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

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article comprising the same. More specifically, the present invention relates to: a thermoplastic resin composition prepared by adding a compatibilizer to a base resin comprising an ASA-based graft copolymer, an SAN-based and / or SAMMA-based resin, and a regenerated or non-regenerated polyalkylene terephthalate, and adjusting the composition ratio thereof; a method for preparing the thermoplastic resin composition; and a molded article including the thermoplastic resin composition. According to the present invention, the intrinsic mechanical properties of the ASA-based resin and the polyester resin can be maintained at a certain level or higher, and the film processability, glossiness, whiteness, weather resistance, and thermal stability can be excellent. In addition, impact resistance, film processability, low gloss characteristics, weather resistance, and thermal stability may be excellent even when the regenerated resin is included.

Description

Technical Field

[0001] [Cross-references to related applications] This application claims priority to Korean Patent Application No. 10-2023-0133757 and Korean Patent Application No. 10-2023-0133758, filed on October 6, 2023, and Korean Patent Application No. 10-2024-0133295 and Korean Patent Application No. 10-2024-0133298, refiled on September 30, 2024, based on the priority of the aforementioned patents, the disclosure of each of which is incorporated herein by reference.

[0002] This invention relates to a thermoplastic resin composition, a method for preparing the same, and molding articles comprising the same. More specifically, this invention relates to: a thermoplastic resin composition having excellent mechanical properties, film processing properties, appearance such as gloss and whiteness, weather resistance, and thermal stability; furthermore, being environmentally friendly by preventing degradation of physical properties even when containing recycled resin, and possessing excellent mechanical properties, film processing properties, low gloss characteristics, weather resistance, and thermal stability; a method for preparing the thermoplastic resin composition; and molding articles comprising the thermoplastic resin composition. Background Technology

[0003] ABS resin, represented by acrylonitrile-butadiene-styrene resin, is used in various fields due to its excellent molding and processing properties, mechanical properties, and appearance. However, because ABS resin is based on conjugated diene rubber with chemically unstable unsaturated bonds, it exhibits poor weather resistance, such as aging easily upon exposure to ultraviolet light. Therefore, ASA-type resins, represented by acrylate compounds-styrene-acrylonitrile copolymers, have been proposed as a potential alternative to ABS resins.

[0004] ASA resins possess excellent weather resistance, thermal stability, aging resistance, and chemical resistance, as well as molding and processing properties, rigidity, and impact resistance. They are widely used in various fields, both indoors and outdoors, such as electrical and electronic components, building materials, automotive interior and exterior materials, marine and leisure products.

[0005] ASA-type resins are based on acrylate rubbers, providing impact resistance to products, and are primarily used in blends with hard resins. A representative example of a hard resin is acrylonitrile resin.

[0006] Furthermore, polyester resins, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PET), possess excellent mechanical and electrical properties, as well as other physical and chemical characteristics, and are widely used in automotive parts, electrical and electronic equipment, and office equipment. In particular, the application of polyester resins is increasingly evident in the automotive parts sector, driven by the development of high-intensity technologies such as electric vehicles and autonomous driving, as well as the current trend towards lightweight materials.

[0007] It was expected that blending ASA resins and polyester resins would provide very useful materials, but in reality, ASA resins and polyester resins are incompatible with each other, resulting in physical properties that are lower than expected.

[0008] Furthermore, while plastics are consumed in large quantities in modern society due to their convenience, they cannot decompose naturally. Therefore, the demand for methods to treat and utilize waste plastics is constantly increasing, and the use of recycled resins as part of environmental regulations is becoming mandatory. However, recycled resins age during manufacturing, consumption, and processing due to physical / chemical factors such as impact, abrasion, heat, ultraviolet radiation, moisture, and exposure to high and low temperatures. Moreover, compared to freshly polymerized virgin resins, recycled resins suffer from significantly lower performance in molding and processing, mechanical rigidity, appearance quality, flexibility, chemical resistance, and thermal stability due to foreign matter contamination.

[0009] Therefore, there is a need to develop a thermoplastic resin composition that exhibits the desired physical properties due to its excellent compatibility when containing ASA-type resins and polyester resins, and still possesses physical properties applicable to existing plastic materials when containing a certain amount of recycled resin.

[0010] [Related Technical Documents] [Patent Literature] KR 10-2009-0038507 A Summary of the Invention

[0011] Technical issues Therefore, the present invention was made in view of the above-mentioned problems. One object of the present invention is to provide a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molding article manufactured using the thermoplastic resin composition, wherein the thermoplastic resin composition is able to maintain the inherent mechanical properties of ASA resin and polyester resin at a certain level or above, and has excellent film processing performance, gloss, whiteness, weather resistance and thermal stability. In addition, even when containing recycled resin, it is environmentally friendly by preventing the deterioration of physical properties, and has excellent film processing performance, low gloss characteristics, weather resistance and thermal stability.

[0012] The above and other objectives can be achieved by the invention described below.

[0013] Technical solution I) According to one aspect of the present invention, a thermoplastic resin composition is provided, comprising 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer, said base resin comprising 60% by weight to 90% by weight of a styrene copolymer and 10% by weight to 40% by weight of recycled or non-recycled polyalkylene terephthalate.

[0014] II) According to another aspect of the invention, a thermoplastic resin composition is provided, comprising 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer, said base resin comprising 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.

[0015] III) According to another aspect of the present invention, a thermoplastic resin composition is provided, comprising 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer, said base resin comprising 15% to 50% by weight of a copolymer comprising alkyl acrylate rubber, aromatic vinyl compounds and vinyl cyanide compounds, 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, wherein the weight ratio of the copolymer comprising alkyl acrylate rubber, aromatic vinyl compounds and vinyl cyanide compounds to the recycled or non-recycled polyalkylene terephthalate is 0.5 to 2.0:1.

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

[0017] V) According to I) to IV), the compatibilizer (D) may preferably include one or more selected from 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) According to I) to V), based on 100% by weight of the base resin, the copolymer (A) may preferably contain 3% to 35% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing alkyl acrylate rubber with an average particle size of 250 nm to 500 nm and 5% to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing alkyl acrylate rubber with an average particle size of 50 nm to 150 nm.

[0019] VII) According to I) to VI), based on their total weight, the graft copolymer (A-1) and the graft copolymer (A-2) may each preferably contain 40% to 60% by weight of alkyl acrylate rubber, 30% to 40% by weight of aromatic vinyl compound and 10% to 20% by weight of vinyl cyanide compound.

[0020] VIII) According to I) to VII), the copolymer (B) may preferably include one or more selected from aromatic vinyl compound-vinyl cyanide compound copolymer (B-1) and heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2), wherein the aromatic vinyl compound-vinyl cyanide compound copolymer (B-1) comprises 55% to 85% by weight of alkyl non-substituted aromatic vinyl compound and 15% to 45% by weight of vinyl cyanide compound, and the heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) comprises 60% to 80% by weight of alkyl substituted aromatic vinyl compound, 20% to 40% by weight of vinyl cyanide compound and 0% to 20% by weight of alkyl non-substituted aromatic vinyl compound.

[0021] According to I) to VIII), the weight-average molecular weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (B-1) can preferably be from 50,000 g / mol to 300,000 g / mol.

[0022] X) According to I) to IX), the weight-average molecular weight of the heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) can preferably be from 30,000 g / mol to 200,000 g / mol.

[0023] XI) According to I) to X), the intrinsic viscosity (IV) of polyalkylene terephthalate (C) can preferably be from 0.5 dl / g to 1.5 dl / g.

[0024] According to I) to XI), the polyalkylene terephthalate (C) may preferably be non-recycled polyethylene terephthalate or recycled polyethylene terephthalate.

[0025] XIII) According to I) to XII), the weight ratio (A:C) of the graft copolymer (A):polyalkylene terephthalate (C) can preferably be 0.5 to 2.0:1.

[0026] XIV) According to I) to XIII), the compatibilizer (D) may preferably comprise 30% to 90% by weight of ethylene and 10% to 70% by weight of methyl acrylate or vinyl acetate, more preferably 50% to 90% by weight of ethylene and 10% to 50% by weight of methyl acrylate or vinyl acetate. More preferably, the compatibilizer (D) may be an ethylene-methyl acrylate copolymer (EMA) comprising 50% to 90% by weight of ethylene and 10% to 50% by weight of methyl acrylate.

[0027] According to XV), alkylene terephthalate (C) can preferably be non-recycled polyethylene terephthalate, and the injection gloss of the thermoplastic resin composition, measured at a 45° angle for a 3 mm thick injection-molded specimen according to ASTM D2457, can preferably be 108 or higher.

[0028] According to (XVI) I) to XV), the alkylene terephthalate (C) can preferably be recycled polyethylene terephthalate, and the gloss of the thermoplastic resin composition, measured at a 45° angle for an extruded film sample with a thickness of 0.08 mm (80 µm) according to ASTM D2457, can preferably be less than 50.

[0029] XVII) According to another aspect of the present invention, a method for preparing a thermoplastic resin composition is provided, the method comprising kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, said base resin comprising 60% to 90% by weight of a styrene copolymer and 10% to 40% by weight of recycled or non-recycled polyalkylene terephthalate.

[0030] XVIII) According to another aspect of the present invention, a method for preparing a thermoplastic resin composition is provided, the method comprising kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, said base resin comprising 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.

[0031] XIX) According to another aspect of the present invention, a method for preparing a thermoplastic resin composition is provided, the method comprising kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, wherein the base resin comprises 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, wherein the weight ratio of the copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound to the recycled or non-recycled polyalkylene terephthalate is 0.5 to 2.0:1.

[0032] According to another aspect of the present invention, a method for preparing a thermoplastic resin composition is provided, the method comprising kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, said base resin comprising 15% to 50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A), 20% to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer (B), and 10% to 40% by weight of recycled or non-recycled polyalkylene terephthalate (C).

[0033] XXI) According to another aspect of the present invention, a molding article is provided, comprising a thermoplastic resin composition according to any one of I) to XX).

[0034] Beneficial effects According to the present invention, the present invention has the following effects: providing a thermoplastic resin composition that can maintain the inherent mechanical properties of ASA-type resin and polyester resin at a certain level and has excellent film processing performance, injection gloss, whiteness, weather resistance and thermal stability; a method for preparing the thermoplastic resin composition; and molded articles manufactured using the thermoplastic resin composition.

[0035] Furthermore, the present invention provides the following advantages: a thermoplastic resin composition that is environmentally friendly by preventing physical property degradation even when containing recycled resin, capable of maintaining the inherent mechanical properties of both ASA-type resins and polyester resins at a certain level or above, and possessing excellent film processing performance, low gloss characteristics, weather resistance, and thermal stability; a method for preparing the thermoplastic resin composition; and molded articles manufactured using the thermoplastic resin composition. Detailed Implementation

[0036] The thermoplastic resin compositions of the present invention, their preparation methods, and molding articles comprising the present invention are described in detail below.

[0037] The inventors have confirmed that when ASA-based resins and polyester resins are alloyed, the addition of a compatibilizer and control of their composition ratio within a predetermined range achieves excellent film processing performance, weather resistance, and thermal stability without deteriorating the inherent mechanical properties of either the ASA-based resin or the polyester resin. In particular, even when mixed with recycled resins, degradation of physical properties is prevented, thereby achieving eco-friendliness. Based on these results, the inventors conducted further research to complete this invention.

[0038] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer. The base resin comprises 60 to 90 wt% of a styrene copolymer and 10 to 40 wt% of a polyethylene terephthalate (PET), wherein the PET is recycled or non-recycled. In this case, compatibility can be significantly improved, thereby maintaining the inherent mechanical properties of ASA-based resins and polyester resins at a certain level or above. Furthermore, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Moreover, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Additionally, film processing performance and low-gloss characteristics can be excellent.

[0039] In this disclosure, styrene copolymers refer to copolymers that preferably contain styrene monomers, i.e., aromatic vinyl compounds, represented by styrene, as the main component in an amount of 5% by weight or more. Specific examples include copolymers containing alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds, and / or aromatic vinyl compound-vinyl cyanide compound copolymers. Furthermore, copolymers containing alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds can be graft copolymers obtained by grafting an aromatic vinyl compound-vinyl cyanide compound copolymer onto an alkyl acrylate rubber core.

[0040] Furthermore, specifically, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer. The base resin comprises 15% to 50% by weight of a copolymer comprising alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds; 20% to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer; and 10% to 40% by weight of polyalkylene terephthalate, wherein the polyalkylene terephthalate is recycled or non-recycled. In this case, compatibility can be greatly improved, thereby maintaining the inherent mechanical properties of ASA-type resins and polyester resins above a certain level. Furthermore, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Moreover, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Furthermore, film processing performance and low gloss characteristics can be excellent.

[0041] Furthermore, specifically, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer. The base resin comprises 15 to 50 wt% of a copolymer comprising alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer, and 10 to 40 wt% of polyalkylene terephthalate. The weight ratio of the copolymer comprising alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds to polyalkylene terephthalate is 0.5 to 2.0:1, and the polyalkylene terephthalate is either recycled or non-recycled. In this case, compatibility can be greatly improved, thereby maintaining the inherent mechanical properties of ASA-type resins and polyester resins at a certain level or above. Furthermore, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thus achieving eco-friendliness. In addition, the film processing performance and low-gloss characteristics can be excellent.

[0042] Furthermore, more specifically, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer. The base resin comprises 15 to 50 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyanide copolymer, and 10 to 40 wt% of polyalkylene terephthalate, wherein the polyalkylene terephthalate is recycled or non-recycled. In this case, compatibility can be significantly improved, thereby maintaining the inherent mechanical properties of ASA-type resins and polyester resins above a certain level. Furthermore, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Moreover, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Furthermore, film processing performance and low gloss characteristics can be excellent.

[0043] In this disclosure, the component ratio of a copolymer or resin may refer to the content of the units constituting the copolymer, or it may refer to the content of monomers added during the polymerization of the copolymer.

[0044] In this disclosure, a polymer containing a certain compound refers to a polymer prepared by polymerizing the compound, wherein the units in the polymer are derived from the compound.

[0045] In this disclosure, a recycled thermoplastic resin can be used in the present invention without particular limitation when it meets the definition of the invention and is considered a conventional recycled thermoplastic resin in the field to which the invention pertains. For example, recycled thermoplastic resin is a thermoplastic resin regenerated from collected waste plastics. As a specific example, recycled thermoplastic resin refers to raw material obtained by sorting, washing, and crushing collected waste plastics. Furthermore, if necessary, the recycled thermoplastic resin can be processed into granules by an extrusion process. In this case, no additional processing, such as additional purification, is required.

[0046] In this disclosure, non-recycled thermoplastic resin is used in contrast to the aforementioned recycled thermoplastic resin, and may also be referred to as virgin or fresh thermoplastic resin, which may be prepared by polymerizing monomers that constitute thermoplastic resin or corresponding commercially available products.

[0047] In this disclosure, resins not specified as recycled or non-recycled (fresh) may be recycled or non-recycled resins, but are preferably non-recycled resins.

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

[0049] (A) Acrylic acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer Based on 100% by weight of a base resin (A+B+C) comprising (A) to (C), the content of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) (hereinafter referred to as 'graft copolymer (A)') can be from 15% by weight to 50% by weight, preferably from 17% by weight to 48% by weight, more preferably from 18% by weight to 46% by weight, even more preferably from 19% by weight to 45% by weight, and even more preferably from 20% by weight to 45% by weight. Within this range, impact resistance, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Additionally, impact resistance, film processing performance, low gloss characteristics, weather resistance, and thermal stability can be excellent.

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

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

[0052] More specifically, for example, based on 100% by weight of the base resin, the graft copolymer (A) may comprise 3% to 35% by weight of graft copolymer (A-1) and 5% to 40% by weight of graft copolymer (A-2), preferably 3% to 33% by weight of graft copolymer (A-1) and 5% to 38% by weight of graft copolymer (A-2), more preferably 4% to 32% by weight of graft copolymer (A-1) and 5% to 37% by weight of graft copolymer (A-2), even more preferably 5% to 30% by weight of graft copolymer (A-1) and 5% to 36% by weight of graft copolymer (A-2), and even more preferably 5% to 27% by weight of graft copolymer (A-1) and 6% to 35% by weight of graft copolymer (A-2). In this case, impact resistance, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thus achieving eco-friendliness. Additionally, low gloss characteristics can be excellent.

[0053] For example, when the thermoplastic resin composition does not contain recycled resin, based on 100% by weight of the base resin, the graft copolymer (A) may comprise 3% to 20% by weight of graft copolymer (A-1) and 5% to 40% by weight of graft copolymer (A-2), preferably 3% to 19% by weight of graft copolymer (A-1) and 5% to 38% by weight of graft copolymer (A-2), more preferably 3% to 18% by weight of graft copolymer (A-1) and 5% to 37% by weight of graft copolymer (A-2), even more preferably 4% to 18% by weight of graft copolymer (A-1) and 5% to 36% by weight of graft copolymer (A-2), and even more preferably 4% to 17% by weight of graft copolymer (A-1) and 6% to 35% by weight of graft copolymer (A-2). In this case, impact resistance, weather resistance, and whiteness can be excellent without reducing other physical properties.

[0054] For example, when the thermoplastic resin composition contains recycled resin, preferably recycled polyalkylene terephthalate, the graft copolymer (A) may contain 10% to 35% by weight of graft copolymer (A-1) and 5% to 20% by weight of graft copolymer (A-2) based on 100% by weight of base resin, preferably 10% to 32% by weight of graft copolymer (A-1) and 5% to 19% by weight of graft copolymer (A-2), more preferably 11% to 30% by weight of graft copolymer (A-1) and 5% to 18% by weight of graft copolymer (A-2), even more preferably 12% to 28% by weight of graft copolymer (A-1) and 5% to 18% by weight of graft copolymer (A-2), and even more preferably 12% to 25% by weight of graft copolymer (A-1) and 5% to 17% by weight of graft copolymer (A-2). In this case, low gloss properties and impact resistance can be excellent without compromising other physical properties.

[0055] For example, the weight ratio (A-1:A-2) of the graft copolymer (A-1):A-2 can be from 0.1 to 3.0:1, specifically from 0.5 to 3.0:1, preferably from 0.8 to 2.8:1, more preferably from 1.0 to 2.6:1, even more preferably from 1.0 to 2.5:1, and even more preferably from 1.1 to 2.5:1. Within this range, the desired effect can be fully achieved. In particular, even when regenerated resin is included, degradation of physical properties can be prevented, thus mechanical properties and low-gloss characteristics can be excellent.

[0056] For example, the graft copolymer (A-1) may comprise rubber with an average particle size of 250 nm to 500 nm, preferably 270 nm to 480 nm, more preferably 300 nm to 470 nm, even more preferably 330 nm to 460 nm, and even more preferably 350 nm to 450 nm. In this case, impact resistance, weather resistance, whiteness, and gloss can be excellent without compromising other physical properties.

[0057] For example, the graft copolymer (A-2) may comprise rubber with an average particle size of 50 nm to 150 nm, preferably 60 nm to 140 nm, more preferably 65 nm to 130 nm, even more preferably 70 nm to 125 nm, and even more preferably 80 nm to 120 nm. In this case, impact resistance, weather resistance, whiteness, and gloss can be excellent without compromising other physical properties.

[0058] For example, the graft copolymer (A-1) may comprise an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) with a weight-average molecular weight of 100,000 g / mol to 400,000 g / mol, preferably 110,000 g / mol to 390,000 g / mol, more preferably 120,000 g / mol to 350,000 g / mol, even more preferably 120,000 g / mol to 330,000 g / mol, and even more preferably 130,000 g / mol to 300,000 g / mol. Within this range, impact resistance, whiteness, thermal stability, and gloss can be excellent without compromising other physical properties.

[0059] For example, the graft copolymer (A-2) may comprise an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) with a weight-average molecular weight of 50,000 g / mol to 300,000 g / mol, preferably 60,000 g / mol to 250,000 g / mol, more preferably 70,000 g / mol to 230,000 g / mol, even more preferably 70,000 g / mol to 200,000 g / mol, and even more preferably 80,000 g / mol to 180,000 g / mol. Within this range, impact resistance, whiteness, thermal stability, and gloss can be excellent without compromising other physical properties.

[0060] For example, the grafting degree of the graft copolymer (A) (each of graft copolymer (A-1) and graft copolymer (A-2) can be 20% or more, preferably 20% to 100%, more preferably 22% to 80%, even more preferably 23% to 65%, and even more preferably 25% to 55%. Within this range, mechanical properties such as impact resistance can be excellent, and gloss and weather resistance can be excellent.

[0061] In this disclosure, the average particle size of the rubber can be measured using measurement methods commonly used in the technical field to which this invention pertains (including electron microscopy methods using SEM, TEM, etc.) or dynamic light scattering, without particular limitation. For example, the average particle size of the rubber can be measured using dynamic light scattering by sampling when the rubber is manufactured. Specifically, the average particle size can be measured as an intensity value using a Nicomp 380 particle size analyzer (manufacturer: PSS) in Gaussian mode. As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (TSC: 35 wt% to 50 wt%) with distilled water by 1,000 to 5,000 times, i.e., appropriately diluting the sample so that it does not deviate significantly from the intensity setpoint of 300 kHz, and placing it in a glass tube. Then, the average particle size of the sample is measured using a flow cell with automatic dilution, in dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis mode. At this time, the settings are as follows: temperature: 23°C; measurement wavelength: 632.8 nm.

[0062] In this disclosure, the average particle size can preferably be based on the average particle size of the dynamic light scattering method.

[0063] In this disclosure, unless otherwise defined, weight-average molecular weight can be measured using gel permeation chromatography (GPC, Waters Breeze). As a specific example, tetrahydrofuran (THF) can be used as the eluent to measure the weight-average molecular weight by gel permeation chromatography (GPC, Waters Breeze). In this case, the weight-average molecular weight is obtained as a relative value to a polystyrene (PS) standard sample. As a specific measurement example, weight-average molecular weight can be measured under the following conditions: solvent: THF, column temperature: 40℃, 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: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): OECD TG 118.

[0064] In this disclosure, to measure the weight-average molecular weight of the copolymer (shell) grafted onto the rubber (core), the rubber (core) can be separated using separation methods employed in the art to which this invention pertains. For example, to separate the sol from the insoluble substance (gel), a solution is prepared by dissolving the sol in a THF solvent using a method for measuring the degree of grafting, described later. This solution is then filtered through a filter to obtain a filtrate, which is used as a sample for measuring the weight-average molecular weight.

[0065] In this disclosure, when measuring the grafting degree, 30 g of acetone was added to 0.5 g of powdered graft polymer, and the mixture was stirred for 12 hours at 210 rpm and room temperature using a shaker (SKC-6075, Lab Companion Co.). The mixture was then centrifuged for 3 hours at 18,000 rpm and 0°C using a centrifuge (Supra R30, Hanil Science Co.) to separate only the insoluble material insoluble in acetone. The separated insoluble material was then dried for 12 hours at 85°C using a forced convection oven (OF-12GW, Lab Companion Co.) via forced circulation. The weight of the dried insoluble material was then measured, and the grafting degree was calculated using Equation 1 below.

[0066] [Equation 1] Grafting degree (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] × 100 In Equation 1, the weight of the grafted monomer is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble substance (gel) obtained by dissolving the graft copolymer in acetone and centrifuging. The weight of the rubber (g) is the theoretical weight of the rubber component contained in the graft copolymer powder.

[0067] For example, based on its total weight (100 wt%), the graft copolymer (A) may comprise 40 wt% to 60 wt% of alkyl acrylate rubber, 30 wt% to 45 wt% of aromatic vinyl compounds, and 5 wt% to 20 wt% of vinyl cyanide compounds, preferably 42 wt% to 58 wt% of alkyl acrylate rubber, 32 wt% to 43 wt% of aromatic vinyl compounds, and 7 wt% to 18 wt% of vinyl cyanide compounds, more preferably 42 wt% to 55 wt% of alkyl acrylate rubber, 33 wt% to 42 wt% of aromatic vinyl compounds, and 10 wt% to 18 wt% of vinyl cyanide compounds, and even more preferably 45 wt% to 52 wt% of alkyl acrylate rubber, 33 wt% to 40 wt% of aromatic vinyl compounds, and 12 wt% to 16 wt% of vinyl cyanide compounds. Within this range, compatibility with other resins can be improved, thus resulting in excellent mechanical properties and molding processability.

[0068] Here, the composition ratio of each component constituting the graft copolymer (A-1) and the graft copolymer (A-2) can be independently and appropriately controlled within the above range.

[0069] For example, graft copolymers (A) can be prepared by emulsion polymerization. In this case, impact resistance and compatibility can be excellent.

[0070] Emulsion polymerization can be carried out without any special limitations by emulsion polymerization methods commonly practiced in the technical field to which this invention pertains, such as emulsion graft polymerization.

[0071] For example, a method for preparing the graft copolymer (A) may include step i): preparing an alkyl acrylate rubber by comprising an alkyl acrylate; and step ii): preparing the graft copolymer by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber. In this case, the mechanical properties, weather resistance, thermal stability, appearance, and molding processability can be excellent.

[0072] The method for preparing the graft copolymer (A) may preferably include the following steps: based on a total amount of 100% by weight, step i): preparing rubber by polymerizing 40% to 60% by weight of alkyl acrylate in the presence of a crosslinking agent, initiator, electrolyte, and emulsifier; and step ii): preparing the graft copolymer by grafting 40% to 60% by weight of aromatic vinyl compounds and vinyl cyanide compounds onto the rubber in the presence of a crosslinking agent, initiator, and emulsifier. In this case, the mechanical properties, weather resistance, thermal stability, appearance, and molding and processing properties can be excellent.

[0073] For example, the graft copolymer (A) may contain polymer seeds. In this case, the polymer seeds may be contained in the alkyl acrylate rubber at 10% to 30% by weight, preferably 15% to 25% by weight (based on a total of 100% by weight of rubber and seeds).

[0074] As a specific example, the graft copolymer (A) may comprise: a polymer seed comprising one or more selected from 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, molding processability, impact resistance, and weather resistance can be excellent.

[0075] The polymer seed can preferably be a rubber seed composed of alkyl acrylate rubber. In this case, the manufacturing process can be easily carried out, thus further improving the balance of physical properties.

[0076] For example, a method for preparing a graft copolymer (A) may include: step i) preparing a polymer seed by comprising one or more selected from (meth)acrylates, aromatic vinyl compounds, and vinyl cyanide compounds; step ii) preparing an alkyl acrylate rubber (core) by comprising an alkyl acrylate in the presence of the polymer seed; and step iii) preparing the graft copolymer by grafting aromatic vinyl compounds and vinyl cyanide compounds onto the rubber (core). In this case, molding processability, impact resistance, and weather resistance can be excellent.

[0077] In this disclosure, the monomer content in the polymer may refer to the content of monomers supplied when preparing the polymer (weight %), or it may refer to a value calculated by converting units in the polymer into monomers (weight %).

[0078] In this disclosure, (meth)acrylate alkyl esters can be defined as a category that includes both alkyl acrylate esters and alkyl methacrylate esters.

[0079] In this disclosure, for example, the alkyl acrylate may be an alkyl acrylate containing an alkyl group having 1 to 15 carbon atoms, preferably including one or more selected from 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 carbon atoms or 8 carbon atoms, even more preferably n-butyl acrylate, 2-ethylhexyl acrylate or mixtures thereof, and even more preferably butyl acrylate.

[0080] In this disclosure, for example, the alkyl methacrylate may be an alkyl methacrylate containing an alkyl group having 1 to 15 carbon atoms, preferably including one or more selected from 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.

[0081] In this disclosure, for example, the aromatic vinyl compound may include one or more selected from: styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably styrene.

[0082] In this disclosure, for example, the vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.

[0083] As the emulsifier used in the steps of preparing polymer seeds (when polymer seeds are included), preparing rubber cores, and preparing copolymer shells, emulsifiers commonly used in the art to which this invention pertains can be used without particular limitation. For example, the emulsifier may include one or more selected from: alkyl sulfosuccinate metal salts having 12 to 18 carbon atoms or derivatives thereof, alkyl sulfates having 12 to 20 carbon atoms or derivatives thereof, alkyl sulfonate metal salts having 12 to 20 carbon atoms or derivatives thereof, fatty acid soaps, and rosin acid soaps.

[0084] Alkyl sulfosuccinate metal salts or their derivatives having 12 to 18 carbon atoms may preferably include one or more of the following: dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, and potassium dioctyl sulfosuccinate.

[0085] Alkyl sulfates or their derivatives having 12 to 20 carbon atoms may preferably include one or more selected from sodium lauryl sulfate, sodium dodecyl sulfate, sodium octadecyl sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate. In addition, other sulfate emulsifiers, such as sodium dodecylbenzene sulfate and sodium oleate sulfate, may also be used in one or more types.

[0086] Fatty acid soaps may preferably include one or more sodium or potassium salts selected from oleic acid, stearic acid, lauric acid, and mixed fatty acids.

[0087] Rosin acid soaps are preferably rosin salts, especially rosin acid metal salts.

[0088] For example, based on a total of 100 parts by weight of graft copolymer (A), the amount of emulsifier used for each step can be from 0.01 parts by weight to 5 parts by weight, preferably from 0.05 parts by weight to 4 parts by weight, and more preferably from 0.5 parts by weight to 3 parts by weight.

[0089] There are no particular restrictions on the initiator, but free radical initiators are preferred.

[0090] For example, free radical initiators may include one or more selected from inorganic peroxides, organic peroxides (excluding ketals, carbonates and azo compounds), peroxyketal peroxides, peroxycarbonate peroxides and azo compounds.

[0091] Inorganic peroxides may preferably include one or more selected from sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, and hydrogen peroxide.

[0092] For example, organic peroxides may include one or more selected from the following: tert-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-pentyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-pentylperoxy)cyclohexane, ethyl 3,3-di(tert-pentylperoxy)butyrate, dicumylbenzene monohydroperoxide, tert-pentyl hydroperoxide, tert-butyl hydroperoxide, tert-butylperoxyneodecanate, tert-butylperoxyneovatate, di(3,3,5-trimethylhexanoyl)peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,3,5-trimethylhexanoyl per ... - Trimethylhexanoyl, tert-amyl peroxyneodecanate, tert-amyl peroxynepentate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleic acid, isopropylphenyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di-2-ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, dilauryl peroxide, 3,5,5-trimethylhexanoyl peroxide and tert-butyl peroxyisobutyrate.

[0093] The peroxyketal peroxide may preferably include one or more selected from the following: 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-pentylperoxy)cyclohexane, ethyl 3,3-di(tert-butylperoxy)butyrate and ethyl 3,3-di(tert-pentylperoxy)butyrate.

[0094] The peroxycarbonate peroxide may preferably include one or more selected from the following: dialkyl peroxides, such as dicumyl peroxide, di(tert-butylperoxy)-m / p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperoxy 2-ethylhexyl monocarbonate and tert-butylperoxybenzoate.

[0095] The azo compound may preferably include one or more selected from azobisisobutyronitrile, azobis-2,4-dimethylpentanonitrile, azobiscyclohexaneformitrile, and dimethyl azobisisobutyrate.

[0096] For example, based on a total of 100 parts by weight of graft copolymer (A), the amount of initiator used for each step can be from 0.001 parts by weight to 2 parts by weight, preferably from 0.01 parts by weight to 1 part by weight.

[0097] In at least one of the polymer seed preparation step (when polymer seeds are included), the rubber (core) preparation step, and the copolymer (shell) preparation step, a redox catalyst may preferably be used in combination with an initiator to further promote the initiation reaction.

[0098] For example, the redox catalyst may include one or more selected from sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate and sodium ethylenediaminetetraacetate, preferably a mixture of sodium pyrophosphate, dextrose and ferrous sulfide, but is not limited thereto.

[0099] For example, based on a total of 100 parts by weight of graft copolymer (A), the amount of catalyst used for each step can be from 0.001 parts by weight to 2 parts by weight, preferably from 0.002 parts by weight to 1 part by weight.

[0100] In at least one of the polymer seed preparation step (when polymer seeds are included), the polymer rubber (core) preparation step, and the copolymer (shell) preparation step, an activator may be used in combination with a polymerization initiator to promote the initiation reaction of the peroxide.

[0101] As an activator, commonly used activators in the technical field to which this invention pertains can be used without any specific limitations.

[0102] Based on a total of 100 parts by weight of graft copolymer (A), the amount of activator can be from 0.01 parts by weight to 3 parts by weight, preferably from 0.01 parts by weight to 1 part by weight. Within this range, a high degree of polymerization can be achieved.

[0103] For example, as an electrolyte, one or more selected from KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO4, Na2S2O7, K3P2O7, K3PO4, Na3PO4, KOH, NaOH, and Na2HPO4 can be used, but not limited thereto.

[0104] Based on a total of 100 parts by weight of the graft copolymer (A), the total amount of electrolyte added can be from 0.001 parts by weight to 1 part by weight, preferably from 0.01 parts by weight to 0.5 parts by weight. Within this range, a high degree of polymerization can be achieved.

[0105] In this disclosure, unless otherwise defined, crosslinking agents commonly used in the art to which this invention pertains can be used without particular limitation. For example, compounds containing unsaturated vinyl groups and capable of being used as crosslinking agents, or compounds containing two or more unsaturated vinyl groups with different reactivity, can be used as crosslinking agents of this invention. As a specific example, the crosslinking agent of the present invention may include one or more selected from the following: 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 propoxylated diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylated diacrylate, neopentyl glycol propoxylated diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylolpropane ethoxylated triacrylate, trimethylolpropane propoxylated triacrylate, pentaerythritol ethoxylated triacrylate, pentaerythritol propoxylated triacrylate, vinyltrimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallylamine, and diallylamine, but is not limited thereto.

[0106] For example, based on a total of 100 parts by weight of graft copolymer (A), for each step, the amount of crosslinking agent can be from 0.01 parts by weight to 5 parts by weight, preferably from 0.01 parts by weight to 3 parts by weight, and more preferably from 0.05 parts by weight to 1 part by weight.

[0107] For example, a molecular weight regulator can be used in the copolymer shell preparation step.

[0108] For example, based on a total of 100 parts by weight of graft copolymer (A), the amount of molecular weight regulator can be from 0.01 parts by weight to 2 parts by weight, preferably from 0.05 parts by weight to 2 parts by weight, and more preferably from 0.05 parts by weight to 1 part by weight. Within this range, polymers with the desired molecular weight can be readily prepared.

[0109] For example, as a molecular weight regulator, one or more of the following can be used, but not limited to: α-methylstyrene dimer, tert-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, dichloromethane, dibromomethane, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanionic acid disulfide.

[0110] In this disclosure, 100 parts by weight of the graft copolymer can refer to: the total weight of the graft copolymer finally obtained; the total weight of the monomers used to prepare the polymer seed (when the polymer seed is included), the rubber core and the graft shell, taking into account that most of the added monomers are used for polymerization; or the total weight of the monomers added in the preparation of the polymer seed (when the polymer seed is included) and the rubber core and the monomers added in the preparation of the graft shell.

[0111] In this disclosure, % means weight%, unless otherwise defined.

[0112] In the steps of seed preparation and kernel preparation, the method of supplying the monomers can be either batch supply or continuous supply, or a combination of both methods.

[0113] In this disclosure, "continuous supply" means supplying components without batches. For example, according to continuous supply, components can be supplied for more than 10 minutes, more than 30 minutes, more than 1 hour, preferably more than 2 hours, in a dropwise, little by little, step by step or continuous flow manner within the polymerization time range.

[0114] For example, there are no particular restrictions on emulsion polymerization, but it can be carried out at 50°C to 85°C, preferably 60°C to 80°C.

[0115] For example, the latex formed after the polymerization of the graft copolymer (A) can be prepared in powder form by conventional processes including coagulation, washing, and drying. As a specific example, a metal salt or acid is added, coagulation is carried out at 60°C to 100°C, and the latex is then cured, dehydrated, washed, and dried to prepare the latex of the copolymer (A) in powder form, but the invention is not limited thereto.

[0116] For example, the graft copolymer (A) can be any commercially available product, as long as it meets the definition of this invention.

[0117] (B) Aromatic vinyl compounds-vinyl cyanide copolymers Based on 100% by weight of the base resin, the content of the aromatic vinyl compound-vinyl cyanide compound copolymer (B) (hereinafter referred to as copolymer (B)) can be from 20% to 55% by weight, preferably from 22% to 55% by weight, more preferably from 25% to 53% by weight, even more preferably from 27% to 52% by weight, and even more preferably from 28% to 50% by weight. Within this range, mechanical properties, film processing properties, gloss, whiteness, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. In addition, low gloss characteristics can be excellent.

[0118] For example, copolymer (B) may include one or more selected from: copolymer (B-1) comprising an aromatic vinyl compound and a vinyl cyanide compound without alkyl-substituted aromatic vinyl compound (hereinafter referred to as "copolymer (B-1)"), and heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) comprising an alkyl-substituted aromatic vinyl compound (hereinafter referred to as "copolymer (B-2)").

[0119] As a specific example, copolymer (B-1) may comprise 55% to 85% by weight of alkyl-unsubstituted aromatic vinyl compounds and 15% to 45% by weight of vinyl cyanide compounds, preferably 60% to 82% by weight of alkyl-unsubstituted aromatic vinyl compounds and 18% to 40% by weight of vinyl cyanide compounds, more preferably 65% ​​to 82% by weight of alkyl-unsubstituted aromatic vinyl compounds and 18% to 35% by weight of vinyl cyanide compounds, and still more preferably 65% ​​to 80% by weight of alkyl-unsubstituted aromatic vinyl compounds and 20% to 35% by weight of vinyl cyanide compounds. In this case, the mechanical properties can be excellent without compromising other physical properties. For example, copolymer (B-1) may be referred to as a "non-heat-resistant SAN resin" or a "conventional SAN resin" because copolymer (B-1) does not contain heat-resistant monomers that impart heat resistance to the copolymer, which consist of alkyl-substituted aromatic vinyl compounds.

[0120] For example, copolymer (B-2) may comprise 60 wt% to 80 wt% of alkyl-substituted aromatic vinyl compounds, 20 wt% to 40 wt% of vinyl cyanide compounds, and 0 wt% to 20 wt% of alkyl-unsubstituted aromatic vinyl compounds, preferably 62 wt% to 80 wt% of alkyl-substituted aromatic vinyl compounds, 20 wt% to 38 wt% of vinyl cyanide compounds, and 0 wt% to 17 wt% of alkyl-unsubstituted aromatic vinyl compounds, more preferably 63 wt% to 77 wt% of alkyl-substituted aromatic vinyl compounds, 23 wt% to 37 wt% of vinyl cyanide compounds, and 0 wt% to 13 wt% of alkyl-unsubstituted aromatic vinyl compounds, and even more preferably 65 wt% to 75 wt% of alkyl-substituted aromatic vinyl compounds, 25 wt% to 35 wt% of vinyl cyanide compounds, and 0 wt% to 10 wt% of alkyl-unsubstituted aromatic vinyl compounds. In this case, heat resistance and mechanical properties can be excellent without compromising other physical properties. For example, copolymer (B-2) can be called "heat-resistant SAN resin" because copolymer (B-2) contains heat-resistant monomers, such as alkyl-substituted aromatic vinyl compounds.

[0121] For example, copolymer (B-2) may not contain alkyl-unsubstituted aromatic vinyl compounds, but may contain 60% to 80% by weight of alkyl-substituted aromatic vinyl compounds and 20% to 40% by weight of vinyl cyanide compounds, preferably 63% to 77% by weight of alkyl-substituted aromatic vinyl compounds and 23% to 37% by weight of vinyl cyanide compounds, and even more preferably 65% ​​to 75% by weight of alkyl-substituted aromatic vinyl compounds and 25% to 35% by weight of vinyl cyanide compounds. In this case, heat resistance can be excellent without reducing other physical properties.

[0122] Here, the weight % of copolymer (B) contained in the matrix resin is expressed as: the weight % of copolymer (B-1) when only copolymer (B-1) is contained; the weight % of copolymer (B-2) when only copolymer (B-2) is contained; and the total weight % of copolymer (B-1) and copolymer (B-2) when a mixture of copolymer (B-1) and copolymer (B-2) is contained, i.e., the sum of their respective weight %.

[0123] For example, alkyl-substituted aromatic vinyl compounds may include one or more selected from α-methylstyrene, α-ethylstyrene, p-methylstyrene and m-methylstyrene, preferably α-methylstyrene.

[0124] For example, the type of alkyl unsubstituted aromatic vinyl compound may be suitably selected from the range of aromatic vinyl compounds without alkyl substituents mentioned in the graft copolymer (A), and may preferably be styrene.

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

[0126] For example, the weight-average molecular weight of copolymer (B) can be from 30,000 g / mol to 300,000 g / mol, preferably from 30,000 g / mol to 200,000 g / mol, more preferably from 40,000 g / mol to 190,000 g / mol, even more preferably from 40,000 g / mol to 180,000 g / mol, and even more preferably from 50,000 g / mol to 180,000 g / mol. In this case, the mechanical properties can be excellent without reducing other physical properties.

[0127] More specifically, the weight-average molecular weight of the copolymer (B-1) can be from 50,000 g / mol to 300,000 g / mol, preferably from 70,000 g / mol to 200,000 g / mol, more preferably from 80,000 g / mol to 190,000 g / mol, even more preferably from 80,000 g / mol to 180,000 g / mol, and even more preferably from 90,000 g / mol to 180,000 g / mol. In this case, the mechanical properties can be excellent without reducing other physical properties.

[0128] For example, the weight-average molecular weight of copolymer (B-2) can be from 30,000 g / mol to 200,000 g / mol, preferably from 30,000 g / mol to 180,000 g / mol, more preferably from 40,000 g / mol to 150,000 g / mol, even more preferably from 50,000 g / mol to 140,000 g / mol, and even more preferably from 50,000 g / mol to 130,000 g / mol. In this case, the heat resistance and mechanical properties can be excellent without reducing other physical properties.

[0129] For example, copolymer (B) can be prepared by methods commonly used in the technical field to which this invention pertains, and commercially available products can also be used, as long as the products conform to the definition of this invention.

[0130] (C) Polyalkylene terephthalate Based on 100% by weight of the base resin, the content of polyalkylene terephthalate (C) can be from 10% to 40% by weight, preferably from 15% to 37% by weight, more preferably from 18% to 35% by weight, even more preferably from 20% to 34% by weight, and even more preferably from 22% to 33% by weight. Within this range, compatibility can be excellent, thus resulting in excellent mechanical properties, gloss, whiteness, film processing properties, weather resistance, and thermal stability. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Additionally, excellent compatibility results in excellent impact resistance, film processing properties, low-gloss characteristics, weather resistance, and thermal stability.

[0131] For example, polyalkylene terephthalate (C) can be selected from recycled polyalkylene terephthalate, non-recycled polyalkylene terephthalate, and mixtures thereof. In this case, mechanical properties, gloss, whiteness, film processing properties, weather resistance, and thermal stability can be ensured. Furthermore, degradation of physical properties due to non-recycled resins can be prevented, thus achieving eco-friendliness. Moreover, when non-recycled polyalkylene terephthalate is applied according to the molding process, high injection gloss can be achieved. Even when recycled polyalkylene terephthalate is applied, excellent low-gloss extrusion characteristics can be achieved. Therefore, recycled and / or non-recycled polyalkylene terephthalate can be appropriately selected as polyalkylene terephthalate (C) as needed.

[0132] Here, the percentage by weight of polyalkylene terephthalate (C) in the base resin represents the percentage by weight of recycled polyalkylene terephthalate when only recycled polyalkylene terephthalate is contained, the percentage by weight of non-recycled polyalkylene terephthalate when only non-recycled polyalkylene terephthalate is contained, and the total weight of recycled and non-recycled polyalkylene terephthalate when a mixture of them is contained.

[0133] For example, the intrinsic viscosity (IV) of polyalkylene terephthalate (C) can be from 0.5 dl / g to 1.5 dl / g, preferably from 0.5 dl / g to 1.2 dl / g, more preferably from 0.5 dl / g to 1.1 dl / g, even more preferably from 0.6 dl / g to 1.0 dl / g, and even more preferably from 0.6 dl / g to 0.8 dl / g. Within this range, compatibility can be excellent, and therefore mechanical properties and molding processability can be excellent.

[0134] In this disclosure, unless otherwise stated, intrinsic viscosity can be measured using methods conventionally performed in the art to which this invention pertains. As a specific example, when measuring intrinsic viscosity, a sample solution with a concentration of 0.05 g / ml is prepared by completely dissolving the sample in dichloromethane as a solvent, and then filtering it using a filter to obtain a filtrate. The intrinsic viscosity is then measured at 20°C using an Ubbelohde viscometer with the obtained filtrate.

[0135] For example, the polyalkylene terephthalate (C) may include one or more selected from polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polypropylene terephthalate (PTT), preferably one or more selected from polybutylene terephthalate and polyethylene terephthalate, and more preferably polyethylene terephthalate. In this case, the intended effects of the present invention can be fully achieved, and the impact resistance can be excellent.

[0136] For example, polyethylene terephthalate resins may include one or more selected from: recycled polyethylene terephthalate resins derived from polyethylene terephthalate homopolymers obtained by polymerization of terephthalic acid and ethylene glycol; and polyethylene terephthalate copolymers comprising terephthalic acid, ethylene glycol, and at least one of 1,4-cyclohexanediol, isophthalic acid, and butanediol as comonomers. In this case, impact resistance and heat resistance can be excellent. Furthermore, when recycled polyethylene terephthalate is used, excellent low-gloss properties can be achieved. Conversely, when non-recycled polyethylene terephthalate is used, high gloss can be achieved.

[0137] Recycled polyalkylene terephthalate (PET) refers to recycled resin obtained by recovering waste PET. In this case, waste PET, including waste PET, can be used, making the raw materials readily available and offering significant environmental advantages.

[0138] For example, the melting point of polyalkylene terephthalate (C) can be 200°C to 280°C, preferably 220°C to 275°C, and more preferably 240°C to 270°C. Within this range, the desired effect can be fully exhibited.

[0139] In this disclosure, the melting point can be measured using methods known in the polymer field; for example, the thermal absorption peak can be measured using differential scanning calorimetry (DSC).

[0140] For example, the glass transition temperature of polyalkylene terephthalate (C) can be from 60°C to 100°C, preferably from 65°C to 90°C. Within this range, impact resistance and molding processability can be excellent.

[0141] In this disclosure, the glass transition temperature can be measured using a differential scanning calorimeter (DSC) according to ASTM D3418, and for example, the glass transition temperature can be measured using a TA Instruments Q100 DSC (differential scanning calorimeter) at a heating rate of 10 °C / min.

[0142] Any recycled or non-recycled poly(alkylene terephthalate) resin commonly used in the technical field to which this invention pertains may be used without particular limitation, provided that the recycled or non-recycled poly(alkylene terephthalate) resin meets the definition of recycled or non-recycled poly(alkylene terephthalate) (C) of this invention, and any commercially available product may be used.

[0143] (D) Compatibilizer Based on 100 parts by weight of the base resin, the compatibilizer (D) content can be from 0.5 parts by weight to 10 parts by weight, preferably from 1 part by weight to 9 parts by weight, more preferably from 1.5 parts by weight to 8.5 parts by weight, and even more preferably from 1.7 parts by weight to 8 parts by weight. Within this range, the compatibility between the graft copolymer (A) and the polyalkylene terephthalate (C) can be greatly improved, thus resulting in excellent mechanical properties, gloss, whiteness, film processing performance, weather resistance, and thermal stability. Furthermore, when recycled polyalkylene terephthalate is used, even when the proportion of recycled resin is, for example, 10% by weight or more, degradation of physical properties can be prevented, thereby achieving eco-friendliness. In addition, impact resistance, film processing performance, and low gloss characteristics can be excellent.

[0144] As a specific example, the content of the compatibilizer (D) can be 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 even more preferably 1.8 to 2.8 parts by weight. In this case, since even a small amount can improve compatibility, the intended effects of the present invention can be fully demonstrated.

[0145] For example, the compatibilizer (D) may include one or more selected from 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 one or more selected from olefin-alkyl acrylate copolymers, and more preferably ethylene-methyl acrylate copolymer. In this case, mechanical properties, gloss, whiteness, film processing performance, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, eco-friendliness can be achieved, and impact resistance, film processing performance, and low gloss characteristics can be excellent.

[0146] For example, the compatibilizer (D) may consist of an olefin compound, an alkyl (meth)acrylate or an alkenyl acetate, and optionally a glycidyl methacrylate. As a specific example, the compatibilizer (D) may contain 30% to 90% by weight of an olefin compound, 10% to 70% by weight of an alkyl (meth)acrylate or an alkenyl acetate, and 0% to 15% by weight of a glycidyl methacrylate. In this case, the desired effect can be fully achieved.

[0147] The compatibilizer (D) preferably comprises 50% to 90% by weight of ethylene and 10% to 50% by weight of methyl acrylate or vinyl acetate, more preferably 55% to 80% by weight of ethylene and 20% to 45% by weight of methyl acrylate or vinyl acetate, and even more preferably 60% to 80% by weight of ethylene and 20% to 40% by weight of methyl acrylate or vinyl acetate. In this case, the desired effect can be fully achieved. More preferably, the compatibilizer (D) can be an ethylene-methyl acrylate copolymer. In this case, the raw materials are readily available.

[0148] For example, the compatibilizer (D) can have a melt index of 1 g / 10 min to 10 g / 10 min, preferably 2 g / 10 min to 5 g / 10 min, as measured according to ASTM D1238 at 190°C under a load of 2.16 kg. Within this range, the film processing performance can be excellent without compromising other physical properties.

[0149] For example, the compatibilizer (D) may have a melting point of 80°C to 110°C, preferably 82°C to 105°C, and more preferably 85°C to 100°C. Within this range, mechanical strength and molding processability can be excellent.

[0150] There are no particular restrictions on the method for preparing the compatibilizer (D), as long as the method is a commonly used method in the technical field and commercially available products can be used, provided that the products meet the definition of this invention.

[0151] Thermoplastic resin composition The thermoplastic resin composition comprises 100 parts by weight of a base resin and 0.5 to 10 parts by weight of a compatibilizer (D). The base resin comprises 15 to 50 wt% of a graft copolymer (A), 20 to 55 wt% of a copolymer (B), and 10 to 40 wt% of polyalkylene terephthalate (C). In this configuration, the inherent mechanical properties of the ASA-type resin and the polyester resin can be maintained at a level above a certain standard, and injection molding gloss, whiteness, film processing performance, weather resistance, and thermal stability can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Additionally, film processing performance, low-gloss extrusion characteristics, weather resistance, and thermal stability can be excellent.

[0152] For example, in the thermoplastic resin composition, the weight ratio (A:C) of the graft copolymer (A) to the polyalkylene terephthalate (C) can be 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, impact resistance, film processing performance, gloss, and whiteness can be excellent. Furthermore, when recycled resin is included, eco-friendliness can be achieved, and low gloss characteristics, film processing performance, and impact resistance can be excellent.

[0153] The thermoplastic resin composition contains acrylate rubber as the rubber component but does not contain conjugated diene rubber, thus exhibiting excellent weather resistance. Therefore, it can maintain its physical properties for extended periods even when exposed to aging environments such as heat or ultraviolet radiation. Furthermore, even when containing ASA-type resins and polyester resins with poor compatibility, the film processing performance and thermal stability can be excellent.

[0154] For example, the injection gloss of a thermoplastic resin composition, measured at a 45° angle for a 3 mm thick injection-molded specimen according to ASTM D2457, can be 108 or higher, preferably 108 to 130, more preferably 108 to 125, and even more preferably 109 to 120. In this case, the gloss can be excellent without degrading other physical properties. Here, the unit of gloss can be GU (gloss unit).

[0155] For example, the thermoplastic resin composition may contain non-recycled polyalkylene terephthalate as polyalkylene terephthalate (C), and may be a high-gloss resin composition with an injection gloss of 108 or higher. In this case, in addition to gloss, film processing performance, impact resistance, weather resistance, and thermal stability can be excellent, thus the thermoplastic resin composition can provide high-quality, high-gloss injection molded articles.

[0156] For example, the extrusion gloss of a thermoplastic resin composition, measured at a 45° angle according to ASTM D2457 for an extruded film sample with a thickness of 0.08 mm, can be 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. In this case, the low gloss characteristic can be excellent without reducing other physical properties.

[0157] For example, the thermoplastic resin composition may contain recycled polyethylene terephthalate as polyethylene terephthalate (C), and may be a low-gloss resin composition with an extrusion gloss of less than 50. In this case, eco-friendliness can be achieved, and the low-gloss properties, film processing performance, impact resistance, weather resistance, and thermal stability can be excellent. Therefore, the thermoplastic resin composition can provide high-quality, eco-friendly, low-gloss films.

[0158] For example, because thermoplastic resin compositions have excellent film processing properties, the torque applied to the extruder during the film extrusion process is low, thus allowing the production of films with uniform thickness and uniform gloss. That is, the film appearance quality can be excellent.

[0159] In this disclosure, torque refers to the amount of output required to rotate the screw at a set rotational speed during the extrusion process of a molten mixture or granules of a thermoplastic resin composition using a film extruder, and can be measured by a sensor built into the extruder. In film extrusion processes, when molding conditions such as molding temperature, screw speed (rpm), and composition feed rate are constant, a higher torque value means a greater load applied to the extruder, which implies poorer composition flowability, i.e., poorer molding processability. Therefore, when molding conditions are constant, as the torque value increases, the film thickness uniformity may deteriorate. Conversely, a lower torque value indicates a lower load on the extruder, which indicates better composition flowability. In this case, film processability and film thickness uniformity can be excellent.

[0160] In this disclosure, as a measurement example, a T-die extruder (Techline 20T manufactured by Collins Co., screw diameter: 20 mm, L / D=25) can be used at a molding temperature of 250°C and a molding pressure of 200 kgf / cm². 2 The torque is measured under extrusion molding conditions of 100 rpm screw speed, 85℃ roller temperature, 3.5 m / min roller speed, and 0.08 mm film thickness. The torque can be expressed as a percentage of the maximum torque value (output limit) that the extruder can operate at. The percentage of the maximum torque value that the extruder can operate at can be measured by a sensor built into the extruder and displayed as a value on the torque display.

[0161] Preparation method of thermoplastic resin composition The method for preparing the thermoplastic resin composition of the present invention includes the steps of kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, wherein the base resin comprises 15% to 50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A), 20% to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer (B), and 10% to 40% by weight of polyalkylene terephthalate (C). In this case, compatibility can be greatly improved, thereby maintaining the inherent mechanical properties of ASA-type resins and polyester resins above a certain level. Furthermore, film processing performance, gloss, whiteness, weather resistance, and thermal stability can be excellent. Moreover, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Furthermore, film processing performance and low gloss characteristics can be excellent.

[0162] For example, the kneading and extrusion steps can be performed using one or more of a single-screw extruder, a twin-screw extruder, and a Banbury mixer. The composition can be uniformly mixed using the aforementioned mixer and then extruded to obtain a granular thermoplastic resin composition. In this case, deterioration of mechanical properties and heat resistance can be prevented, and the appearance can be excellent.

[0163] For example, the kneading and extrusion steps can be carried out at an extruder barrel temperature of 170°C to 300°C, preferably 200°C to 280°C, and more preferably 220°C to 270°C. In this case, the processing capacity per unit time can be appropriate, sufficient melt kneading can be achieved, and thermal decomposition can be suppressed.

[0164] For example, kneading and extrusion can be performed at screw speeds of 100 rpm to 400 rpm, preferably 110 rpm to 350 rpm, and more preferably 120 rpm to 270 rpm. In this case, the processing capacity per unit time can be appropriate, and therefore the processing efficiency can be excellent.

[0165] Where necessary, based on 100 parts by weight of the base resin, the thermoplastic resin composition may further comprise 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 of one or more additives selected from lubricants, heat stabilizers, light stabilizers, pigments, mold release agents, antistatic agents, antibacterial agents, processing aids, metal passivators, flame retardants, flame inhibitors, anti-drip agents, inorganic fillers, friction reducers, and anti-wear agents. Within this range, the desired physical properties can be achieved well without reducing the expected physical properties.

[0166] For example, the lubricant may include one or more selected from fatty acid amide compounds, lignite waxes, silicone oils, and olefin waxes, preferably olefin waxes, and more preferably polyethylene waxes. In this case, molding processability and mold release properties can be excellent.

[0167] For example, fatty acid amide compounds may include one or more selected from stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide and ethylene bisoleamide.

[0168] For example, lignite waxes can be lignite waxes, lignite ester waxes, or mixtures thereof.

[0169] For example, silicone oil may include one or more selected from dimethyl silicone oil, methylhydrosilicone oil, ester-modified silicone oil, hydroxyl silicone oil, methanol-modified silicone oil, vinyl silicone oil, and organosilicon acrylates.

[0170] For example, olefin waxes may include one or more selected from oxidized polyethylene wax, polyethylene wax, and polypropylene wax.

[0171] For example, heat stabilizers may include phenolic heat stabilizers, phosphorus heat stabilizers, or mixtures thereof, with phenolic heat stabilizers being preferred. In this case, oxidation due to heat can be prevented during the extrusion process, thus resulting in excellent mechanical properties and heat resistance.

[0172] For example, phenolic heat stabilizers may include one or more selected from the following: N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate. In this case, heat resistance can be significantly improved while maintaining a high balance of physical properties.

[0173] For example, phosphorus heat stabilizers may include one or more selected from the following: 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, monobutyl diphenyl phosphite. Monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylene bis(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] For example, light stabilizers may include one or more selected from: triazine compounds, benzophenone compounds, benzotriazole compounds, indole compounds, quinolinone compounds, benzoate compounds, cyanoacrylate compounds, and amine compounds, preferably benzotriazole compounds or amine compounds. In this case, the balance of physical properties can be excellent, thus further improving lightfastness.

[0175] For example, triazine compounds may include one or more selected from the following: 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, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,6-diphenyl-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-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-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-methoxycarbonylpropoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-ethoxycarbonylethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropyl-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-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-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-methoxycarbonylpropoxyphenyl)-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-Ethoxycarbonylethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropyl-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] For example, benzophenone compounds may include one or more selected from the following: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'- -Dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfonate sodium benzophenone, 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] For example, benzotriazole compounds may include one or more selected from the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenylbenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentyl)benzotriazole, 2-(2'- 2-(2-hydroxy-3',5'-di-tert-pentylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3″,4″,5″,6″-tetrahydrophthaliminomethyl)-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 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-butylphenol; preferably 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-tert-butylphenol.

[0178] For example, indole compounds can be 2-[(1-methyl-2-phenyl-1H-indole-3-yl)methylene]malononitrile.

[0179] For example, quinolinone compounds can be 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

[0180] For example, benzoate compounds may include one or more selected from 2,4-di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, 2,6-di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0181] For example, cyanoacrylate compounds may be 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl) acrylate, or mixtures thereof.

[0182] For example, the amine compound can be a hindered amine ultraviolet stabilizer (HALS), preferably comprising one or more selected from the following: 1,1-bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-penta ... (2,2,6,6-Tetramethyl-4-piperidinyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 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-piperidinyl)hexanediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantoin triacetate, tetra(2,2,6,6- Tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylic acid ester, 1,1'-(1,2-ethylidene)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 7,7,9,9-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, The reaction product of methyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane with 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-hexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]; preferably bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0183] Pigments can be inorganic or organic.

[0184] For example, organic pigments may include one or more of the following: perylene ketone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, indigo pigments, dioxazine pigments, quinacridone pigments, methane pigments, quinoline pigments, isoindolinone pigments, and phthaloyl ketone pigments.

[0185] For example, inorganic pigments may include one or more selected from ultramarine pigments, titanium dioxide, zinc sulfide, zinc oxide, iron oxide, and carbon black.

[0186] For example, as a release agent, one or more selected from glyceryl stearate and polyethylene glycol tetrastearate can be used, but not limited thereto.

[0187] As an antistatic agent, any antistatic agent used in the technical field to which this invention pertains can be used without any particular limitation. For example, as an antistatic agent, at least one selected from anionic surfactants such as sulfates, sulfonates, and phosphates, and nonionic surfactants such as quaternary ammonium salts and alkylamine sulfates can be used, but the invention is not limited thereto.

[0188] For example, as an anti-drip agent, one or more selected from polytetrafluoroethylene (PTFE), a mixture of PTFE and styrene-acrylonitrile (SAN) resin (PTFE / SAN), a mixture of PTFE and polymethyl methacrylate (PMMA) (PTFE / PMMA), polyamide, polysiloxane and tetrafluoroethylene-hexafluoropropylene (TFE-HFP) copolymer can be used, preferably one or more selected from PTFE / SAN and PTFE / PMMA, more preferably PTFE / SAN.

[0189] PTFE / SAN and PTFE / PMMA can preferably be mixtures of PTFE and SAN or PMMA in a weight ratio of 1:0.5 to 1.5, for example, a mixture in a weight ratio of 1:1.

[0190] The antibacterial agents, processing aids, metal passivating agents, flame inhibitors, anti-drip agents, inorganic fillers, friction reducers, and anti-wear agents used in this invention can be used in this invention without special limitations, as long as the additives meet the definition of this invention.

[0191] Molded products The molded articles of the present invention comprise the aforementioned thermoplastic resin composition. In this case, impact resistance, film processing properties, gloss, whiteness, weather resistance, and heat resistance can be excellent. Furthermore, even when recycled resin is included, degradation of physical properties can be prevented, thereby achieving eco-friendliness. Additionally, low gloss characteristics can be excellent.

[0192] Even when containing recycled resin, the molded article has comparable or superior physical properties to that of a molded article containing only virgin resin. Therefore, it can be used in fields where conventional ASA-type thermoplastic resin compositions are applied, such as interior and exterior building materials, automotive interior and exterior trim materials, marine and leisure and sports equipment, without additional processing.

[0193] For example, the molded article has excellent film processing performance and high whiteness, so it can be manufactured into films of various colors. The molded article also has excellent weather resistance, making it particularly suitable as an outer material. For example, the molded article can be an injection-molded article with a thickness of 1 mm to 5 mm, preferably 1.5 mm to 4 mm, more preferably 2 to 3 mm. As a specific example, under a thickness of 3 mm, according to the CIE 1976 L*a*b* color system, measured using a colorimeter (model: X-lite Color Eye7000A) under a UV D65 light source at a 10° viewing angle, and then measuring the L value in reflective mode according to the CIE Lab method based on the Munsell system, the whiteness of the molded article can be 85 or higher, preferably 85 to 100, more preferably 88 to 98, and even more preferably 89 to 97. In this case, the whiteness can be excellent, thus achieving vibrant colors.

[0194] For example, molded articles possess excellent film processing properties and low gloss characteristics, and therefore can be used for low-gloss films. As a specific example, the molded article can be an extruded film with a thickness of 40 μm to 600 μm, preferably 50 μm to 500 μm, and more preferably 60 μm to 300 μm. Specifically, when measured at 45° for a thickness of 0.08 mm (80 µm) according to ASTM D2457, the gloss of the extruded film can be less than 50, preferably 20 to 47, more preferably 22 to 45, even more preferably 23 to 42, and still more preferably 25 to 40. In this case, a high-quality low-gloss film with excellent low gloss and uniform thickness can be provided.

[0195] The molded articles can be manufactured using methods commonly found in the technical field to which this invention pertains. For example, using melt-kneaded products or granules of the thermoplastic resin composition according to the invention as raw materials, the molded articles can be manufactured using molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, pressing molding, compression molding, hot bending molding, calendering, or rotational molding. In this case, the size, thickness, shape, etc., of the molded articles can be appropriately adjusted according to the intended use.

[0196] The molded articles can preferably be manufactured by injecting a melt-kneaded product or granules of the thermoplastic resin composition according to the invention into a barrel at a temperature of 180°C to 300°C using an injection molding machine. The manufactured molded articles can be used in areas where weather resistance, gloss, molding processability, and impact strength are required.

[0197] In describing the thermoplastic resin composition of the present invention, the method of preparing the thermoplastic resin composition, and the molded article comprising the thermoplastic resin composition, it should be noted that other conditions or equipment not explicitly described herein may be suitably selected within the scope commonly practiced in the art, without particular limitation.

[0198] The invention will now be described in more detail with reference to the preferred embodiments described below. However, these embodiments are provided for illustrative purposes only and should not be construed as limiting the scope and concept of the invention. Furthermore, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the concept and scope of the invention, and such changes and modifications are also within the scope of the appended claims.

[0199] [Example] The materials used in the following embodiments and comparative examples are as follows.

[0200] (A) Graft copolymer: (A-1) Large-diameter ASA resin: ASA graft copolymer containing 50% by weight butyl acrylate rubber with an average particle size of 400 nm, 36% by weight styrene, and 14% by weight acrylonitrile. (A-2) Small-diameter ASA resin: ASA graft copolymer containing 50% by weight butyl acrylate rubber with an average particle size of 100 nm, 36% by weight styrene, and 14% by weight acrylonitrile. (A-3) ABS resin: ABS graft copolymer comprising 60% by weight butadiene rubber with an average particle size of 300 nm and 8% to 12% by weight acrylonitrile. (B) Copolymer: (B-1) SAN resin: a conventional SAN copolymer with a molecular weight of 150,000 g / mol and containing 70% by weight styrene and 30% by weight acrylonitrile. (B-2) Heat-resistant SAN resin: A heat-resistant SAN copolymer with a Mw of 100,000 g / mol and containing 70% by weight α-methylstyrene and 30% by weight acrylonitrile. (C) Polyethylene terephthalate: (C-1) Non-recycled polyethylene terephthalate: PET resin with an IV of 0.6 dl / g to 0.8 dl / g (C-2) Recycled polyethylene terephthalate: Recycled PET resin with an IV of 0.6 dl / g to 0.8 dl / g (D) Compatibilizer: (D-1) Ethylene-methyl acrylate copolymer (EMA; Lotyl 29MA03T, SK Co.), which contains 71% by weight ethylene and 29% by weight methyl acrylate. (D-2) Ethylene-vinyl acetate copolymer (EVA; EVEA28025, LG Chem Co.), which contains 72% by weight ethylene and 28% by weight vinyl acetate. Examples 1-1 to 1-7, Examples 2-1 to 2-9, Comparative Examples 1-1 to 1-11 and Comparative Examples 2-1 to 2-12 According to Tables 1 and 3, (A) to (D) were mixed using a super mixer and then extruded using a twin-screw extruder (screw diameter: 26 mm, L / D = 40) at a barrel temperature of 230°C and a screw speed of 200 rpm to obtain pellets.

[0201] A granular thermoplastic resin composition was dried at 100°C for more than 2 hours, and then injection molded in an injection molding machine at a barrel temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm / s to produce specimens for measuring physical properties. The physical properties of the specimens were measured after being left at room temperature (23±3°C) for more than 48 hours.

[0202] Furthermore, when using manufactured granules to produce extruded films, at a molding temperature of 250°C and a density of 200 kgf / cm³, 2 Films with a thickness of 0.08 mm were manufactured using a T-die extruder (Collins Co.'s Techline 20T, screw diameter: 20 nm, L / D=25) under the conditions of molding pressure, screw rotation speed of 100 rpm, roll temperature of 85 °C, and roll rotation speed of 3.5 m / min, and the gloss and torque characteristics of the manufactured films were measured.

[0203] [Experimental Example] The physical properties of the samples manufactured in the Examples and Comparative Examples were measured using the methods described below, and the results are shown in Tables 2 and 4 below.

[0204] *Injection gloss (unit: Gloss; GU): Gloss is measured at 45° on a 3mm thick injection molded sample using a VG7000 gloss meter, according to ASTM D2457.

[0205] *Whiteness (L value): Based on the CIE 1976 L*a*b* color system, using a 3mm thick injection-molded sample, a colorimeter (model: X-lite Color Eye 7000 A) was used to measure the whiteness at a 10° angle under a UV D65 light source. The L value was measured in reflective mode according to the CIE Lab method based on the Munsell system.

[0206] *Extruded film gloss (gloss unit; GU): Gloss was measured at 45° on an extruded film sample with a thickness of 0.08 mm using a gloss meter VG7000 according to ASTM D2457.

[0207] *1 / 8" Cantilever Impact Strength (kgf·cm / cm): The cantilever impact strength is measured at room temperature using a 1 / 8" thick injection molded specimen according to ASTM D256.

[0208] *1 / 4" Cantilever Impact Strength (kgf·cm / cm): The cantilever impact strength is measured at room temperature using a 1 / 4" thick injection molded specimen according to ASTM D256.

[0209] *Processing performance (%): Using a T-die extruder (Techline 20T manufactured by Collins Co., screw diameter: 20mm, L / D=25), at a molding temperature of 250°C and a molding temperature of 200kgf / cm², 2 In the extrusion molding process of a 0.08 mm thick film under the conditions of molding pressure, screw rotation speed of 100 rpm, roll temperature of 85°C, and roll rotation speed of 3.5 m / min, the torque value applied to the motor connected to the screw to rotate the screw at the set rotation speed is expressed as a ratio to the maximum torque value of the extruder. As the torque value decreases, the processing performance improves.

[0210] *Weather resistance (ΔE): For injection molded samples with a thickness of 3 mm, according to SAE J1960, under accelerated weathering testing (Weather-O-Meter, Ci4000, ATLAS Co., xenon arc lamp, quartz (inner) / S.Boro (outer) filter, 340 nm, 0.55 W / m 2 Weather resistance was measured for 2,000 hours at an irradiance of [a specific irradiance value], and evaluated using ΔE calculated using Equation 2 below. ΔE below is the arithmetic mean of the Hunter Lab (L, a, b) values ​​measured before and after the accelerated weathering test. Weather resistance increases as the value of ΔE approaches zero. Hunter Lab (L, a, b) values ​​were measured using a colorimeter (X-lite Color-eye 7000A) according to the CIE 1976 L*a*b* color system.

[0211] [Equation 2] ΔE = √{(L-L') 2 + (a-a') 2 + (b-b') 2 (√: square root symbol) *Thermal Stability: During the injection molding process for evaluating physical properties, Hunter Lab (L, a, b) values ​​were measured for specimens injected at a barrel temperature of 260°C with and without an additional 5-minute dwell time. The color values ​​measured before and after the additional 5-minute dwell time at 260°C were substituted into Equation 3 below to calculate the ΔE value. Thermal stability increases as the ΔE value approaches zero.

[0212] [Equation 3] Before and after the stop, ΔE = √{(L-L')}2 + (a-a') 2 + (b-b') 2 (√: square root symbol) [Table 1] [Table 2] [Table 3] [Table 4] As shown in Tables 1 and 2, in the cases of Examples 1-1 to 1-7 according to the present invention, when non-recycled PET is used as polyalkylene terephthalate (C), the injection gloss is 110 or higher, indicating excellent gloss. The whiteness L value is 90.0 or higher, indicating excellent whiteness. The impact strength is 9.6 kgf·cm / cm or higher, indicating excellent impact resistance. Furthermore, compared with Comparative Example 1-1, which did not contain PET and compatibilizer in the ASA / SAN alloy resin, the torque value is reduced by at least 29.2%, indicating a significant improvement in film processing performance. In addition, the ΔE value before and after the accelerated weathering test is less than 1.7, and the ΔE value before and after an additional 5 minutes at 260°C is less than 3.4, indicating excellent weather resistance and thermal stability.

[0213] On the other hand, in the cases of Comparative Examples 1-1 to 1-11, which are outside the scope of this invention, it was found that gloss was significantly reduced in all cases except for Comparative Examples 1-8. Comparative Examples 1-8 exhibited very poor weather resistance and thermal stability, and also exhibited very poor impact resistance, processing performance (torque), whiteness, weather resistance, and / or thermal stability. Based on these results, it can be confirmed that the thermoplastic resin composition of this invention has excellent mechanical properties, film processing performance, gloss, whiteness, weather resistance, and thermal stability.

[0214] Furthermore, as shown in Tables 3 and 4, in the cases of Examples 2-1 to 2-9 according to the present invention, when recycled PET is used as polyalkylene terephthalate (C), the gloss of the extruded film is 37 or less, exhibiting low gloss. The impact strength is 9.8 kgf·cm / cm or more, indicating excellent impact resistance. Moreover, compared to Comparative Example 2-1, in which no recycled PET and compatibilizer were added to the ASA / SAN alloy resin, the torque value decreased by at least 27.1%, indicating a significant improvement in film processing performance. Furthermore, the ΔE value before and after the accelerated weathering test is 2.0 or less, and the ΔE value before and after an additional 5 minutes at 260°C is 3.8 or less, indicating excellent weather resistance and thermal stability.

[0215] On the other hand, in Comparative Examples 2-1 to 2-12, which are outside the scope of this invention, the gloss was excessively increased, and the impact resistance, processing performance (torque), weather resistance, and / or thermal stability were very poor. In particular, it was confirmed that in the case of Comparative Examples 2-8, although recycled PET was not included, the processing performance and thermal stability were lower and the low gloss characteristics were very poor compared to the examples.

[0216] Therefore, in the thermoplastic resin composition of the present invention, the inherent mechanical properties of the ASA-type resin and the polyester resin are maintained above a certain level, and the film processing performance, weather resistance, thermal stability, mechanical rigidity (impact resistance), and molding processing performance are excellent. Thus, this thermoplastic resin composition can provide high-quality molded articles. In particular, when recycled resin (recycled PET) is not included, physical properties suitable for providing high-gloss injection molded articles with excellent injection gloss and whiteness, as well as a variety of colors, can be achieved. Furthermore, even when recycled resin (recycled PET) is included, degradation of physical properties can be prevented, and eco-friendliness can be achieved. In addition, excellent low-gloss characteristics can be achieved, thus enabling the provision of eco-friendly low-gloss extruded films.

Claims

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

2. The thermoplastic resin composition according to claim 1, wherein, The compatibilizer (D) includes one or more selected from 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, wherein, Based on 100% by weight of the base resin, the copolymer (A) comprises 3% to 35% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) comprising alkyl acrylate rubber with an average particle size of 250 nm to 500 nm and 5% to 40% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) comprising alkyl acrylate rubber with an average particle size of 50 nm to 150 nm.

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

5. The thermoplastic resin composition according to claim 1, wherein, The copolymer (B) comprises one or more selected from aromatic vinyl compound-vinyl cyanide compound copolymer (B-1) and heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2), wherein the aromatic vinyl compound-vinyl cyanide compound copolymer (B-1) comprises 55% to 85% by weight of alkyl non-substituted aromatic vinyl compound and 15% to 45% by weight of vinyl cyanide compound, and the heat-resistant aromatic vinyl compound-vinyl cyanide compound copolymer (B-2) comprises 60% to 80% by weight of alkyl substituted aromatic vinyl compound, 20% to 40% by weight of vinyl cyanide compound and 0% to 20% by weight of alkyl non-substituted aromatic vinyl compound.

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

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

8. The thermoplastic resin composition according to claim 1, wherein, The intrinsic viscosity (IV) of the polyalkylene terephthalate (C) is from 0.5 dl / g to 1.5 dl / g.

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

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

1.

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

12. The thermoplastic resin composition according to claim 1, wherein, The polyalkylene terephthalate (C) is non-recycled polyethylene terephthalate, and the injection gloss of the thermoplastic resin composition, measured at 45° on a 3 mm thick injection-molded specimen according to ASTM D2457, is 108 or higher.

13. The thermoplastic resin composition according to claim 1, wherein, The polyalkylene terephthalate (C) is recycled polyethylene terephthalate, and the gloss of the thermoplastic resin composition, measured at 45°, for an extruded film sample with a thickness of 0.08 mm according to ASTM D2457, is less than 50.

14. A method for preparing a thermoplastic resin composition, comprising kneading and extruding 100 parts by weight of a base resin and 0.5 parts by weight to 10 parts by weight of a compatibilizer (D) at 170°C to 300°C and 100 rpm to 400 rpm, wherein the base resin comprises 15% to 50% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A), 20% to 55% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer (B), and 10% to 40% by weight of recycled or non-recycled polyalkylene terephthalate (C).

15. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 13.

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