Thermoplastic resin composition, method for producing the same, and molded article containing the same

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, in which a compatibilizer is added to a base resin containing an ASA-based graft copolymer, a SAN-based and / or SAMMA-based resin, and recycled or non-recycled polyalkylene terephthalate, and the composition ratio is adjusted, thereby maintaining the intrinsic mechanical properties of the ASA-based resin and polyester resin at an equivalent or higher level, while exhibiting excellent film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, the present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, in which excellent impact resistance, film processability, low gloss characteristics, weather resistance, and thermal stability are all achieved.

Description

[Technical Field]

[0001] [Cross-reference with related applications] This application is an application claiming priority rights based on Korean Patent Application No. 10-2023-0133757 and Korean Patent Application No. 10-2023-0133758 dated October 6, 2023, and Korean Patent Application No. 10-2024-0133295 and Korean Patent Application No. 10-2024-0133298, which were refiled on September 30, 2024, respectively, and all content disclosed in the documents of said Korean Patent Applications is incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, and further relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, which have excellent mechanical properties, film processability, appearance characteristics such as gloss and whiteness, weather resistance, and thermal stability, and also have the advantage of being environmentally friendly as deterioration of physical properties is prevented even when recycled resin is included, and further relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same that have excellent mechanical properties, film processability, low gloss characteristics, weather resistance, and thermal stability. [Background technology]

[0003] ABS resins, typified by acrylonitrile-butadiene-styrene resin, have been used in various fields due to their excellent moldability, mechanical properties, and appearance characteristics. However, because they are based on conjugated diene rubber with chemically unstable unsaturated bonds, they suffer from poor weather resistance, easily degrading when exposed to ultraviolet light. Therefore, ASA resins, typified by acrylate compound-styrene-acrylonitrile copolymers, have been proposed as alternative materials to ABS resins.

[0004] ASA resins offer excellent weather resistance, thermal stability, degradation resistance, and chemical resistance, while also possessing excellent moldability, rigidity, and impact resistance. Therefore, they are widely applied in various fields, both indoors and outdoors, including electrical and electronic components, building materials, automotive interior and exterior materials, ships, and leisure goods.

[0005] The aforementioned ASA-based resins are derived from acrylate rubber to impart impact resistance and are mainly consumed in blends with rigid resins. A typical example of a rigid resin is styrene-acrylonitrile resin.

[0006] On the other hand, polyester resins, such as polyethylene terephthalate resin and polybutylene terephthalate resin, are widely used in automotive parts, electrical and electronic equipment, and office equipment due to their excellent mechanical, electrical, and other physical and chemical properties. In particular, their use has increased even further in the automotive parts sector recently, with the development of lightweight materials and highly intensive technologies such as electric vehicles and autonomous driving technology.

[0007] Incidentally, while it is expected that a very useful material will be provided when the aforementioned ASA resin and polyester resin are blended, in reality, there is a problem that the resulting physical properties do not meet expectations because the ASA resin and polyester resin do not have good compatibility with each other.

[0008] On the other hand, while plastics are consumed in considerable quantities in modern society due to their convenience, they do not decompose naturally, leading to increasing demands for waste disposal and utilization solutions. As part of environmental regulations, the use of recycled resins is becoming increasingly mandatory. However, recycled resins deteriorate due to physical and chemical factors such as impact, abrasion, heat, UV, humidity, and exposure to high and low temperature environments during the manufacturing, consumption, and disposal processes. Furthermore, contamination such as the influx of foreign matter results in significantly inferior moldability, mechanical rigidity, appearance quality, flexibility, chemical resistance, and thermal stability compared to newly polymerized (virgin) resins.

[0009] Therefore, there is a need to develop thermoplastic resin compositions that, while containing ASA-based resins and polyester resins, exhibit the expected physical properties due to their excellent compatibility, and that, even when containing a certain level or more of recycled resin, possess physical properties at a level applicable to existing plastic material fields. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Korean Published Patent No. 10-2009-0038507 [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] In order to solve the problems of the conventional technology described above, the present invention aims to provide a thermoplastic resin composition, a method for producing the same, and molded articles produced therefrom, which have the advantage of being environmentally friendly, as well as maintaining the unique mechanical properties of ASA resin and polyester resin at an equivalent or higher level, while also having excellent film processability, gloss, whiteness, weather resistance, and thermal stability, and preventing a decrease in physical properties even when recycled resin is included, and also having excellent film processability, low gloss characteristics, weather resistance, and thermal stability.

[0012] The above-mentioned and other objectives of the present invention can all be achieved by the present invention as described below. [Means for solving the problem]

[0013] To achieve the above objective, the present invention provides a thermoplastic resin composition characterized by comprising: I) 100 parts by weight of a base resin containing 60 to 90% by weight of a styrene copolymer and 10 to 40% by weight of a regenerated or non-regenerated polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer.

[0014] Furthermore, the present invention provides a thermoplastic resin composition characterized by comprising 100 parts by weight of a base resin containing 15 to 50% by weight of a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound, 20 to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10 to 40% by weight of recycled or non-recycled polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer.

[0015] Furthermore, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of a base resin containing 15 to 50% by weight of a copolymer comprising an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound, 20 to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10 to 40% by weight of regenerated or unregenerated polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the weight ratio of the copolymer comprising the alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound to the regenerated or unregenerated polyalkylene terephthalate is 0.5 to 2.0:1.

[0016] Furthermore, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of a base resin containing IV) (A) 15 to 50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) 20 to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and (C) 10 to 40% by weight of a regenerated or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0017] V) In I) to IV) above, the (D) compatibilizer may preferably be one or more selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA).

[0018] VI) In any one of the above I) to V), the (A) copolymer preferably comprises, based on 100% by weight of the base resin: 3 to 35% by weight of (A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 250 to 500 nm; and 5 to 40% by weight of (A-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 50 to 150 nm.

[0019] VII) In any one of the above I) to VI), the (A-1) graft copolymer and the (A-2) graft copolymer each preferably may comprise 40 to 60% by weight of the alkyl acrylate rubber, 30 to 40% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyan compound, based on the total weight of the respective copolymer.

[0020] VIII) In any one of the above I) to VII), the (B) copolymer is preferably one or more selected from the group consisting of: (B-1) an aromatic vinyl compound-vinyl cyan compound copolymer comprising 55 to 85% by weight of an alkyl-unsubstituted aromatic vinyl compound and 15 to 45% by weight of a vinyl cyan compound; and (B-2) a heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer comprising 60 to 80% by weight of an alkyl-substituted aromatic vinyl compound, 20 to 40% by weight of a vinyl cyan compound, and 0 to 20% by weight of an alkyl-unsubstituted aromatic vinyl compound.

[0021] IX) In any one of the above I) to VIII), the (B-1) aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of 50,000 to 300,000 g / mol.

[0022] X) In any one of the above I) to IX), the (B-2) heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of 30,000 to 200,000 g / mol.

[0023] XI) In any one of the above items I) to X), the (C) polyalkylene terephthalate preferably has an intrinsic viscosity (I.V.) of 0.5 to 1.5 dl / g.

[0024] XII) In any one of the above items I) to XI), the (C) polyalkylene terephthalate is preferably non-recycled polyethylene terephthalate or recycled polyethylene terephthalate.

[0025] XIII) In any one of the above items I) to XII), the weight ratio (A:C) of the (A) graft copolymer to the (C) polyalkylene terephthalate is preferably 0.5 to 2.0:1.

[0026] XIV) In any one of the above items I) to XIII), the (D) compatibilizer may preferably contain 30 to 90% by weight of ethylene and 10 to 70% by weight of methyl acrylate or vinyl acetate, and more preferably may contain 50 to 90% by weight of ethylene and 10 to 50% by weight of methyl acrylate or vinyl acetate. The (D) compatibilizer is even more preferably an ethylene-methyl acrylate copolymer (EMA) comprising 50 to 90% by weight of ethylene and 10 to 50% by weight of methyl acrylate.

[0027] XV) In any one of the above items I) to XIV), the (C) polyalkylene terephthalate is preferably non-recycled polyethylene terephthalate, and the thermoplastic resin composition preferably has an injection gloss of 108 or higher as measured in accordance with ASTM D2457 on an injection test piece having a thickness of 3 mm at an angle of 45°.

[0028] XVI) In any one of the above items I) to XV), the (C) polyalkylene terephthalate is preferably recycled polyethylene terephthalate, and the thermoplastic resin composition preferably has a gloss of less than 50 as measured in accordance with ASTM D2457 on an extruded film test piece having a thickness of 0.08 mm (80 µm) at an angle of 45°.

[0029] The present invention also provides a method for producing a thermoplastic resin composition, characterized by comprising the steps of kneading and extruding 100 parts by weight of a base resin containing 60 to 90% by weight of (XVII) styrene copolymer and 10 to 40% by weight of regenerated or unregenerated polyalkylene terephthalate, and 0.5 to 10 parts by weight of (D) a compatibilizer, under conditions of 170 to 300°C and 100 to 400 rpm.

[0030] The present invention also provides a method for producing a thermoplastic resin composition, characterized by comprising the steps of kneading and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising 100 parts by weight of a base resin containing 15 to 50% by weight of a copolymer comprising (XVIII) alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound, 20 to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10 to 40% by weight of recycled or non-recycled polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0031] The present invention also provides a method for producing a thermoplastic resin composition comprising the steps of kneading and extruding at 170 to 300°C and 100 to 400 rpm, wherein the weight ratio of the copolymer comprising the alkyl acrylate rubber, aromatic vinyl compound and vinyl cyanide compound to the regenerated or unregenerated polyalkylene terephthalate is 0.5 to 2.0:1.

[0032] The present invention also provides a method for producing a thermoplastic resin composition, characterized by comprising the steps of kneading and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising 100 parts by weight of a base resin containing XX)(A) 15 to 50% by weight of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) 20 to 55% by weight of aromatic vinyl compound-vinyl cyanide compound copolymer, and (C) 10 to 40% by weight of regenerated or unregenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0033] Furthermore, the present invention provides a molded article characterized by containing a thermoplastic resin composition described in any one of the above items XXI) to XX). [Effects of the Invention]

[0034] The present invention provides a thermoplastic resin composition, a method for producing the same, and molded articles produced therefrom, which maintain the unique mechanical properties of ASA resin and polyester resin at an equivalent or higher level, while exhibiting excellent film processability, injection gloss, whiteness, weather resistance, and thermal stability.

[0035] The present invention also has the advantage of being environmentally friendly, as it prevents a decrease in physical properties even when recycled resin is included, and at the same time provides a thermoplastic resin composition, a method for producing the same, and molded articles produced therefrom, which have excellent film processability, low gloss characteristics, weather resistance, and thermal stability, while maintaining the respective unique mechanical properties of ASA-based resin and polyester resin at an equivalent or higher level. [Modes for carrying out the invention]

[0036] The thermoplastic resin composition, its manufacturing method, and molded article described herein will be explained in detail below.

[0037] The inventors of the present invention have confirmed that when alloying ASA resin and polyester resin, by adding a compatibilizer and adjusting the composition ratio within a predetermined range, the unique mechanical properties of both the ASA resin and the polyester resin are retained without degradation, and the alloy possesses excellent film processability, weather resistance, and thermal stability. In particular, even when recycled resin is mixed, the degradation of physical properties is prevented, and it has the advantage of being environmentally friendly. Based on this, the inventors continued their research and completed the present invention.

[0038] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin containing 60-90% by weight of a styrene copolymer and 10-40% by weight of polyalkylene terephthalate, and 0.5-10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is either recycled or non-recycled polyalkylene terephthalate. In this case, the compatibility is greatly improved, maintaining the mechanical properties inherent to ASA resins and polyester resins at an equivalent or higher level, while simultaneously exhibiting excellent film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, offering the advantage of being environmentally friendly, while also exhibiting excellent film processability and low-gloss characteristics.

[0039] In this description, styrene copolymer refers to a copolymer mainly composed of a styrene monomer, represented by styrene, i.e., an aromatic vinyl compound, preferably containing 5% by weight or more. Specific examples include copolymers comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound, and / or aromatic vinyl compound-vinyl cyanide compound copolymers. Furthermore, the copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound may be a graft copolymer in which an aromatic vinyl compound-vinyl cyanide compound copolymer is grafted onto an alkyl acrylate rubber core.

[0040] Furthermore, the thermoplastic resin composition of the present invention specifically comprises 100 parts by weight of a base resin containing 15-50% by weight of a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound, 20-55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10-40% by weight of polyalkylene terephthalate, and 0.5-10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is either recycled or non-recycled polyalkylene terephthalate. In this case, the compatibility is greatly improved, maintaining the mechanical properties inherent to ASA-based resins and polyester resins at an equivalent or higher level, while simultaneously exhibiting excellent film processability, gloss, whiteness, weather resistance, and thermal stability. Moreover, even when recycled resin is included, a decrease in physical properties is prevented, offering the advantage of being environmentally friendly, while simultaneously exhibiting excellent film processability and low-gloss characteristics.

[0041] Furthermore, the thermoplastic resin composition of the present invention specifically comprises 100 parts by weight of a base resin containing 15-50% by weight of a copolymer comprising alkyl acrylate rubber, aromatic vinyl compound and vinyl cyanide compound, 20-55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10-40% by weight of polyalkylene terephthalate, and 0.5-10 parts by weight of a compatibilizer, wherein the weight ratio of the copolymer comprising alkyl acrylate rubber, aromatic vinyl compound and vinyl cyanide compound to the polyalkylene terephthalate is 0.5-2.0:1, and the polyalkylene terephthalate is either recycled polyalkylene terephthalate or non-recycled polyalkylene terephthalate. In this case, the compatibility is greatly improved, maintaining the mechanical properties inherent to ASA-based resins and polyester resins at an equivalent or higher level, while simultaneously providing excellent film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, the deterioration of physical properties is prevented, offering the advantage of being environmentally friendly, while also providing excellent film processability and low-gloss characteristics.

[0042] Furthermore, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin containing 15-50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, 20-55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10-40% by weight of polyalkylene terephthalate, and 0.5-10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is either recycled or non-recycled polyalkylene terephthalate. In this case, the compatibility is greatly improved, maintaining the mechanical properties inherent to ASA-based resins and polyester resins at an equivalent or higher level, while simultaneously exhibiting excellent film processability, gloss, whiteness, weather resistance, and thermal stability. In addition, even when recycled resin is included, a decrease in physical properties is prevented, providing the advantage of being environmentally friendly, while also exhibiting excellent film processability and low-gloss characteristics.

[0043] In this description, the component ratio of the copolymer or resin may mean the content of the units constituting the copolymer, or the content of the monomers added during polymerization of the copolymer.

[0044] In this description, a polymer containing a certain compound means a polymer polymerized with that compound, and the units within the polymerized polymer are derived from that compound.

[0045] In this description, recycled thermoplastic resin is not particularly limited as long as it is generally recognized as recycled thermoplastic resin in the art to which this invention belongs, in accordance with the definition of this invention. For example, it is a thermoplastic resin recycled from collected waste plastics, and more specifically, it means a material prepared in a usable state after sorting, washing, and crushing of collected waste plastics. If necessary, a material processed into pellets through an extrusion process can also be used, which has the advantage of not requiring additional processing such as purification.

[0046] In this description, non-recycled thermoplastic resin is used in contrast to the recycled thermoplastic resin defined above, and may also be called a virgin (fresh) thermoplastic resin. It may be prepared by directly manufacturing it by polymerizing the monomers that constitute the thermoplastic resin, or it may be an equivalent commercially available product.

[0047] In this description, resins not referred to as recycled or non-recycled (newly produced) can be either recycled or non-recycled resins, but preferably refer to non-recycled resins.

[0048] The thermoplastic resin composition of the present invention will be described in detail below, component by component.

[0049] (A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer The (A) alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (hereinafter referred to as "(A) graft copolymer") is included in an amount of 15 to 50% by weight relative to 100% by weight of the base resin (A+B+C) containing (A) to (C), preferably 17 to 48% by weight, more preferably 18 to 46% by weight, even more preferably 19 to 45% by weight, and even more preferably 20 to 45% by weight. Within this range, there is the advantage of excellent impact resistance, film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, which is an advantage of being environmentally friendly, while also having the advantage of excellent impact resistance, film processability, low gloss characteristics, weather resistance, and thermal stability.

[0050] The (A) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding it.

[0051] The aforementioned (A) graft copolymer may, for example, be a mixture of two or more graft copolymers with different particle sizes of alkyl acrylate rubber cores. Specifically, it may be a mixture of (A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with an average particle size of 250 to 500 nm and (A-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with an average particle size of 50 to 150 nm. In this case, there is the advantage of even better film processability, impact resistance, weather resistance, and whiteness. Furthermore, if recycled resin is included, there is the advantage of even better low gloss properties, film processability, and impact resistance.

[0052] More specifically, the (A) graft copolymer may, for example, contain 3 to 35% by weight of the (A-1) graft copolymer and 5 to 40% by weight of the (A-2) graft copolymer based on 100% by weight of the base resin, preferably 3 to 33% by weight of the (A-1) graft copolymer and 5 to 38% by weight of the (A-2) graft copolymer, more preferably 4 to 32% by weight of the (A-1) graft copolymer and 5 to 37% by weight of the (A-2) graft copolymer, and even more preferably The material may contain 5 to 30% by weight of the (A-1) graft copolymer and 5 to 36% by weight of the (A-2) graft copolymer, more preferably 5 to 27% by weight of the (A-1) graft copolymer and 6 to 35% by weight of the (A-2) graft copolymer. In this case, the material has excellent impact resistance, film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, and it has the advantage of being environmentally friendly, while also having the advantage of even better low-gloss properties.

[0053] As an example, if the thermoplastic resin composition does not contain recycled resin, the (A) graft copolymer may contain 3 to 20% by weight of the (A-1) graft copolymer and 5 to 40% by weight of the (A-2) graft copolymer based on 100% by weight of the base resin, preferably 3 to 19% by weight of the (A-1) graft copolymer and 5 to 38% by weight of the (A-2) graft copolymer, more preferably 3 to 18% by weight of the (A-1) graft copolymer and 5 to 37% by weight of the (A-2) graft copolymer, even more preferably 4 to 18% by weight of the (A-1) graft copolymer and 5 to 36% by weight of the (A-2) graft copolymer, and even more preferably 4 to 17% by weight of the (A-1) graft copolymer and 6 to 35% by weight of the (A-2) graft copolymer. In this case, there is the advantage that impact resistance, weather resistance and whiteness are further improved without a decrease in other physical properties.

[0054] As an example, when the thermoplastic resin composition contains a recycled resin, preferably recycled polyalkylene terephthalate, the (A) graft copolymer can, for example, contain 10 to 35% by weight of the (A-1) graft copolymer and 5 to 20% by weight of the (A-2) graft copolymer based on 100% by weight of the base resin, preferably 10 to 32% by weight of the (A-1) graft copolymer and 5 to 19% by weight of the (A-2) graft copolymer, more preferably 11 to 30% by weight of the (A-1) graft copolymer and 5 to 18% by weight of the (A-2) graft copolymer, even more preferably 12 to 28% by weight of the (A-1) graft copolymer and 5 to 18% by weight of the (A-2) graft copolymer, and even more preferably 12 to 25% by weight of the (A-1) graft copolymer and 5 to 17% by weight of the (A-2) graft copolymer. In this case, there is the advantage that low gloss properties and impact resistance are further improved without a decrease in other physical properties.

[0055] The weight ratio (A-1:A-2) of the (A-1) graft copolymer to the (A-2) graft copolymer may be, for example, 0.1 to 3.0:1, and as a specific example, it may be 0.5 to 3.0:1, preferably 0.8 to 2.8:1, more preferably 1.0 to 2.6:1, even more preferably 1.0 to 2.5:1, and even more preferably 1.1 to 2.5:1. Within this range, there is the advantage that the desired effect can be fully expressed, and in particular, even if recycled resin is included, a decrease in physical properties is prevented, resulting in the advantage of excellent mechanical properties and low gloss characteristics.

[0056] The (A-1) graft copolymer may, for example, have an average particle size of 250 to 500 nm of rubber contained therein, preferably 270 to 480 nm, more preferably 300 to 470 nm, even more preferably 330 to 460 nm, and even more preferably 350 to 450 nm. In this case, there is the advantage that impact resistance, weather resistance, whiteness, and gloss characteristics are further improved without a decrease in other physical properties.

[0057] The (A-2) graft copolymer may, for example, have an average particle size of 50 to 150 nm of rubber contained therein, preferably 60 to 140 nm, more preferably 65 to 130 nm, even more preferably 70 to 125 nm, and even more preferably 80 to 120 nm. In this case, there is the advantage that impact resistance, weather resistance, whiteness, and gloss characteristics are further improved without a decrease in other physical properties.

[0058] The (A-1) graft copolymer may, for example, have a weight-average molecular weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) contained therein of 100,000 to 400,000 g / mol, preferably 110,000 to 390,000 g / mol, more preferably 120,000 to 350,000 g / mol, even more preferably 120,000 to 330,000 g / mol, and even more preferably 130,000 to 300,000 g / mol. Within this range, there is the advantage that impact resistance, whiteness, thermal stability, and gloss characteristics are further improved without a decrease in other physical properties.

[0059] The (A-2) graft copolymer may, for example, have a weight-average molecular weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) contained therein of 50,000 to 300,000 g / mol, preferably 60,000 to 250,000 g / mol, more preferably 70,000 to 230,000 g / mol, even more preferably 70,000 to 200,000 g / mol, and even more preferably 80,000 to 180,000 g / mol. Within this range, there is the advantage that impact resistance, whiteness, thermal stability, and gloss properties are further improved without a decrease in other physical properties.

[0060] The (A) graft copolymer (each of the (A-1) graft copolymer and the (A-2) graft copolymer) may, for example, have a graft ratio of 20% or more, preferably 20-100%, more preferably 22-80%, even more preferably 23-65%, and even more preferably 25-55%. Within this range, it is possible to have excellent mechanical properties such as impact resistance while also having even better gloss and weather resistance.

[0061] In this description, the average particle size of rubber is not particularly limited, as long as it is measured by a measurement method commonly used in the art to which the present invention belongs, including electron microscopy measurement methods using SEM, TEM, etc., or by a method such as dynamic light scattering. For example, the rubber can be sampled at the time of completion of manufacturing and measured using dynamic light scattering, and in detail, the intensity value can be measured using a particle detector (product name: Nicomp380, manufacturer: PSS) in Gaussian mode. As a specific measurement example, the sample is prepared by diluting 0.1g of latex (total solids content TSC 35-50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, by appropriately diluting it so as not to deviate significantly from the intensity setpoint of 300 kHz, and placing it in a glass tube. The measurement method involves auto-dilution and measurement in a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weight Gaussian analysis, and the setting values ​​being a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0062] In this description, the average particle size may preferably be the average particle size determined by dynamic light scattering.

[0063] In this description, unless otherwise defined, the weight-average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze). Specifically, THF (tetrahydrofuran) can be used as the eluate, and the weight-average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample via GPC. In this case, as a specific measurement example, measurements can be performed under the following conditions: 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): OECD TG 118.

[0064] In this description, the rubber, i.e., the copolymer grafted onto the core, i.e., the shell, can be separated from the rubber (core) by separation methods commonly used in the art to which the present invention pertains, for the purpose of measuring the weight-average molecular weight. For example, a solution can be prepared by dissolving the sol (sol) from which the insoluble matter (gel) has been separated in THF solvent by the method described later for measuring the grafting rate, and the filtrate obtained by filtering this solution can be used as a sample for measuring the weight-average molecular weight.

[0065] The graft rate described herein can be calculated using the following formula 1, as a specific measurement example: 0.5 g of graft copolymer powder is mixed with 30 g of acetone, stirred at room temperature at 210 rpm for 12 hours (SKC-6075, Lab companion), then centrifuged at 0°C at 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co.), and only the insoluble portion (gel) that did not dissolve in acetone is collected. After drying at 85°C using a forced circulation method for 12 hours (OF-12GW, Lab companion), the weight is measured and the graft rate can be calculated.

[0066] [Formula 1] Grafting rate (%) = [Weight of grafted monomers (g) / Weight of rubbery material (g)] × 100

[0067] In the above formula 1, the weight (g) of the grafted monomer is the weight obtained by subtracting the weight (g) of the rubbery component from the weight (g) of the insoluble material obtained after dissolving the graft copolymer in acetone and centrifuging it, and the weight (g) of the rubbery component is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.

[0068] The (A) graft copolymer can, as an example, contain 40-60% by weight of alkyl acrylate rubber, 30-45% by weight of aromatic vinyl compound, and 5-20% by weight of vinyl cyanide compound, based on its total weight (100% by weight). Preferably, it can contain 42-58% by weight of alkyl acrylate rubber, 32-43% by weight of aromatic vinyl compound, and 7-18% by weight of vinyl cyanide compound. More preferably, it can contain 42-55% by weight of alkyl acrylate rubber, 33-42% by weight of aromatic vinyl compound, and 10-18% by weight of vinyl cyanide compound. Even more preferably, it can contain 45-52% by weight of alkyl acrylate rubber, 33-40% by weight of aromatic vinyl compound, and 12-16% by weight of vinyl cyanide compound. Within this range, compatibility with other resins is improved, and there is an advantage in that mechanical properties and moldability are further superior.

[0069] Here, the composition ratios of each component constituting the (A-1) graft copolymer and the (A-2) graft copolymer can be appropriately adjusted independently of each other within the ranges described above.

[0070] The aforementioned (A) graft copolymer may be produced by emulsion polymerization, for example, which has the advantage of excellent impact resistance and compatibility.

[0071] The emulsion polymerization described above is not particularly limited, as long as it is carried out by an emulsion polymerization method commonly used in the art to which the present invention pertains. For example, it may be an emulsion graft polymerization method.

[0072] The method for producing the graft copolymer described above (A) may include, as an example, the steps of i) producing alkyl acrylate rubber by including alkyl acrylate, and ii) producing a graft copolymer by graft polymerization of aromatic vinyl compound and vinyl cyanide compound in the presence of the rubber, which has the advantage of having excellent mechanical properties, weather resistance, thermal stability, appearance characteristics, and moldability.

[0073] The method for producing the graft copolymer (A) preferably includes, based on a total of 100% by weight, the steps of: i) polymerizing 40 to 60% by weight of alkyl acrylate with a crosslinking agent, initiator, electrolyte and emulsifier to produce rubber; and ii) graft polymerizing a total of 40 to 60% by weight of aromatic vinyl compound and vinyl cyanide compound with a crosslinking agent, initiator and emulsifier in the presence of the rubber to produce a graft copolymer. In this case, there is the advantage that mechanical properties, weather resistance, thermal stability, appearance characteristics and moldability are all excellent.

[0074] The (A) graft copolymer may, for example, include polymer seeds, in which case it may be present in the alkyl acrylate rubber in an amount of 10 to 30% by weight, preferably 15 to 25% by weight (based on a total of 100% by weight of the rubber and seeds).

[0075] The (A) graft copolymer may, as a specific example, comprise a polymer seed comprising one or more selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, and vinyl cyanide compounds; an alkyl acrylate rubber (core) surrounding the polymer seed; and an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding the rubber (core). In this case, there is an advantage in terms of moldability, impact resistance, and weather resistance.

[0076] The polymer seed may preferably be a rubber seed made of alkyl acrylate rubber, which has the advantages of being easier to manufacture and having an even better balance of physical properties.

[0077] The method for producing the graft copolymer (A) may include, as an example, the steps of: i) producing a polymer seed containing one or more selected from the group consisting of alkyl (meth)acrylate, aromatic vinyl compounds, and vinyl cyanide compounds; ii) producing an alkyl acrylate rubber (core) containing alkyl acrylate in the presence of the polymer seed; and iii) producing a graft copolymer by graft polymerization containing aromatic vinyl compounds and vinyl cyanide compounds in the presence of the rubber (core). In this case, there is the advantage of excellent moldability, impact resistance, and weather resistance.

[0078] In this description, the monomer content within a polymer may refer to the weight percentage of monomers added during the production of the polymer, or the monomer-equivalent weight percentage of the units within the polymer.

[0079] In this description, alkyl (meth)acrylate can be defined as a range that includes both alkyl acrylate and alkyl methacrylate.

[0080] In this description, the alkyl acrylate may, for example, be an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, preferably 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 alkyl acrylate containing an alkyl group having 1 to 4 or 8 carbon atoms, even more preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof, and even more preferably butyl acrylate.

[0081] In this description, the alkyl methacrylate may, for example, be an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, preferably 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 an alkyl methacrylate containing an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl methacrylate.

[0082] In this 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 styrene is preferred.

[0083] In this description, the vinyl cyanide compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0084] The emulsifier used in each of the polymer seed manufacturing step (if polymer seeds are included), the rubber core manufacturing step, and the copolymer shell manufacturing step is not particularly limited as long as it is an emulsifier commonly used in the art to which the present invention belongs. For example, it may be one or more selected from the group consisting of C12-C18 alkyl sulfosuccinate metal salts or derivatives thereof, C12-C20 alkyl sulfate esters or derivatives thereof, C12-C20 alkyl sulfonic acid metal salts or derivatives thereof, fatty acid soaps, and rosinate soaps.

[0085] The C12-C18 alkyl sulfosuccinate metal salt or its derivative is preferably one or more selected from the group consisting of dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt, and dioctyl sulfosuccinate potassium salt.

[0086] The C12-C20 alkyl sulfate ester or its derivative is preferably one or more selected from the group consisting of sodium lauryl sulfate, sodium dodecyl sulfate, sodium octadecyl sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate. In addition, one or more other sulfate ester emulsifiers such as sodium dodecylbenzene sulfate and sodium oleate sulfate can also be used.

[0087] The fatty acid soap may preferably be one or more selected from the group consisting of oleic acid, stearic acid, lauric acid, and sodium or potassium salts of mixed fatty acids.

[0088] The rosinate soap may preferably be an abietate, and more specifically, a metal abietate.

[0089] As an example, the emulsifier can be used in amounts of 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight, for each step, based on a total of 100 parts by weight of the (A) graft copolymer.

[0090] The initiator is not particularly limited, but a radical initiator can be preferably used.

[0091] The radical initiator may, for example, be one or more selected from the group consisting of inorganic peroxides, organic peroxides (excluding ketal, carbonate, and azo compounds), peroxyketal peroxides, peroxycarbonate peroxides, and azo compounds.

[0092] The inorganic peroxide may preferably be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, and hydrogen peroxide.

[0093] Examples of the aforementioned organic peroxides include t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, di-t-amyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)-cyclohexane, and 1,1-di(t-amylperoxy) (C)-Cyclohexane, ethyl 3,3-di(t-amylperoxy)-butyrate, diisopropylbenzene mono-hydroperoxide, t-amylhydroperoxide, t-butylhydroperoxide, t-butylperoxyneodecanoate, t-butylperoxypivalate, di-(3,3,5-trimethylhexanoyl)-peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,3,5-trimethylhexanoyl, t-amylperoxyne Decanoate, t-amylperoxypivalate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-amylperoxy-2-ethylhexyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, It may be one or more selected from the group consisting of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di-2-ethylhexylperoxydicarbonate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, acetylperoxide, isobutylperoxide, octanoylperoxide, dibenzoylperoxide, dilauroylperoxide, 3,5,5-trimethylhexanolperoxide, and t-butylperoxyisobutyrate.

[0094] The peroxyketal peroxide may preferably be one or more selected from the group consisting of 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, ethyl-3,3-di(t-butylperoxy)butyrate, and ethyl-3,3-di(t-amylperoxy)butyrate.

[0095] The peroxycarbonate peroxide may preferably be one or more selected from the group consisting of dialkyl peroxides such as dicumylperoxide, di(t-butylperoxy)-m / p-diisopropylbenzene, 2,5-dimethyl-2,5-(t-butylperoxy)hexane, t-butylcumylperoxide, 2,5-methyl-2,5-(t-butylperoxy)hexine-3, t-butylperoxy 2-ethylhexyl monocarbonate, and t-butylperoxybenzoate.

[0096] The azo compound may preferably be one or more selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrate, and methyl azobisisobutyrate.

[0097] As an example, the initiator can be used in amounts of 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, for each step, based on a total of 100 parts by weight of the (A) graft copolymer.

[0098] In at least one of the steps of the polymer seed manufacturing step (if it includes polymer seeds), the rubber (core) manufacturing step, and the copolymer (shell) manufacturing step, preferably, an oxidation-reduction catalyst can be used together with the initiator to further promote the initiation reaction.

[0099] The oxidation-reduction catalyst may, for example, be one or more selected from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate, and preferably a mixture of sodium pyrophosphate, dextrose, and ferrous sulfide, but is not limited thereto.

[0100] As an example, the catalyst can be used in amounts of 0.001 to 2 parts by weight, preferably 0.002 to 1 part by weight, for each step, based on a total of 100 parts by weight of the (A) graft copolymer.

[0101] In at least one of the steps described above—the polymer seed manufacturing step (if it includes polymer seeds), the rubber (core) manufacturing step, and the copolymer (shell) manufacturing step—preferably, an activator can be used together with the polymerization initiator to promote the peroxide initiation reaction.

[0102] The activator is not particularly limited as long as it is an activator commonly used in the art to which the present invention pertains.

[0103] The total amount of the activator added may be 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on a total of 100 parts by weight of the (A) graft copolymer. Within this range, there is the advantage that a high degree of polymerization can be achieved.

[0104] The aforementioned electrolyte may, for example, be one or more selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO4, Na2S2O7, K3P2O7, K3PO4, Na3PO4, KOH, NaOH, and Na2HPO4, but is not limited thereto.

[0105] The total amount of electrolyte added may be 0.001 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on a total of 100 parts by weight of the (A) graft copolymer, and within this range, there is the advantage that a high degree of polymerization can be achieved.

[0106] In this description, the crosslinking agent is not particularly limited as long as it is a crosslinking agent commonly used in the art to which the present invention belongs. For example, one or more compounds containing unsaturated vinyl groups that can act as a crosslinking agent, or compounds containing two or more unsaturated vinyl groups having two or more different reactivity, can be used. Specific examples include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol propoxy It should be explicitly stated that one or more of the following may be selected from the group consisting of silate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropane ethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallylamine, and diallylamine, but is not limited thereto.

[0107] As an example, the crosslinking agent can be used in amounts of 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 1 part by weight, for each step, based on a total of 100 parts by weight of the (A) graft copolymer.

[0108] The copolymer shell manufacturing step may, for example, use a molecular weight modifier.

[0109] The molecular weight modifier may, for example, be 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total (A) graft copolymer. Within this range, a polymer having the desired molecular weight can be easily produced.

[0110] The molecular weight modifier may, but is not limited to, one or more selected from the group consisting of α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylenethiuram disulfide, and diisopropyl xanthogen disulfide.

[0111] In this description, 100 parts by weight of graft copolymer means 100 parts by weight of the total weight of the graft copolymer obtained at the end, or, since almost all of the added monomers participate in polymerization, it may conveniently mean the combined weight of all monomers used in the polymer seed (if polymer seeds are included), rubber core and graft shell, or the combined weight of all monomers added during the production of the polymer seed (if polymer seeds are included) and rubber core and the monomers added during the production of the graft shell, with 100 parts by weight as the basis.

[0112] In this document, % refers to weight percentage unless otherwise defined. In the step of producing the polymer seeds and rubber, the monomers may be introduced by introducing them in a batch or by introducing them continuously, either individually or in combination.

[0113] In this description, "continuous addition" means that the material is not added all at once. For example, it refers to adding the material drop by drop, little by little, step by step, or in a continuous flow for 10 minutes or more, 30 minutes or more, 1 hour or more, preferably 2 hours or more, within the range of the polymerization reaction time.

[0114] The polymerization temperature during emulsion polymerization is not particularly limited, but may be 50 to 85°C, preferably 60 to 80°C.

[0115] The latex formed after polymerization of the (A) graft copolymer can, for example, be obtained in powder form through conventional processes such as agglomeration, washing, and drying. Specifically, it can be produced in powder form by adding a metal salt or acid, agglomerating at a temperature of 60-100°C, and then undergoing maturation, dehydration, washing, and drying processes, but is not limited to this.

[0116] The aforementioned (A) graft copolymer may, for example, be a commercially available product, insofar as it conforms to the definition of the present invention.

[0117] (B) Aromatic vinyl compound-vinyl cyanide compound copolymer The (B) aromatic vinyl compound-vinyl cyanide compound copolymer (hereinafter referred to as "(B) copolymer") is included in an amount of 20 to 55% by weight relative to 100% by weight of the base resin, preferably 22 to 55% by weight, more preferably 25 to 53% by weight, even more preferably 27 to 52% by weight, and even more preferably 28 to 50% by weight. Within this range, the mechanical properties, film processability, gloss, whiteness, weather resistance, and thermal stability are all excellent, and even when recycled resin is included, a decrease in physical properties is prevented, which is an advantage in terms of being environmentally friendly, as well as the advantage of having even better low-gloss characteristics.

[0118] The (B) copolymer may be one or more selected from the group consisting of, for example, (B-1) copolymers comprising an aromatic vinyl compound and a vinyl cyanide compound that do not contain an alkyl-substituted aromatic vinyl compound (hereinafter referred to as "(B-1) copolymer"), and (B-2) heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymers comprising an alkyl-substituted aromatic vinyl compound (hereinafter referred to as "(B-2) copolymer").

[0119] Specifically, the (B-1) copolymer can, for example, contain 55-85% by weight of an alkyl-unsubstituted aromatic vinyl compound and 15-45% by weight of a vinyl cyanide compound, preferably 60-82% by weight of an alkyl-unsubstituted aromatic vinyl compound and 18-40% by weight of a vinyl cyanide compound, more preferably 65-82% by weight of an alkyl-unsubstituted aromatic vinyl compound and 18-35% by weight of a vinyl cyanide compound, and even more preferably 65-80% by weight of an alkyl-unsubstituted aromatic vinyl compound and 20-35% by weight of a vinyl cyanide compound. In this case, there is the advantage that the mechanical properties are further improved without a decrease in other physical properties. The (B-1) copolymer can be referred to as a "non-heat-resistant SAN resin" or "general SAN resin" in that it does not contain a heat-resistant monomer that imparts heat resistance to the copolymer containing it, such as an alkyl-substituted aromatic vinyl compound.

[0120] The (B-2) copolymer can, as an example, contain 60-80% by weight of an alkyl-substituted aromatic vinyl compound, 20-40% by weight of a vinyl cyanide compound, and 0-20% by weight of an alkyl-unsubstituted aromatic vinyl compound. Preferably, it contains 62-80% by weight of an alkyl-substituted aromatic vinyl compound, 20-38% by weight of a vinyl cyanide compound, and 0-17% by weight of an alkyl-unsubstituted aromatic vinyl compound. More preferably, it contains 63-77% by weight of an alkyl-substituted aromatic vinyl compound, 23-37% by weight of a vinyl cyanide compound, and 0-13% by weight of an alkyl-unsubstituted aromatic vinyl compound. Even more preferably, it contains 65-75% by weight of an alkyl-substituted aromatic vinyl compound, 25-35% by weight of a vinyl cyanide compound, and 0-10% by weight of an alkyl-unsubstituted aromatic vinyl compound. In this case, there is the advantage of excellent heat resistance and mechanical properties without a decrease in other physical properties. The (B-2) copolymer can be referred to as a "heat-resistant SAN resin" in that it contains, as an example, a heat-resistant monomer such as an alkyl-substituted aromatic vinyl compound.

[0121] The (B-2) copolymer, as an example, may contain 60-80% by weight of an alkyl-substituted aromatic vinyl compound and 20-40% by weight of a vinyl cyanide compound, preferably 63-77% by weight of an alkyl-substituted aromatic vinyl compound and 23-37% by weight of a vinyl cyanide compound, and more preferably 65-75% by weight of an alkyl-substituted aromatic vinyl compound and 25-35% by weight of a vinyl cyanide compound. In this case, there is the advantage that heat resistance is further improved without a decrease in other physical properties.

[0122] Here, the weight percentage of copolymer (B) contained in the base resin refers to the weight percentage of copolymer (B-1) if it contains only copolymer (B-1), the weight percentage of copolymer (B-2) if it contains only copolymer (B-2), and the sum of the weight percentages of each copolymer if it contains a mixture of copolymers (B-1) and (B-2).

[0123] The alkyl-substituted aromatic vinyl compound may be, for example, one or more selected from the group consisting of α-methylstyrene, α-ethylstyrene, p-methylstyrene, and m-methylstyrene, and preferably α-methylstyrene.

[0124] The type of alkyl-unsubstituted aromatic vinyl compound may be, for example, appropriately selected from the aromatic vinyl compounds mentioned in (A) graft copolymer, within a range that does not contain alkyl substituents, and preferably styrene.

[0125] The type of vinyl cyanide compound included in the copolymer (B) can be appropriately selected from the range of vinyl cyanide compounds mentioned in the graft copolymer (A).

[0126] The copolymer (B) may, for example, have a weight-average molecular weight of 30,000 to 300,000 g / mol, preferably 30,000 to 200,000 g / mol, more preferably 40,000 to 190,000 g / mol, even more preferably 40,000 to 180,000 g / mol, and even more preferably 50,000 to 180,000 g / mol. In this case, there is the advantage that the mechanical properties are further improved without a decrease in other physical properties.

[0127] More specifically, the (B-1) copolymer may, for example, have a weight-average molecular weight of 50,000 to 300,000 g / mol, preferably 70,000 to 200,000 g / mol, more preferably 80,000 to 190,000 g / mol, even more preferably 80,000 to 180,000 g / mol, and even more preferably 90,000 to 180,000 g / mol. In this case, there is the advantage that mechanical properties are further improved without a decrease in other physical properties.

[0128] The (B-2) copolymer may, for example, have a weight-average molecular weight of 30,000 to 200,000 g / mol, preferably 30,000 to 180,000 g / mol, more preferably 40,000 to 150,000 g / mol, even more preferably 50,000 to 140,000 g / mol, and even more preferably 50,000 to 130,000 g / mol. In this case, there is the advantage that heat resistance and mechanical properties are further improved without a decrease in other physical properties.

[0129] The copolymer (B) may, for example, be produced by a manufacturing method commonly applied in the art to which the present invention pertains, and commercially available products may be used insofar as they conform to the definitions of the present invention.

[0130] (C) Polyalkylene terephthalate The (C) polyalkylene terephthalate is included in an amount of 10 to 40% by weight relative to 100% by weight of the base resin, preferably 15 to 37% by weight, more preferably 18 to 35% by weight, even more preferably 20 to 34% by weight, and even more preferably 22 to 33% by weight. Within this range, excellent compatibility is achieved, resulting in the advantage of excellent mechanical properties, gloss, whiteness, film processability, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, making it environmentally friendly. In addition, excellent compatibility is achieved, resulting in excellent impact resistance, film processability, low gloss characteristics, weather resistance, and thermal stability.

[0131] The (C) polyalkylene terephthalate may be selected, for example, from recycled polyalkylene terephthalate, non-recycled polyalkylene terephthalate, and mixtures thereof. In this case, mechanical properties, gloss, whiteness, film processability, weather resistance, and thermal stability can be ensured, and the deterioration of physical properties due to non-recycled resin can be prevented, providing the advantage of being environmentally friendly. Furthermore, when non-recycled polyalkylene terephthalate is applied depending on the molding process, high injection gloss can be achieved, and when recycled polyalkylene terephthalate is applied, excellent extrusion low gloss characteristics can be achieved, providing the advantage of being environmentally friendly. Therefore, recycled polyalkylene terephthalate and / or non-recycled polyalkylene terephthalate can be appropriately selected as (C) polyalkylene terephthalate as needed.

[0132] Here, the weight percentage of (C) polyalkylene terephthalate contained in the base resin represents the weight percentage of the recycled polyalkylene terephthalate if it contains only recycled polyalkylene terephthalate, the weight percentage of the non-recycled polyalkylene terephthalate if it contains only non-recycled polyalkylene terephthalate, and the sum of the weight percentages of each if it contains a mixture of recycled polyalkylene terephthalate and non-recycled polyalkylene terephthalate.

[0133] The (C) polyalkylene terephthalate may, for example, have an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, more preferably 0.5 to 1.1 dl / g, even more preferably 0.6 to 1.0 dl / g, and even more preferably 0.6 to 0.8 dl / g. Within this range, it has excellent compatibility, which has the advantage of excellent mechanical properties and moldability.

[0134] In this description, unless otherwise specified, intrinsic viscosity can be measured by methods commonly used in the art to which the present invention pertains. As a specific example, the sample can be completely dissolved in a methylene chloride solvent at a concentration of 0.05 g / ml, and the filtrate, obtained by filtering using a filter, can be measured at 20°C using an Ubbelohde viscometer.

[0135] The (C) polyalkylene terephthalate may, for example, include one or more selected from polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polytrimethylene terephthalate (PTT), preferably one or more selected from the group consisting of polybutylene terephthalate and polyethylene terephthalate, and more preferably polyethylene terephthalate. In this case, the effects intended by the present invention are fully exhibited, and there is the advantage of even better impact resistance.

[0136] The polyethylene terephthalate resin may be one or more selected from the group consisting of, for example, recycled polyethylene terephthalate resin derived from a polyethylene terephthalate monopolymer obtained by polymerizing terephthalic acid and ethylene glycol; and polyethylene terephthalate copolymer comprising terephthalic acid, ethylene glycol, and one or more of 1,4-cyclohexanedimethanol, isophthalic acid, and butanediol as a copolymer. In this case, there is the advantage of even better impact resistance and heat resistance. In addition, when recycled polyethylene terephthalate is used, it is possible to achieve excellent low gloss properties, and when non-recycled polyethylene terephthalate is used, it is possible to achieve high gloss.

[0137] The aforementioned recycled polyalkylene terephthalate refers to recycled resin obtained by recycling waste polyalkylene terephthalate. In this case, since waste polyalkylene terephthalate, including waste PET, which is one of the most abundant waste plastics, can be utilized, the supply and demand of raw materials is easy, and it has the advantage of being even more environmentally friendly.

[0138] The (C) polyalkylene terephthalate may, for example, have a melting point of 200 to 280°C, preferably 220 to 275°C, and more preferably 240 to 270°C, and within this range, the desired effect can be fully achieved.

[0139] In this description, the melting point can be measured using methods known in the field of polymer science. For example, the thermal absorption peak can be measured using a differential scanning calorimetry (DSC).

[0140] The aforementioned (C) polyalkylene terephthalate may, for example, have a glass transition temperature of 60 to 100°C, preferably 65 to 90°C, and within this range, it has the advantage of excellent impact resistance and moldability.

[0141] In this description, the glass transition temperature can be measured using a differential scanning calorimetry (DSC) in accordance with ASTM D3418. Specifically, it can be measured using TA Instruments' Q100 DSC (Differential Scanning Calorimetry) at a heating rate of 10°C / min.

[0142] The (C) recycled or non-recycled polyalkylene terephthalate described above is not particularly limited as long as it is a recycled or non-recycled polyalkylene terephthalate resin commonly used in the art to which the present invention belongs, insofar as it conforms to the definition of the present invention, and commercially available products may also be used.

[0143] (D) Compatibilizer The (D) compatibilizer is included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the base resin, preferably 1 to 9 parts by weight, more preferably 1.5 to 8.5 parts by weight, and even more preferably 1.7 to 8 parts by weight. Within this range, the compatibility of the (A) graft copolymer and the (C) polyalkylene terephthalate is greatly improved, which has the advantage of excellent mechanical properties, gloss, whiteness, film processability, weather resistance, and thermal stability. Furthermore, when recycled polyalkylene terephthalate is used, even if the ratio of recycled resin is, for example, 10% by weight or more, a decrease in physical properties is prevented, which has the advantage of being even more environmentally friendly, as well as having excellent impact resistance, film processability, and low gloss characteristics.

[0144] The aforementioned (D) compatibilizer may be included in an amount of 1.3 to 6 parts by weight, preferably 1.5 to 5 parts by weight, more preferably 1.6 to 4.5 parts by weight, even more preferably 1.7 to 4 parts by weight, and also preferably 1.8 to 2.8 parts by weight. In this case, even with a smaller content, the compatibility improvement effect is excellent, which has the advantage of being able to fully exhibit the effects intended in the present invention.

[0145] The (D) compatibilizer may, for example, be one or more selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA). Preferably, it may be one or more selected from olefin-alkyl acrylate copolymers, and more preferably, it may be ethylene-methyl acrylate copolymer. In this case, there is the advantage that mechanical properties, gloss, whiteness, film processability, weather resistance, and thermal stability are all excellent. Furthermore, when recycled resin is included, there is the advantage of being environmentally friendly, as well as having excellent impact resistance, film processability, and low gloss characteristics.

[0146] The aforementioned (D) compatibilizer may, for example, comprise an olefin compound, an alkyl (meth)acrylate or alkenyl acetate, and selectively glycidyl methacrylate. Specifically, one example may comprise 30-90% by weight of an olefin compound, 10-70% by weight of an alkyl (meth)acrylate or alkenyl acetate, and 0-15% by weight of glycidyl methacrylate. In this case, the desired effect can be fully achieved.

[0147] The (D) compatibilizer may preferably contain 50-90% by weight of ethylene and 10-50% by weight of methyl acrylate or vinyl acetate, more preferably 55-80% by weight of ethylene and 20-45% by weight of methyl acrylate or vinyl acetate, and even more preferably 60-80% by weight of ethylene and 20-40% by weight of methyl acrylate or vinyl acetate, in which case the desired effect can be fully realized. The (D) compatibilizer may more preferably be an ethylene-methyl acrylate copolymer, in which case there is an advantage in manufacturing because the supply and demand of raw materials is easy.

[0148] The aforementioned (D) compatibilizer may, for example, have a melting index of 1 to 10 g / 10 min, preferably 2 to 5 g / 10 min, as measured under conditions of 190°C and 2.16 kg in accordance with ASTM D1238. Within this range, there is an advantage that film processability is further improved without any deterioration of other physical properties.

[0149] The aforementioned (D) compatibilizer may, for example, have a melting point of 80 to 110°C, preferably 82 to 105°C, and more preferably 85 to 100°C, and within this range, it has the effect of having excellent mechanical strength and formability.

[0150] The method for producing the compatibilizer (D) is not particularly limited, as long as it is a manufacturing method commonly applied in the art, and commercially available products may be used insofar as they conform to the definitions of the present invention.

[0151] thermoplastic resin composition The thermoplastic resin composition comprises 100 parts by weight of a base resin containing (A) 15-50% by weight of graft copolymer, (B) 20-55% by weight of copolymer, and (C) 10-40% by weight of polyalkylene terephthalate; and 0.5-10 parts by weight of a compatibilizer; thereby maintaining the mechanical properties inherent to ASA resins and polyester resins at a level equal to or higher than those of ASA resins, while also having the advantage of excellent injection gloss, whiteness, film processability, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, making it environmentally friendly, while also having the advantage of excellent film processability, extrusion low gloss characteristics, weather resistance, and thermal stability.

[0152] The thermoplastic resin composition may, for example, have a weight ratio (A:C) of (A) graft copolymer to (C) polyalkylene terephthalate of 0.5 to 2.0:1, preferably 0.5 to 1.8:1, more preferably 0.6 to 1.5:1, and even more preferably 0.7 to 1.3:1. In this case, there is the advantage that impact resistance, film processability, gloss, and whiteness are all excellent. Furthermore, if recycled resin is included, there is the advantage of being environmentally friendly, as well as even better low-gloss properties, film processability, and impact resistance.

[0153] The aforementioned thermoplastic resin composition contains acrylate-based rubber as a rubber component but does not contain conjugated diene-based rubber, thus exhibiting excellent weather resistance. Therefore, it has the advantage of maintaining its physical properties for a long period of time even when exposed to environments that cause degradation, such as heat and ultraviolet rays. Furthermore, despite containing both ASA-based resin and polyester resin, which have poor compatibility with each other, it has the advantage of excellent film processability and thermal stability.

[0154] The thermoplastic resin composition may, for example, have an injection gloss of 108 or higher, as measured on an injection-molded test piece with a thickness of 3 mm at 45° in accordance with ASTM D2457, preferably 108 to 130, more preferably 108 to 125, and even more preferably 109 to 120. In this case, there is the advantage that gloss is further improved without a decrease in other physical properties. Here, the unit of gloss may be GU (gloss unit).

[0155] The thermoplastic resin composition may, for example, be a high-gloss resin composition containing (C) polyalkylene terephthalate as non-recycled polyalkylene terephthalate and having an injection gloss of 10⁸ or higher. In this case, in addition to excellent gloss, the film processability, impact resistance, weather resistance, and thermal stability are all excellent, which has the advantage of providing high-quality high-gloss injection molded products.

[0156] The thermoplastic resin composition may, for example, have an extruded gloss of less than 50 when measured on an extruded film test piece with a thickness of 0.08 mm at 45° in accordance with ASTM D2457, preferably 20 to 47, more preferably 22 to 45, even more preferably 23 to 42, and even more preferably 25 to 40. In this case, there is an advantage that it has excellent low-gloss properties without any deterioration of other physical properties.

[0157] The thermoplastic resin composition may, for example, include recycled polyalkylene terephthalate as (C) polyalkylene terephthalate and be a low-gloss resin composition with an extrusion gloss of less than 50. In this case, in addition to the advantages of being environmentally friendly and having low gloss characteristics, it also has the advantage of excellent film processability, impact resistance, weather resistance, and thermal stability, thus providing a high-quality, environmentally friendly, low-gloss film.

[0158] For example, the aforementioned thermoplastic resin composition has excellent film processability, resulting in low torque applied to the extruder during the film extrusion process. This leads to excellent uniformity of film thickness and uniform gloss across the entire film surface, resulting in superior film appearance quality.

[0159] In this description, torque refers to the magnitude of the output required to rotate the screw at a set rotational speed during the process of extruding the molten mixture or pellets of the thermoplastic resin composition in a film extruder, and this can be measured by a sensor built into the extruder. In the film extrusion process, when the molding conditions such as molding temperature, screw rotational speed (rpm), and composition injection speed (feed rate) are the same, a higher torque value means that a greater load is applied to the extruder, which means that the flowability of the composition, i.e., the moldability, is poor. Therefore, when the molding conditions are the same, a higher torque value may reduce the uniformity of the film thickness. Conversely, a lower torque value means that a lower load is applied to the extruder, which means that the flowability of the composition is excellent, and in this case, there is the advantage of excellent film processability and excellent uniformity of film thickness.

[0160] In this description, torque is measured as an example using a T-die extruder (Techline 20T, Collins, screw diameter 20 nm, L / D = 25) at a molding temperature of 250°C and a molding pressure of 200 kgf / cm². 2 The torque can be measured under the conditions of extrusion molding of a film with a thickness of 0.08 mm, with a screw rotation speed of 100 rpm, a roll temperature of 85°C, and a roll rotation speed of 3.5 m / min, and can be expressed as a ratio (%) to the maximum torque value (output limit) on which the extruder can operate. The ratio to the maximum torque value on which the extruder can operate can be expressed as a value measured by a sensor built into the extruder and displayed on the torque display unit.

[0161] Method for manufacturing thermoplastic resin compositions The present invention 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) 15-50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) 20-55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer, and (C) 10-40% by weight of a polyalkylene terephthalate, and (D) 0.5-10 parts by weight of a compatibilizer, under conditions of 170-300°C and 100-400 rpm. In this case, the compatibility is greatly improved, maintaining the mechanical properties inherent to ASA-based resins and polyester resins at an equivalent or higher level, while simultaneously exhibiting excellent film processability, gloss, whiteness, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, offering the advantage of being environmentally friendly, while also exhibiting excellent film processability and low-gloss characteristics.

[0162] The aforementioned kneading and extrusion steps may, for example, be carried out using one or more selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer. After uniformly mixing the composition using this method, it can be extruded to obtain a pellet-shaped thermoplastic resin composition. In this case, a decrease in mechanical properties and heat resistance is prevented, and the appearance quality is excellent.

[0163] The aforementioned kneading and extrusion steps may, for example, be carried out within a range where the extruder cylinder temperature is 170 to 300°C, preferably 200 to 280°C, and more preferably 220 to 270°C. In this case, there are advantages such as an appropriate processing rate per unit time, sufficient melt kneading, and suppression of thermal decomposition.

[0164] The kneading and extrusion may, for example, be carried out under conditions where the screw rotation speed is 100 to 400 rpm, preferably 110 to 350 rpm, and more preferably 120 to 270 rpm. In this case, the processing amount per unit time is appropriate, which has the advantage of excellent process efficiency.

[0165] The thermoplastic resin composition may optionally contain one or more other additives selected from the group consisting of lubricants, heat stabilizers, light stabilizers, pigments, mold release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, anti-dripping agents, inorganic fillers, friction inhibitors, and abrasion inhibitors, in amounts of 0.01 to 15 parts by weight, 0.05 to 12 parts by weight, 0.1 to 5 parts by weight, 0.3 to 10 parts by weight, 0.3 to 7 parts by weight, or 0.3 to 5 parts by weight based on 100 parts by weight of the base resin. Within this range, there is the advantage that the desired physical properties can be achieved well without degrading the intended physical properties.

[0166] The lubricant may, for example, be one or more selected from the group consisting of fatty acid amide compounds, montan waxes, silicone oils, and olefin waxes, preferably an olefin wax, and more preferably a polyethylene wax, in which case there is the advantage of excellent moldability and mold release properties.

[0167] The aforementioned fatty acid amide compound may be one or more selected from the group consisting of, for example, stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bis oleamide.

[0168] The montan wax may, for example, be montan wax, montan ester wax, or a mixture thereof.

[0169] The silicone oil may, for example, be one or more selected from the group consisting of dimethyl silicone oil, methyl hydrogen silicone oil, ester-modified silicone oil, hydroxy silicone oil, carbinol-modified silicone oil, vinyl silicone oil, and silicone acrylate.

[0170] The olefin-based wax may, for example, be one or more selected from the group consisting of oxidized polyethylene wax, polyethylene wax, and polypropylene wax.

[0171] The heat stabilizer may include, for example, a phenolic heat stabilizer, a phosphorus-based heat stabilizer, or a mixture thereof, and preferably a phenolic heat stabilizer. In this case, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0172] Examples of the phenolic heat stabilizers include N,N'-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), and triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl] It may also be one or more selected from the group consisting of [xyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, in which case the heat resistance can be greatly improved while maintaining a high balance of physical properties.

[0173] Examples of the phosphorus-based heat stabilizers include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyldiphenyl phosphite, and monooctyldiphenyl phosphite. It may be one or more selected from the group consisting of yl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, stearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, and trimethyl phosphate.

[0174] The aforementioned light stabilizer may, as an example, include one or more compounds selected from the group consisting of triazine compounds, benzophenone compounds, benzotriazole compounds, indole compounds, quinolinone compounds, benzoate compounds, cyanoacrylate compounds, and amine compounds. Preferably, it may be a benzotriazole compound or an amine compound, in which case it has the effect of having an excellent balance of physical properties and further improving light resistance.

[0175] Examples of the aforementioned triazine compounds include 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, and 2,6-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine. Phenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4 -Butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2, 4,6-Tris(2-hydroxy-4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropane-2-yloxy)phenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-ethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine Toxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3 Tris(2-hydroxy-3-methyl-4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-ethoxycarbonylethyloxyphenyl) It may also be one or more selected from the group consisting of )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol.

[0176] Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridebenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and 2,2'-dihydroxy-4-methylbenzophenone. It may be one or more selected from the group consisting of toxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0177] Examples of the benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-2'-hydroxy-3',2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenyl-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, and 2-(2'-hydroxy It may be one or more selected from the group consisting of -3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol] and 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol, preferably 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol.

[0178] The indole compound may, for example, be 2-[(1-methyl-2-phenyl-1H-indole-3-yl)methylene]propanedinitrile.

[0179] The quinolinone compound may, for example, be 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

[0180] The benzoate compound may be one or more selected from the group consisting of, for example, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0181] The cyanoacrylate compound may, for example, be 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)acrylate, or a mixture thereof.

[0182] The aforementioned amine compound may, for example, be a hindered amine light stabilizer (HALS), 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, or bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. T, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-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-butanetetracarboxylate, 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, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethyl Linear or cyclic condensation products of diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 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,It may be one or more selected from the group consisting of [6-tetramethyl-4-piperidinyl)imino], preferably bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

[0183] The aforementioned pigment may be an inorganic pigment or an organic pigment.

[0184] The organic pigment may, for example, be one or more selected from the group consisting of perinone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, indigo pigments, dioxazine pigments, quinacridone pigments, methane pigments, quinoline pigments, isoindolinone pigments, and phthalone pigments.

[0185] The inorganic pigment may, for example, be one or more selected from the group consisting of ultramarine pigments, titanium dioxide, zinc sulfide, zinc oxide, iron oxide, and carbon black.

[0186] The aforementioned release agent may be, for example, one or more selected from the group consisting of glycerin stearate, polyethylene tetrastearate, etc., and is not limited thereto.

[0187] The aforementioned antistatic agent can be applied without particular limitation as long as it is used as an antistatic agent in the art to which the present invention pertains. For example, one or more anionic surfactants such as sulfate-based, sulfonate-based, and phosphate-based surfactants, and nonionic surfactants such as quaternary ammonium salt-based and alkylamine sulfate-based surfactants may be used, but the invention is not limited thereto.

[0188] The anti-dripping agent can be, for example, one or more selected from the group consisting of PTFE (polytetrafluoroethylene), a mixture of PTFE and SAN (styrene-acrylonitrile) resin (PTFE / SAN), a mixture of PTFE and PMMA (polymethyl methacrylate) (PTFE / PMMA), polyamide, polysilicon, and TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymer. Preferably, one or more selected from the group consisting of PTFE / SAN and PTFE / PMMA, and more preferably PTFE / SAN.

[0189] The PTFE / SAN and PTFE / PMMA mixtures may preferably be a mixture of PTFE and SAN or PMMA in a weight ratio of 1:0.5 to 1.5, respectively, or, as one embodiment, a mixture in a weight ratio of 1:1.

[0190] The aforementioned antibacterial agents, processing aids, metal deactivators, smoke suppressants, anti-dripping agents, inorganic fillers, friction inhibitors, abrasion inhibitors, etc., are not particularly limited as long as they are commonly used in the art to which the present invention belongs, in accordance with the definitions of the present invention.

[0191] molded product The molded article described herein is characterized by containing the thermoplastic resin composition, which has the advantage of having excellent impact resistance, film processability, gloss, whiteness, weather resistance, and heat resistance. Furthermore, even when recycled resin is included, a decrease in physical properties is prevented, making it environmentally friendly, while also having the advantage of excellent low-gloss properties.

[0192] The aforementioned molded product has the advantage of being usable without additional processing in fields where conventional ASA-based thermoplastic resin compositions are applied, such as interior and exterior building materials, automobile interior and exterior materials, ships, and leisure and sports goods, even when it contains recycled resin, as it ensures physical properties at a level equivalent to or better than molded products containing only newly produced resin.

[0193] The aforementioned molded product has the advantage of being particularly suitable as an exterior material because it has excellent film processability and high whiteness, allowing it to be manufactured as a film with a variety of colors, and also has excellent weather resistance. The aforementioned molded product may be an injection molded product with a thickness of 1 to 5 mm, preferably 1.5 to 4 mm, more preferably 2 to 3 mm. As a specific example, the aforementioned molded product may have a thickness of 3 mm, and after measuring the L value in the reflection mode according to the CIE Lab method using a colorimeter (model name: X-lite Color Eye 7000A) under a UV D65 light source with a Degree Observer at 10° in accordance with the CIE1976 L*a*b* color system, the whiteness obtained by measuring the L value in the reflection mode according to the Munsell color system may be 85 or higher, preferably 85 to 100, more preferably 88 to 98, and even more preferably 89 to 97, in which case, the whiteness is excellent, which has the advantage of enabling vivid color realization.

[0194] The molded article, for example, has the advantage of being useful for low-gloss films because it is excellent in film processability and low-gloss properties. The molded article may, as a specific example, be an extruded film with a thickness of 40 to 600 μm, preferably 50 to 500 μm, and more preferably 60 to 300 μm. In particular, the extruded film may, for example, have a gloss score of less than 50, preferably 20 to 47, more preferably 22 to 45, even more preferably 23 to 42, and even more preferably 25 to 40, as measured under conditions of 0.08 mm (80 μm) thickness at 45° in accordance with ASTM D2457. In this case, it has the advantage of being able to provide a high-grade low-gloss film because it is excellent in low-gloss properties and has a uniform thickness.

[0195] The molded article can be manufactured by methods commonly used in the art to which the present invention belongs. For example, the molded article can be manufactured using a molten kneaded or pelletized thermoplastic resin composition according to the present invention as a raw material, by applying molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, pressure molding, hot bending molding, compression molding, calendering, or rotational molding. In this case, the size, thickness, shape, etc. of the molded article can be appropriately adjusted depending on the intended use.

[0196] The molded article may preferably be manufactured by injecting a molten paste or pellet of the thermoplastic resin composition according to the present invention using an injection molding machine at a barrel temperature of 180 to 300°C. The molded article thus manufactured may be used in fields where weather resistance, gloss, moldability, and impact strength are all required.

[0197] In describing the thermoplastic resin compositions, their manufacturing methods, and molded articles described herein, it is explicitly stated that other conditions and equipment not explicitly mentioned may be selected as appropriate within the range of practices commonly used in the industry, and are not particularly limited.

[0198] The following are preferred embodiments to aid in understanding the present invention. However, these embodiments are merely illustrative of the present invention, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the technical concept, and that such changes and modifications fall within the scope of the appended claims.

[0199] [Examples] The substances used in the following examples and comparative examples are as follows: (A) Graft copolymer: (A-1) Large particle size ASA resin: ASA graft copolymer comprising 50% by weight of butyl acrylate rubber, 36% by weight of styrene, and 14% by weight of acrylonitrile, with an average particle size of 400 nm. (A-2) Small particle size ASA resin: ASA graft copolymer comprising 50% by weight of butyl acrylate rubber, 36% by weight of styrene, and 14% by weight of acrylonitrile, with an average particle size of 100 nm. (A-3) ABS resin: ABS graft copolymer comprising 60% by weight of butadiene rubber with an average particle size of 300 nm and 8-12% by weight of acrylonitrile.

[0200] (B) Copolymer: (B-1)SAN resin: Mw 150,000 g / mol, general SAN copolymer containing 70% by weight of styrene and 30% by weight of acrylonitrile. (B-2) Heat-resistant SAN resin: Mw 100,000 g / mol, comprising a heat-resistant SAN copolymer containing 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile.

[0201] (C) Polyethylene terephthalate: (C-1) Non-recycled polyethylene terephthalate: PET resin with a concentration of IV of 0.6-0.8 dl / g (C-2) Recycled polyethylene terephthalate: IV 0.6~0.8 dl / g, which is recycled PET resin.

[0202] (D) Compatibilizer: (D-1) Ethylene methyl acrylate copolymer (EMA; Lotyl 29MA03T, manufactured by SK Corporation) comprising 71% by weight of ethylene and 29% by weight of methyl acrylate. (D-2) Ethylene vinyl acetate copolymer (EVA; EVEA28025, manufactured by LG Chem Co., Ltd.) comprising 72% by weight of ethylene and 28% by weight of vinyl acetate.

[0203] Examples 1-1 to 1-7, 2-1 to 2-9, and Comparative Examples 1-1 to 1-11, 2-1 to 2-12 The above (A) to (D) were mixed using a super mixer in the proportions shown in Tables 1 and 3 below, and extruded into pellets using a twin-screw extruder (screw diameter 26 mm, L / D = 40) under extrusion conditions of cylinder temperature 230°C and screw rotation speed 200 rpm.

[0204] The manufactured pelletized thermoplastic resin composition was dried at 100°C for at least 2 hours. Then, it was injection molded in an injection molding machine under the conditions of an injection machine barrel temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to produce test specimens for physical property measurement. These specimens were left at room temperature (23±3°C) for at least 48 hours, after which their physical properties were measured.

[0205] Furthermore, during the production of the extruded film, the manufactured pellets are used in a T-die extruder (Collins Techline 20T, screw diameter 20 nm, L / D = 25) at a molding temperature of 250°C and a molding pressure of 200 kgf / cm². 2 Under the conditions of a screw rotation speed of 100 rpm, a roll temperature of 85°C, and a roll rotation speed of 3.5 m / min, a film with a thickness of 0.08 mm was prepared, and the glossiness and torque characteristics of the film were measured.

[0206] [Example Test] The physical properties of the test specimens produced in the above examples and comparative examples were measured by the following method, and the results are shown in Tables 2 and 4 below. *Injection gloss (gloss unit; GU): In accordance with ASTM D2457, gloss was measured using a gloss meter VG7000 on an injection-molded test specimen with a thickness of 3 mm at a 45° angle. *Whiteness (L value): Measured in accordance with the CIE1976 L*a*b* color system using a colorimeter (model name: X-lite Color Eye 7000A) on a 3mm thick injection-molded specimen under a UV D65 light source with a Degree Observer at 10°. The L value was measured in Reflectance Mode according to the CIE Lab method, in accordance with the Munsell color system. *Gloss unit (GU) of extruded film: In accordance with ASTM D2457, gloss was measured using a gloss meter VG7000 on an extruded film test specimen with a thickness of 0.08 mm at 45°. *1 / 8" Izod impact strength (kgf·cm / cm): Measured at room temperature using an injection-molded specimen with a thickness of 1 / 8" in accordance with ASTM D256. *1 / 4" Izod impact strength (kgf·cm / cm): Measured at room temperature using a 1 / 4" thick injection-molded test specimen in accordance with ASTM D256. *Processability (%): Using a T-die extruder (Techline 20T, Collins, screw diameter 20nm, L / D=25), molding temperature 250°C, molding pressure 200kgf / cm². 2 Under the conditions of a screw rotation speed of 100 rpm, a roll temperature of 85°C, and a roll rotation speed of 3.5 m / min, the torque value applied to the motor connected to the screw in order to rotate the screw at the set rotation speed is shown as a ratio to the maximum torque value of the extruder during the process of extruding a film to a thickness of 0.08 mm. A lower torque value indicates better processability. *Weather resistance (ΔE): Accelerated weathering test (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filters, irradiation dose 0.55 W / m²) on a 3 mm thick injection-molded test specimen. 2 After applying a 340nm (at 340nm) and measuring for 2,000 hours under SAE J1960 conditions, the ΔE was evaluated using the following formula 2. The ΔE below is the arithmetic mean of the Hunter Lab(L,a,b) values ​​measured before and after the accelerated weathering experiment, and a ΔE value closer to 0 indicates superior weather resistance. The Hunter Lab(L,a,b) values ​​were measured using a colorimeter (X-lite Color-eye 7000A) in accordance with the CIE1976 L*a*b* color system.

[0207] [Formula 2] ΔE = √{(LL') 2 +(aa´) 2 +(bb´) 2}(√: square root symbol)

[0208] *Thermal stability: In the injection molding process of physical property evaluation test pieces, Hunter Lab (L, a, b) values were measured respectively for a test piece injected after an additional residence time of 5 minutes in the cylinder of the injection machine at a cylinder temperature of 260°C, and a test piece not subjected to the additional 5-minute residence. The ΔE value was calculated by substituting the color values measured before and after the additional 5-minute residence at 260°C into the following Mathematical Formula 3. A ΔE value closer to 0 indicates better thermal stability.

[0209] [Mathematical Formula 3] ΔE before and after residence = √{(L-L´) 2 +(a-a´) 2 +(b-b´) 2}(√: radical sign)

[0210] [Table 1] [Table 2] [Table 3] [Table 4] Referring to Tables 1 and 2 above, for Examples 1-1 to 1-7 according to the present invention, when non-recycled PET is used as (C) polyalkylene terephthalate, the injection gloss is 110 or more, indicating excellent gloss; the whiteness L value is 90.0 or more, indicating excellent whiteness; the impact strength is 9.6 kgf·cm / cm or more, indicating excellent impact resistance. Compared with Comparative Example 1-1, in which PET and a compatibilizer are not blended into the ASA / SAN alloy resin, the torque value is reduced by at least 29.2%, and it can be confirmed that film processability is greatly improved. Furthermore, the ΔE value before and after the accelerated weather resistance test is 1.7 or less, and the ΔE value before and after the additional 5-minute residence at 260°C is within the range of 3.4 or less, confirming that the weather resistance and thermal stability are also excellent.

[0211] On the other hand, in the case of Comparative Examples 1-1 to 1-11, which fall outside the scope of the present invention, it was found that the gloss level decreased significantly in all cases except for Comparative Example 1-8. Comparative Example 1-8 had significantly inferior weather resistance and thermal stability, and overall, its impact resistance, processability (torque), whiteness, weather resistance, and / or thermal stability were very poor. Therefore, it was confirmed that the thermoplastic resin composition according to the present invention has excellent mechanical properties, film processability, gloss level, whiteness, weather resistance, and thermal stability.

[0212] On the other hand, referring to Tables 3 and 4 above, in Examples 2-1 to 2-9 according to the present invention, when recycled PET was applied as (C) polyalkylene terephthalate, the gloss of the extruded film was 37 or less, showing low gloss, and the impact strength was 9.8 kgf·cm / cm or more, showing excellent impact resistance. Compared to Comparative Example 2-1, in which recycled PET and a compatibilizer were not blended into the ASA / SAN alloy resin, the torque value decreased by at least 27.1%, confirming a significant improvement in film processability. Furthermore, the ΔE value before and after the accelerated weathering test was 2.0 or less, and the ΔE value measured before and after an additional 5 minutes of retention at 260°C was within the range of 3.8 or less, confirming excellent weather resistance and thermal stability.

[0213] On the other hand, in the case of Comparative Examples 2-1 to 2-12, which fall outside the scope of the present invention, it was confirmed that the gloss level was excessively high in all cases, and that the impact resistance, processability (torque), weather resistance, and / or thermal stability were very poor. In particular, in the case of Comparative Example 2-8, even though it did not contain recycled PET, it was confirmed that the processability and thermal stability were lower compared to the examples, and the low-gloss characteristics were very poor.

[0214] Therefore, it has been confirmed that the thermoplastic resin composition according to the present invention maintains the mechanical properties inherent to ASA-based resins and polyester resins at an equivalent or higher level, while also exhibiting excellent film processability, weather resistance, and thermal stability, as well as mechanical rigidity (impact resistance) and moldability, thereby enabling the provision of high-quality thermoplastic resin molded products. In particular, when recycled resin (recycled PET) is not included, it exhibits excellent injection gloss and whiteness, making it suitable for providing high-gloss injection-molded products in a variety of colors. Furthermore, even when recycled resin (recycled PET) is included, the deterioration of physical properties is prevented, offering the advantage of being environmentally friendly, while also exhibiting excellent low-gloss characteristics, making it suitable for providing environmentally friendly low-gloss extruded films.

Claims

1. (A) 15 to 50% by weight of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) Aromatic vinyl compound-vinyl cyanide compound copolymer 20 to 55% by weight, (C) 100 parts by weight of a base resin containing 10 to 40% by weight of recycled or non-recycled polyalkylene terephthalate, (D) A thermoplastic resin composition characterized by comprising 0.5 to 10 parts by weight of a compatibilizer.

2. The thermoplastic resin composition according to claim 1, characterized in that the (D) compatibilizer is one or more selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA).

3. The thermoplastic resin composition according to claim 1, characterized in that the copolymer (A) comprises, based on 100% by weight of the base resin, 3 to 35% by weight of (A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with an average particle size of 250 to 500 nm, and 5 to 40% by weight of (A-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with an average particle size of 50 to 150 nm.

4. The thermoplastic resin composition according to claim 3, characterized in that the (A-1) graft copolymer and the (A-2) graft copolymer each contain 40 to 60% by weight of alkyl acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound.

5. The thermoplastic resin composition according to claim 1, characterized in that the (B) copolymer is one or more selected from the group consisting of (B-1) an aromatic vinyl compound-vinyl cyanide copolymer comprising 55 to 85% by weight of an alkyl-unsubstituted aromatic vinyl compound and 15 to 45% by weight of a vinyl cyanide compound, and (B-2) a heat-resistant aromatic vinyl compound-vinyl cyanide copolymer comprising 60 to 80% by weight of an alkyl-substituted aromatic vinyl compound, 20 to 40% by weight of a vinyl cyanide compound, and 0 to 20% by weight of an alkyl-unsubstituted aromatic vinyl compound.

6. The thermoplastic resin composition according to claim 5, characterized in that the (B-1) aromatic vinyl compound-vinyl cyanide compound copolymer has a weight-average molecular weight of 50,000 to 300,000 g / mol.

7. The thermoplastic resin composition according to claim 5, characterized in that the (B-2) heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer has a weight-average molecular weight of 30,000 to 200,000 g / mol.

8. The thermoplastic resin composition according to claim 1, characterized in that the (C) polyalkylene terephthalate has an intrinsic viscosity (I.V.) of 0.5 to 1.5 dl / g.

9. The thermoplastic resin composition according to claim 1, characterized in that the (C) recycled or non-recycled polyalkylene terephthalate is recycled polyethylene terephthalate or non-recycled polyethylene terephthalate.

10. The thermoplastic resin composition according to claim 1, characterized in that the weight ratio (A:C) of the copolymer (A) and polyalkylene terephthalate (C) is 0.5 to 2.0:

1.

11. The thermoplastic resin composition according to claim 2, characterized in that the (D) compatibilizer comprises 50 to 90% by weight of ethylene and 10 to 50% by weight of methyl acrylate or vinyl acetate.

12. The aforementioned (C) polyalkylene terephthalate is non-recycled polyethylene terephthalate. The thermoplastic resin composition according to claim 1, characterized in that the injection gloss measured on an injection-molded test piece with a thickness of 3 mm at 45° in accordance with ASTM D2457 is 108 or higher.

13. The aforementioned (C) polyalkylene terephthalate is recycled polyethylene terephthalate. The thermoplastic resin composition according to claim 1, characterized in that the gloss level measured on an extruded film test piece with a thickness of 0.08 mm at 45° in accordance with ASTM D2457 is less than 50.

14. A method for producing a thermoplastic resin composition, comprising the steps of kneading and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising: 100 parts by weight of a base resin containing (A) 15 to 50% by weight of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) 20 to 55% by weight of aromatic vinyl compound-vinyl cyanide compound copolymer, and (C) 10 to 40% by weight of regenerated or unregenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

15. A molded article characterized by comprising the thermoplastic resin composition described in any one of claims 1 to 13.