Thermoplastic resin composition, its manufacturing method and molded article manufactured therefrom

Abstract

The present invention relates to a thermoplastic resin composition, its manufacturing method, and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition, characterized in that the composition contains 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm and not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant, and the total rubber content measured by FT-IR is 15 to 21% by weight relative to 100% by weight of the total thermoplastic resin composition, the manufacturing method thereof, and a molded article manufactured therefrom. According to the present invention, the material does not contain phthalate compounds, which are environmental hormones harmful to the human body, does not emit toxic gases in the event of a fire, and has equal or better processability than PVC resin, which is a conventional material for calendars, and is excellent in tensile strength, elongation, surface gloss and surface hardness, thereby ensuring the quality of appearance and durability.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0135350, filed on October 20, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition, a method for producing the same, and molded articles produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition that does not contain phthalate compounds, which are endocrine disrupters harmful to the human body, does not emit toxic gases in the event of a fire, and has processability equal to or better than that of PVC resin, a conventional calendering material, and is excellent in tensile strength, elongation, surface gloss, and surface hardness, thereby ensuring appearance quality and durability, as well as a method for producing the same and molded articles produced therefrom. [Background technology]

[0003] A calender is a rolling machine with an arrangement of multiple heated rollers. The process of forming films and sheets using a calender, and coating plastic on the surface of cloth, paper, etc., is called calendering. While calendering requires a higher capital investment than the extrusion process, it produces superior quality and is therefore widely used, especially in the production of PVC film.

[0004] Polyvinyl chloride resin (hereinafter referred to as "PVC resin") is a vinyl chloride homopolymer or a hybrid polymer containing 50% or more by weight of vinyl chloride. It is one of the five major general-purpose thermoplastic resins manufactured by suspension polymerization and emulsion polymerization. Among these, PVC resin manufactured by suspension polymerization is widely used in the manufacture of films, sheets, electrical wires, pipes, and other products by blending it with plasticizers, stabilizers, fillers, pigments, titanium dioxide (TiO2), and auxiliary materials with special functions. It is processed in various ways. Due to its low cost, excellent physical properties, and high processability, PVC resin is currently widely used as a surface finishing material for furniture. However, due to its material characteristics, it is difficult to reprocess, generates chlorine and hydrogen chloride gases during combustion, which are highly toxic in the event of a fire, and contains phthalate compounds, a plasticizer used to impart flexibility, which are harmful to the human body. It also generates toxic substances during production and disposal. As a result, the market is making efforts to replace PVC with environmentally friendly materials.

[0005] In the T-die extrusion market, polyethylene terephthalate resin is attracting attention due to its excellent physical properties and high colorability. In calendaring extrusion, polypropylene resin is used in some cases due to its high economic efficiency, but its applications are limited due to the difficulty in achieving a high-quality appearance due to its low colorability and gloss, and there is an increasing demand for environmentally friendly materials that can be used in calendaring extrusion.

[0006] To solve these problems, active research is being conducted into materials that can replace PVC resin, and among them, acrylonitrile-styrene-acrylate resin (hereinafter referred to as "ASA resin") is used in a wide range of applications, including automobiles, building materials, and miscellaneous goods, because it has excellent weather resistance, light resistance, colorability, chemical resistance, and impact resistance as well. In particular, ASA resin has better processing stability than PVC resin and is in the spotlight as an environmentally friendly material because it does not contain heavy metal components.

[0007] However, existing ASA resins for calendering have insufficient stretching properties, resulting in poor calendering processability and insufficient durability after molding, resulting in problems such as reduced quality of the produced sheets.

[0008] Therefore, there is a need to develop an ASA resin for calendering that has excellent calendering processability and durability. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent Publication No. 10-2006-0118820 Summary of the Invention [Problem to be solved by the invention]

[0010] In order to solve the above-mentioned problems of the prior art, the present invention aims to provide a thermoplastic resin composition which does not contain phthalate compounds, which are endocrine disrupting substances harmful to the human body, does not emit toxic gases in the event of a fire, and has excellent tensile strength and elongation, and therefore has processability equal to or better than that of PVC resin, which is a conventional calendering material, and excellent durability, as well as a manufacturing method thereof and a molded article manufactured from the same.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0012] To achieve the above object, the present disclosure provides a thermoplastic resin composition comprising: 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm; (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm; and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant; wherein the total rubber content, as measured by FT-IR, is 15 to 21% by weight based on 100% by weight of the total thermoplastic resin composition.

[0013] The present disclosure also provides a thermoplastic resin composition comprising 100 parts by weight of a base resin including (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant, wherein the thermoplastic resin composition has a surface hardness of 95 or greater as measured in accordance with ASTM D785.

[0014] The (A-1) graft copolymer may preferably contain, based on its total weight, 30 to 70% by weight of alkyl acrylate rubber, 20 to 50% by weight of aromatic vinyl compound, and 1 to 25% by weight of vinyl cyanide compound.

[0015] The (A-2) graft copolymer may preferably contain, relative to its total weight, 30 to 70% by weight of alkyl acrylate rubber, 20 to 50% by weight of aromatic vinyl compound, and 1 to 25% by weight of vinyl cyanide compound.

[0016] The weight ratio (A-1:A-2) of the graft copolymer (A-1) to the graft copolymer (A-2) may be preferably 1:1.5 to 1:7.

[0017] The (B) copolymer may preferably have a weight average molecular weight of 50,000 to 180,000 g / mol.

[0018] The copolymer (B) may preferably contain, based on its total weight, 50 to 90% by weight of an aromatic vinyl compound and 10 to 50% by weight of a vinyl cyan compound.

[0019] The (C) lubricant may preferably be at least one selected from the group consisting of aliphatic amide lubricants, fatty acid ester lubricants, montan waxes, and olefin waxes.

[0020] The thermoplastic resin composition may include an antioxidant, a UV stabilizer, or a mixture thereof.

[0021] The thermoplastic resin composition preferably has a tensile strength of 450 kgf / cm as measured in accordance with ASTM D638. 2 It may be more than that.

[0022] The thermoplastic resin composition may preferably have an elongation of 28% or more as measured in accordance with ASTM D638.

[0023] The present disclosure also provides a method for producing a thermoplastic resin composition, comprising the steps of kneading and extruding 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant at 200 to 300°C and 100 to 300 rpm to produce an extrudate, wherein the produced extrudate has a total rubber content of 15 to 21% by weight, based on 100% by weight of the total, as measured by FT-IR.

[0024] The present disclosure also provides a method for producing a thermoplastic resin composition, comprising the steps of kneading and extruding 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant at 200 to 300°C and 100 to 300 rpm, wherein the produced thermoplastic resin composition has a surface hardness of 95 or more as measured in accordance with ASTM D785.

[0025] The present disclosure also provides a molded article comprising the thermoplastic resin composition.

[0026] The molded article may preferably be a calendered article. [Effects of the Invention]

[0027] According to the present invention, there are provided a thermoplastic resin composition that does not contain phthalate compounds, which are environmental hormones harmful to the human body, does not emit toxic gases in the event of a fire, and has processability equal to or better than that of PVC resin, a conventional material for calendars, and is excellent in tensile strength, elongation, surface gloss, and surface hardness, thereby ensuring appearance quality and durability, as well as a manufacturing method thereof and a molded article manufactured from the same.

[0028] Furthermore, the thermoplastic resin composition according to the present invention has excellent calendering processability, and can be used as a surface finishing material, particularly for furniture, by manufacturing it into a film to replace PVC resin. DETAILED DESCRIPTION OF THE INVENTION

[0029] The thermoplastic resin composition of the present invention, its production method, and molded articles produced therefrom will be described in detail below.

[0030] The present inventors have confirmed that when a base resin containing two types of alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymers with different average particle sizes and an aromatic vinyl compound-vinyl cyanide copolymer in a specified content ratio is combined with a specified content of lubricant and the rubber content in the thermoplastic resin composition is adjusted within a specified range, the resulting thermoplastic resin composition does not contain phthalate compounds, which are endocrine disruptors harmful to the human body, does not emit toxic gases in the event of a fire, has equal or superior processability to PVC resin, a conventional calendering material, and has excellent tensile strength, elongation, surface gloss, and surface hardness, thereby ensuring appearance quality and durability and serving as a substitute for PVC materials. Based on this, further research led to the completion of the present invention.

[0031] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin containing (A-1) 3 to 22 weight percent of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40 weight percent of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72 weight percent of an aromatic vinyl compound-vinyl cyanide compound copolymer; and (C) 0.6 to 1.9 weight parts of a lubricant, where the total rubber content, as measured by FT-IR, is 15 to 21 weight percent based on 100 weight percent of the total thermoplastic resin composition. In this case, the composition does not contain phthalate compounds, which are endocrine disruptors harmful to the human body, does not emit toxic gases in the event of a fire, has excellent tensile strength and elongation, is comparable to or better than PVC resin, a conventional calender material, and has excellent scratch resistance, ensuring durability and making it a viable alternative to PVC materials.

[0032] The thermoplastic resin composition of the present invention will be described in detail below, by constituent.

[0033] (A-1) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber having an average particle size of 50 to 200 nm The alkyl acrylate rubber of the (A-1) graft copolymer may have, for example, an average particle size of 50 to 200 nm, preferably 80 to 180 nm, and more preferably 110 to 160 nm, and within this range, excellent mechanical properties and processability can be imparted.

[0034] In this description, the average particle size can be measured using dynamic light scattering, specifically, by measuring the intensity value in Gaussian mode using a particle size analyzer (product name: Nicomp380, manufacturer: PSS). As a specific measurement example, 0.1 g of sample latex (TSC 35-50 wt%) is diluted 1,000-5,000 times with deionized or distilled water, i.e., diluted appropriately so as not to deviate significantly from the intensity setpoint of 300 kHz, and placed in a glass tube. The measurement method is auto-dilution and measurement is performed using a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis, and the settings are a temperature of 23°C, a measurement wavelength of 632.8 nm, and a channel width of 10 μsec.

[0035] The (A-1) graft copolymer may be, for example, 3 to 22% by weight, preferably 3 to 17% by weight, and more preferably 4 to 10% by weight, based on the total weight of the base resin. Within this range, the effect of achieving excellent mechanical properties such as tensile strength and elongation, surface gloss, surface hardness, and fluidity is achieved.

[0036] The (A-1) graft copolymer preferably comprises an alkyl acrylate rubber (core) surrounded by a shell containing an aromatic vinyl compound and a vinyl cyanide compound. In this case, the graft copolymer has excellent tensile strength, elongation, and surface gloss.

[0037] The (A-1) graft copolymer may contain, for example, 30 to 70% by weight, preferably 35 to 65% by weight, and more preferably 40 to 60% by weight of alkyl acrylate rubber relative to its total weight, and within this range, the copolymer has the effect of providing excellent tensile strength, elongation, and processability.

[0038] The (A-1) graft copolymer may contain, for example, 20 to 50% by weight, preferably 25 to 45% by weight, and more preferably 30 to 40% by weight of an aromatic vinyl compound relative to its total weight, and within this range, the copolymer has the effect of achieving excellent surface gloss, surface hardness, and processability.

[0039] The (A-1) graft copolymer may contain, for example, 1 to 25% by weight, preferably 5 to 20% by weight, and more preferably 10 to 20% by weight of a vinyl cyanide compound relative to its total weight. Within this range, the copolymer has the effect of achieving excellent surface gloss, surface hardness, and processability.

[0040] The alkyl acrylate rubber described in the present invention may be, for example, one or more selected from the group consisting of alkyl acrylate rubbers in which the alkyl group has 1 to 10 carbon atoms, preferably one or more selected from the group consisting of ethyl acrylate rubber, propyl acrylate rubber, butyl acrylate rubber, hexyl acrylate rubber, octyl acrylate rubber, and 2-ethylhexyl acrylate rubber, more preferably butyl acrylate rubber, 2-ethylhexyl acrylate rubber, or a mixture thereof, in which case the effect of excellent gloss and surface hardness is achieved.

[0041] In the present description, the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, ο-methylstyrene, ρ-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, ο-bromostyrene, ρ-bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably styrene.

[0042] The vinyl cyanide compound described herein may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and preferably acrylonitrile.

[0043] In this description, a polymer comprising a certain compound (monomer) means a polymer that is polymerized containing that compound (monomer), and the units in the polymerized polymer are derived from that compound.

[0044] The (A-1) graft copolymer may be prepared by emulsion polymerization, for example, and in this case, it has the effect of providing excellent surface gloss and surface hardness.

[0045] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and may be, for example, an emulsion graft polymerization method.

[0046] (A-2) An alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm and not more than 600 nm The alkyl acrylate rubber of the (A-2) graft copolymer may have, for example, an average particle size of more than 200 nm and not more than 600 nm, preferably 250 to 570 nm, more preferably 300 to 550 nm, and even more preferably 400 to 550 nm. Within this range, excellent gloss, tensile strength, and surface hardness can be imparted.

[0047] The (A-2) graft copolymer may be, for example, 20 to 40% by weight, preferably 23 to 35% by weight, and more preferably 23 to 30% by weight, based on the total weight of the base resin. Within this range, the effect of excellent fluidity and tensile strength is achieved.

[0048] The (A-2) graft copolymer may preferably comprise an alkyl acrylate rubber and a shell surrounding the alkyl acrylate rubber, the shell containing an aromatic vinyl compound and a vinyl cyanide compound. In this case, the graft copolymer has excellent mechanical properties, processability, and surface gloss.

[0049] The (A-2) graft copolymer may contain, for example, 30 to 70% by weight, preferably 35 to 65% by weight, and more preferably 40 to 60% by weight of alkyl acrylate rubber relative to its total weight. Within this range, the copolymer has the effect of exhibiting excellent mechanical properties such as tensile strength and elongation, surface gloss, surface hardness, and processability.

[0050] The (A-2) graft copolymer may contain, for example, 20 to 50% by weight, preferably 25 to 45% by weight, and more preferably 30 to 40% by weight of an aromatic vinyl compound relative to its total weight, and within this range, the copolymer has the effect of providing excellent tensile strength, elongation, and processability.

[0051] The (A-2) graft copolymer may contain, for example, 1 to 25% by weight, preferably 5 to 20% by weight, and more preferably 10 to 20% by weight of a vinyl cyanide compound relative to its total weight. Within this range, the copolymer has the effect of achieving excellent surface gloss, surface hardness, and processability.

[0052] The types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (A-2) graft copolymer may be within the same category as the types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (A-1) graft copolymer of the present invention.

[0053] The (A-2) graft copolymer may be produced by emulsion polymerization, for example, and in this case, it has the effect of being excellent in tensile strength, elongation, gloss, and surface hardness.

[0054] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and may be, for example, an emulsion graft polymerization method.

[0055] The weight ratio (A-1:A-2) of the graft copolymer (A-1) to the graft copolymer (A-2) may be, for example, 1:1.5 to 1:7, preferably 1:2.5 to 1:6, more preferably 1:3 to 1:6, and even more preferably 1:4 to 1:5.5. Within this range, the tensile strength, elongation, gloss, surface hardness, and processability are all excellent.

[0056] The difference between the average particle size of the acrylate rubber of the graft copolymer (A-1) and the average particle size of the acrylate rubber of the graft copolymer (A-2) may be, for example, 100 to 550 nm, preferably 150 to 500 nm, more preferably 200 to 450 nm, and even more preferably 250 to 450 nm. Within this range, there is an effect of further improving the tensile strength, elongation, surface gloss, and surface hardness.

[0057] The sum of the (A-1) graft copolymer and the (A-2) graft copolymer may be, for example, 25 to 50% by weight, preferably 30 to 45% by weight, and more preferably 30 to 40% by weight, relative to 100% by weight of the total base resin. Within this range, the tensile strength, elongation, surface gloss, surface hardness, and fluidity are further improved, which has the advantage of improving processability.

[0058] (B) Aromatic vinyl compound-vinyl cyanide copolymer The (B) copolymer may be, for example, 50 to 72% by weight, preferably 55 to 70% by weight, and more preferably 60 to 70% by weight, based on the total weight of the base resin. Within this range, there are advantages such as excellent tensile strength, elongation, surface hardness, and processability.

[0059] The (B) copolymer may have a weight average molecular weight of, for example, 50,000 to 180,000 g / mol, preferably 60,000 to 180,000 g / mol, more preferably 70,000 to 180,000 g / mol, and even more preferably 80,000 to 180,000 g / mol. Within this range, the copolymer has the effect of being excellent in mechanical properties such as tensile strength and elongation, surface gloss, and surface hardness.

[0060] In this description, unless otherwise specified, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, water breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using THF (tetrahydrofuran) as an eluent. In this case, as a specific measurement example, the following conditions can be used: solvent: THF, column temperature: 40°C, flow rate: 0.3 ml / min, 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, test method (Mn, Mw and PDI): Measurement can be performed under the conditions of OECD TG 118.

[0061] The copolymer (B) may contain, for example, 50 to 90% by weight, preferably 60 to 80% by weight, and more preferably 65 to 75% by weight of an aromatic vinyl compound relative to the total weight of the copolymer (B). Within this range, the copolymer (B) has the effect of exhibiting excellent mechanical properties such as tensile strength and elongation, as well as excellent surface gloss and surface hardness.

[0062] For example, the copolymer (B) may contain, relative to its total weight, 10 to 50% by weight, preferably 20 to 40% by weight, and more preferably 25 to 35% by weight of a vinyl cyan compound. Within this range, the copolymer (B) has the effect of providing excellent mechanical properties such as tensile strength and elongation, as well as excellent surface gloss and surface hardness.

[0063] The types of aromatic vinyl compounds and vinyl cyan compounds contained in the copolymer (B) may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds contained in the graft copolymer (A-1) described herein.

[0064] The copolymer (B) is preferably a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, and more preferably a styrene-acrylonitrile copolymer (SAN resin). In this case, the copolymer has the effect of providing excellent surface gloss, surface hardness, and processability.

[0065] The copolymer (B) may be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and preferably by bulk polymerization, which has the effect of providing excellent mechanical properties.

[0066] The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited as long as they are solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization methods commonly used in the technical field to which the present invention pertains.

[0067] (C)Lubricant The (C) lubricant may be, for example, 0.6 to 1.9 parts by weight, preferably 0.8 to 1.8 parts by weight, and more preferably 0.8 to 1.5 parts by weight, based on 100 parts by weight of the base resin. Within this range, the tensile strength, elongation, gloss, and surface hardness are all excellent, and the calendering processability is excellent. Therefore, the sheet is not deformed or damaged during calendering, and it can be attached and detached on the roll, which is effective as a substitute for PVC materials.

[0068] The lubricant (C) may be, for example, one or more selected from the group consisting of aliphatic amide-based lubricants, fatty acid ester-based lubricants, montan waxes, and olefin-based waxes, and is preferably a fatty acid ester-based lubricant, more preferably pentaerythrityl tetrastearate. In this case, the lubricant has excellent tensile strength, elongation, gloss, and surface hardness, and therefore can be used in calendering instead of PVC resin, resulting in excellent calendering processability.

[0069] The aliphatic amide lubricant may be at least one selected from the group consisting of stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bisoleamide. In this case, the aliphatic amide lubricant has excellent tensile strength, elongation, gloss, and surface hardness, and therefore can be used in calendering instead of PVC resin, resulting in excellent calendering processability.

[0070] The fatty acid ester-based lubricant may be, for example, at least one selected from the group consisting of fatty acid esters of alcohols or polyhydric alcohols, hydrogenated oils, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphate esters, and is preferably pentaerythritol tetrastearate. In this case, since the lubricant has excellent tensile strength, elongation, gloss, and surface hardness, it can be calendered instead of PVC resin, and has the effect of excellent calendering processability.

[0071] The montan wax may be, for example, a montan wax or a montan ester wax. In this case, since the montan wax has excellent tensile strength, elongation, gloss, and surface hardness, it can be used in place of PVC resin for calendering, and has the effect of excellent calendering processability.

[0072] The olefin wax may be, for example, a polyolefin wax, preferably a polyethylene wax, a polypropylene wax, or a mixture thereof, more preferably a polyethylene wax, and even more preferably an oxidized high density polyethylene wax. In this case, the olefin wax has excellent tensile strength, elongation, gloss, and surface hardness, and therefore can be calendered instead of PVC resin, resulting in excellent calendering processability.

[0073] additives The thermoplastic resin composition may include, for example, an antioxidant, a UV stabilizer, or a mixture thereof. In this case, the required physical properties can be effectively achieved without deteriorating the inherent physical properties of the thermoplastic resin composition described herein.

[0074] The antioxidant may be, for example, 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, and more preferably 0.3 to 1 part by weight, per 100 parts by weight of the base resin, and within this range, there is an effect of improving heat resistance.

[0075] The antioxidant may be, for example, one or more selected from the group consisting of phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants, and is preferably a phenol-based antioxidant or a phosphite-based antioxidant.

[0076] The phenolic antioxidant may be, for example, one or more selected from the group consisting of tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris-(4-t-butyl-3-hydroxy-2,6-dimethylbenzene)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0077] The phosphite-based antioxidant may be, for example, trisnonylphenyl phosphite, tris-(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0078] The thioether antioxidant may be, for example, one or more selected from the group consisting of dilauryl thiodipropionate, dimyristyl thiodipropionate, laurylstearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

[0079] For example, the UV stabilizer may be present in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 1.5 parts by weight, and more preferably 0.5 to 1 part by weight, per 100 parts by weight of the base resin, which has the effect of improving weather resistance.

[0080] The UV stabilizer may be, for example, a hindered amine light stabilizer (HALS), and preferably, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzyl methyl malonate, condensation products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanediol Tanethene tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], more preferably bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], or a mixture thereof The resin may be a mixture of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl)), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], or a mixture thereof, which has the advantage of not impairing impact strength and fluidity and significantly improving weather resistance.

[0081] The thermoplastic resin composition may optionally further contain one or more selected from the group consisting of dyes, pigments, colorants, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, anti-dripping agents, anti-friction agents, and anti-wear agents in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.5 to 1 part by weight, based on 100 parts by weight of the total base resin.Within these ranges, the required physical properties are effectively achieved without deteriorating the inherent physical properties of the thermoplastic resin composition described herein.

[0082] thermoplastic resin composition The thermoplastic resin composition may preferably have a total rubber content of 15 to 21 wt %, more preferably 15 to 20 wt %, even more preferably 15 to 19 wt %, and even more preferably 15 to 18 wt %, relative to the total weight of the thermoplastic resin composition, as measured by FT-IR.Within this range, the composition has excellent tensile strength, elongation, gloss, and surface hardness, and also has excellent calendering processability, making it advantageous as a substitute for PVC resin.

[0083] The thermoplastic resin composition preferably has a tensile strength of 450 kgf / cm, measured at the point where a 3 mm thick test piece breaks after being pulled at a crosshead speed of 50 mm / min in accordance with ASTM D638. 2 More preferably, 470 kgf / cm 2 More preferably, 500 kgf / cm 2 More preferably, 500 to 650 kgf / cm 2 Within this range, the resin has an excellent balance of physical properties and excellent processability, particularly calender processability, and is therefore advantageous in replacing PVC resin.

[0084] The thermoplastic resin composition preferably has an elongation of 28% or more, more preferably 28 to 60%, even more preferably 28 to 50%, and even more preferably 28 to 45%, as measured on a 3 mm thick test piece at a crosshead speed of 50 mm / min in accordance with ASTM D638. Within this range, the thermoplastic resin composition has an excellent balance of physical properties and excellent processability, particularly calender processability, making it advantageous as a substitute for PVC resin.

[0085] The thermoplastic resin composition may preferably have a surface hardness measured in accordance with ASTM D785 of 95 or more, more preferably 100 or more, and even more preferably 100 to 115. Within this range, the thermoplastic resin composition has the advantage of having an excellent balance of physical properties and excellent durability.

[0086] The thermoplastic resin composition preferably has a surface gloss of 90 GU or more, more preferably 90 to 100 GU, as measured at 45° on a ¼-inch thick injection test piece in accordance with ASTM D528. Within this range, the composition has an excellent balance of physical properties and excellent transparency, resulting in a beautiful appearance.

[0087] The thermoplastic resin composition may preferably have a pencil hardness of B or more, preferably HB or more, measured in accordance with ASTM D219. Within this range, the thermoplastic resin composition has the advantage of having an excellent balance of physical properties and excellent durability.

[0088] When the thermoplastic resin composition is produced as a sheet having a thickness of 0.3 mm, preferably at a roll temperature of 180 to 220°C, a calender roll speed of 8 to 12 rpm, and a gap between the calender rolls of 0.3 mm, the thermoplastic resin composition is stabilized within 3 minutes after plasticization on the surface of the roll and application, and the formed sheet can be attached to and detached from the roll without deformation or damage, resulting in excellent calender processability.

[0089] The following describes a method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition. The description of the method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition includes all of the above-mentioned thermoplastic resin compositions.

[0090] Method for producing thermoplastic resin composition The method for producing a thermoplastic resin composition described herein includes the steps of kneading and extruding 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant at 200 to 300°C and 100 to 300 rpm to produce an extrudate, wherein the produced extrudate has a total rubber content of 15 to 21% by weight based on 100% by weight of the total rubber as measured by FT-IR. In this case, it does not contain phthalate compounds, which are environmental hormones harmful to the human body, does not emit toxic gases in the event of a fire, and has the same or better processability as PVC resin, a conventional calendering material, and is excellent in tensile strength, elongation, surface gloss and surface hardness, ensuring appearance quality and durability.It also has excellent calendering processability, making it an advantageous alternative to PVC resin.

[0091] The kneading and extrusion may be carried out using, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, which has the effect of uniformly dispersing the composition and providing excellent compatibility.

[0092] The kneading and extrusion may be carried out, for example, at a barrel temperature in the range of 200 to 300°C, preferably 210 to 280°C, and more preferably 220 to 270°C. In this case, the processing amount per unit time is appropriate, sufficient melt-kneading is possible, and problems such as thermal decomposition of the resin component are not caused.

[0093] The kneading and extrusion may be carried out under conditions where, for example, the screw rotation speed is 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, or 200 to 310 rpm, preferably 250 to 350 rpm. Within this range, the throughput per unit time is high, and the process efficiency is excellent.

[0094] The extrudate may preferably be in the form of pellets or plates.

[0095] In this description, the plate-like shape is not particularly limited as long as it is defined as a normal plate-like shape in the technical field to which the present invention belongs, and examples thereof include a flat shape, a sheet shape, a film shape, etc.

[0096] Molded product The molded article described herein may, for example, contain the thermoplastic resin composition described herein. In this case, the molded article does not contain phthalate compounds, which are endocrine disruptors harmful to the human body, does not emit toxic gases in the event of a fire, and has the same or better processability as PVC resin, a conventional calendering material, and is excellent in tensile strength, elongation, surface gloss, and surface hardness, ensuring appearance quality and durability. This has the advantage of being applicable as a high-quality finishing material that can replace PVC resin.

[0097] The molded product may be, for example, a calendered product, and preferably may be a building finishing material, a roof finishing material, or a furniture finishing material. In this case, the molded product has the advantage of being excellent in appearance quality and durability, and can therefore be provided with a quality higher than that required in the market.

[0098] The method for producing a molded article described herein includes the steps of: kneading and extruding 100 parts by weight of a base resin containing (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm, (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm, and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and (C) 0.6 to 1.9 parts by weight of a lubricant; and producing an extrudate under conditions of 200 to 300°C and 100 to 300 rpm; and calendering the extrudate at a molding temperature of 120 to 300°C to produce a molded article; wherein the extrudate has a total rubber content of 15 to 21% by weight relative to 100% by weight of the total, as measured by FT-IR. In this case, it does not contain phthalate compounds, which are environmental hormones harmful to the human body, and does not emit toxic gases in the event of a fire. It also has excellent tensile strength and elongation, making it easier to process than PVC resin, a conventional calendar material. It also has excellent surface gloss and scratch resistance, ensuring durability and appearance quality, making it an excellent alternative to PVC resin as a high-quality finishing material.

[0099] The calendering process, for example, involves rolling the extrudate using a calendering process including a calender roll, and is not particularly limited as long as it is a method commonly used in the technical field to which the present invention pertains, but preferably includes the steps of mixing the raw materials for the sheet in a mixer at 130 to 220°C, producing the mixed raw materials as a base sheet at 170 to 240°C, and producing the base sheet as a sheet using a calender roll at 140 to 220°C. Here, for example, a mixing roll can be used in the base sheet production step.

[0100] In describing the thermoplastic resin composition, its manufacturing method, and molded articles described herein, other conditions, equipment, etc. not explicitly described can be appropriately selected within the range commonly used in the art, and are not particularly limited.

[0101] Below, preferred examples are presented to help understand the present invention. However, the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical idea of ​​the present invention, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0102] [Example] *(A-1) ASA graft copolymer: ASA graft copolymer (a graft copolymer containing 50% by weight of butyl acrylate rubber, 35% by weight of styrene, and 15% by weight of acrylonitrile) produced by emulsion polymerization, with an average particle size of alkyl acrylate rubber of 150 nm. *(A-2) ASA graft copolymer: ASA graft copolymer (a graft copolymer containing 50% by weight of butyl acrylate rubber, 35% by weight of styrene, and 15% by weight of acrylonitrile) produced by emulsion polymerization, with an average particle size of alkyl acrylate rubber of 450 nm. *(B) Bulk polymerization SAN copolymer: A copolymer containing 70% by weight of styrene and 30% by weight of acrylonitrile (weight average molecular weight 150,000 g / mol) *(C) Lubricant: Pentaerythritol tetrastearate *(D) Additives: Antioxidant: Irganox 1076 (BASF) 0.5 parts by weight, Irgafox 168 (BASF) 0.5 parts by weight UV stabilizer: Tinuvin 770 (BASF) 0.5 parts by weight, Sunsorb 329 (SUNFINE GLOBAL) 0.5 parts by weight

[0103] Examples 1 to 7 and Comparative Examples 1 to 9 Two parts by weight of additives were mixed and extruded in an extruder (SM Twin screw extruder, 25mm diameter) at an extrusion temperature of 230°C, a feed rate of 20 kg / hr, and a screw speed of 300 rpm, to produce pellets. The pellets were then injected into an injector (ENGEL 120MT) at an injection temperature of 200-240°C and a screw speed of 100-200 rpm to prepare test specimens for measuring appearance and physical properties. The extruded resin pellets were then calendered into a 0.3 mm-thick sheet in a roll mill (MIRAE RPM Co., Ltd., MR-LM0820) equipped with two 30 cm diameter calender rolls spaced 0.3 mm apart, with the rolls maintained at 180-210°C.

[0104] [Test example] The properties of the pellets and injection test pieces produced in Examples 1 to 7 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 1 and 2 below. *Rubber content (wt%): Quantitatively measured using FT-IR. *Tensile strength (kgf / cm 2 ): According to ASTM D638, the point at which a 3 mm thick test piece was broken was measured after pulling at a crosshead speed of 50 mm / min. *Elongation (%): The elongation was measured on a 3 mm thick test piece at a crosshead speed of 50 mm / min in accordance with ASTM D638. *Surface hardness: Rockwell hardness was measured on an R scale in accordance with ASTM D785 using a 1 / 4" thick test piece. *Surface gloss (GU): Measured in accordance with ASTM D523 using a gloss meter on a 3.2 mm thick injection test piece at an incident angle of 45°. The higher the gloss at 45°, the better the surface gloss. Here, the unit of surface gloss is GU (Gloss Unit). *Pencil hardness: Pencil hardness was measured in accordance with ASTM D219. *Processability: Thermoplastic resin composition pellets were roll-mill extruded into a 0.3 mm-thick sheet at a roll temperature of 180 to 220°C, a calender roll speed of 8 to 12 rpm, and a gap between the calender rolls of 0.3 mm. The plasticization, roll application, and roll stabilization times of the thermoplastic resin composition were measured and evaluated as follows: If the roll stabilization time was 3 minutes or less, the processability was evaluated as excellent. ○: When forming the sheet, the resin is stably applied to the surface of the roll and stabilized within 3 minutes, and the formed sheet can be attached and detached from the roll without deformation or damage. ×: When forming the sheet, the resin is applied unstably on the surface of the roll, the stabilization time exceeds 3 minutes, and deformation or damage occurs when the formed sheet is attached to or detached from the roll.

[0105] [Table 1] [Table 2] (In Tables 1 and 2, the contents of (A-1), (A-2), and (B) are in weight percent based on the total weight of these, and the contents of (C) and (D) are in parts by weight based on 100 parts by weight of the total weight of (A-1), (A-2), and (B).)

[0106] As shown in Tables 1 and 2, the thermoplastic resin compositions according to the present invention (Examples 1 to 7) are superior in tensile strength, elongation, surface hardness, surface gloss, pencil hardness and processability compared to Comparative Examples 1 to 9, and it has been confirmed that they can be applied to high-quality calendar-molded products.

[0107] Specifically, Comparative Examples 1 and 2, in which the rubber content was outside the range of the present invention and the content of the graft copolymer (A-1) or the content of the graft copolymer (A-2) was outside the range of the present invention, had low elongation and pencil hardness and poor processability.

[0108] In addition, Comparative Example 3, in which the rubber content exceeded the range of the present invention, had low tensile strength and surface hardness, and Comparative Examples 4 and 5, in which the rubber content exceeded the range of the present invention and did not satisfy the range of the (B) copolymer content, and in which the content of the (A-1) graft copolymer or the (A-2) graft copolymer did not satisfy the range of the present invention, had poor tensile strength, surface hardness, and pencil hardness.

[0109] In addition, Comparative Examples 6 and 7, in which the content of lubricant (C) was outside the range of the present invention, had poor processability. In particular, Comparative Example 6 also had low elongation, and Comparative Example 8, in which the content of rubber exceeded the range of the present invention, had poor tensile strength, surface hardness, and pencil hardness.

[0110] In addition, although the rubber content was within the range of the present invention, Comparative Example 9, in which the contents of the (A-1) graft copolymer and the (A-2) graft copolymer were outside the range of the present invention, had poor processability during sheet molding, resulting in damage to the sheet.

[0111] In conclusion, the thermoplastic resin composition according to the present invention, which is obtained by mixing a base resin containing two types of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymers with different average particle sizes and an aromatic vinyl compound-vinyl cyanide compound copolymer in a predetermined content ratio, with a predetermined content of lubricant, and adjusting the rubber content within a predetermined range, does not contain phthalate compounds, which are environmental hormones harmful to the human body, does not emit toxic gases in the event of a fire, and has processability equivalent to or better than that of PVC resin, a conventional calendering material, and is excellent in tensile strength, elongation, surface gloss and surface hardness, thereby confirming the effect of ensuring appearance quality and durability.

Claims

1. 100 parts by weight of a base resin including: (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm; (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm but not more than 600 nm; and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 0.6 to 1.9 parts by weight of a fatty acid ester-based lubricant, A thermoplastic resin composition characterized in that the total content of rubber measured by FT-IR is 15 to 21 wt % relative to 100 wt % of the total thermoplastic resin composition.

2. The thermoplastic resin composition according to claim 1, wherein the graft copolymer (A-1) contains, relative to its total weight, 30 to 70% by weight of an alkyl acrylate rubber, 20 to 50% by weight of an aromatic vinyl compound, and 1 to 25% by weight of a vinyl cyan compound.

3. The thermoplastic resin composition according to claim 1, wherein the (A-2) graft copolymer contains, relative to its total weight, 30 to 70% by weight of an alkyl acrylate rubber, 20 to 50% by weight of an aromatic vinyl compound, and 1 to 25% by weight of a vinyl cyan compound.

4. The thermoplastic resin composition according to claim 1, wherein the weight ratio (A-1:A-2) of the graft copolymer (A-1) to the graft copolymer (A-2) is 1:1.5 to 1:

7.

5. 2. The thermoplastic resin composition according to claim 1, wherein the copolymer (B) has a weight average molecular weight of 50,000 to 180,000 g / mol.

6. 2. The thermoplastic resin composition according to claim 1, wherein the copolymer (B) contains, based on the total weight of the copolymer, 50 to 90% by weight of an aromatic vinyl compound and 10 to 50% by weight of a vinyl cyan compound.

7. The thermoplastic resin composition of claim 1 , wherein the thermoplastic resin composition comprises an antioxidant, a UV stabilizer, or a mixture thereof.

8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a surface hardness of 95 or more as measured in accordance with ASTM D785.

9. The thermoplastic resin composition has a tensile strength of 450 kgf / cm as measured in accordance with ASTM D638. ２ The thermoplastic resin composition according to claim 1, characterized in that

10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an elongation of 28% or more as measured in accordance with ASTM D638.

11. the method comprises the steps of kneading and extruding 100 parts by weight of a base resin comprising: (A-1) 3 to 22% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 200 nm; (A-2) 20 to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of more than 200 nm and not more than 600 nm; and (B) 50 to 72% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and (C) 0.6 to 1.9 parts by weight of a fatty acid ester-based lubricant under conditions of 200 to 300°C and 100 to 300 rpm to produce an extrudate; A method for producing a thermoplastic resin composition, characterized in that the produced extrudate has a total rubber content of 15 to 21 wt % as measured by FT-IR, based on 100 wt % of the total.

12. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 10.

13. The molded article according to claim 12, characterized in that the molded article is a calendered article.

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