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

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing same, and a molded article including same and, more specifically, to: a thermoplastic resin composition which has a compatibilizer added to a base resin including an ASA-based graft copolymer, a SAN-based and / or SAMMA-based resin, and recycled or non-recycled polyalkylene terephthalate and which has the composition ratio thereof adjusted, so as to maintain the mechanical properties inherent respectively to the ASA-based resin and polyester resin at equal or higher levels and to exhibit excellent film processability, glossiness, whiteness, weather resistance, and thermal stability and, even when a recycled resin is included, exhibit excellent impact resistance, film processability, low-gloss characteristics, weather resistance, and thermal stability; a method for preparing same; and a molded article including same.

Description

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

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0133757, filed on October 6, 2023, and Korean Patent Application No. 10-2023-0133758, filed on October 6, 2023, and refiled Korean Patent Application No. 10-2024-0133295, filed on September 30, 2024, and refiled Korean Patent Application No. 10-2024-0133298, filed on September 30, 2024, which are each incorporated herein by reference. The entire disclosure of the relevant Korean patent applications is hereby incorporated by reference herein.

[0003] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, wherein the thermoplastic resin composition is excellent in mechanical properties, film processability, appearance characteristics such as gloss and whiteness, weather resistance, and heat stability, and further has an environmentally friendly advantage by preventing deterioration of properties even when a recycled resin is included, and wherein the thermoplastic resin composition is excellent in mechanical properties, film processability, low-light characteristics, weather resistance, and heat stability, a method for producing the same, and a molded article comprising the same.

[0004] ABS resins, represented by acrylonitrile-butadiene-styrene resins, have been used in various fields due to their excellent molding processability, mechanical properties, and appearance characteristics. However, because they are based on conjugated diene rubbers with chemically unstable unsaturated bonds, they have problems with poor weather resistance, such as easy aging due to exposure to ultraviolet rays. Therefore, ASA resins, represented by acrylate compound-styrene-acrylonitrile copolymers, have been proposed as a material that can replace ABS resins.

[0005] ASA resins have excellent weather resistance, heat stability, aging resistance, and chemical resistance, as well as moldability, rigidity, and impact resistance, and are widely used in various fields regardless of indoor / outdoor use, such as electrical and electronic components, construction materials, automobile interior and exterior materials, ships, and leisure goods.

[0006] The above ASA resin is based on acrylate rubber and provides impact resistance, and is mainly consumed by blending with hard resins, and a representative example of hard resins is styrene-acrylonitrile resin.

[0007] Meanwhile, polyester resins, such as polyethylene terephthalate and polybutylene terephthalate, boast outstanding mechanical, electrical, and other physical and chemical properties, making them widely used in automotive components, electrical and electronic devices, and office equipment. Their utility is particularly increasing in the automotive component sector, where lightweight materials are becoming increasingly common and advanced technologies, such as electric vehicles and autonomous driving, are advancing rapidly.

[0008] However, although it is expected that blending the above ASA resin and polyester resin will provide a very useful material, in reality, there is a problem that the ASA resin and polyester resin do not have good compatibility with each other, and thus the properties that are expressed are not up to expectations.

[0009] Meanwhile, while plastics are consumed in significant quantities in modern society due to their convenience, they do not decompose naturally, which has led to a growing demand for waste disposal and utilization methods. Furthermore, environmental regulations are mandating the use of recycled resins. However, recycled resins age due to physical and chemical factors such as impact, wear, heat, UV, moisture, and exposure to high and low temperatures during the manufacturing, consumption, and disposal processes. Furthermore, they are susceptible to contamination from foreign substances, resulting in significantly lower moldability, mechanical strength, appearance quality, flexibility, chemical resistance, and thermal stability compared to newly polymerized virgin resins.

[0010] Therefore, there is a need to develop a thermoplastic resin composition that contains ASA resin and polyester resin, yet has excellent compatibility and exhibits expected properties, and also has properties that can be applied to existing plastic material fields even when containing a certain level of recycled resin.

[0011]

[0012] [Prior Art Literature]

[0013] [Patent Document]

[0014] Korean Patent Publication No. 10-2009-0038507

[0015] In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition which has excellent film processability, gloss and whiteness, weather resistance and heat stability while maintaining the inherent mechanical properties of ASA resin and polyester resin at an equivalent or higher level, and which also has an environmentally friendly advantage by preventing deterioration of properties even when including recycled resin, and which has excellent film processability, low-light characteristics, weather resistance and heat stability, a method for producing the same, and a molded article produced therefrom.

[0016] The above and other objects of the present invention can all be achieved by the present invention described below.

[0017] In order to achieve the above object, the present invention provides a thermoplastic resin composition characterized by comprising: I) 100 parts by weight of a base resin comprising 60 to 90 parts by weight of a styrene-based copolymer and 10 to 40 parts by weight of a recycled or non-recycled polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer.

[0018] In addition, the present invention provides a thermoplastic resin composition characterized in that it comprises 100 parts by weight of a base resin comprising 15 to 50 wt% of a copolymer comprising II) alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer.

[0019] In addition, the present invention provides a thermoplastic resin composition comprising III) 100 parts by weight of a base resin comprising 15 to 50 wt% of a copolymer comprising an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the weight ratio of the copolymer comprising the alkyl acrylate rubber, the aromatic vinyl compound, and the vinyl cyan compound to the recycled or non-regenerated polyalkylene terephthalate is 0.5 to 2.0:1.

[0020] In addition, the present invention provides a thermoplastic resin composition characterized in that it comprises (IV) 100 parts by weight of a base resin comprising (A) 15 to 50 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, (B) 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and (C) 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0021] V) In the above I) to IV), the (D) compatibilizer may preferably be at least one selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinylacetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA).

[0022] VI) In the above I) to V), the (A) copolymer may preferably include, based on 100 wt% of the base resin, 3 to 35 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 250 to 500 nm (A-1), and 5 to 40 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 150 nm (A-2).

[0023] VII) In the above I) to VI), the graft copolymer (A-1) and the graft copolymer (A-2) may preferably comprise 40 to 60 wt% of alkyl acrylate rubber, 30 to 40 wt% of aromatic vinyl compound, and 10 to 20 wt% of vinyl cyan compound, each based on the total weight thereof.

[0024] VIII) In the above I) to VII), the (B) copolymer may preferably be at least one selected from the group consisting of (B-1) an aromatic vinyl compound-vinyl cyan compound copolymer comprising 55 to 85 wt% of an alkyl unsubstituted aromatic vinyl compound and 15 to 45 wt% of a vinyl cyan compound, and (B-2) a heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer comprising 60 to 80 wt% of an alkyl-substituted aromatic vinyl compound, 20 to 40 wt% of a vinyl cyan compound, and 0 to 20 wt% of an alkyl unsubstituted aromatic vinyl compound.

[0025] IX) In the above I) to VIII), the (B-1) aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 50,000 to 300,000 g / mol.

[0026] X) In the above I) to IX), the (B-2) heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 30,000 to 200,000 g / mol.

[0027] XI) In the above I) to X), the polyalkylene terephthalate (C) may preferably have an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g.

[0028] XII) In the above I) to XI), the (C) polyalkylene terephthalate may preferably be non-recycled polyethylene terephthalate or recycled polyethylene terephthalate.

[0029] XIII) In the above I) to XII), the weight ratio (A:C) of the (A) graft copolymer and (C) polyalkylene terephthalate may preferably be 0.5 to 2.0:1.

[0030] XIV) In the above I) to XIII), the (D) compatibilizer may preferably comprise 30 to 90 wt% of ethylene and 10 to 70 wt% of methyl acrylate or vinyl acetate, more preferably 50 to 90 wt% of ethylene and 10 to 50 wt% of methyl acrylate or vinyl acetate. The (D) compatibilizer may be an ethylene-methyl acrylate copolymer (EMA) more preferably comprising 50 to 90 wt% of ethylene and 10 to 50 wt% of methyl acrylate.

[0031] XV) In the above I) to XIV), the (C) polyalkylene terephthalate is preferably non-recycled polyethylene terephthalate, and the thermoplastic resin composition may preferably have an injection gloss of 108 or more measured at 45° with an injection specimen having a thickness of 3 mm according to ASTM D2457.

[0032] XVI) In the above I) to XV), the (C) polyalkylene terephthalate is preferably a recycled polyethylene terephthalate, and the thermoplastic resin composition may preferably have a gloss of less than 50 as measured at 45° with an extruded film specimen having a thickness of 0.08 mm (80 μm) according to ASTM D2457.

[0033] In addition, the present invention provides a method for producing a thermoplastic resin composition, characterized in that it comprises the step of mixing and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising (XVII) 100 parts by weight of a base resin comprising 60 to 90 parts by weight of a styrene-based copolymer and 10 to 40 parts by weight of a recycled or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0034] In addition, the present invention provides a method for producing a thermoplastic resin composition, characterized in that it comprises the step of mixing and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising (XVIII) 100 parts by weight of a base resin comprising 15 to 50 wt% of a copolymer comprising an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0035] In addition, the present invention provides a method for producing a thermoplastic resin composition, comprising the steps of mixing and extruding under conditions of 170 to 300° C. and 100 to 400 rpm, comprising (XIX) 15 to 50 wt% of a copolymer comprising an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 wt% of a compatibilizer, wherein the weight ratio of the copolymer comprising the alkyl acrylate rubber, the aromatic vinyl compound, and the vinyl cyan compound to the recycled or non-regenerated polyalkylene terephthalate is 0.5 to 2.0:1.

[0036] In addition, the present invention provides a method for producing a thermoplastic resin composition, characterized in that it comprises the steps of kneading and extruding under conditions of 170 to 300°C and 100 to 400 rpm, comprising 100 parts by weight of a base resin comprising XX)(A) 15 to 50 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, (B) 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and (C) 10 to 40 wt% of a recycled or non-regenerated polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer.

[0037] In addition, the present invention provides a molded article characterized in that it comprises a thermoplastic resin composition according to any one of the above I) to XX).

[0038] According to the present invention, there is provided a thermoplastic resin composition having excellent film processability, injection gloss, whiteness, weather resistance and thermal stability while maintaining the inherent mechanical properties of each of the ASA resin and the polyester resin at an equivalent or higher level, a method for producing the same and a molded article produced therefrom.

[0039] The present invention also has the effect of providing a thermoplastic resin composition having excellent film processability, low-light characteristics, weather resistance, and thermal stability while maintaining the inherent mechanical properties of ASA resin and polyester resin at an equivalent or higher level, and having an environmentally friendly advantage by preventing deterioration of physical properties even when including recycled resin, a method for producing the same, and a molded article produced therefrom.

[0040] Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and molded product are described in detail.

[0041] The present inventors have confirmed that when adding a compatibilizer when alloying an ASA resin and a polyester resin and adjusting their composition ratio within a predetermined range, the inherent mechanical properties of each of the ASA resin and the polyester resin are all maintained without deterioration, while also having excellent film processability, weather resistance, and thermal stability characteristics, and that, in particular, even when mixing a recycled resin, deterioration of properties is prevented, thereby providing an environmentally friendly advantage. Based on this, they have devoted themselves to further research and completed the present invention.

[0042]

[0043] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising 60 to 90 wt% of a styrene-based copolymer and 10 to 40 wt% of a polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is a recycled or non-regenerated polyalkylene terephthalate, and in this case, compatibility is greatly improved, so that the inherent mechanical properties of ASA-based resins and polyester resins are maintained at an equivalent or higher level, while film processability, gloss, whiteness, weather resistance, and heat stability are all excellent. In addition, even when a recycled resin is included, deterioration of properties is prevented, so that it has an environmentally friendly advantage, and at the same time, film processability and low-light characteristics are both excellent.

[0044]

[0045] In the present invention, a styrenic copolymer means a copolymer comprising a styrenic monomer represented by styrene, i.e., an aromatic vinyl compound as a main component, preferably at least 5 wt%, and as a specific example, may refer to a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, and / or an aromatic vinyl compound-vinyl cyan compound copolymer. In addition, the copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound may be a graft copolymer in which an aromatic vinyl compound-vinyl cyan compound copolymer is grafted onto an alkyl acrylate rubber core.

[0046]

[0047] In addition, the thermoplastic resin composition of the present invention specifically comprises 100 parts by weight of a base resin comprising 15 to 50 wt% of a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is a recycled or non-regenerated polyalkylene terephthalate, and in this case, compatibility is greatly improved so that the mechanical properties inherent to ASA resins and polyester resins are maintained at an equivalent or higher level, while film processability, gloss, whiteness, weather resistance, and heat stability are all excellent. In addition, even when a recycled resin is included, deterioration of properties is prevented, so that it has an environmentally friendly advantage, and at the same time, film processability and low-light characteristics are both excellent.

[0048]

[0049] In addition, the thermoplastic resin composition of the present invention is characterized in that it specifically comprises 100 parts by weight of a base resin comprising 15 to 50 wt% of a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the weight ratio of the copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound to the polyalkylene terephthalate is 0.5 to 2.0:1, and the polyalkylene terephthalate is a recycled polyalkylene terephthalate or a non-regenerated polyalkylene terephthalate, and in this case, compatibility is greatly improved, so that the mechanical properties inherent to ASA resins and polyester resins are maintained at an equivalent or higher level, and at the same time, film processability, gloss, whiteness, weather resistance, and heat stability are all excellent. In addition, it has the advantage of being environmentally friendly as it prevents deterioration of physical properties even when including recycled resin, and it has the effect of having both excellent film processability and low-light characteristics.

[0050]

[0051] In addition, the thermoplastic resin composition of the present invention more specifically comprises 100 parts by weight of a base resin including 15 to 50 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and 10 to 40 wt% of a polyalkylene terephthalate, and 0.5 to 10 parts by weight of a compatibilizer, wherein the polyalkylene terephthalate is a recycled or non-regenerated polyalkylene terephthalate, and in this case, compatibility is greatly improved so that the inherent mechanical properties of ASA resins and polyester resins are maintained at an equivalent or higher level, while film processability, gloss, whiteness, weather resistance, and heat stability are all excellent. In addition, even when a recycled resin is included, deterioration of properties is prevented, so that it has an environmentally friendly advantage, and at the same time, film processability and low-light characteristics are both excellent.

[0052]

[0053] In this description, the component ratio of a copolymer or resin may mean the content of a unit constituting the copolymer, or may mean the content of a monomer introduced during polymerization of the copolymer.

[0054]

[0055] In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units in the polymerized polymer are derived from the compound.

[0056]

[0057] In this description, the term "regenerated thermoplastic resin" is not particularly limited to any resin commonly recognized as a regenerated thermoplastic resin in the technical field to which the present invention pertains, as long as it complies with the definition of the present invention. For example, it refers to a thermoplastic resin regenerated from collected waste plastics. A specific example refers to a resin prepared into a usable raw material state through sorting, washing, and crushing from collected waste plastics. In addition, if necessary, a resin processed into a pellet form through an extrusion process may be used, in which case there is an advantage of not requiring additional purification or other separate processing.

[0058]

[0059] In this description, a non-regenerated thermoplastic resin is in contrast to the regenerated thermoplastic resin defined above, and may also be referred to as a virgin or fresh thermoplastic resin, and may be prepared by directly manufacturing and polymerizing monomers constituting the thermoplastic resin, or may be an equivalent available product.

[0060]

[0061] Resins not referred to as regenerated or non-regenerated (new) in this description may be either regenerated or non-regenerated resins, but preferably refer to non-regenerated resins.

[0062]

[0063] Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

[0064]

[0065] (A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer

[0066] The above (A) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as “(A) graft copolymer”) is included in an amount of 15 to 50 wt%, preferably 17 to 48 wt%, more preferably 18 to 46 wt%, even more preferably 19 to 45 wt%, and even more preferably 20 to 45 wt%, based on 100 wt% of the base resin (A+B+C) comprising (A) to (C), and within this range, it has the advantages of excellent impact resistance, film processability, gloss, whiteness, weather resistance, and heat stability. In addition, even when a recycled resin is included, it has the advantage of being environmentally friendly because deterioration of physical properties is prevented, and at the same time, it has the advantages of excellent impact resistance, film processability, low-light characteristics, weather resistance, and heat stability.

[0067]

[0068] The above (A) graft copolymer may preferably be formed by including an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) surrounding the core.

[0069]

[0070] The above (A) graft copolymer may be, for example, a mixture of two or more graft copolymers having different particle sizes of alkyl acrylate rubber cores, and specifically, may be a mixture of (A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle size of 250 to 500 nm, and (A-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle size of 50 to 150 nm. In this case, there are advantages of superior film processability, impact resistance, weather resistance, and whiteness, and further, when a recycled resin is included, there are advantages of superior low-light characteristics, film processability, and impact resistance.

[0071] More specifically, the (A) graft copolymer may comprise, for example, 3 to 35 wt% of the (A-1) graft copolymer and 5 to 40 wt% of the (A-2) graft copolymer based on 100 wt% of the base resin, preferably 3 to 33 wt% of the (A-1) graft copolymer and 5 to 38 wt% of the (A-2) graft copolymer, more preferably 4 to 32 wt% of the (A-1) graft copolymer and 5 to 37 wt% of the (A-2) graft copolymer, more preferably 5 to 30 wt% of the (A-1) graft copolymer and 5 to 36 wt% of the (A-2) graft copolymer, and even more preferably 5 to 27 wt% of the (A-1) graft copolymer and 6 to 35 wt% of the (A-2) graft copolymer. It can be included in weight %, and in this case, it has excellent impact resistance, film processability, gloss, whiteness, weather resistance and heat stability, and also has the advantage of being environmentally friendly as it prevents deterioration of physical properties even when it includes recycled resin, and has the advantage of having better low-light characteristics.

[0072] For example, when the thermoplastic resin composition does not include a recycled resin, the (A) graft copolymer may include 3 to 20 wt% of the (A-1) graft copolymer and 5 to 40 wt% of the (A-2) graft copolymer based on 100 wt% of the base resin, preferably 3 to 19 wt% of the (A-1) graft copolymer and 5 to 38 wt% of the (A-2) graft copolymer, more preferably 3 to 18 wt% of the (A-1) graft copolymer and 5 to 37 wt% of the (A-2) graft copolymer, more preferably 4 to 18 wt% of the (A-1) graft copolymer and 5 to 36 wt% of the (A-2) graft copolymer, and even more preferably 4 to 17 wt% of the (A-1) graft copolymer and (A-2) The graft copolymer may be included in an amount of 6 to 35 wt%, in which case it has the advantage of superior impact resistance, weather resistance, and whiteness without deterioration of other physical properties.

[0073] For example, when the thermoplastic resin composition includes a recycled resin, preferably a recycled polyalkylene terephthalate, the (A) graft copolymer may include, for example, 10 to 35 wt% of the (A-1) graft copolymer and 5 to 20 wt% of the (A-2) graft copolymer, based on 100 wt% of the base resin, preferably 10 to 32 wt% of the (A-1) graft copolymer and 5 to 19 wt% of the (A-2) graft copolymer, more preferably 11 to 30 wt% of the (A-1) graft copolymer and 5 to 18 wt% of the (A-2) graft copolymer, more preferably 12 to 28 wt% of the (A-1) graft copolymer and 5 to 18 wt% of the (A-2) graft copolymer, and even more preferably 10 to 32 wt% of the (A-1) graft copolymer and 5 to 19 wt% of the (A-2) graft copolymer, based on 100 wt% of the base resin, It can contain 12 to 25 wt% of graft copolymer and 5 to 17 wt% of (A-2) graft copolymer, in which case it has the advantage of superior low-light properties and impact resistance without deterioration of other properties.

[0074]

[0075] The weight ratio (A-1:A-2) of the above (A-1) graft copolymer and (A-2) graft copolymer may be, for example, 0.1 to 3.0:1, and as a specific example, 0.5 to 3.0:1, preferably 0.8 to 2.8:1, more preferably 1.0 to 2.6:1, even more preferably 1.0 to 2.5:1, and even more preferably 1.1 to 2.5:1, and there is an advantage that the desired effect can be sufficiently expressed within this range, and in particular, there is an advantage that the deterioration of physical properties is prevented even when a recycled resin is included, so that the mechanical properties and low-light characteristics are excellent.

[0076]

[0077] The above (A-1) graft copolymer may, for example, have an average particle diameter of the rubber included therein of 250 to 500 nm, preferably 270 to 480 nm, more preferably 300 to 470 nm, even more preferably 330 to 460 nm, and even more preferably 350 to 450 nm, and in this case, it has the advantage of having superior impact resistance, weather resistance, whiteness, and gloss characteristics without deterioration of other physical properties.

[0078] The above (A-2) graft copolymer may have, for example, an average particle diameter of the rubber included therein of 50 to 150 nm, preferably 60 to 140 nm, more preferably 65 to 130 nm, even more preferably 70 to 125 nm, and even more preferably 80 to 120 nm, and in this case, it has the advantage of superior impact resistance, weather resistance, whiteness, and gloss characteristics without deterioration of other physical properties.

[0079]

[0080] The above (A-1) graft copolymer may have, for example, a weight average molecular weight of an aromatic vinyl compound-vinyl cyan compound copolymer (shell) included therein of 100,000 to 400,000 g / mol, preferably 110,000 to 390,000 g / mol, more preferably 120,000 to 350,000 g / mol, even more preferably 120,000 to 330,000 g / mol, and even more preferably 130,000 to 300,000 g / mol, and within this range, it has the advantage of superior impact resistance, whiteness, heat stability, and gloss characteristics without deterioration of other physical properties.

[0081] The above (A-2) graft copolymer may have, for example, a weight average molecular weight of an aromatic vinyl compound-vinyl cyan compound copolymer (shell) included therein of 50,000 to 300,000 g / mol, preferably 60,000 to 250,000 g / mol, more preferably 70,000 to 230,000 g / mol, even more preferably 70,000 to 200,000 g / mol, and even more preferably 80,000 to 180,000 g / mol, and within this range, it has the advantage of superior impact resistance, whiteness, heat stability, and gloss characteristics without deterioration of other physical properties.

[0082]

[0083] The above (A) graft copolymer (each of the above (A-1) graft copolymer and (A-2) graft copolymer) may have, for example, a graft ratio of 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%, and within this range, it has excellent mechanical properties such as impact resistance while also having superior gloss and weather resistance.

[0084]

[0085] In this description, the average particle size of the rubber is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention pertains, including an electron microscope measurement method using SEM, TEM, etc., or a dynamic light scattering method, etc. For example, the measurement can be performed by sampling at the time when the rubber is completed and using the dynamic light scattering method, and specifically, the measurement is performed as an intensity value in Gaussian mode using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of latex (total solid content TSC 35-50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, diluting it appropriately so as not to greatly exceed the Intensity Setpoint 300 kHz, placing it in a glass tube, and measuring it using an auto-dilution flow cell. The measurement mode is dynamic light scattering / Intensity 300 kHz / Intensity-weight Gaussian Analysis, and the setting values ​​are a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0086] In this description, the average particle diameter may preferably be an average particle diameter based on the dynamic light scattering method.

[0087]

[0088] In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, solvent: THF, column temperature: 40℃, flow rate: 0.3ml / min, sample concentration: 20mg / ml, injection volume: 5㎕, column model: 1xPLgel 10㎛ MiniMix-B(250x4.6mm) + 1xPLgel 10㎛ MiniMix-B(250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard(50x4.6mm), equipment name: 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 conditions can be measured.

[0089] In the present invention, the copolymer grafted onto the rubber, i.e., the core, i.e., the shell, can be separated from the rubber (core) by a separation method commonly used in the technical field to which the present invention pertains for measuring the weight average molecular weight. For example, a sol from which insoluble matter (gel) is separated by a method described in the graft ratio measurement method described below is dissolved in a THF solvent to prepare a solution, and the filtrate obtained by filtering this can be used as a sample for measuring the weight average molecular weight.

[0090]

[0091] The grafting ratio of this invention can be obtained by, as a specific measurement example, adding 30 g of acetone to 0.5 g of graft copolymer powder, stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion), centrifuging at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30, Hanil Science), collecting only the insoluble matter (gel) that is not dissolved in acetone, and then drying at 85°C for 12 hours using a forced circulation method (OF-12GW, Lab companion), and measuring the weight, and calculating using the following mathematical formula 1.

[0092] [Mathematical Formula 1]

[0093] Grafting ratio (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] * 100

[0094] In the above mathematical expression 1, the weight (g) of the grafted monomer is the weight (g) of the insoluble matter obtained after dissolving the graft copolymer in acetone and centrifuging it, minus the rubber weight (g), and the rubber weight (g) is the weight (g) of the rubber component theoretically added in the graft copolymer powder.

[0095]

[0096] The above (A) graft copolymer may be, for example, composed of 40 to 60 wt% of alkyl acrylate rubber, 30 to 45 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound based on its total weight (100 wt%), preferably 42 to 58 wt% of alkyl acrylate rubber, 32 to 43 wt% of aromatic vinyl compound, and 7 to 18 wt% of vinyl cyan compound, more preferably 42 to 55 wt% of alkyl acrylate rubber, 33 to 42 wt% of aromatic vinyl compound, and 10 to 18 wt% of vinyl cyan compound, and even more preferably 45 to 52 wt% of alkyl acrylate rubber, 33 to 40 wt% of aromatic vinyl compound, and 12 to 16 wt% of vinyl cyan compound, and within this range, compatibility with other resins is improved, so that mechanical properties and molding processability are superior, and the like.

[0097] Here, the composition ratio of each component constituting the (A-1) graft copolymer and (A-2) graft copolymer can be appropriately adjusted independently within the above-described range.

[0098]

[0099] The above (A) graft copolymer can be produced, for example, by emulsion polymerization, in which case it has the advantages of excellent impact resistance and compatibility.

[0100] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and may be performed using an emulsion graft polymerization method, for example.

[0101]

[0102] The method for producing the above (A) graft copolymer may include, for example, i) a step of producing an alkyl acrylate rubber including an alkyl acrylate; and ii) a step of producing a graft copolymer by graft polymerization including an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber; in which case, there are advantages in that mechanical properties, weather resistance, thermal stability, appearance characteristics, and molding processability are all excellent.

[0103] The method for producing the above (A) graft copolymer may preferably include the steps of: i) polymerizing 40 to 60 wt% of an alkyl acrylate, including a crosslinking agent, an initiator, an electrolyte and an emulsifier, based on a total of 100 wt% thereof, to produce a rubber; and ii) graft polymerizing 40 to 60 wt% of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber, including a crosslinking agent, an initiator and an emulsifier, to produce a graft copolymer; in which case, there are advantages in that mechanical properties, weather resistance, thermal stability, appearance characteristics and molding processability are all excellent.

[0104]

[0105] The above (A) graft copolymer may be formed by including, for example, a polymer seed, in which case it may be included in the alkyl acrylate rubber at 10 to 30 wt%, preferably 15 to 25 wt% (based on 100 wt% of the sum of the rubber and the seed).

[0106] The above (A) graft copolymer may be formed by including a polymer seed comprising, as a specific example, at least one selected from the group consisting of alkyl (meth)acrylate, aromatic vinyl compound, and vinyl cyan compound; an alkyl acrylate rubber (core) wrapping the polymer seed; and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) wrapping the rubber (core), and in this case, there is an advantage of excellent molding processability, impact resistance, and weather resistance.

[0107] The above polymer seed may preferably be a rubber seed made of alkyl acrylate rubber, in which case it has the advantage of being easier to manufacture and having a better balance of physical properties.

[0108]

[0109] The method for producing the above (A) graft copolymer may include, for example, i) a step of producing a polymer seed including at least one selected from the group consisting of an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; ii) a step of producing an alkyl acrylate rubber (core) including an alkyl acrylate in the presence of the polymer seed; and iii) a step of producing a graft copolymer by graft polymerization including an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber (core). In this case, there are advantages of excellent molding processability, impact resistance, and weather resistance.

[0110]

[0111] In this description, the content of monomer in the polymer may mean the weight % of monomer added during polymer production or the weight % of monomer converted to a unit in the polymer.

[0112]

[0113] In this description, alkyl (meth)acrylate may be defined as a range that includes both alkyl acrylate and alkyl methacrylate.

[0114]

[0115] In the present invention, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and preferably may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, and more preferably may be an alkyl acrylate containing 1 to 4 or 8 carbon atoms in the alkyl group, and even more preferably may be n-butylacrylate, 2-ethylhexyl acrylate, or a mixture thereof, and even more preferably may be butyl acrylate.

[0116]

[0117] In the present invention, the alkyl methacrylate may be, for example, an alkyl methacrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, more preferably an alkyl methacrylate containing an alkyl group having 1 to 4 carbon atoms, and even more preferably, methyl methacrylate.

[0118]

[0119] In the present invention, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-bromo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably, styrene.

[0120]

[0121] In the present invention, the vinyl cyanide compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0122]

[0123] The emulsifier used in each of the above polymer seed manufacturing step (when including polymer seeds), the rubber core manufacturing step, and the copolymer shell manufacturing step is not particularly limited as long as it is an emulsifier generally used in the technical field to which the present invention pertains, and may be, for example, at least one selected from the group consisting of an alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms or a derivative thereof, an alkyl sulfuric acid ester having 12 to 20 carbon atoms or a derivative thereof, an alkyl sulfonic acid metal salt having 12 to 20 carbon atoms or a derivative thereof, a fatty acid soap, and a rosin acid soap.

[0124]

[0125] The above-mentioned alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms or a derivative thereof may preferably be at least one selected from the group consisting of dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt and dioctyl sulfosuccinate potassium salt.

[0126] The above-mentioned alkyl sulfate ester having 12 to 20 carbon atoms or a derivative thereof may preferably be at least one selected from the group consisting of sodium lauryl sulfate, sodium dodecyl sulfate, sodium octadecyl sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate. In addition, one or more types of other sulfuric acid ester emulsifiers such as sodium dodecyl benzene sulfate, sodium oleic sulfate, etc. may also be used.

[0127] The above fatty acid soap may preferably be at least one selected from the group consisting of oleic acid, stearic acid, lauric acid, and sodium or potassium salts of mixed fatty acids.

[0128] The above rosin acid soap may preferably be an abietic acid salt, and specifically may be an abietic metal salt.

[0129] For example, the above emulsifier may be used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight, for each step based on 100 parts by weight of the total (A) graft copolymer.

[0130]

[0131] The above initiator is not particularly limited, but a radical initiator can be preferably used.

[0132] The above radical initiator may be, for example, at least one selected from the group consisting of inorganic peroxides, organic peroxides (excluding ketal, carbonate and azo compounds), peroxyketal peroxides, peroxycarbonate peroxides, and azo compounds.

[0133] The above inorganic peroxide may preferably be at least one selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide.

[0134] The organic peroxides include, for example, t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)-hexane, di-t-amyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)-cyclohexane, 1,1-di(t-amylperoxy)-cyclohexane, ethyl 3,3-di(t-amylperoxy)-butyrate, diisopropylbenzene mono-hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyneodecanoate, t-Butyl peroxypivalate, di-(3,3,5-trimethylhexanoyl)-peroxide, t-Butyl peroxy-2-ethylhexanoate, t-Butyl peroxy-3,3,5-trimethylhexanoyl, t-Amyl peroxy neodecanoate, t-Amyl peroxy pivalate, t-Amyl peroxy-2-ethylhexanoate, t-Butyl peroxyacetate, t-Butyl peroxybenzoate, t-Amyl peroxy 2-ethylhexyl carbonate, t-Butyl peroxy 2-ethylhexyl carbonate, t-Butyl peroxy isopropyl monocarbonate, t-Butyl peroxy maleate, Cumyl peroxyneodecanoate, 1,1,3,3,-tetramethylbutyl peroxy neodecanoate, It may be at least one selected from the group consisting of 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, di-2-2-ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate.

[0135] The above peroxyketal peroxide may preferably be at least one selected from the group consisting of 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, ethyl-3,3-di(t-butylperoxy)butyrate, and ethyl-3,3-di(t-amylperoxy)butyrate.

[0136] The above peroxycarbonate peroxide may preferably be at least one selected from the group consisting of dialkyl peroxides such as dicumylperoxide, di(t-butylperoxy)-m / p-diisopropylbenzene, 2,5-dimethyl-2,5-(t-butylperoxy)hexane, t-butylcumyl peroxide, 2,5-methyl-2,5-(t-butylperoxy)hexyne-3, t-butyl peroxy 2-ethylhexyl monocarbonate, and t-butyl peroxybenzoate.

[0137] The above azo compound may preferably be at least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyrate methyl.

[0138] For example, the above initiator may be used in an amount of 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, for each step based on 100 parts by weight of the total (A) graft copolymer.

[0139]

[0140] In at least one of the above polymer seed manufacturing step (when including polymer seeds), rubber (core) manufacturing step and copolymer (shell) manufacturing step, an oxidation-reduction catalyst may be used, preferably together with the above initiator, to further promote the initiation reaction.

[0141] The above oxidation-reduction catalyst may be, for example, at least one selected from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate, and may preferably be a mixture of sodium pyrophosphate, dextrose, and ferrous sulfide, but is not limited thereto.

[0142] For example, the above catalyst may be used in an amount of 0.001 to 2 parts by weight, preferably 0.002 to 1 part by weight, for each step based on 100 parts by weight of the total (A) graft copolymer.

[0143]

[0144] In at least one of the polymer seed preparation step (when including a polymer seed), the polymer rubber (core) preparation step and the copolymer (shell) preparation step, an activator may be used to promote the initiation reaction of the peroxide together with the polymerization initiator.

[0145] The above activator is not particularly limited as long as it is an activator commonly used in the technical field to which the present invention belongs.

[0146] The total amount of the above activator may be added in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the above (A) graft copolymer, and there is an advantage in that a high degree of polymerization can be achieved within this range.

[0147]

[0148] The electrolyte may be, for example, at least one selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO4, Na2S2O7, K3P2O7, K3PO4, Na3PO4, KOH, NaOH and Na2HPO4, but is not limited thereto.

[0149] The total amount of the electrolyte may be added in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the (A) graft copolymer, and there is an advantage in that a high degree of polymerization can be achieved within this range.

[0150]

[0151] In the present invention, the crosslinking agent is not particularly limited as long as it is a crosslinking agent generally used in the technical field to which the present invention belongs, and for example, one or more compounds containing an unsaturated vinyl group and capable of performing the role of a crosslinking agent or a compound containing an unsaturated vinyl group having two or more different reactivities may be used, and specific examples thereof include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, and trimethylolmethane. It is specified that the polymer may be at least one selected from the group consisting of triacrylate, trimethylpropanethoxylate triacrylate, trimethylpropanepropoxylate triacrylate, pentaerythritolethoxylate triacrylate, pentaerythritolpropoxylate triacrylate, vinyltrimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallyl amine, and diallyl amine, but is not limited thereto.

[0152] For example, the crosslinking agent may be used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 1 part by weight, for each step based on 100 parts by weight of the total (A) graft copolymer.

[0153]

[0154] The above copolymer shell manufacturing step may use, for example, a molecular weight modifier.

[0155] The above-mentioned molecular weight regulator may be, for example, 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total (A) graft copolymer, and within this range, a polymer having a desired molecular weight can be easily produced.

[0156] The above molecular weight modifier may be, for example, at least one selected from the group consisting of α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide, but is not limited thereto.

[0157]

[0158] In this description, 100 parts by weight of the graft copolymer means 100 parts by weight of the total weight of the graft copolymer finally obtained, or, since almost all of the introduced monomers participate in the polymerization, conveniently, it may mean the combined weight of all monomers used in the polymer seed (when including the polymer seed), the rubber core, and the graft shell, or the combined weight of the polymer seed (when including the polymer seed) and the monomers introduced during the manufacture of the rubber core and the monomers introduced during the manufacture of the graft shell, based on 100 parts by weight.

[0159]

[0160] In this document, % means weight % unless otherwise defined.

[0161]

[0162] In the step of manufacturing the above polymer seed and rubber, the monomer input method may be batch input or continuous input, or the two methods may be used in combination.

[0163] In this description, 'continuous injection' means not 'batch injection', and for example, it refers to injection in a drop-by-drop, little-by-little, step-by-step or continuous flow manner for 10 minutes or more, 30 minutes or more, 1 hour or more, and preferably 2 hours or more within the polymerization reaction time range.

[0164]

[0165] The polymerization temperature during the above emulsion polymerization is not particularly limited, but may be performed at, for example, 50 to 85°C, preferably 60 to 80°C.

[0166]

[0167] The latex formed after polymerization of the graft copolymer (A) above can be obtained in powder form through conventional processes such as coagulation, washing, and drying, for example. Specifically, it can be manufactured in powder form by adding a metal salt or acid, coagulating at a temperature of 60 to 100°C, and then going through maturation, dehydration, washing, and drying processes, but is not limited thereto.

[0168] The above (A) graft copolymer may be, for example, a commercially available product as long as it follows the definition of the present invention.

[0169]

[0170] (B) Aromatic vinyl compound-vinyl cyanide compound copolymer

[0171] The above (B) aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter referred to as “(B) copolymer”) is included in an amount of 20 to 55 wt%, preferably 22 to 55 wt%, more preferably 25 to 53 wt%, even more preferably 27 to 52 wt%, and even more preferably 28 to 50 wt%, based on 100 wt% of the base resin, and within this range, the mechanical properties, film processability, gloss, whiteness, weather resistance, and thermal stability are all excellent, and even when a recycled resin is included, deterioration of properties is prevented, so there is an advantage of excellent low-light characteristics along with an environmentally friendly advantage.

[0172]

[0173] The above (B) copolymer may be at least one selected from the group consisting of, for example, (B-1) a copolymer comprising an aromatic vinyl compound and a vinyl cyan compound that does not include an alkyl-substituted aromatic vinyl compound (hereinafter referred to as “(B-1) copolymer”), and (B-2) a heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer comprising an alkyl-substituted aromatic vinyl compound (hereinafter referred to as “(B-2) copolymer”).

[0174] Specifically, the above (B-1) copolymer can be formed by including, for example, 55 to 85 wt% of an alkyl unsubstituted aromatic vinyl compound and 15 to 45 wt% of a vinyl cyan compound, preferably 60 to 82 wt% of an alkyl unsubstituted aromatic vinyl compound and 18 to 40 wt% of a vinyl cyan compound, more preferably 65 to 82 wt% of an alkyl unsubstituted aromatic vinyl compound and 18 to 35 wt% of a vinyl cyan compound, and even more preferably 65 to 80 wt% of an alkyl unsubstituted aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound, in which case there is an advantage of superior mechanical properties without deterioration of other properties. The above (B-1) copolymer can be called a 'non-heat-resistant SAN resin' or a 'general SAN resin' in that it does not include a heat-resistant monomer that imparts heat resistance to a copolymer formed by including it, such as, for example, an alkyl-substituted aromatic vinyl compound.

[0175] The above (B-2) copolymer may be formed by, for example, including 60 to 80 wt% of an alkyl-substituted aromatic vinyl compound, 20 to 40 wt% of a vinyl cyan compound, and 0 to 20 wt% of an alkyl-unsubstituted aromatic vinyl compound, preferably 62 to 80 wt% of an alkyl-substituted aromatic vinyl compound, 20 to 38 wt% of a vinyl cyan compound, and 0 to 17 wt% of an alkyl-unsubstituted aromatic vinyl compound, more preferably 63 to 77 wt% of an alkyl-substituted aromatic vinyl compound, 23 to 37 wt% of a vinyl cyan compound, and 0 to 13 wt% of an alkyl-unsubstituted aromatic vinyl compound, and even more preferably 65 to 75 wt% of an alkyl-substituted aromatic vinyl compound, 25 to 35 wt% of a vinyl cyan compound, and 0 to 10 wt% of an alkyl-unsubstituted aromatic vinyl compound, in which case there is an advantage of excellent heat resistance and mechanical properties without deterioration of other properties. The above (B-2) copolymer can be called a 'heat-resistant SAN resin' in that it contains a heat-resistant monomer such as an alkyl-substituted aromatic vinyl compound, for example.

[0176] The above (B-2) copolymer may be formed by, for example, not including an alkyl unsubstituted aromatic vinyl compound, but including 60 to 80 wt% of an alkyl substituted aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound, preferably 63 to 77 wt% of an alkyl substituted aromatic vinyl compound and 23 to 37 wt% of a vinyl cyan compound, more preferably 65 to 75 wt% of an alkyl substituted aromatic vinyl compound and 25 to 35 wt% of a vinyl cyan compound, and in this case, there is an advantage of superior heat resistance without deterioration of other physical properties.

[0177]

[0178] Here, the weight % of the (B) copolymer included in the base resin represents the weight % of the (B-1) copolymer when only the (B-1) copolymer is included, the weight % of the (B-2) copolymer when only the (B-2) copolymer is included, and the weight % of the (B-1) copolymer and the (B-2) copolymer when a mixture of the (B-1) copolymer and the (B-2) copolymer is included, represents the sum of the weight % of each of them.

[0179]

[0180] The above alkyl-substituted aromatic vinyl compound may be, for example, at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, and m-methyl styrene, and preferably α-methyl styrene.

[0181]

[0182] The type of the above-mentioned alkyl unsubstituted aromatic vinyl compound may be appropriately selected within the range of aromatic vinyl compounds not including an alkyl substituent among the aromatic vinyl compounds mentioned in the above-mentioned (A) graft copolymer, and may preferably be styrene.

[0183]

[0184] The type of vinyl cyanide compound included in the above (B) copolymer can be appropriately selected within the range of vinyl cyanide compounds mentioned in the above (A) graft copolymer.

[0185]

[0186] The above (B) copolymer may have, for example, a weight average molecular weight of 30,000 to 300,000 g / mol, preferably 30,000 to 200,000 g / mol, more preferably 40,000 to 190,000 g / mol, even more preferably 40,000 to 180,000 g / mol, and even more preferably 50,000 to 180,000 g / mol, and in this case, there is an advantage of superior mechanical properties without deterioration of other properties.

[0187] More specifically, the above (B-1) copolymer may have a weight average molecular weight of, for example, 50,000 to 300,000 g / mol, preferably 70,000 to 200,000 g / mol, more preferably 80,000 to 190,000 g / mol, even more preferably 80,000 to 180,000 g / mol, and even more preferably 90,000 to 180,000 g / mol, and in this case, there is an advantage of superior mechanical properties without deterioration of other properties.

[0188] The above (B-2) copolymer may have, for example, a weight average molecular weight of 30,000 to 200,000 g / mol, preferably 30,000 to 180,000 g / mol, more preferably 40,000 to 150,000 g / mol, even more preferably 50,000 to 140,000 g / mol, and even more preferably 50,000 to 130,000 g / mol, and in this case, it has the advantage of superior heat resistance and mechanical properties without deterioration of other properties.

[0189]

[0190] The above (B) copolymer can be manufactured, for example, by a manufacturing method commonly applied in the technical field to which the present invention pertains, and a commercially available product can also be used as long as it follows the definition of the present invention.

[0191]

[0192] (C) polyalkylene terephthalate

[0193] The above (C) polyalkylene terephthalate may be included in an amount of 10 to 40 wt%, preferably 15 to 37 wt%, more preferably 18 to 35 wt%, even more preferably 20 to 34 wt%, and even more preferably 22 to 33 wt%, based on 100 wt% of the base resin. Within this range, the composition has excellent compatibility, so that mechanical properties, gloss, whiteness, film processability, weather resistance, and thermal stability are all excellent, and further, even if a recycled resin is included, deterioration of properties is prevented, so that there is an environmentally friendly advantage, and the composition has excellent compatibility, so that impact resistance, film processability, low-light characteristics, weather resistance, and thermal stability are all excellent.

[0194]

[0195] The above (C) polyalkylene terephthalate may be selected from, for example, recycled polyalkylene terephthalate, non-recycled polyalkylene terephthalate, and mixtures thereof. In this case, mechanical properties, gloss, whiteness, film processability, weather resistance, and heat stability can be secured, and further, deterioration of properties due to non-recycled resin can be prevented, thereby providing an environmentally friendly advantage. Furthermore, depending on the molding processing method, when non-recycled polyalkylene terephthalate is applied, high injection gloss can be realized, and when recycled polyalkylene terephthalate is applied, it can also provide an advantage of implementing excellent extrusion low-gloss characteristics. Therefore, recycled polyalkylene terephthalate and / or non-recycled polyalkylene terephthalate can be appropriately selected as the (C) polyalkylene terephthalate as needed.

[0196]

[0197] Here, the weight % of (C) polyalkylene terephthalate included in the base resin represents the weight % of the recycled polyalkylene terephthalate when only the recycled polyalkylene terephthalate is included, the weight % of the non-recycled polyalkylene terephthalate when only the non-recycled polyalkylene terephthalate is included, and the weight % of the recycled polyalkylene terephthalate and the non-recycled polyalkylene terephthalate when a mixture thereof is included, represents the sum of the weight % of each of them.

[0198]

[0199] The above (C) polyalkylene terephthalate may have, for example, an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, more preferably 0.5 to 1.1 dl / g, even more preferably 0.6 to 1.0 dl / g, and even more preferably 0.6 to 0.8 dl / g, and within this range, it has excellent compatibility and thus has the advantage of excellent mechanical properties and molding processability.

[0200]

[0201] In this description, the intrinsic viscosity can be measured by a method commonly performed in the technical field to which the present invention pertains unless otherwise specified, and as a specific measurement example, a sample is completely dissolved in a methylene chloride solvent at a concentration of 0.05 g / ml, and then the filtrate is filtered using a filter, and the filtrate can be measured at 20°C using an Ubbelohde viscometer.

[0202]

[0203] The above (C) polyalkylene terephthalate may include, for example, at least one selected from polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polytrimethylene terephthalate (PTT), preferably at least one selected from the group consisting of polybutylene terephthalate and polyethylene terephthalate, and more preferably polyethylene terephthalate, in which case there is an advantage of having even better impact resistance while sufficiently expressing the effect aimed at by the present invention.

[0204]

[0205] The polyethylene terephthalate resin may be at least one selected from the group consisting of, for example, a recycled polyethylene terephthalate resin derived from a polyethylene terephthalate homopolymer polymerized by polymerizing terephthalic acid and ethylene glycol; and a polyethylene terephthalate copolymer comprising terephthalic acid, ethylene glycol, and at least one of 1,4-cyclohexanedimethanol, isophthalic acid, and butanediol as a comonomer. In this case, there is an advantage of superior impact resistance and heat resistance, and in addition, when recycled polyethylene terephthalate is applied, excellent low-light characteristics can be realized, and when non-recycled polyethylene terephthalate is applied, there is an advantage of high gloss.

[0206]

[0207] The above-mentioned recycled polyalkylene terephthalate refers to a recycled resin obtained by recycling waste polyalkylene terephthalate. In this case, waste polyalkylene terephthalate, including waste PET, which is one of the waste plastics with the largest amount of emissions, can be utilized, making it easy to procure raw materials and providing an advantage in terms of environmental friendliness.

[0208]

[0209] The above (C) polyalkylene terephthalate may have, for example, a melting point of 200 to 280°C, preferably 220 to 275°C, and more preferably 240 to 270°C, and can sufficiently exhibit the desired effect within this range.

[0210] In this description, the melting point can be measured using a method known in the polymer field, for example, a heat absorption peak can be measured using differential scanning calorimetry (DSC).

[0211]

[0212] The above (C) polyalkylene terephthalate may have, for example, a glass transition temperature of 60 to 100°C, preferably 65 to 90°C, and has the advantage of excellent impact resistance and molding processability within this range.

[0213] In this paper, the glass transition temperature can be measured using a differential scanning calorimeter (DSC) according to ASTM D3418, and as a specific example, it can be measured at a heating rate of 10℃ / min using a Q100 DSC (Differential Scanning Calorimetry) from TA Instrument.

[0214]

[0215] The above (C) recycled or non-regenerated polyalkylene terephthalate is not particularly limited as long as it is a recycled or non-regenerated polyalkylene terephthalate resin commonly used in the technical field to which the present invention belongs, as long as it follows the definition of the present invention, and a commercially available product may be used.

[0216]

[0217] (D) Commercialization agent

[0218] The above (D) compatibilizer may be included in an amount of 0.5 to 10 parts by weight, preferably 1 to 9 parts by weight, more preferably 1.5 to 8.5 parts by weight, and even more preferably 1.7 to 8 parts by weight, based on 100 parts by weight of the base resin. Within this range, the compatibility of the (A) graft copolymer and (C) polyalkylene terephthalate is significantly improved, so that there is an advantage in that mechanical properties, gloss, whiteness, film processability, weather resistance, and heat stability are all excellent. In addition, when a recycled polyalkylene terephthalate is applied, even when the proportion of the recycled resin is, for example, 10% by weight or more, the deterioration of properties is prevented, so that there is an advantage in that it is more environmentally friendly, and at the same time, impact resistance, film processability, and low-light characteristics are all excellent.

[0219] The above (D) compatibilizer may be included in a specific amount of 1.3 to 6 parts by weight, preferably 1.5 to 5 parts by weight, more preferably 1.6 to 4.5 parts by weight, even more preferably 1.7 to 4 parts by weight, and further preferably 1.8 to 2.8 parts by weight. In this case, even with a smaller amount, the effect of improving compatibility is excellent, so there is an advantage that the effect desired in the present invention can be sufficiently expressed.

[0220]

[0221] The above (D) compatibilizer may be, for example, at least one selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinylacetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA), and among these, preferably at least one selected from olefin-alkyl acrylate copolymers, and more preferably an ethylene-methyl acrylate copolymer, in which case it has the advantages of excellent mechanical properties, gloss, whiteness, film processability, weather resistance, and heat stability, and further, in the case of including a recycled resin, it has the advantages of excellent impact resistance, film processability, and low-light characteristics along with an environmentally friendly advantage.

[0222]

[0223] The above (D) compatibilizer may be, for example, composed of an olefin-based compound, an alkyl (meth)acrylate or alkenyl acetate, and optionally, a glycidyl methacrylate. As a specific example, the compatibilizer may be composed of 30 to 90 wt% of an olefin-based compound, 10 to 70 wt% of an alkyl (meth)acrylate or alkenyl acetate, and 0 to 15 wt% of a glycidyl methacrylate. In this case, the desired effect can be sufficiently expressed.

[0224] The above (D) compatibilizer may preferably comprise 50 to 90 wt% of ethylene and 10 to 50 wt% of methyl acrylate or vinyl acetate, more preferably 55 to 80 wt% of ethylene and 20 to 45 wt% of methyl acrylate or vinyl acetate, and even more preferably 60 to 80 wt% of ethylene and 20 to 40 wt% of methyl acrylate or vinyl acetate, in which case the desired effect can be sufficiently expressed. The above (D) compatibilizer may even more preferably be an ethylene-methyl acrylate copolymer, in which case there is an advantage in that the raw material supply is easy, which is advantageous for manufacturing.

[0225]

[0226] The above (D) commercializing agent may have a melting index of 1 to 10 g / 10 min, preferably 2 to 5 g / 10 min, measured under conditions of 190°C and 2.16 kg according to ASTM D1238, for example, and has the advantage of superior film processability without deterioration of other physical properties within this range.

[0227]

[0228] The above (D) commercializing agent may have, for example, a melting point of 80 to 110°C, preferably 82 to 105°C, and more preferably 85 to 100°C, and within this range, it has excellent mechanical strength and molding processability.

[0229]

[0230] The method for manufacturing the above (D) commercialization agent is not particularly limited as long as it is a manufacturing method commonly applied in this technical field, and a commercially available product may be used as long as it follows the definition of the present invention.

[0231]

[0232] thermoplastic resin composition

[0233] The thermoplastic resin composition comprises 100 parts by weight of a base resin comprising 15 to 50 wt% of the (A) graft copolymer, 20 to 55 wt% of the (B) copolymer, and 10 to 40 wt% of the (C) polyalkylene terephthalate; and 0.5 to 10 parts by weight of a compatibilizer; and has the advantage of excellent injection gloss, whiteness, film processability, weather resistance, and heat stability while maintaining the mechanical properties inherent to ASA resins and polyester resins at a level equivalent to or higher, and further has the advantage of being environmentally friendly because property degradation is prevented even when a recycled resin is included, and has the advantage of excellent film processability, extrusion low-light characteristics, weather resistance, and heat stability.

[0234]

[0235] The thermoplastic resin composition may have, for example, a weight ratio (A:C) of the (A) graft copolymer and (C) polyalkylene terephthalate of 0.5 to 2.0:1, preferably 0.5 to 1.8:1, more preferably 0.6 to 1.5:1, and even more preferably 0.7 to 1.3:1, in which case it has the advantages of excellent impact resistance, film processability, gloss, and whiteness, and further, when it includes a recycled resin, it has the advantage of being environmentally friendly, while also having the advantages of excellent low-light properties, film processability, and impact resistance.

[0236]

[0237] The thermoplastic resin composition above contains acrylate rubber as a rubber component, but does not contain conjugated diene rubber, so it has excellent weather resistance, and thus has an excellent effect of maintaining properties for a long period of time even when exposed to an environment that causes aging, such as heat or ultraviolet rays. In addition, it has the advantage of excellent film processability and heat stability even though it contains ASA resin and polyester resin, which have low compatibility with each other.

[0238]

[0239] The thermoplastic resin composition may have an injection gloss of, for example, 108 or more, preferably 108 to 130, more preferably 108 to 125, and even more preferably 109 to 120, as measured at 45° according to ASTM D2457 using an injection molded specimen having a thickness of 3 mm. In this case, there is an advantage of superior gloss without deterioration of other physical properties. Here, the unit of gloss may be GU (gloss unit).

[0240] The thermoplastic resin composition may be a high-gloss resin composition including, for example, (C) polyalkylene terephthalate, a non-recycled polyalkylene terephthalate, and having an injection gloss of 108 or more. In this case, in addition to excellent gloss, it has the advantage of being able to provide a high-quality, high-gloss injection-molded product with excellent film processability, impact resistance, weather resistance, and thermal stability.

[0241]

[0242] The thermoplastic resin composition may have an extrusion gloss of, for example, less than 50, measured at 45° according to ASTM D2457 on an extruded film specimen having a thickness of 0.08 mm, preferably 20 to 47, more preferably 22 to 45, even more preferably 23 to 42, and even more preferably 25 to 40, and in this case, it has the advantage of excellent low-light characteristics without deterioration of other physical properties.

[0243] The thermoplastic resin composition may be a low-gloss resin composition including, for example, (C) a recycled polyalkylene terephthalate, and having an extrusion gloss of less than 50. In this case, in addition to the environmentally friendly advantage and low-gloss properties, it has the advantage of being able to provide a high-quality, environmentally friendly, low-gloss film with excellent film processability, impact resistance, weather resistance, and thermal stability.

[0244]

[0245] The thermoplastic resin composition has, for example, excellent film processability, low torque applied to the extruder during the film extrusion process, and thus excellent film thickness uniformity and even glossiness are realized over the entire film, resulting in excellent film appearance quality.

[0246] In this description, the torque refers to the magnitude of the output required to rotate the screw at a set rotation speed during the process of extruding the molten mixture or pellets of the thermoplastic resin composition with a film extruder, and this can be measured by a sensor built into the extruder. During the film extrusion process, when the molding conditions such as the molding temperature, screw rotation speed (rpm), and composition feed rate are the same, the higher the torque value means the greater the load applied to the extruder, which means that the flowability of the composition, i.e., the molding processability, is poor. Therefore, when the molding conditions are the same, the higher the torque value may be, the lower the thickness uniformity of the film may be. Conversely, the lower the torque value means the lower the load applied to the extruder, which means that the flowability of the composition is excellent, and in this case, there is an advantage of excellent film processability and excellent thickness uniformity of the film.

[0247] In this paper, the torque is measured as an example, using a T-die extruder (Techline 20T, Collins, screw diameter 20 nm, L / D = 25) at a molding temperature of 250°C and a molding pressure of 200 kgf / cm. 2 , can be measured under extrusion molding conditions of a film thickness of 0.08 mm under the conditions of a screw rotation speed of 100 rpm, a roll temperature of 85°C, and a roll rotation speed of 3.5 m / min, and can be expressed as a ratio (%) to the maximum torque value (output limit) at which the extruder can operate. The ratio to the maximum torque value at which the extruder can operate can be expressed as a value measured by a sensor built into the extruder and displayed on the torque display unit.

[0248]

[0249] Method for producing a thermoplastic resin composition

[0250] The method for producing a thermoplastic resin composition of the present invention is characterized by including the steps of kneading and extruding 100 parts by weight of a base resin including (A) 15 to 50 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, (B) 20 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, and (C) 10 to 40 wt% of a polyalkylene terephthalate, and (D) 0.5 to 10 parts by weight of a compatibilizer under the conditions of 170 to 300°C and 100 to 400 rpm, in which case compatibility is greatly improved, so that the inherent mechanical properties of ASA resins and polyester resins are maintained at an equivalent or higher level, and at the same time, film processability, gloss, whiteness, weather resistance, and heat stability are all excellent. In addition, even when a recycled resin is included, deterioration of properties is prevented, so that it has an environmentally friendly advantage, and at the same time, film processability and low-light characteristics are both excellent.

[0251]

[0252] The above mixing and extruding step can be performed using, for example, at least one selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer, and by using this, the composition can be uniformly mixed and then extruded to obtain a thermoplastic resin composition in the form of pellets. In this case, there is an effect of preventing deterioration of mechanical properties and heat resistance and providing excellent appearance quality.

[0253]

[0254] The above mixing and extruding steps can be performed, for example, within a range where the cylinder temperature of the extruder is 170 to 300°C, preferably 200 to 280°C, and more preferably 220 to 270°C. In this case, there is an advantage in that the processing amount per unit time is appropriate, melt mixing is sufficiently achieved, and thermal decomposition, etc., are suppressed.

[0255] The above mixing and extrusion can be performed under conditions where the screw rotation speed is, for example, 100 to 400 rpm, preferably 110 to 350 rpm, and more preferably 120 to 270 rpm, in which case the throughput per unit time is appropriate, so there is an advantage of excellent process efficiency.

[0256]

[0257] The thermoplastic resin composition may further include, if necessary, at least one other additive selected from the group consisting of a lubricant, a heat stabilizer, a light stabilizer, a pigment, a release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame suppressor, an anti-drip agent, an inorganic filler, an antifriction agent, and an antiwear agent, in an amount of 0.01 to 15 parts by weight, 0.05 to 12 parts by weight, 0.1 to 5 parts by weight, 0.3 to 10 parts by weight, 0.3 to 7 parts by weight, or 0.3 to 5 parts by weight, based on 100 parts by weight of the base resin, and within this range, there is an advantage in that the desired physical properties are well implemented without deteriorating the desired physical properties.

[0258]

[0259] The above-mentioned active agent may be, for example, at least one selected from the group consisting of fatty acid amide compounds, montan waxes, silicone oils, and olefin waxes, preferably an olefin wax, and more preferably a polyethylene wax, in which case there is an advantage of excellent molding processability and mold releasability.

[0260] The above fatty acid amide compound may be, for example, at least one selected from the group consisting of stearamide, behanamide, ethylene bis(stearamide), ethylene bis 12-hydroxy stearamide, erucamide, oleamide, and ethylene bis oleamide.

[0261] The above-mentioned montan wax may be, for example, montan wax, montan ester wax, or a mixture thereof.

[0262] The above silicone oil may be, for example, at least one selected from the group consisting of dimethyl silicone oil, methyl hydrogen silicone oil, ester-modified silicone oil, hydroxy silicone oil, carbinol-modified silicone oil, vinyl silicone oil, and silicone acrylate.

[0263] The above olefin wax may be, for example, at least one selected from the group consisting of polyethylene oxide wax, polyethylene wax, and polypropylene wax.

[0264]

[0265] The above heat stabilizer may include, for example, a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, or a mixture thereof, and may preferably be a phenol-based heat stabilizer. In this case, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0266] The above phenolic heat stabilizers include, for example, N,N′-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N′-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and It may be at least one selected from the group consisting of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, and in this case, heat resistance can be greatly improved while maintaining a high balance of physical properties.

[0267] The above-mentioned heat stabilizer is, for example, 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-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, It may be at least one selected from the group consisting of bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, stearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, and trimethyl phosphate.

[0268]

[0269] The above-mentioned light stabilizer may include, for example, at least one selected from the group consisting of triazine compounds, benzophenone compounds, benzotriazole compounds, indole compounds, quinolinone compounds, benzoate compounds, cyanoacrylate compounds, and amine compounds, and may preferably be a benzotriazole compound or an amine compound. In this case, there is an effect of further improving light resistance while providing excellent physical property balance.

[0270]

[0271] The above triazine compounds include, for example, 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-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-ethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 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-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, It may be at least one selected from the group consisting of 2,4,6-tris(2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol.

[0272]

[0273] The above benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, It may be at least one selected from the group consisting of 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0274]

[0275] The above benzotriazole compounds include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-2'-hydroxy-3',2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenyl-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3”,4”,5”,6”-tetrahydrophthalimidomethyl)-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] and It may be at least one selected from the group consisting of 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and preferably 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol.

[0276] The above indole compound may be, for example, 2-[(1-methyl-2-phenyl-1H-indol-3-yl)methylene]propanedinitrile.

[0277] The above quinolinone compound may be, for example, 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

[0278] The above benzoate compound may be, for example, at least one selected from the group consisting of 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0279] The above cyanoacrylate compound may be, for example, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate, or a mixture thereof.

[0280] The above amine compound may be, for example, a hindered amine UV stabilizer (HALS), and preferably, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate [(bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate), bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, Condensation products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, and It may be at least one selected from the group consisting of poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], and preferably bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate may be used.

[0281]

[0282] The above pigment may be an inorganic pigment or an organic pigment.

[0283] The above organic pigment may be, for example, at least one selected from the group consisting of perinone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, indigo pigments, dioxazine pigments, quinacridone pigments, methane pigments, quinoline pigments, isoindrinone pigments, and phthalone pigments.

[0284] The above-mentioned inorganic pigment may be, for example, at least one selected from the group consisting of ultramarine pigments, titanium dioxide, zinc sulfide, zinc oxide, iron oxide, and carbon black.

[0285]

[0286] It is stated that the above-mentioned release agent may be at least one selected from the group consisting of, for example, glycerin sterolate, polyethylene tetrasterolate, etc., but is not limited thereto.

[0287]

[0288] The above antistatic agent may be applied without particular limitation as long as it is used as an antistatic agent in the technical field to which the present invention belongs. For example, one or more types of anionic surfactants such as sulfate-based, sulfonate-based, and phosphate-based surfactants and nonionic surfactants such as quaternary ammonium salt-based and alkylamine sulfate-based surfactants may be used, but it is to be noted that the present invention is not limited thereto.

[0289]

[0290] The above anti-dropping agent may be, for example, at least one selected from the group consisting of PTFE (polytetrafluoroethylene), a mixture of PTFE and SAN (styrene-acrylonitrile) resin (PTFE / SAN), a mixture of PTFE and PMMA (poly methyl methacrylate) (PTFE / PMMA), polyamide, polysilicon, and TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymer, and preferably at least one selected from the group consisting of PTFE / SAN and PTFE / PMMA, more preferably PTFE / SAN.

[0291] The above PTFE / SAN and PTFE / PMMA may preferably be a mixture of PTFE and SAN or PMMA in a weight ratio of 1:0.5 to 1.5, and in one embodiment, a mixture in a weight ratio of 1:1.

[0292]

[0293] The above antibacterial agents, processing aids, metal deactivators, inhibitors, anti-loading agents, inorganic fillers, anti-friction agents, anti-wear agents, etc. are not particularly limited as long as they follow the definition of the present invention and are commonly used in the technical field to which the present invention belongs.

[0294]

[0295] molded products

[0296] The molded article of the present invention is characterized by including the thermoplastic resin composition, and in this case, has the advantages of excellent impact resistance, film processability, gloss, whiteness, weather resistance, and heat resistance, and also has the advantage of being environmentally friendly because it prevents deterioration of physical properties even when including recycled resin, and has the advantage of excellent low-light characteristics.

[0297]

[0298] The above molded product has properties equivalent to or higher than those of a molded product containing only a new resin even when it contains a recycled resin, and thus has the advantage of being usable without additional processing in fields to which conventional ASA thermoplastic resin compositions are applied, such as building interior and exterior materials, automobile interior and exterior materials, ships, and leisure and sports equipment.

[0299]

[0300] The above-mentioned molded article has the advantage that, for example, it can be manufactured into a film having excellent film processability and high whiteness, thus having various colors, and is also excellent in weather resistance, making it particularly suitable as an exterior material. The above-mentioned molded article may be, for example, an injection-molded article having a thickness of 1 to 5 mm, preferably 1.5 to 4 mm, and more preferably 2 to 3 mm. As a specific example, the above-mentioned molded article may have a whiteness of 85 or more, preferably 85 to 100, more preferably 88 to 98, and even more preferably 89 to 97, obtained by measuring the L value in Reflectance Mode under a UV D65 light source using a colorimeter (model name: X-lite Color Eye 7000A) according to the CIE1976 L*a*b* colorimetric system under a thickness of 3 mm, and more preferably 89 to 97, and in this case, there is an advantage that the whiteness is excellent and vivid colors can be realized.

[0301] The above-mentioned molded article has, for example, excellent film processability and low-light characteristics, and thus has advantages useful for low-light films. The above-mentioned molded article may be, for example, an extruded film having a thickness of 40 to 600 μm, preferably 50 to 500 μm, and more preferably 60 to 300 μm. In particular, the extruded film may have, for example, a glossiness measured under conditions of a thickness of 0.08 mm (80 μm) at 45° according to ASTM D2457 of 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 which case, there is an advantage of being able to provide a high-quality low-light film with excellent low-gloss characteristics and a uniform thickness.

[0302]

[0303] The above molded article can be manufactured by a method commonly used in the technical field to which the present invention pertains. For example, the molded article can be manufactured by applying a molding method such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, pressure molding, hot bending molding, compression molding, calendar molding, or rotational molding using a molten mixture or pellet of the thermoplastic resin composition according to the present invention as a raw material. At this time, the size, thickness, shape, etc. of the molded article can be appropriately adjusted depending on the intended use.

[0304] The above molded article can be manufactured by including a step of injecting a molten mixture or pellets of the thermoplastic resin composition according to the present invention using an injection molding machine at a barrel temperature of 180 to 300°C, and the molded article manufactured in this way can be a molded article used in a field requiring weather resistance, gloss, molding processability, and impact strength.

[0305]

[0306] In describing the thermoplastic resin composition, the manufacturing method thereof, and the molded product of the present invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0307]

[0308] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0309]

[0310] [Example]

[0311] The materials used in the following examples and comparative examples are as follows.

[0312]

[0313] (A) Graft copolymer:

[0314] (A-1) Large-diameter ASA resin: ASA graft copolymer comprising 50 wt% of butyl acrylate rubber having an average particle diameter of 400 nm, 36 wt% of styrene, and 14 wt% of acrylonitrile.

[0315] (A-2) Small-diameter ASA resin: ASA graft copolymer comprising 50 wt% of butyl acrylate rubber having an average particle size of 100 nm, 36 wt% of styrene, and 14 wt% of acrylonitrile.

[0316] (A-3) ABS resin: ABS graft copolymer comprising 60 wt% of butadiene rubber having an average particle size of 300 nm and 8 to 12 wt% of acrylonitrile.

[0317] (B) Copolymer:

[0318] (B-1) SAN resin: A general SAN copolymer having an Mw of 150,000 g / mol and comprising 70 wt% of styrene and 30 wt% of acrylonitrile.

[0319] (B-2) Heat-resistant SAN resin: Heat-resistant SAN copolymer having an Mw of 100,000 g / mol and comprising 70 wt% of α-methylstyrene and 30 wt% of acrylonitrile.

[0320] (C) Polyethylene terephthalate:

[0321] (C-1) Non-recycled polyethylene terephthalate: PET resin with IV 0.6 to 0.8 dl / g

[0322] (C-2) Recycled polyethylene terephthalate: Recycled PET resin with IV 0.6 to 0.8 dl / g

[0323] (D) Commercialization agent:

[0324] (D-1) Ethylene methyl acrylate copolymer comprising 71 wt% of ethylene and 29 wt% of methyl acrylate (EMA; Lotyl 29MA03T, SK Corporation)

[0325] (D-2) Ethylene vinyl acetate copolymer (EVA; EVEA28025, LG Chemical Co., Ltd.) comprising 72 wt% ethylene and 28 wt% vinyl acetate

[0326]

[0327] Examples 1-1 to 1-7, 2-1 to 2-9, and Comparative Examples 1-1 to 1-11, 2-1 to 2-12

[0328] The above (A) to (D) were mixed using a super mixer in the contents shown in Tables 1 and 3 below and extruded using a twin-screw extruder (screw diameter 26 mm, L / D=40) under extrusion conditions of a cylinder temperature of 230°C and a screw rotation speed of 200 rpm to produce pellets.

[0329] The thermoplastic resin composition in the form of pellets was dried at 100°C for 2 hours or more, and then injection-molded in an injection molding machine under the conditions of an injection molding machine barrel temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to produce a specimen for measuring physical properties. The specimen was left at room temperature (23 ± 3°C) for 48 hours or more, and then the physical properties were measured.

[0330] In addition, when manufacturing extrusion film, the above manufactured pellets are used in a T-die extruder (Collins' Techline 20T, screw diameter 20 nm, L / D=25) at a molding temperature of 250 ℃ and a molding pressure of 200 kgf / cm. 2 , a film with a thickness of 0.08 mm was produced under the conditions of a screw rotation speed of 100 rpm, a roll temperature of 85 ℃, and a roll rotation speed of 3.5 m / min, and the film gloss and torque characteristics were measured.

[0331]

[0332] [Example Exam]

[0333] The physical properties of the specimens manufactured in the above examples and comparative examples were measured by the following methods, and the results are shown in Tables 2 and 4 below.

[0334]

[0335] * Injection gloss (gloss unit; GU): Gloss was measured using a gloss meter VG7000 at 45° on an injection specimen with a thickness of 3 mm according to ASTM D2457.

[0336] * Whiteness (L value): Based on the CIE1976 L*a*b* colorimetric system, the L value was measured at Degree Observer 10° under a UV D65 light source using a colorimeter (model name X-lite Color Eye 7000A) with a 3 mm thick injection molded specimen, and the L value was measured in Reflectance Mode according to the Munsell System and CIE Lab method.

[0337] * Extruded film gloss (gloss unit; GU): Gloss was measured using a gloss meter VG7000 at 45° on an extruded film specimen with a thickness of 0.08 mm according to ASTM D2457.

[0338] * 1 / 8" Izod impact strength (kgf·cm / cm): Measured at room temperature with 1 / 8" thick injection-molded specimens according to ASTM D256.

[0339] * 1 / 4" Izod impact strength (kgf·cm / cm): Measured at room temperature with 1 / 4" thick injection-molded specimens according to ASTM D256.

[0340] * Processability (%): Molding temperature 250℃, molding pressure 200 kgf / cm using a T-die extruder (Techline 20T, Collins, screw diameter 20 nm, L / D = 25) 2 , in the process of extrusion molding with a film thickness of 0.08 mm under the conditions of a screw rotation speed of 100 rpm, a roll temperature of 85°C, and a roll rotation speed of 3.5 m / min, the torque value applied to the motor connected to the screw to rotate the screw at the set rotation speed was expressed as a ratio to the maximum torque value of the extruder. A lower torque value means better processability.

[0341] * Weatherability (ΔE): For injection molded specimens with a thickness of 3 mm, accelerated weatherability test equipment (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiance 0.55 W / m 2At 340 nm), after 2,000 hours of measurement under the applied SAE J1960 conditions, ΔE was evaluated by calculating with the following mathematical formula 2. The ΔE below is the arithmetic mean of the Hunter Lab (L, a, b) values ​​measured before and after the accelerated weathering test, and the closer the ΔE value is to 0, the better the weathering resistance is. The Hunter Lab (L, a, b) values ​​were measured using a color meter (X-lite Color-eye 7000A) according to the CIE1976 L*a*b* colorimetric system.

[0342] [Equation 2]

[0343] ΔE= √{(L-L') 2 + (a-a') 2 + (b-b') 2} (√: radical symbol)

[0344] * Thermal stability: During the injection molding process of the property evaluation specimen, the Hunter Lab (L, a, b) values ​​were measured for the specimens injected with an additional 5 minutes of residence time in the cylinder at a cylinder temperature of 260°C of the injection molding machine and for the specimens without an additional 5-minute residence time, and the color values ​​measured before and after the additional 5-minute residence time at 260°C were substituted into the following mathematical formula 3 to calculate the ΔE value. The closer the ΔE value is to 0, the better the thermal stability is.

[0345] [Equation 3]

[0346] Before and after stay ΔE= √{(L-L') 2 + (a-a') 2 + (b-b') 2} (√: radical symbol)

[0347]

[0348] (Weight part) A+B+C 100 standard (A-1) Large diameter ASA (A-2) Small diameter ASA (A-3) ABS (B-1) General SAN (B-2) Heat-resistant SAN (C-1) Non-renewable PET (D-1) EMA (D-2) EVA Example 1-1147-49-302-1-2535-30-302-1-3147-49-305-1-4147--49305-1-5147-49-30-21-61515-37-332-1-71020-45-252- Comparative Example 1-1147-79----1-2147-4 9-30--1-3147---792-1-4350-17-302-1-553-62-302-1-61030-60--2-1-7---60-402-1-8--2149-302-1-957-48-402-1-101730-50-32-1-111010-30-502-

[0349] Classification Gloss (GU) Whiteness (L value) Impact strength (kgf·cm / cm) Processability (%) Torque reduction compared to Comparative Example 1 (%) Weatherability (ΔThermal stability (ΔE after residence) Example 1-1110.090.09.63331.31.73.11-2112.092.010.93331.31.23.41-3120.091.010.53135.41.63.21-4114.090.010.83429.21.13.01-511 2.090.09.83331.31.53.31-6111.092.011.03331.31.43.31-7113.090.010.83429.21.33.4Comparative Example 1-1105.086.09.548-1.83.41-278.088.06.555-1 4.63.54.31-382.091.04.83527.14.24.51-488.089.010.848-1.93.81-5108.088.03.83331.36.55.81-689.087.014.048-1.63.21-7100.089.02 .13527.18.24.81-8110.090.010.53331.39.16.41-989.089.04.33233.36.85.01-1087.086.011.84212.51.73.21-1185.089.03.83135.46.85.0

[0350] (Weight part) A+B+C 100 standard (A-1) Large diameter ASA (A-2) Small diameter ASA (A-3) ABS (B-1) Non-heat-resistant SAN (C-2) Recycled PET (D-1) EMA (D-2) EVA Example 2-1147-49302-2-2138-49302-2-3156-49302-2-42416-30302-2-5147-49308-2-6147-49304-2-7147-4930-22-81715-35332-2-91712-46252-Comparative Example 2-1147-79---2- 2147-4930--2-3-10-60302-2-410--60302-2-53427-9302-2-6147-493012-2-7147-27522-2-83017-53-2-2-9---65352-2-10--2149302-2-1175-48402-2-123020-4732-

[0351] Gloss (GU) of the film, impact strength (kgf cm / cm), processability (%), torque reduction compared to comparative example 1 (%), weather resistance (Δ), thermal stability (after residence ΔE) Example 2-130.910.13331.31.83.42-231.09.83135.42.03.32-330.710.23527.11.73.62-434.012.13429.21.63.82-537.010.83233.31.93.52-631.210.33233.31.93.42-733.210.03527.11.83.52-830.811.33331.31.73.82-930.710.93135.41.73.6 Comparative Example 2-178.38.048-1.83.42-272.1 7.955-14.62.14.12-370.43.73820.82.53.82-468.84.53918.82.83.92-558.76.052-8.32.04.52-660.18.349-2.12.43.92-755.73.03820.82.74.22-880.312.650-4.21.94.32-965.22.13625.09.16.52-1041.313.53722.99.58.32-1150.64.23135.46.85.02-1276.812.04310.42.06.2

[0352] Referring to Tables 1 and 2 above, in the case of Examples 1-1 to 1-7 according to the present invention, when non-recycled PET was applied as (C) polyalkylene terephthalate, the injection gloss was excellent with a gloss of 110 or higher, the whiteness L value was excellent with a whiteness of 90.0 or higher, the impact strength was excellent with a impact resistance of 9.6 kgf·cm / cm or higher, and the torque value was reduced by at least 29.2% or more compared to Comparative Example 1-1 in which PET and a compatibilizer were not mixed with the ASA / SAN alloy resin, confirming that the film processability was greatly improved. Furthermore, the ΔE value before and after the accelerated weathering test was 1.7 or lower, and the ΔE value before and after the additional residence at 260°C for 5 minutes was within a range of 3.4 or lower, confirming that the weathering resistance and heat stability were also excellent.

[0353] On the other hand, in the case of Comparative Examples 1-1 to 1-11, which are outside the scope of the present invention, the gloss was found to be greatly reduced in all cases except for Comparative Example 1-8, and Comparative Example 1-8 showed significantly poor weather resistance and heat stability, and overall, the impact resistance, processability (torque), whiteness, weather resistance, and / or heat stability were found to be very poor, confirming that the mechanical properties, film processability, gloss, whiteness, weather resistance, and heat stability of the thermoplastic resin composition according to the present invention were excellent.

[0354]

[0355] Meanwhile, referring to Tables 3 and 4 above, in the case of Examples 2-1 to 2-9 according to the present invention, when recycled PET was applied as (C) polyalkylene terephthalate, the gloss of the extruded film was low gloss of 37 or less, and the impact strength was excellent impact resistance of 9.8 kgf·cm / cm or more, and the torque value was reduced by at least 27.1% compared to Comparative Example 2-1 in which recycled PET and compatibilizer were not mixed with ASA / SAN alloy resin, confirming that the film processability was greatly improved. Furthermore, the ΔE value before and after the accelerated weathering test was 2.0 or less, and the ΔE value measured before and after an additional residence time of 5 minutes at 260℃ was within the range of 3.8 or less, confirming that the weathering resistance and heat stability were also excellent.

[0356] On the other hand, in the case of Comparative Examples 2-1 to 2-12, which are outside the scope of the present invention, it was confirmed that the gloss was all excessively increased, and the impact resistance, processability (torque), weather resistance, and / or thermal stability were very poor. In particular, in the case of Comparative Example 2-8, it was confirmed that the processability and thermal stability were lowered compared to the examples, and the low-light characteristics were very poor, even though it did not include recycled PET.

[0357]

[0358] Therefore, it was confirmed that the thermoplastic resin composition according to the present invention can provide a high-quality thermoplastic resin molded product while maintaining the inherent mechanical properties of ASA resin and polyester resin at an equivalent or higher level, while also having excellent film processability, weather resistance, and thermal stability, and possessing both mechanical rigidity (impact resistance) and molding processability. In particular, it was confirmed that it has properties suitable for providing high-gloss injection molded products in various colors due to excellent injection gloss and whiteness when not containing recycled resin (recycled PET). In addition, it was confirmed that it has properties suitable for providing an environmentally friendly low-gloss extrusion film because it prevents deterioration of properties even when containing recycled resin (recycled PET) and has an environmentally friendly advantage with excellent low-gloss properties.

Claims

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

2. In paragraph 1, The above (D) compatibilizer is characterized in that it is at least one selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-vinylacetate copolymer (EVA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA). Thermoplastic resin composition.

3. In paragraph 1, The above (A) copolymer is characterized in that it comprises, based on 100 wt% of the base resin, (A-1) 3 to 35 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 250 to 500 nm; and (A-2) 5 to 40 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 150 nm. Thermoplastic resin composition.

4. In paragraph 3, The above (A-1) graft copolymer and the above (A-2) graft copolymer are characterized in that they each comprise 40 to 60 wt% of alkyl acrylate rubber, 30 to 40 wt% of aromatic vinyl compound, and 10 to 20 wt% of vinyl cyan compound. Thermoplastic resin composition.

5. In paragraph 1, The above (B) copolymer is characterized in that it is at least one selected from the group consisting of (B-1) an aromatic vinyl compound-vinyl cyan compound copolymer comprising 55 to 85 wt% of an alkyl unsubstituted aromatic vinyl compound and 15 to 45 wt% of a vinyl cyan compound, and (B-2) a heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer comprising 60 to 80 wt% of an alkyl-substituted aromatic vinyl compound, 20 to 40 wt% of a vinyl cyan compound, and 0 to 20 wt% of an alkyl unsubstituted aromatic vinyl compound. Thermoplastic resin composition.

6. In paragraph 5, The above (B-1) aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that the weight average molecular weight is 50,000 to 300,000 g / mol. Thermoplastic resin composition.

7. In paragraph 5, The above (B-2) heat-resistant aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that the weight average molecular weight is 30,000 to 200,000 g / mol. Thermoplastic resin composition.

8. In paragraph 1, The above (C) polyalkylene terephthalate is characterized by an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g. Thermoplastic resin composition.

9. In paragraph 1, The above (C) non-regenerated or recycled polyalkylene terephthalate is characterized in that it is non-regenerated polyethylene terephthalate or recycled polyethylene terephthalate. Thermoplastic resin composition.

10. In paragraph 1, The weight ratio (A:C) of the above (A) copolymer and (C) polyalkylene terephthalate is 0.5 to 2.0:

1. Thermoplastic resin composition.

11. In paragraph 2, The above (D) commercializing agent is characterized in that it comprises 50 to 90 wt% of ethylene and 10 to 50 wt% of methyl acrylate or vinyl acetate. Thermoplastic resin composition.

12. In paragraph 1, The above (C) polyalkylene terephthalate is non-recycled polyethylene terephthalate, The thermoplastic resin composition is characterized in that it has an injection gloss of 108 or more as measured at 45° using an injection molded specimen with a thickness of 3 mm according to ASTM D2457. Thermoplastic resin composition.

13. In paragraph 1, The above (C) polyalkylene terephthalate is recycled polyethylene terephthalate, The thermoplastic resin composition is characterized in that it has a gloss of less than 50 as measured on an extruded film specimen having a thickness of 0.08 mm at 45° according to ASTM D2457. Thermoplastic resin composition.

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

15. Characterized in that it comprises a thermoplastic resin composition of any one of claims 1 to 13. Molded product.