample (g)] × 100

[0085] For example, the conjugated diene rubber used in emulsion polymerization may be a polybutadiene rubber latex having a swelling index of 12 to 40, preferably a polybutadiene rubber latex having a swelling index of 20 to 35. In this case, excellent mechanical properties and processability can be achieved.

[0086] In the present invention, when measuring the swelling index, 1 g of the graft copolymer is added to 30 mL of acetone, and then stirred at room temperature for 12 hours. Then, centrifugation is performed to separate the insoluble matter insoluble in acetone, and then dried for 12 hours. Then, the weight of the insoluble matter is measured, and the swelling index is calculated by the following Equation 2. As a specific measurement example, when measuring the swelling index, 1 g of the graft copolymer is added to 30 mL of acetone, and then stirred at 210 rpm and room temperature for 12 hours using a gyratory shaker (equipment name: Lab companion SKC-6075). Then, centrifugation is performed at 0 °C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co., Ltd.) to separate the insoluble matter insoluble in acetone, and then dried for 12 hours in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C by forced circulation. Then, the weight of the insoluble matter is measured, and the swelling index is calculated by the following Equation 2.

[0087] [Equation 2]

[0088] Swelling index = weight before drying after centrifugation / weight after drying after centrifugation

[0089] The conjugated diene rubber may preferably include one or more selected from the group consisting of butadiene, polybutadiene, styrene-butadiene, polyisoprene, and butadiene-isoprene. In this case, excellent mechanical properties and processability can be achieved.

[0090] For example, the emulsifier may include one or more selected from the group consisting of alkyl aryl sulfonates, alkali metal methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali metal salts of rosin acid.

[0091] For example, based on 100 parts by weight of the monomer mixture, the content of the emulsifier may be 0.2 to 1.5 parts by weight, preferably 0.5 to 1.0 parts by weight.

[0092] For example, the polymerization initiator may include one or more selected from the group consisting of water-soluble persulfates, fat-soluble peroxides, and redox polymerization initiators.

[0093] For example, the water-soluble persulfate may include one or more selected from the group consisting of persulfate, sodium persulfate, and potassium persulfate.

[0094] For example, the fat-soluble peroxide may include one or more selected from the group consisting of: cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide, paramenthane hydroperoxide, and benzoyl peroxide.

[0095] For example, the redox polymerization initiator may include one or more selected from the group consisting of: sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, glucose, sodium pyrophosphate, and sodium sulfite.

[0096] For example, based on 100 parts by weight of the monomer mixture, the amount of the polymerization initiator may be 0.02 to 0.3 parts by weight, preferably 0.1 to 0.2 parts by weight.

[0097] For example, the electrolyte may include one or more selected from the group consisting of: KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, K4P2O7, K3PO4, Na3PO4, K2HPO4, and Na2HPO4.

[0098] For example, the molecular weight regulator may include a thiol, preferably tert-dodecyl mercaptan.

[0099] For example, the emulsion polymerization may be carried out at 65 to 85 °C, preferably 70 to 80 °C. Within this range, the gel content and swelling index of the rubber latex can be easily controlled.

[0100] For example, the graft copolymer (b-1) of the present invention can be prepared by grafting a monomer mixture containing an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto the prepared conjugated diene rubber latex by emulsion polymerization.

[0101] For example, the emulsion polymerization may be carried out at 65 to 85 °C for 3 to 10 hours, preferably at 70 to 80 °C for 4 to 9 hours.

[0102] For example, based on the total weight of the base resin, the content of the graft copolymer (b-1) may be 0 to 21% by weight, preferably 0 to 18% by weight, more preferably 3 to 18% by weight, still more preferably 5 to 18% by weight, still more preferably 5 to 14% by weight, still more preferably 5 to 11% by weight, still more preferably 7 to 11% by weight, and as the most preferred example is 8 to 10% by weight. Within this range, excellent mechanical properties, light transmittance, gloss, and colorability can be obtained.

[0103] In the present invention, for example, the conjugated diene compound may include one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, and piperylene, preferably 1,3-butadiene.

[0104] In the present invention, for example, the aromatic vinyl compound may include one or more selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably one or more selected from the group consisting of styrene and α-methylstyrene, and more preferably styrene. In this case, due to the appropriate fluidity, it can have excellent processability and mechanical properties such as impact resistance.

[0105] The types of the (meth)acrylic acid alkyl ester and vinyl cyanide contained in the graft copolymer (b-1) may be the types within the same category as the types of the (meth)acrylic acid alkyl ester and vinyl cyanide contained in the non-grafted copolymer (A) of the present invention.

[0106] (b-2) Alkyl acrylate - aromatic vinyl Compound - vinyl cyanide graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 400 nm

[0107] For example, the graft copolymer (b-2) may include an acrylic acid alkyl ester rubber (core) and an aromatic vinyl compound-vinyl cyanide copolymer (shell) surrounding the core.

[0108] For example, based on its total weight, the graft copolymer (b-2) may include 30 to 70% by weight of an acrylic acid alkyl ester rubber, 10 to 55% by weight of an aromatic vinyl compound, and 1 to 30% by weight of vinyl cyanide, preferably 40 to 60% by weight of an acrylic acid alkyl ester rubber, 20 to 45% by weight of an aromatic vinyl compound, and 5 to 20% by weight of vinyl cyanide, and more preferably 45 to 55% by weight of an acrylic acid alkyl ester rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 15% by weight of vinyl cyanide. Within this range, it can have excellent mechanical properties, processability, weather resistance, light transmittance, gloss, and colorability.

[0109] The average particle diameter of the acrylic acid alkyl ester rubber may preferably be 80 to 400 nm, more preferably 100 to 400 nm, still more preferably 100 to 150 nm or 300 to 400 nm. Within this range, it can have an excellent balance of physical properties, mechanical properties, gloss, light transmittance, and colorability.

[0110] For example, an acrylic alkyl ester rubber can be prepared by emulsion polymerization of an acrylic alkyl ester, preferably by mixing an acrylic alkyl ester, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent and subjecting the mixture to emulsion polymerization. In this case, excellent mechanical properties can be achieved due to excellent grafting efficiency.

[0111] For example, the acrylic alkyl ester rubber may contain seeds, preferably rubber seeds.

[0112] For example, based on 100% by weight of the graft copolymer (b-2), the seeds can be prepared by polymerizing 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 3 to 10% by weight of one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanides, and acrylic alkyl esters. Within this range, excellent impact strength, weather resistance, and balance of physical properties can be achieved.

[0113] For example, the weight average molecular weight of the aromatic vinyl compound-vinyl cyanide copolymer (shell) can be 40,000 to 120,000 g / mol, preferably 50,000 to 110,000 g / mol, more preferably 60,000 to 110,000 g / mol. Within this range, excellent impact strength, tensile strength, and processability can be achieved.

[0114] For example, the graft copolymer (b-2) can be prepared by emulsion polymerization. In this case, excellent mechanical properties, processability, weather resistance, light transmittance, gloss, and colorability can be achieved.

[0115] The emulsion polymerization can be carried out using an emulsion polymerization method commonly practiced in the technical field to which the present invention pertains, without particular limitation. For example, an emulsion graft polymerization method can be used.

[0116] For example, the grafting rate calculated by the following Equation 3 of the graft copolymer (b-2) can be 25% or more, preferably 30% or more, more preferably 30 to 70%, still more preferably 30 to 60%, still more preferably 30 to 50%. Within this range, excellent mechanical properties and processability can be achieved.

[0117] [Equation 3]

[0118] Grafting rate (%) = [weight of graft monomer (g) / weight of rubber (g)] × 100

[0119] In Equation 3, the weight of the graft monomer (g) is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging, and the weight of the rubber (g) is the weight (g) of the rubber component theoretically added to the graft copolymer powder.

[0120] When measuring the weight of the insoluble matter (gel), 0.5 g of the powdered graft copolymer is added to 50 mL of acetone, and then stirred at room temperature for 12 hours. Then, centrifugation is carried out to separate the insoluble matter insoluble in acetone, and then dried for 12 hours. Then, the weight of the insoluble matter (gel) is measured. The rubber weight (g) is the weight (g) of the rubber component theoretically added to 0.5 g of the graft copolymer powder.

[0121] As a specific example, when measuring the weight of the insoluble matter (gel), 0.5 g of the graft copolymer is added to 50 mL of acetone, and then stirred at 210 rpm and room temperature for 12 hours using a gyratory shaker (equipment name: Lab companion SKC-6075). Then, centrifugation is carried out at 0 °C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co., Ltd.) to separate the insoluble matter insoluble in acetone, and then dried for 12 hours by forced circulation in a forced convection oven (equipment name: Labcompanion OF-12GW) set at 85 °C. Then, the weight of the insoluble matter is measured, and the weight of the insoluble matter (gel) is calculated by the following Equation 1.

[0122] For example, the weight-average molecular weight of the graft copolymer (b-2) can be 60,000 to 200,000 g / mol, preferably 70,000 to 180,000 g / mol, more preferably 80,000 to 170,000 g / mol, still more preferably 100,000 to 160,000 g / mol. Within this range, excellent mechanical properties, processability, weather resistance, light transmittance, gloss, and colorability can be achieved.

[0123] For example, based on the total weight of the base resin, the content of the graft copolymer (b-2) can be 0 to 21% by weight, preferably 0 to 18% by weight, more preferably 3 to 18% by weight, still more preferably 5 to 18% by weight, still more preferably 5 to 14% by weight, still more preferably 5 to 11% by weight, still more preferably 7 to 11% by weight, and as a most preferred example, 8 to 10% by weight. Within this range, excellent mechanical properties, processability, weather resistance, light transmittance, gloss, and colorability can be achieved.

[0124] The types of the alkyl acrylate, aromatic vinyl compound, and vinyl cyanide contained in the graft copolymer (b-2) can be the types within the same category as the types of the alkyl acrylate, aromatic vinyl compound, and vinyl cyanide contained in the non-grafted copolymer (A) of the present invention.

[0125] (C) Thermoplastic polyester elastomer

[0126] For example, based on 100 parts by weight of the base resin, the content of the thermoplastic polyester elastomer (C) can be 8 to 21 parts by weight, preferably 9 to 21 parts by weight, more preferably 10 to 21 parts by weight, and still more preferably 13 to 21 parts by weight. Within this range, excellent mechanical properties, weather resistance, light transmittance, low whitening characteristics, and film processability can be achieved, and the appearance quality and emotional quality can be improved.

[0127] For example, the thermoplastic polyester elastomer (C) can be an elastomer containing an aromatic dicarboxylic acid or its ester derivative; an aliphatic diol; and a polyalkylene oxide. In this case, flexibility, mechanical strength, and heat resistance can be improved, and excellent physical balance can be achieved.

[0128] For example, the crystalline hard segment can be formed from an aromatic dicarboxylic acid or its ester derivative and an aliphatic diol, and the soft segment can be formed from a polyalkylene oxide, and the crystalline hard segment and the soft segment can be randomly arranged.

[0129] For example, the aromatic dicarboxylic acid can include one or more selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, preferably terephthalic acid, isophthalic acid, or a mixture thereof.

[0130] For example, the ester derivative of the aromatic dicarboxylic acid can include one or more selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, dimethyl 2,6-naphthalate, dimethyl 1,5-naphthalate, and dimethyl 1,4-cyclohexanedicarboxylate, preferably dimethyl terephthalate, dimethyl isophthalate, or a mixture thereof.

[0131] Based on the total weight of the thermoplastic polyester elastomer, the content of the aromatic dicarboxylic acid or its ester derivative can be 25 to 70% by weight, preferably 30 to 65% by weight, and more preferably 35 to 60% by weight. Within this range, the reaction can proceed easily.

[0132] For example, the number average molecular weight of the aliphatic diol can be 300 g / mol or less, preferably 60 to 300 g / mol.

[0133] In the present invention, unless otherwise defined, the number-average molecular weight can be measured using a gel permeation chromatograph (GPC, Waters Breeze). As a specific example, the number-average molecular weight can be measured by using tetrahydrofuran (THF) as an eluent passing through the gel permeation chromatograph (GPC, Waters Breeze). In this case, the number-average molecular weight is obtained as a value relative to a polystyrene (PS) standard sample. As a specific example, the number-average molecular weight can be measured under the following conditions: solvent: THF, column temperature: 40.0 °C, flow rate 0.3 mL / minute, sample concentration: 20 mg / ml, injection volume: 5 μl, column type: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35 °C, data processing: Agilent ChemStation S / W, and test method (Mn, Mw and PDI): OECD TG 118.

[0134] The aliphatic diol may preferably include one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, more preferably 1,4-butanediol.

[0135] For example, based on the total weight of the thermoplastic polyester elastomer, the content of the aliphatic diol may be 15 to 45% by weight, preferably 20 to 40% by weight, more preferably 25 to 40% by weight. Within this range, the reaction can proceed smoothly, and an excellent balance of physical properties between flexibility and mechanical strength can be obtained.

[0136] For example, the polyalkylene oxide may be an aliphatic polyether, and as the soft segment, it may include one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of polypropylene glycol, and copolymers of ethylene oxide and tetrahydrofuran, preferably polytetramethylene glycol.

[0137] For example, based on the total weight of the thermoplastic polyester elastomer, the content of the polyalkylene oxide may be 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 40% by weight. Within this range, excellent flexibility, mechanical strength, heat resistance, and balance of physical properties can be obtained.

[0138] For example, the number-average molecular weight of the polyalkylene oxide can be from 600 to 3000 g / mol, preferably from 1000 to 2000 g / mol. Within this range, the polymerization reaction can proceed stably, and a thermoplastic polyester elastomer having an excellent balance of physical properties can be obtained.

[0139] The polyalkylene oxide can preferably be ethylene oxide-capped polypropylene glycol. In this case, excellent polymerization reactivity can be achieved.

[0140] The thermoplastic polyester elastomer (C) can preferably contain a branching agent. In this case, the melt viscosity and melt strength of the elastomer can be increased.

[0141] For example, the branching agent can include one or more selected from the group consisting of glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylolpropane, and neopentyl glycol, preferably trimellitic anhydride. In this case, the melt viscosity and melt strength of the elastomer can be increased.

[0142] For example, based on the total amount of 100% of the thermoplastic polyester elastomer, the content of the branching agent can be from 0.05 to 0.1% by weight, preferably from 0.05 to 0.09% by weight, more preferably from 0.06 to 0.09% by weight. Within this range, the melt strength can be increased.

[0143] For example, the thermoplastic polyester elastomer (C) can be prepared by melt-polymerizing an aromatic dicarboxylic acid or its ester derivative, an aliphatic diol, and a polyalkylene oxide. In this case, an excellent balance of physical properties among flexibility, mechanical strength, and heat resistance can be achieved, and the moldability can also be improved.

[0144] The thermoplastic polyester elastomer (C) can preferably be prepared by additionally subjecting the resin prepared by melt polymerization to solid-state polymerization. In this case, an excellent balance of physical properties among flexibility, mechanical strength, and heat resistance can be achieved, and the moldability can also be improved.

[0145] Preferably, when preparing the thermoplastic polyester elastomer, the transesterification of the aromatic dicarboxylic acid, the aliphatic diol, and the polyalkylene oxide is carried out at 140 to 215 °C for 110 to 130 minutes under a tetrabutyl titanate (TBT) catalyst to obtain bis(4-hydroxy)butyl terephthalate (BHBT) oligomer, the TBT catalyst is added again, and then the melt polymerization is carried out at 215 to 245 °C for 110 to 130 minutes under a pressure gradually reduced from 760 Torr to 0.3 Torr.

[0146] The melt polymerization reaction can be carried out until the melt flow rate measured at a temperature of 230 °C under a load of 2.16 kg according to ASTM D1238 reaches 20 g / 10 min. After the reaction is completed, the product can be discharged from the reactor by nitrogen pressure and obtained in the form of pellets by strand pelletization.

[0147] Then, the pellets can be subjected to solid-state polymerization at 140 to 200 °C for 10 to 24 hours in an inert atmosphere (such as a nitrogen atmosphere) in a solid-state polymerization reactor or a rotary vacuum dryer.

[0148] High viscosity can be achieved by solid-state polymerization until the melt flow rate measured at a temperature of 230 °C under a load of 2.16 kg according to ASTM D1238 is below 10 g / 10 min, preferably 0.5 to 10 g / 10 min, more preferably 1 to 10 g / 10 min, and still more preferably 3 to 8 g / 10 min.

[0149] The degree of vacuum applied during the solid-state polymerization can be selected within the degree of vacuum commonly used in the technical field to which the present invention pertains, without particular limitation.

[0150] The solid-state polymerization reactor can be a container-type vacuum dryer connected to a rotary high-vacuum pump, and the inert atmosphere can be a nitrogen atmosphere.

[0151] In the present invention, the monomer content in the polymer can refer to the weight (wt%) of the monomer added during the preparation of the polymer or the weight (wt%) of the unit derived from the monomer (based on the monomer).

[0152] The melt flow rate of the thermoplastic polyester elastomer (C) measured at a temperature of 230 °C under a load of 2.16 kg according to ASTM D1238 can be 0.5 to 10 g / 10 min, preferably 1 to 10 g / 10 min, and more preferably 3 to 8 g / 10 min. Within this range, excellent moldability can be achieved.

[0153] For example, the Shore hardness of the thermoplastic polyester elastomer (C) can be 30D to 50D, preferably 35D to 47D, and more preferably 35D to 40D. Within this range, the flexibility and mechanical strength of the composition can be excellent.

[0154] In the present invention, unless otherwise specified, the Shore hardness can be measured according to the method described in ISO 868 (Type D).

[0155] In the present invention, the elastomer can also be referred to as an elastic polymer or elastic rubber as described in the technical field to which the present invention pertains, and commercially available products can be used as long as they meet the definition of the present invention.

[0156] Thermoplastic resin composition

[0157] For example, based on 100 parts by weight of a base resin, the thermoplastic resin composition may contain 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 0.5 to 2 parts by weight of a dye, a pigment, or a mixture thereof. Within this range, excellent mechanical properties, processability, weather resistance, light transmittance, gloss, heat resistance, chemical resistance, and colorability can be achieved.

[0158] For example, the sunscreen resistance property of the thermoplastic resin composition may be 3 or more in gray scale level, preferably 3 or more in gray scale level and "no swelling or cracking" as measured by the following method. Within this range, an excellent balance of physical properties and chemical resistance can be achieved, the appearance quality can be improved, and high-quality automotive parts can be provided.

[0159] In the present invention, according to the sunscreen resistance property measurement method, first, 100 mg of an SPF 50+ sunscreen is applied to a white cotton pad for sunscreen resistance property testing having a size of at least 3 cm × 3 cm, preferably 5 cm × 5 cm. At this time, the application is performed such that the sunscreen is uniformly applied to the entire surface of the white cotton pad, and the application can be performed using a hand wearing chemical-resistant latex gloves. The white cotton pad uniformly coated with the sunscreen is placed on a disk-shaped specimen having a size of 10 cm × 10 cm × 2 mm, placed in a constant temperature bath at 80 ± 2°C for 1 hour, then taken out, the white cotton pad is removed, the disk-shaped specimen is washed with a neutral detergent and dried. Then, the surface condition of the dried disk-shaped specimen is inspected and judged by referring to the gray scale level of dyeing according to ISO 105 (Textiles - Colorfastness tests). The sunscreen resistance property evaluation is performed at least twice, preferably three times, for the same composition. Here, the size of the disk-shaped specimen should be larger than the white cotton pad and should be flat.

[0160] In the present invention, the room temperature may be any point within the range of 23 ± 3°C.

[0161] For example, the heat distortion temperature measured according to ISO 75 / Be at 1.8 MPa of the thermoplastic resin composition may be 85°C or higher, preferably 85 to 100°C. Within this range, an excellent balance of physical properties and heat resistance can be achieved, and thus high-quality in-vehicle materials can be provided.

[0162] For example, the brightness value (L value) measured by a color difference meter for a square disk-shaped injection specimen of the thermoplastic resin composition in a manner that excludes the specular reflection component (SCE) according to the CIE1976 L*a*b* color system may be 1.5 or less, preferably 1.3 or less, more preferably 1.2 or less, and still more preferably from 0.1 to 1.2. Within this range, due to the excellent balance of physical properties and blackness, a color similar to that of paint can be achieved, and an aesthetically pleasing appearance can be provided. As the L value decreases, the blackness becomes better.

[0163] In the present invention, the color difference meter is not particularly limited as long as it is a color difference meter commonly used in the technical field to which the present invention pertains, and it may specifically be Ci7800 (X-rite CO.).

[0164] For example, the glossiness measured for a square disk-shaped injection specimen of the thermoplastic resin composition at 60° according to ASTM D523 may be 90 or more, preferably 93 or more, more preferably 95 or more, and still more preferably from 95 to 120. Within this range, an excellent balance of physical properties can be achieved, high glossiness can be realized, and excellent colorability can be obtained.

[0165] For example, when visually observing a square disk-shaped injection specimen injected at an injection temperature of 270°C and an injection speed of 70 mm / minute, the thermoplastic resin composition may not produce flow marks or fogging. In this case, excellent appearance quality can be obtained.

[0166] Based on 100 parts by weight of the base resin, the thermoplastic resin composition may further contain 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 part by weight of one or more selected from the groups consisting of: heat stabilizers, light stabilizers, colorants, lubricants, mold release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke inhibitors, anti-dripping agents, anti-friction agents, and anti-wear agents. Within this range, the desired properties can be effectively achieved without deteriorating the inherent properties of the thermoplastic resin composition of the present invention.

[0167] The heat stabilizer may preferably contain a first heat stabilizer and a second heat stabilizer.

[0168] For example, the first heat stabilizer may be a phenolic heat stabilizer. Preferably, the first heat stabilizer may include one or more selected from the group consisting of: 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2,2-bis[4-(2-3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, more preferably octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IR1076).

[0169] For example, the second heat stabilizer may be a phosphorus-based heat stabilizer. Preferably, the second heat stabilizer may include one or more selected from the group consisting of: bis(dialkylphenyl)pentaerythritol diphosphite, phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, tris(mono and di mixed nonylphenyl) phosphite, hydrogenated 4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris[4,4'-isopropylidenebis(2-tert-butylphenol)] phosphite, bis(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-tert-butylphenol) bis(nonylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2-[{2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]-dioxaphosphin-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1.3.2]-dioxaphosphin-6-yl}oxy]ethyl]ethylamine, and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]-dioxaphosphin, and more preferably tris(2,4-di-tert-butylphenyl) phosphite (IF168).

[0170] The lubricant may preferably contain one or more selected from the group consisting of aliphatic amide lubricants, fatty acid ester lubricants, and olefin waxes.

[0171] The aliphatic amide lubricants may preferably contain one or more selected from the group consisting of: stearamide, oleamide, erucamide, ethylene bisstearamide, and ethylene bisoleamide.

[0172] The fatty acid ester lubricants may preferably contain one or more selected from the group consisting of: fatty acid esters of monohydric or polyhydric alcohols, hydrogenated oils, butyl stearate, monoglyceryl stearate, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphates.

[0173] The olefin wax may preferably be polyethylene wax.

[0174] Method for preparing a thermoplastic resin composition

[0175] The method for preparing the thermoplastic resin composition of the present invention includes a step of kneading and extruding 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C) at 190 to 280 °C and 100 to 800 rpm. The base resin contains 79 to 86% by weight of a non-grafted copolymer (A) containing (meth)acrylic acid alkyl ester, alkyl-substituted styrene compounds, and vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B) containing one or more selected from the group consisting of a graft copolymer (b-1) obtained by grafting (meth)acrylic acid alkyl ester, aromatic vinyl compound, and vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm and an acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an acrylic acid alkyl ester rubber having an average particle size of 50 to 400 nm. In this case, it can have excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance, can exhibit high blackness, and can achieve colors and appearances similar to those of painted products due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0176] The method for preparing the thermoplastic resin composition shares all the technical features of the above thermoplastic resin composition. Therefore, the description of the repeated parts will be omitted.

[0177] The kneading and extrusion can be carried out using an extruder at 190 to 280 °C, more preferably 200 to 260 °C, and still more preferably 220 to 250 °C. Within this range, stable extrusion can be carried out, and the mixing effect is excellent. At this time, the temperature is the temperature set inside the cylinder.

[0178] For example, the kneading and extrusion can be carried out at a screw rotation speed of 100 to 800 rpm, preferably 200 to 700 rpm, and more preferably 300 to 600 rpm. In this case, since the production amount per unit time is appropriate, excellent process efficiency can be achieved.

[0179] For example, the thermoplastic resin composition obtained by extrusion can be made into pellets using a pelletizer.

[0180] In the present invention, any extruder commonly used in the technical field to which the present invention belongs can be used without any particular limitation. Preferably, a twin-screw extruder can be used.

[0181] Molded article

[0182] The molded article of the present invention comprises the thermoplastic resin composition of the present invention. In this case, it can have excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance, can exhibit high blackness, and can achieve a color and appearance similar to those of a painted product due to a uniform injection appearance. Therefore, the molded article can be applied to unpainted molded articles.

[0183] For example, the injection molded article can be an interior or exterior part of an automobile and a part of an electrical or electronic product, specifically a decorative or covering part of an automobile door and a center console part.

[0184] The method for manufacturing a molded article may preferably include the step of preparing an extrudate by kneading and extruding 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C) at 190 to 280 °C and 100 to 800 rpm, and a method for molding the extrudate into a molded article. The base resin contains 79 to 86% by weight of a non-grafted copolymer (A) containing (meth)acrylic acid alkyl ester, an alkyl-substituted styrene compound, and vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B) containing at least one selected from the group consisting of a graft copolymer (b-1) obtained by grafting (meth)acrylic acid alkyl ester, an aromatic vinyl compound, and vinyl cyanide onto a conjugated diene rubber having an average particle size of 200 to 500 nm and an acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an acrylic acid alkyl ester rubber having an average particle size of 50 to 400 nm. In this case, it can have excellent mechanical properties, heat resistance, chemical resistance, and sunscreen lotion resistance, can exhibit high blackness, and can achieve a color and appearance similar to those of a painted product due to a uniform injection appearance. Therefore, the thermoplastic resin composition can be applied to unpainted molded articles.

[0185] For example, the extrudate can be pellet-shaped or plate-shaped.

[0186] In the present invention, the plate shape is not particularly limited as long as it is defined as a plate shape in the technical field to which the present invention pertains, and may include a planar shape, a sheet shape, a film shape, a foil shape, etc.

[0187] When describing the thermoplastic resin composition of the present invention, its preparation method, and the molded article containing the same, it should be noted that other conditions or equipment not explicitly described herein can be appropriately selected within the range commonly used in the art without particular limitation.

[0188] In the following, the present invention will be described in more detail with reference to the following preferred embodiments. However, these embodiments are provided for illustrative purposes only and should not be construed as limiting the scope or spirit of the present invention. In addition, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention, and these changes and modifications also fall within the scope of the appended claims.

[0189] [Examples]

[0190] The materials used in the examples and comparative examples are as follows.

[0191] *(A-1) MMA-α-methylstyrene-acrylonitrile copolymer: A non-grafted copolymer containing (meth)acrylic acid alkyl ester, alkyl-substituted styrenic compounds, and vinyl cyanide (LG Chem Ltd., 290UH)

[0192] *(A-2) PMMA resin: Polymethyl methacrylate resin (LX MMA Co., IH830)

[0193] *(b-1) MABS graft copolymer: A graft copolymer obtained by grafting (meth)acrylic acid alkyl ester, aromatic vinyl compound, and vinyl cyanide onto a conjugated diene rubber with a particle size of 250 to 350 nm (LG Chem Ltd., TR550)

[0194] *(b-2) ASA graft copolymer: An acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylic acid alkyl ester rubber with a particle size of 100 to 150 nm (LG Chem Ltd., SA130)

[0195] *(b-3) ABS graft copolymer: An acrylonitrile-butadiene-styrene graft copolymer containing a butadiene rubber with a particle size of 250 to 350 nm (LG Chem Ltd., DP270)

[0196] *(b-4) SAN copolymer: Styrene-acrylonitrile copolymer (LG Chem Ltd., 81HF)

[0197] *(b-5) ASA graft copolymer: An acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylic acid alkyl ester rubber with a particle size of 450 to 550 nm (LG Chem Ltd., SA927)

[0198] *(b-6) ASA graft copolymer: An acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylic acid alkyl ester rubber with a particle size of 300 to 400 nm (LG Chem Ltd., SA928)

[0199] *(C) TPEE: Thermoplastic polyester elastomer (Melt flow rate (230 °C, 2.16 kg): 5 g / 10 min, Shore D hardness: 40D, KEYFLEX BT2140D, LG Chem, Ltd.)

[0200] *(D) Black dye: Sumiplast Black HLC (Sumitomo Chemical Co., Ltd.)

[0201] Here, MMA refers to methyl methacrylate, PMMA refers to polymethyl methacrylate, MABS refers to methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer, and TPEE refers to thermoplastic polyester elastomer.

[0202] Examples 1 to 10 and Comparative Examples 1 to 12

[0203] According to the content shown in Table 1 and Table 2 below, the components at the "yes" positions in Table 1 and Table 2 were introduced into a twin-screw extruder (25Φ), and melt kneading and extrusion were carried out to obtain pellets. The obtained pellets were used to manufacture injection-molded specimens using an injection molding machine.

[0204] In addition, specimens for measuring glossiness, brightness value, and appearance quality were manufactured using the obtained pellets in an injection machine with a high-gloss mold. The high-gloss mold means that the mold surface has been smoothed.

[0205] [Test Example]

[0206] The properties of the pellets or specimens obtained in Examples 1 to 10 and Comparative Examples 1 to 12 were measured by the following methods, and the results are shown in Table 1 and Table 2 below.

[0207] Measurement method

[0208] * Sunscreen resistance performance: 100 mg of SPF 50+ sunscreen was applied to a white cotton pad for sunscreen resistance performance testing with a size of 5 cm × 5 cm. At this time, the application was carried out so that the sunscreen was evenly applied to the entire surface of the white cotton pad, and the application was carried out using a hand wearing chemical-resistant latex gloves. The white cotton pad evenly coated with sunscreen was placed on a disk-shaped specimen with a size of 10 cm × 10 cm × 2 mm, placed in a constant temperature bath at 80 ± 2 °C for 1 hour, then taken out, the white cotton pad was removed, the disk-shaped specimen was washed with a neutral detergent and dried. Then, the surface condition of the dried disk-shaped specimen was checked and judged by referring to the gray scale of staining in ISO 105 (Textiles - Colorfastness tests). In addition, whether there was swelling or cracking of the disk-shaped specimen was also evaluated. At this time, the sunscreen resistance performance was evaluated three times for the same composition. And the results are shown. Here, as the gray scale increases, the sunscreen resistance performance becomes better.

[0209] *Heat distortion temperature (HDT, °C): Measure the heat distortion temperature according to ISO 75 / Be at 1.8 MPa.

[0210] *Luminance value (L value): Measure the luminance value (L value) of a square disk-shaped injection specimen using a color difference meter in accordance with the CIE1976 L*a*b* color system in a manner that excludes the specular reflection component (SCE). For black, as the L value decreases, the blackness improves.

[0211] *Glossiness: Measure the glossiness at 60° using a square disk-shaped injection specimen according to ASTM D523.

[0212] *Visually determine whether flow marks and atomization occur in the square disk-shaped injection specimen, and the results are shown below.

[0213] O: Since no flow marks or atomization occur, the appearance is excellent

[0214] X: Flow marks or atomization occur, resulting in a poor appearance

[0215] [Table 1]

[0216]

[0217] [Table 2]

[0218]

[0219] In Tables 1 and 2, the contents of (A-1), (A-2), (b-1), (b-2), (b-3), (b-4), (b-5), and (b-6) are in weight % based on their total weight, and the contents of (C) and (D) are in parts by weight based on the total amount of 100 parts by weight of (A-1), (A-2), (b-1), (b-2), (b-3), (b-4), (b-5), and (b-6).

[0220] As described in Tables 1 and 2, in the case of the thermoplastic resin compositions of Examples 1 to 10 of the present invention, the sunscreen lotion resistance, heat distortion temperature, luminance value, glossiness, and appearance quality are excellent compared to Comparative Examples 1 to 12.

[0221] On the other hand, Comparative Examples 1 to 3 that do not contain TPEE (C) or contain a small amount of TPEE (C) have poor sunscreen lotion resistance. Comparative Example 10 that contains an excessive amount of TPEE (C) has poor heat distortion temperature and appearance quality.

[0222] In addition, Comparative Example 4 containing a non-grafted copolymer (A) below the scope of the present invention and a non-grafted copolymer (B) above the scope of the present invention has a low heat distortion temperature and thus poor heat resistance. Comparative Example 9 containing a non-grafted copolymer (A) above the scope of the present invention and a non-grafted copolymer (B) below the scope of the present invention has poor sunscreen milk resistance.

[0223] In addition, Comparative Example 5 containing a graft copolymer (b-3) and Comparative Example 6 containing a non-grafted copolymer (A-2) and a graft copolymer (b-3) exhibit poor colorability due to deteriorated appearance quality and increased brightness value.

[0224] In addition, Comparative Example 7 containing a non-grafted copolymer (A-2) and not containing TPEE (C) has poor sunscreen milk resistance, heat distortion temperature, and glossiness.

[0225] In addition, Comparative Examples 8, 11, and 12 containing a non-grafted copolymer (A-2), a SAN copolymer (b-4), or an ASA graft copolymer (b-5) exhibit poor sunscreen milk resistance, heat distortion temperature, brightness, or appearance.

[0226] In summary, the thermoplastic resin composition of the present invention comprises a base resin and a predetermined content of a thermoplastic polyester elastomer. The base resin comprises: a non-grafted copolymer containing an alkyl (meth)acrylate, an alkyl-substituted styrenic compound, and a vinyl cyanide; and one or more graft copolymers selected from a graft copolymer obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide onto a conjugated diene rubber having a predetermined average particle size and an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylate rubber having a predetermined average particle size. The thermoplastic resin composition of the present invention exhibits excellent mechanical properties, heat resistance, and sunscreen milk resistance and exhibits high blackness. Therefore, the thermoplastic resin composition of the present invention has a uniform injection appearance and can be applied to unpainted molded articles.

Claims

1. A thermoplastic resin composition comprising: 100 parts by weight of a base resin, the base resin comprising: 79 to 86% by weight of a non-grafted copolymer (A) comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound and vinyl cyanide, and 14 to 21% by weight of a copolymer (B) comprising a rubber component, an aromatic vinyl compound and vinyl cyanide; and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C), in, The thermoplastic resin composition has a brightness value (L value) of 1.5 or less measured by using a colorimeter on a square disk injection sample in accordance with the CIE1976 L*a*b* color system in a manner that excludes the specular reflection component (SCE); and The thermoplastic resin composition has a heat deformation temperature of 85° C. or higher measured at 1.8 MPa according to ISO 75 / Be.

2. The thermoplastic resin composition according to claim 1, wherein The rubber component is a conjugated diene rubber, an alkyl acrylate rubber or a mixture thereof.

3. A thermoplastic resin composition comprising: 100 parts by weight of a base resin, the base resin comprising 79 to 86% by weight of a non-grafted copolymer (A) comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound and a vinyl cyanide, and 14 to 21% by weight of a grafted copolymer (B), the grafted copolymer (B) comprising one or more selected from the group consisting of a grafted copolymer (b-1) obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyanide onto a conjugated diene rubber having an average particle diameter of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide grafted copolymer (b-2) containing an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm; and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C).

4. The thermoplastic resin composition according to claim 1 or 3, wherein The non-graft copolymer (A) comprises 30 to 60 wt % of an alkyl (meth)acrylate, 20 to 50 wt % of an alkyl-substituted styrene compound, and 5 to 35 wt % of a vinyl cyanide, based on the total weight of the non-graft copolymer (A).

5. The thermoplastic resin composition according to claim 3, wherein The graft copolymer (b-1) comprises 35 to 65 wt % of a conjugated diene rubber, 20 to 50 wt % of an alkyl (meth)acrylate, 1 to 30 wt % of an aromatic vinyl compound and 1 to 20 wt % of a vinyl cyanide, based on the total weight of the graft copolymer (b-1).

6. The thermoplastic resin composition according to claim 3, wherein The graft copolymer (b-2) comprises 30 to 70 wt% of an alkyl acrylate rubber, 10 to 55 wt% of an aromatic vinyl compound, and 1 to 30 wt% of a vinyl cyanide, based on the total weight of the graft copolymer (b-2).

7. The thermoplastic resin composition according to claim 1 or 3, wherein The thermoplastic polyester elastomer (C) has a melt flow rate of 0.5 to 10 g / 10 min, measured at a temperature of 230° C. and a load of 2.16 kg according to ASTM D1238.

8. The thermoplastic resin composition according to claim 1 or 3, wherein The thermoplastic polyester elastomer (C) is an elastomer comprising an aromatic dicarboxylic acid or an ester derivative thereof; an aliphatic diol; and a polyalkylene oxide.

9. The thermoplastic resin composition according to claim 8, wherein The aromatic dicarboxylic acid includes one or more selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid.

10. The thermoplastic resin composition according to claim 8, wherein The aliphatic diol includes one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol.

11. The thermoplastic resin composition according to claim 8, wherein The polyalkylene oxide includes one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of polypropylene glycol, and copolymers of ethylene oxide and tetrahydrofuran.

12. The thermoplastic resin composition according to claim 1 or 3, wherein The thermoplastic resin composition includes 0.1 to 5 parts by weight of a dye, a pigment, or a mixture thereof, based on 100 parts by weight of the base resin.

13. The thermoplastic resin composition according to claim 1 or 3, wherein The thermoplastic resin composition has a sunscreen resistance performance of grayscale level 3 or above.

14. The thermoplastic resin composition according to claim 3, wherein The thermoplastic resin composition has a heat deformation temperature of 85° C. or higher measured at 1.8 MPa according to ISO 75 / Be.

15. A method for preparing a thermoplastic resin composition, the method comprising kneading and extruding 100 parts by weight of a base resin and 8 to 21 parts by weight of a thermoplastic polyester elastomer (C) at 190° C. to 280° C. and 100 to 800 rpm, the base resin comprising 79 to 86% by weight of a non-grafted copolymer (A) comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound and a vinyl cyanide, and 14 to 21% by weight of a graft copolymer (B), the graft copolymer (B) comprising one or more selected from the group consisting of a graft copolymer (b-1) obtained by grafting an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyanide onto a conjugated diene rubber having an average particle diameter of 200 to 500 nm and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer (b-2) containing an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm.

16. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 14.

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