Thermoplastic resin composition, its method of manufacture and molded article containing same

Abstract

The present invention relates to a thermoplastic resin composition, a production method thereof, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition which contains a specified ASA-based graft copolymer and recycled resin and is therefore environmentally friendly and has excellent moldability, mechanical rigidity, heat resistance, and colorability, a production method thereof, and a molded article containing the same.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0136778 filed on October 21, 2022, and Korean Patent Application No. 10-2023-0091902, refiled on July 14, 2023 based thereon, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same. The present invention relates to a thermoplastic resin composition that has excellent physical properties such as moldability, impact strength, tensile strength, heat resistance, and colorability, and is environmentally friendly because it contains recycled resins, a method for producing the same, and a molded article containing the same. [Background technology]

[0003] Acrylonitrile-butadiene-styrene resin (hereinafter referred to as "ABS resin"), which is based on conjugated diene rubber, has been used in a variety of fields due to its excellent moldability, mechanical properties, and appearance characteristics. However, because it is based on butadiene rubber, which has chemically unstable unsaturated bonds, it has the problem of poor weather resistance, such as easily aging when exposed to ultraviolet rays. As a possible alternative material, an acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as "ASA resin"), which has excellent weather resistance, has been proposed.

[0004] ASA resin has excellent weather resistance, aging resistance, and chemical resistance, as well as moldability, rigidity, impact resistance, and processability. As a result, it is widely used in a variety of fields, both indoors and outdoors, including electrical and electronic parts, building materials, automotive interior and exterior materials, ships, and leisure goods.

[0005] On the other hand, plastics are widely consumed in modern society due to their convenience, but because they do not decompose naturally, there is a gradual increase in demand for waste disposal and utilization methods. In addition, there is a trend toward making the use of recycled resins mandatory as part of environmental regulations.

[0006] However, recycled resins age due to impact, abrasion, heat, UV rays, humidity, high and low temperature environments during the manufacturing, consumption and disposal processes, and are contaminated by the inflow of foreign matter, resulting in problems such as significantly inferior moldability, mechanical rigidity, appearance quality, flexibility, chemical resistance and thermal stability compared to newly polymerized virgin resins. Therefore, unless a small amount of recycled resin is used, even mixing it with virgin resin is insufficient to solve these problems.

[0007] Therefore, there is an urgent need to develop a recycled resin composition that contains a certain level of recycled resin and yet exhibits physical properties that are applicable to existing plastic materials. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent No. 10-1271250 Summary of the Invention [Problem to be solved by the invention]

[0009] In order to solve the above-mentioned problems of the prior art, an object of the present invention is to provide a thermoplastic resin composition that is environmentally friendly by containing recycled resin and has excellent moldability, impact strength, tensile strength, heat resistance, and colorability, a method for producing the same, and a molded article produced from the same.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0011] In order to achieve the above object, the present invention provides a polymerizable composition comprising: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber core having an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the alkyl acrylate rubber core; and (B) a matrix resin; the copolymer shell of the (A) graft copolymer comprises, relative to 100% by weight of the total, 85 to 99% by weight of an aromatic vinyl compound and 1 to 15% by weight of a vinyl cyan compound, and has a weight average molecular weight of 100,000 to 400,000 g / mol; The present invention provides a thermoplastic resin composition characterized in that the (B) matrix resin contains 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide, with respect to a total of 100% by weight of the (B) matrix resin.

[0012] The thermoplastic resin composition preferably contains 20 to 60% by weight of the (A) graft copolymer and 40 to 80% by weight of the (B) matrix resin, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin.

[0013] The (A) graft copolymer may preferably comprise 40 to 70% by weight of the alkyl acrylate rubber core and 30 to 60% by weight of the copolymer shell, with the total being 100% by weight.

[0014] The (A) graft copolymer may preferably contain a polymer seed containing one or more compounds selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, and vinyl cyan compounds. In this case, the (A) graft copolymer may preferably contain 1 to 20% by weight of the polymer seed, 35 to 65% by weight of the alkyl acrylate rubber core, and 30 to 60% by weight of the copolymer shell.

[0015] The recycled polystyrene may preferably include any one selected from the group consisting of recycled non-expanded polystyrene, recycled expanded polystyrene, and a mixture thereof.

[0016] The recycled polystyrene may preferably have a weight average molecular weight of 100,000 to 350,000 g / mol.

[0017] The (B) matrix resin may preferably further contain virgin general-purpose polystyrene (GPPS), and in this case, may contain 50 to 90% by weight of recycled polystyrene, 8 to 45% by weight of polyarylene oxide, and 1 to 30% by weight of virgin general-purpose polystyrene.

[0018] For example, the (B) matrix resin may further contain an aromatic vinyl compound-vinyl cyan compound copolymer, preferably an aromatic vinyl compound-vinyl cyan compound copolymer containing 75 to 95% by weight of an aromatic vinyl compound and 5 to 25% by weight of a vinyl cyan compound. In this case, the (B) matrix resin may contain 1 to 15% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer relative to a total of 100% by weight of the (B) matrix resin.

[0019] The thermoplastic resin composition may preferably contain (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber core having an average particle size of more than 200 nm and not more than 500 nm, and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the alkyl acrylate rubber core. In this case, the content may be 0.1 to 12 parts by weight based on 100 parts by weight of the total of the (A) graft copolymer and the (B) matrix resin.

[0020] The thermoplastic resin composition may preferably contain 0.1 to 7 parts by weight of (D) a light stabilizer based on 100 parts by weight in total of the (A) graft copolymer and (B) matrix resin.

[0021] The thermoplastic resin composition may preferably have a heat distortion temperature (HDT) of 82° C. or higher, measured in accordance with ASTM D 648 under a load of 18.5 kgf.

[0022] The thermoplastic resin composition preferably has a tensile strength of 400 kgf / cm measured at a speed of 50 mm / min in accordance with ASTM D 638. 2 It may be more than that.

[0023] The present invention also provides a method for producing a thermoplastic resin composition, comprising the steps of kneading and extruding (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, which comprises an alkyl acrylate rubber core having an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyanide compound copolymer shell surrounding the alkyl acrylate rubber core, and (B) a matrix resin, at 180 to 300°C and 100 to 400 rpm, wherein the copolymer shell of the (A) graft copolymer comprises, relative to 100% by weight of the total, 85 to 99% by weight of the aromatic vinyl compound and 1 to 15% by weight of the vinyl cyanide compound and has a weight-average molecular weight of 100,000 to 400,000 g / mol, and the (B) matrix resin comprises, relative to 100% by weight of the total, 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide.

[0024] The present invention also provides a molded article comprising the thermoplastic resin composition. [Effects of the Invention]

[0025] According to the present invention, by incorporating recycled resin into an ASA-based resin composition, it is possible to provide an environmentally friendly thermoplastic resin composition that is excellent in moldability, impact strength, tensile strength, heat resistance, and colorability, a method for producing the same, and molded articles produced from the same. DETAILED DESCRIPTION OF THE INVENTION

[0026] The thermoplastic resin composition of the present invention, its production method, and molded articles thereof will be described in detail below.

[0027] The present inventors have been researching how to produce an environmentally friendly ASA-based resin composition containing recycled resin while ensuring that the composition has physical properties at or above the level of replacing existing virgin ASA resin-based compositions. They have found that adjusting the size and composition of the rubber core and shell of the virgin ASA resin to be partially added, as well as the composition ratio of recycled resin to virgin resin, can significantly improve physical properties such as moldability, impact strength, and heat resistance. Based on this, they have continued their research and have completed the present invention.

[0028] The thermoplastic resin composition of the present invention comprises: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, which comprises an alkyl acrylate rubber core having an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the alkyl acrylate rubber core; and (B) a matrix resin, wherein the copolymer shell of the (A) graft copolymer comprises, relative to 100% by weight of the total, 85 to 99% by weight of the aromatic vinyl compound and 1 to 15% by weight of the vinyl cyan compound, and has a weight-average molecular weight of 100,000 to 400,000 g / mol; and (B) the matrix resin comprises, relative to 100% by weight of the total, 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide. In this case, the inclusion of recycled resins provides environmental friendliness and excellent moldability, impact strength, tensile strength, heat resistance, and colorability.

[0029] In this description, the component ratio of a copolymer or resin may refer to the content of units constituting the copolymer, or may refer to the content of monomers added during polymerization of the copolymer.

[0030] In this description, a polymer comprising a certain compound means a polymer that is polymerized containing that compound, and the units in the polymerized polymer are derived from that compound.

[0031] In this description, the term "recycled thermoplastic resin" is not particularly limited as long as it is generally recognized as a recycled 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 recycled from recycled waste plastic. Specifically, it refers to a thermoplastic resin prepared in a usable raw material state after sorting, washing, and crushing the recycled waste plastic. If necessary, a recycled thermoplastic resin processed into pellets through an extrusion process can also be used, which has the advantage of eliminating the need for additional processing such as purification. Because such recycled thermoplastic resin has undergone one or more processes, it may contain residual additives such as colorants, lubricants, and / or mold release agents.

[0032] In this description, non-recycled thermoplastic resins are contrasted with the recycled thermoplastic resins defined above, and may be prepared by directly polymerizing the monomers that constitute the thermoplastic resin, or may be a commercially available product equivalent thereto, and may be referred to as a virgin resin, for example.

[0033] The thermoplastic resin composition of the present invention will be described in detail below, by constituent.

[0034] (A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer The alkyl acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer (hereinafter referred to as "(A) graft copolymer") having an average particle size of 60 to 200 nm in the (A) rubber core may be contained in an amount of, for example, 20 to 65% by weight or 20 to 60% by weight, preferably 25 to 60% by weight, more preferably 30 to 58% by weight, and even more preferably 35 to 55% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, the resulting composition has the advantages of being environmentally friendly, as well as excellent moldability, impact strength, tensile strength, heat resistance, and colorability.

[0035] For example, the (A) graft copolymer may be contained in an amount of 40 to 58% by weight, preferably 40 to 55% by weight, and more preferably 40 to 50% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, there are advantages such as even better environmental friendliness, moldability, tensile strength, and heat resistance.

[0036] For example, the (A) graft copolymer may be contained in an amount of 45 to 60% by weight, preferably 48 to 60% by weight, and more preferably 50 to 60% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, there is an advantage that the impact strength and colorability are further improved.

[0037] The (A) graft copolymer, for example, has an average particle size of 60 to 200 nm and comprises an alkyl acrylate rubber core containing an alkyl acrylate compound; and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the rubber core and containing an aromatic vinyl compound and a vinyl cyan compound. The copolymer shell may contain 85 to 99% by weight of the aromatic vinyl compound and 1 to 15% by weight of the vinyl cyan compound, relative to a total of 100% by weight of the copolymer shell, and may have a weight average molecular weight of 100,000 to 400,000 g / mol. In this case, even if recycled resin is contained, there are advantages in that the molding processability, impact strength, tensile strength, heat resistance, and colorability are all excellent.

[0038] In this description, the average particle size of the polymer seed, rubber core, or graft shell of the graft copolymer may be measured by a method commonly used in the technical field to which the present invention pertains, including electron microscopy using SEM, TEM, etc., and is not particularly limited thereto. For example, samples may be taken at the completion of the preparation of the polymer seed, the preparation of the rubber core, and the preparation of the graft shell, and the measurements may be made using dynamic light scattering. More specifically, the measurements may be made using a particle size analyzer (product name: Nicomp380, manufacturer: PSS) in Gaussian mode, as intensity values. As a specific measurement example, 0.1 g of sample latex (total solid content TSC 35-50 wt%) is diluted 1,000-5,000 times with deionized or distilled water, i.e., diluted appropriately so as not to deviate significantly from the intensity setpoint of 300 kHz, and placed in a glass tube. The measurement method is auto-dilution and measurement is performed using a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis, and the settings are a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0039] In this description, unless otherwise specified, the weight average molecular weight can be measured using GPC (gel permeation chromatography, water breeze), and specifically, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using THF (tetrahydrofuran) as an eluent. In this case, as a specific measurement example, the following conditions can be used: solvent: THF, column temperature: 40°C, flow rate: 0.3 ml / min, sample concentration: 20 mg / ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35°C, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): Measurement can be performed under the conditions of OECD TG 118.

[0040] In this description, the copolymer (shell) grafted to the rubber (core) can be separated from the rubber (core) by a separation method commonly used in the technical field to which the present invention pertains in order to measure the weight average molecular weight. For example, a sol from which an insoluble component (gel) has been separated by the method described below in the method for measuring the graft ratio can be dissolved in a THF solvent to prepare a solution, which can then be filtered to obtain a filtrate, which can be used as a sample for measuring the weight average molecular weight.

[0041] The (A) graft copolymer may, for example, comprise 40 to 70% by weight of an alkyl acrylate rubber core and 30 to 60% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer shell, based on a total of 100% by weight, preferably 40 to 65% by weight of an alkyl acrylate rubber core and 35 to 60% by weight of the copolymer shell, more preferably 42 to 63% by weight of an alkyl acrylate rubber core and 37 to 58% by weight of the copolymer shell, and even more preferably 45 to 60% by weight of an alkyl acrylate rubber core and 40 to 55% by weight of the copolymer shell. In this case, compatibility with the matrix resin is improved, resulting in advantages such as excellent improvements in moldability, impact strength, tensile strength, heat resistance, and colorability.

[0042] As an example, the (A) graft copolymer may comprise: a polymer seed comprising at least one selected from the group consisting of alkyl (meth)acrylate, aromatic vinyl compound, and vinyl cyan compound; an alkyl acrylate rubber core surrounding the polymer seed; and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the rubber core. As a specific example, the (A) graft copolymer may contain, based on its total weight, 1 to 20% by weight of polymer seed, 35 to 65% by weight of alkyl acrylate rubber core, and 30 to 60% by weight of copolymer shell, preferably 2 to 18% by weight of polymer seed, 38 to 63% by weight of alkyl acrylate rubber core, and 30 to 60% by weight of copolymer shell, more preferably 3 to 15% by weight of polymer seed, 40 to 60% by weight of alkyl acrylate rubber core, and 35 to 55% by weight of copolymer shell, and even more preferably 5 to 10% by weight of polymer seed, 40 to 57% by weight of alkyl acrylate rubber core, and 35 to 52% by weight of copolymer shell. In this case, compatibility with the matrix resin is improved, and there are advantages such as excellent improvements in moldability, impact strength, and gloss.

[0043] The polymer seed may, for example, comprise an alkyl acrylate, an aromatic vinyl compound, and a vinyl cyan compound, and preferably comprises an alkyl acrylate. In this case, there is an advantage in that it has excellent effects of improving moldability, impact strength, tensile strength, heat resistance, and colorability.

[0044] As another example, the polymer seed may comprise one or more compounds selected from the group consisting of alkyl methacrylate, aromatic vinyl compound, and vinyl cyan compound, preferably aromatic vinyl compound and vinyl cyan compound. Specifically, based on the total weight of the polymer seed, the polymer seed may comprise 50 to 90 wt% of aromatic vinyl compound and 10 to 50 wt% of vinyl cyan compound, preferably 55 to 85 wt% of aromatic vinyl compound and 15 to 45 wt% of vinyl cyan compound, more preferably 60 to 80 wt% of aromatic vinyl compound and 20 to 40 wt% of vinyl cyan compound. Within these ranges, there are advantages in that appearance quality, such as gloss and colorability, mechanical properties, and moldability are further improved.

[0045] The polymer seeds of the graft copolymer (A) may have an average particle size of, for example, 40 to 140 nm, preferably 50 to 100 nm, and more preferably 60 to 90 nm. In this case, the average particle size of the polymer seeds is smaller than the average particle size of the rubber core surrounding them, and within this range, there is an advantage in that the moldability, impact strength, tensile strength, heat resistance, and colorability are even more excellent.

[0046] The rubber core of the graft copolymer (A) may have an average particle size of, for example, 60 to 200 nm, preferably 65 to 170 nm, more preferably 70 to 150 nm, and even more preferably 80 to 120 nm, and preferably 100 to 150 nm. In this case, the average particle size of the rubber core, when it contains the polymer seeds, is larger than the average particle size of the polymer seeds. Within this range, there are advantages such as even better moldability, impact strength, tensile strength, heat resistance, and colorability.

[0047] In this description, the average particle size of the rubber core means the average particle size including the seeds, if the seeds are included.

[0048] The graft shell of the graft copolymer (A) may, for example, comprise 85 to 99% by weight of an aromatic vinyl compound and 1 to 15% by weight of a vinyl cyan compound, preferably 85 to 98% by weight of an aromatic vinyl compound and 2 to 15% by weight of a vinyl cyan compound, and more preferably 90 to 98% by weight of an aromatic vinyl compound and 2 to 10% by weight of a vinyl cyan compound. Within these ranges, there are advantages in that the molding processability, impact strength, and gloss are further improved.

[0049] The graft shell of the graft copolymer (A) may have a weight average molecular weight of, for example, 100,000 to 400,000 g / mol, preferably 110,000 to 395,000 g / mol, more preferably 120,000 to 350,000 g / mol, and even more preferably 130,000 to 300,000 g / mol. Within this range, there are advantages such as even better moldability, impact strength, and gloss.

[0050] In this description, alkyl (meth)acrylates can be defined as a range that includes both alkyl acrylates and alkyl methacrylates.

[0051] In the present description, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, preferably one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, more preferably an alkyl acrylate containing an alkyl group having 1 to 4 carbon atoms, even more preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof, and even more preferably butyl acrylate.

[0052] In the present description, the alkyl methacrylate may be, for example, an alkyl methacrylate having an alkyl group with 1 to 15 carbon atoms, preferably one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, more preferably an alkyl methacrylate containing an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl methacrylate.

[0053] In the present description, the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably styrene.

[0054] In the present description, the vinyl cyanide compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, and preferably acrylonitrile.

[0055] The graft copolymer (A) may have a graft ratio of, for example, 20% or more, preferably 20 to 100%, more preferably 25 to 80%, even more preferably 30 to 70%, and even more preferably 30 to 60%. Within this range, the graft copolymer has excellent mechanical properties such as impact resistance, while also exhibiting excellent weather resistance.

[0056] As a specific example of the graft ratio described herein, 30 g of acetone is added to 0.5 g of graft copolymer powder, and the mixture is stirred at room temperature at 210 rpm for 12 hours (SKC-6075, Lab Companion). The mixture is then centrifuged at 18,000 rpm for 3 hours at 0°C using a centrifuge (Supra R30, Hanil Science). Only the insoluble matter (gel) that did not dissolve in acetone is collected, and the collected matter is dried at 85°C for 12 hours using a forced circulation method (OF-12GW, Lab Companion), after which the weight is measured and the result can be calculated using the following equation 1.

[0057] [Formula 1] Graft rate (%) = [weight of grafted monomer (g) / weight of rubber (g)] × 100

[0058] In Equation 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 weight (g) of the rubbery material, and the weight (g) of the rubbery material is the weight (g) of the rubbery component theoretically added to the graft copolymer powder.

[0059] The method for producing the graft copolymer (A) may, for example, include the steps of: i) preparing an alkyl acrylate rubber core by adding an alkyl acrylate; and ii) preparing a graft copolymer by adding an aromatic vinyl compound and a vinyl cyan compound and graft polymerizing them in the presence of the rubber core. In this case, the graft copolymer has advantages such as excellent moldability, impact strength, and gloss.

[0060] The method for producing the graft copolymer (A) preferably includes the steps of: i) polymerizing 40 to 70% by weight of an alkyl acrylate with a crosslinking agent, an initiator, and an emulsifier, based on a total of 100% by weight, to produce a rubber core; and ii) graft polymerizing 30 to 60% by weight of an aromatic vinyl compound and a vinyl cyan compound with a crosslinking agent, an initiator, and an emulsifier in the presence of the rubber core, to produce a graft copolymer. In this case, the graft copolymer has advantages such as excellent moldability, impact strength, and gloss.

[0061] The method for producing the graft copolymer (A) may, for example, include the steps of: i) preparing a polymer seed containing at least one selected from the group consisting of alkyl (meth)acrylate, aromatic vinyl compound, and vinyl cyan compound; ii) preparing an alkyl acrylate rubber core containing alkyl acrylate in the presence of the polymer seed; and iii) preparing a graft copolymer by graft polymerizing an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core. In this case, the graft copolymer has advantages such as excellent moldability, impact strength, and gloss.

[0062] The method for producing the graft copolymer (A) preferably includes the steps of: i) polymerizing 1 to 20% by weight of one or more selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, and vinyl cyan compounds with an electrolyte, a crosslinking agent, an initiator, and an emulsifier to produce a polymer seed; ii) polymerizing 35 to 65% by weight of an alkyl acrylate with a crosslinking agent, an initiator, and an emulsifier in the presence of the polymer seed to produce a rubber core; and iii) graft polymerizing 30 to 60% by weight of an aromatic vinyl compound and a vinyl cyan compound with a crosslinking agent, an initiator, and an emulsifier in the presence of the rubber core to produce a graft copolymer, which has the advantages of excellent moldability, impact strength, and gloss.

[0063] In this description, the content of a monomer in a polymer may refer to the weight % of the monomer added when the polymer is produced, or the weight % of the unit in the polymer converted to the monomer.

[0064] The emulsifier used in each of the polymer seed production step (when a polymer seed is included), the rubber core production step, and the copolymer shell production step is not particularly limited as long as it is an emulsifier commonly used in the technical field to which the present invention pertains, and may be, for example, one or more selected from the group consisting of a metal salt of alkyl sulfosuccinate having 12 to 18 carbon atoms or a derivative thereof, an alkyl sulfate ester having 12 to 20 carbon atoms or a derivative thereof, a metal salt of alkyl sulfonate having 12 to 20 carbon atoms or a derivative thereof, a fatty acid soap, and a rosin acid soap.

[0065] The metal salt of alkyl sulfosuccinate 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.

[0066] The alkyl sulfate 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 dodecylbenzene sulfate, sodium octadecyl sulfate, sodium oleate sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate.

[0067] The fatty acid soap may preferably be one or more selected from the group consisting of sodium salts or potassium salts of oleic acid, stearic acid, lauric acid, and mixed fatty acids.

[0068] The rosin acid soap may preferably be an abietic acid salt, specifically a metal abietic acid salt.

[0069] The emulsifiers can be used in an amount of, for example, 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 1 to 3 parts by weight, based on a total of 100 parts by weight of the graft copolymer (A).

[0070] The initiator is not particularly limited, but a radical initiator can be preferably used.

[0071] The radical initiator may be, for example, one or more selected from the group consisting of inorganic peroxides, organic peroxides, peroxyketal peroxides, peroxycarbonate peroxides, and azo compounds.

[0072] The inorganic peroxide may preferably be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide.

[0073] Examples of the organic peroxide include t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, di-t-amyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)-cyclohexane, 1,1-di(t-amylperoxide), (iii)-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-butylperoxy-3,3,5-trimethylhexanoyl, t-amyl peroxyneo Decanoate, t-amyl peroxypivalate, 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 peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, The peroxide may be one or more selected from the group consisting of 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, di-2-ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxyisobutyrate.

[0074] The peroxyketal peroxide may preferably be one or more selected from the group consisting of 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, ethyl-3,3-di(t-butylperoxy)butyrate, and ethyl-3,3-di(t-amylperoxy)butyrate.

[0075] The peroxycarbonate peroxide may preferably be at least one selected from the group consisting of dicumyl peroxide, di(t-butylperoxy)-m / p-diisopropylbenzene, 2,5-dimethyl-2,5-(t-butylperoxy)hexane, t-butylcumyl peroxide, dialkyl peroxides such as 2,5-methyl-2,5-(t-butylperoxy)hexyne-3, t-butylperoxy 2-ethylhexyl monocarbonate, and t-butylperoxybenzoate.

[0076] The azo compound may preferably be at least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate (butyrate).

[0077] In at least one of the steps of preparing the polymer seed (if the polymer seed is included), preparing the rubber core, and preparing the copolymer shell, an oxidation-reduction catalyst may be used together with the initiator to further promote the initiation reaction.

[0078] The oxidation-reduction catalyst may be, for example, one or more selected from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediaminetetraacetate, and preferably may be a mixture of sodium pyrophosphate, dextrose, and ferrous sulfide, but is not limited thereto.

[0079] In at least one of the steps of preparing the polymer seed (if the polymer seed is included), preparing the rubber core, and preparing the copolymer shell, an activator may be used together with the polymerization initiator to promote the initiation reaction of the peroxide.

[0080] The activator is not particularly limited as long as it is an activator commonly used in the technical field to which the present invention pertains.

[0081] The 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 a total of 100 parts by weight of the (A) graft copolymer, and within this range, there is an advantage that a high degree of polymerization can be achieved.

[0082] The electrolyte may be, for example, one or more selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO4, Na2S2O7, K3P2O7, K3PO4, Na3PO4, KOH, NaOH, and Na2HPO4, but is not limited thereto.

[0083] The electrolyte may be added in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total of the graft copolymer (A). Within this range, there is an advantage that a high degree of polymerization can be achieved.

[0084] In this description, unless otherwise defined, the crosslinking agent is not particularly limited as long as it is a crosslinking agent commonly used in the technical field to which the present invention pertains. For example, one or more compounds containing an unsaturated vinyl group and capable of functioning as a crosslinking agent, or compounds containing unsaturated vinyl groups having two or more different reactivities may be used. Specific examples include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexane ...

[0039] It is clearly stated that the hydroxybenzoate may be one or more selected from the group consisting of, but is not limited to, pentaerythritol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropane ethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallylamine, and diallylamine.

[0085] The crosslinking agent can be used in an amount of, for example, 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.1 to 1 part by weight, based on a total of 100 parts by weight of the graft copolymer (A).

[0086] In the copolymer shell preparation step, for example, a molecular weight modifier may be used.

[0087] The amount of the molecular weight modifier 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 of the (A) graft copolymer, and within this range, a polymer having the target molecular weight can be easily produced.

[0088] The 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, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanthogen disulfide, but is not limited thereto.

[0089] In this description, 100 parts by weight of the graft copolymer means 100 parts by weight of the total weight of the final graft copolymer, or, since almost all of the added monomers participate in the polymerization, it can conveniently mean the combined weight of all the monomers used in the polymer seed (if polymer seed is included), rubber core, and graft shell, or the combined weight of all the monomers added during the preparation of the polymer seed (if polymer seed is included) and rubber core and the graft shell, which is 100 parts by weight.

[0090] In this description, % means % by weight unless otherwise specified.

[0091] In the step of preparing the seeds and cores, the monomer may be added in one batch or continuously, or the two methods may be used in combination.

[0092] In this description, "continuous addition" means not "added all at once" and refers to addition, for example, drop by drop, little by little, step by step, or continuous flow, for 10 minutes or more, 30 minutes or more, 1 hour or more, preferably 2 hours or more within the polymerization reaction time.

[0093] The graft copolymer (A) may be produced by emulsion polymerization, for example, and in this case, it has the effect of being excellent in chemical resistance, weather resistance, fluidity, tensile strength, and impact strength.

[0094] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and specifically may be emulsion graft polymerization.

[0095] The polymerization temperature during the emulsion polymerization is not particularly limited, but may be, for example, 50 to 85°C, and preferably 60 to 80°C.

[0096] The latex formed after polymerization of the graft copolymer (A) can be obtained in the form of powder through, for example, common processes such as coagulation, washing, and drying. Specifically, the latex can be prepared in the form of powder through processes of adding a metal salt or an acid, coagulating at a temperature of 60 to 100°C, aging, dehydrating, washing, and drying, but is not limited thereto.

[0097] The graft copolymer (A) may be, for example, a commercially available product as long as it complies with the definition of the present invention.

[0098] (B) Matrix resin For example, the (B) matrix resin may be contained in an amount of 35 to 80% by weight or 40 to 80% by weight, preferably 40 to 75% by weight, more preferably 42 to 70% by weight, and even more preferably 45 to 65% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, by containing a certain level or more of recycled resin, there are advantages in that the resin is environmentally friendly, while also providing excellent moldability, impact strength, tensile strength, and heat resistance.

[0099] For example, the (B) matrix resin may be contained in an amount of 48 to 60% by weight, preferably 45 to 60% by weight, and more preferably 50 to 60% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, there are advantages such as even better environmental friendliness, moldability, tensile strength, and heat resistance.

[0100] For example, the (B) matrix resin may be contained in an amount of 40 to 55% by weight, preferably 40 to 52% by weight, and more preferably 40 to 50% by weight, relative to 100% by weight of the total of the (A) graft copolymer and the (B) matrix resin. In this case, there is an advantage that the impact strength and colorability are further improved.

[0101] The recycled polystyrene refers to a recycled resin of polystyrene (PS), which is a polymer derived from an aromatic vinyl compound.

[0102] The recycled polystyrene is, for example, a general purpose polystyrene (GPPS) resin. To fat In this case, even if conventional virgin polystyrene is replaced with the recycled resin, there is an advantage that the recycled resin provides physical properties equivalent to or exceeding those of virgin polystyrene.

[0103] The general-purpose polystyrene resin may be, for example, a homopolymer of an aromatic vinyl compound, preferably styrene.

[0105] The (B) matrix resin may contain, for example, 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide, relative to a total of 100% by weight, and preferably 50 to 85% by weight of recycled polystyrene and 9 to 50% by weight of polyarylene oxide, or 50 to 80% by weight of recycled polystyrene and 10 to 48% by weight of polyarylene oxide, or 50 to 70% by weight of recycled polystyrene and 12 to 47% by weight of polyarylene oxide. Within these ranges, there are advantages in that the molding processability, impact strength, tensile strength, and heat resistance are all excellent.

[0106] For example, the (B) matrix resin may contain, relative to a total of 100% by weight, 50 to 68% by weight of recycled polystyrene and 25 to 50% by weight of polyarylene oxide, preferably 50 to 67% by weight of recycled polystyrene and 30 to 50% by weight of polyarylene oxide, or 50 to 65% by weight of recycled polystyrene and 35 to 50% by weight of polyarylene oxide. Within these ranges, there are advantages such as improved impact strength, tensile strength, heat resistance, and colorability without any deterioration in other physical properties.

[0107] As a specific example, the composition may contain 50 to 90% by weight of recycled polystyrene and 10 to 50% by weight of polyarylene oxide, preferably 50 to 85% by weight of recycled polystyrene and 15 to 50% by weight of polyarylene oxide, more preferably 52 to 80% by weight of recycled polystyrene and 20 to 48% by weight of polyarylene oxide, and even more preferably 53 to 70% by weight of recycled polystyrene and 30 to 47% by weight of polyarylene oxide. By containing a certain level or more of recycled resin within these ranges, the composition has the advantages of being environmentally friendly while also having excellent moldability, impact strength, tensile strength, heat resistance, and colorability.

[0108] In this description, resins not designated as regenerated or virgin can refer to preferably virgin resins, although both are possible.

[0109] The matrix resin (B) may contain, for example, virgin general-purpose polystyrene, which has the advantage of being more excellent in moldability, impact strength, tensile strength, and heat resistance.

[0110] For example, the (B) matrix resin may contain, relative to its total weight, 50 to 90% by weight of recycled polystyrene, 8 to 45% by weight of polyarylene oxide, and 0 to 30% by weight of virgin general-purpose polystyrene. A specific example is 50 to 90% by weight of recycled polystyrene, 8 to 45% by weight of polyarylene oxide, and 1 to 30% by weight of virgin general-purpose polystyrene, preferably 50 to 85% by weight of recycled polystyrene, 10 to 45% by weight of polyarylene oxide, and 2 to 28% by weight of general-purpose polystyrene, more preferably Preferably, the composition may contain 50 to 75% by weight of recycled polystyrene, 13 to 42% by weight of polyarylene oxide, and 3 to 27% by weight of general-purpose polystyrene, more preferably 50 to 70% by weight of recycled polystyrene, 15 to 40% by weight of polyarylene oxide, and 3 to 27% by weight of general-purpose polystyrene, and even more preferably 50 to 65% by weight of recycled polystyrene, 15 to 40% by weight of polyarylene oxide, and 5 to 25% by weight of general-purpose polystyrene, and within these ranges, there is an advantage in that the moldability and balance of physical properties are even better.

[0111] For example, the (B) matrix resin may further contain an aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter referred to as "SAN-based resin") containing 70 to 95% by weight of an aromatic vinyl compound and 5 to 30% by weight of a vinyl cyan compound. In this case, there is an advantage that the mechanical rigidity and weather resistance are even more excellent.

[0112] As a specific example, the SAN-based resin may be contained in an amount of 1 to 15 wt %, preferably 1 to 13 wt %, more preferably 2 to 12 wt %, even more preferably 2 to 10 wt %, and even more preferably 3 to 10 wt %, relative to a total of 100 wt % of the matrix resin (B). In this case, there is an advantage that the mechanical rigidity and weather resistance are further improved without deteriorating other physical properties.

[0113] The aromatic vinyl compounds contained in the recycled polystyrene and the virgin general-purpose polystyrene may be appropriately selected from the aromatic vinyl compounds mentioned in the copolymer (A), and may preferably be styrene.

[0114] The general-purpose polystyrene may be, for example, a homopolymer of styrene.

[0115] The polystyrene can be produced by any method commonly used in the technical field of the present invention. For example, an aromatic vinyl compound can be produced by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof. The polymerization can be thermal polymerization or polymerization in the presence of a polymerization initiator. The polymerization initiator can be, for example, a peroxide initiator, an azo initiator, or a mixture thereof. The peroxide initiator can be preferably at least one selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide. The azo initiator can be preferably azobisisobutyronitrile.

[0116] The recycled polystyrene may include, for example, recycled expanded polystyrene (EPS). The recycled polystyrene may include, for example, recycled non-expanded polystyrene alone; recycled expandable polystyrene alone; or a mixture of recycled non-expanded polystyrene and recycled expandable polystyrene. In this case, there is an advantage that a recycled resin composition having desired physical properties can be provided by using recycled polystyrene, regardless of whether the recycled polystyrene is expanded or not.

[0117] As a specific example, the recycled polystyrene may contain 0 to 100% by weight of recycled non-expanded polystyrene and 0 to 100% by weight of recycled expanded polystyrene, based on a total of 100% by weight. More specifically, the recycled polystyrene may contain 30 to 80% by weight of recycled non-expanded polystyrene and 20 to 70% by weight of recycled expanded polystyrene, preferably 40 to 75% by weight of recycled non-expanded polystyrene and 25 to 60% by weight of recycled expanded polystyrene, and more preferably 45 to 75% by weight of recycled non-expanded polystyrene and 25 to 55% by weight of recycled expanded polystyrene, and within these ranges, there are advantages in that, despite containing recycled resins, the molding processability, impact strength, tensile strength, and heat resistance are even more excellent.

[0118] Expanded polystyrene is chemically or physically foamed to contain air inside, providing heat insulation and cushioning properties, and is mainly used as a heat-insulating / cushioning packaging material and building insulation material.

[0119] The expandable polystyrene is not particularly limited as long as it is generally recognized as expandable polystyrene in the technical field to which the present invention pertains. As a specific example, when a foaming agent is contained in polystyrene, expanded polystyrene containing 0.2 to 10 wt % of the foaming agent based on the total weight of the polystyrene may be used.

[0120] The foamed polystyrene is not particularly limited as long as it can be produced by a method commonly used in the technical field to which the present invention pertains. As a specific example, the foamed polystyrene may be produced by a foaming process containing a melt of a polymer constituting the foamed polystyrene and a foaming agent.

[0121] In the case of using the expanded polystyrene, for example, a separate volume reduction process may be performed to reduce the expanded volume, or a commercially available volume-reduced product may be used, which has the advantage of further improving manufacturing efficiency.

[0122] The recycled polystyrene may have a weight average molecular weight of, for example, 100,000 to 400,000 g / mol, preferably 110,000 to 350,000 g / mol, more preferably 130,000 to 300,000 g / mol, and even more preferably 150,000 to 280,000 g / mol. Within this range, the recycled polystyrene has the effect of providing excellent balance of physical properties and impact resistance.

[0123] For example, the recycled polystyrene may have a glass transition temperature of 80 to 180°C, preferably 85 to 170°C, and more preferably 90 to 160°C. Within this range, the recycled polystyrene has the effect of providing even better mechanical properties and moldability.

[0124] In this description, the glass transition temperature (Tg) can be measured, for example, in accordance with ASTM D 3418 using a differential scanning calorimetry (DSC, manufactured by TA Instruments, model Q100) at a heating rate of 10°C / min.

[0125] For example, the recycled polystyrene may have a flow index of 20 to 60 g / 10 min, preferably 30 to 55 g / 10 min, and more preferably 40 to 50 g / 10 min, measured in accordance with ASTM D1238 at a temperature of 220°C under a load of 10 kg. Within this range, the recycled polystyrene has the effect of exhibiting excellent moldability and a good balance of physical properties.

[0126] As the recycled polystyrene, for example, commercially available products can be used as long as they comply with the definition of the present invention.

[0127] The weight average molecular weight, glass transition temperature, flow index, etc. of the general-purpose polystyrene may be appropriately selected within the same range as that of the recycled polystyrene.

[0128] The polyarylene oxide may be a recycled or virgin polyarylene oxide, preferably a virgin polyarylene oxide, and may be, for example, a homopolymer or copolymer of aromatic arylene oxide units, preferably polyphenylene oxide (PPO).

[0129] Specific examples of the homopolymer of aromatic arylene oxide units include poly(2,6-dimethyl-1,4-phenylene oxide), poly(2,6-diethyl-1,4-phenylene oxide), poly(2,6-dipropyl-1,4-phenylene) oxide, poly(2-methyl-6-ethyl-1,4-phenylene) oxide, poly(2-methyl-6-propyl-1,4-phenylene oxide), poly(2-ethyl-6-propyl-1,4-phenylene) oxide, poly(2,5-dimethyl-1,4-phenylene oxide), poly( The poly(2,6-diphenyl-1,4-phenylene)oxide may include one or more selected from the group consisting of poly(2,3,6-trimethyl-1,4-phenylene)oxide, poly(2,3,6-triethyl-1,4-phenylene)oxide, poly(2,6-dimethoxy-1,4-phenylene oxide), poly(2,6-dichloromethyl-1,4-phenylene oxide), poly(2,6-dibromomethyl-1,4-phenylene oxide), and poly(2,6-diphenyl-1,4-phenylene)oxide, and preferably poly(2,6-dimethyl-1,4-phenylene oxide).

[0130] The copolymer of aromatic arylene oxide units refers to a polymer in which a comonomer is copolymerized with an aromatic arylene oxide unit as a main monomer. A specific example thereof may be selected from the group consisting of a copolymer of poly(2,6-dimethyl-1,4-phenylene) oxide and poly(2,3,6-trimethyl-1,4-phenylene) oxide; a copolymer of poly(2,6-dimethyl-1,4-phenylene) oxide and poly(2,3,6-triethyl-1,4-phenylene) oxide; and combinations thereof. A preferred example thereof may be a copolymer of poly(2,6-dimethyl-1,4-phenylene) oxide and poly(2,3,6-trimethyl-1,4-phenylene) oxide.

[0131] The polyarylene oxide may have a number average molecular weight of, for example, 10,000 to 100,000 g / mol, preferably 10,000 to 70,000 g / mol, and more preferably 15,000 to 45,000 g / mol. Within this range, there is an advantage in that the balance between processability and physical properties is even better.

[0132] In the present description, the number average molecular weight may be calculated as a number average value, although it is measured in the same manner as the weight average molecular weight, as a specific example.

[0133] The polyarylene oxide may have an intrinsic viscosity of, for example, 0.15 to 0.6 dL / g, preferably 0.2 to 0.5 dL / g, more preferably 0.2 to 0.4 dL / g, and even more preferably 0.25 to 0.4 dL / g. Within this range, the composition has the advantage of having a better balance of physical properties, such as mechanical strength and moldability.

[0134] In this description, unless otherwise specified, the intrinsic viscosity can be measured at 25°C using an Ubbelohde viscometer after dissolving the sample to be measured in chloroform solvent at a concentration of 0.5 g / dl.

[0135] The polyarylene oxide may be produced by, for example, a production method commonly used in the technical field to which the present invention pertains, and commercially available products may also be used as long as they comply with the definition of the present invention.

[0136] The SAN resin may be a recycled or virgin SAN resin, preferably a virgin SAN resin. For example, the SAN resin may contain 70 to 95% by weight of an aromatic vinyl compound and 5 to 30% by weight of a vinyl cyan compound, preferably 70 to 90% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyan compound, and more preferably 80 to 90% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyan compound. In this case, there is an advantage that the fluidity and impact strength are further improved without deteriorating other physical properties.

[0137] The aromatic vinyl compound and vinyl cyan compound contained in the SAN-based resin can be appropriately selected from the aromatic vinyl compound and vinyl cyan compound mentioned in the graft copolymer (A), respectively.

[0138] The SAN resin may have a weight average molecular weight of, for example, 70,000 to 200,000 g / mol, preferably 80,000 to 180,000 g / mol, and more preferably 90,000 to 160,000 g / mol. Within this range, the resin has the advantage of being even more excellent in mechanical strength and weather resistance.

[0139] The SAN-based resin may be produced by a production method commonly used in the technical field to which the present invention pertains, and commercially available products may also be used as long as they comply with the definition of the present invention.

[0140] (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer having a rubber core with an average particle size of more than 200 nm and not more than 500 nm; The thermoplastic resin composition may, for example, comprise an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as "(C) graft copolymer"), which includes an alkyl acrylate rubber core having an average particle size of more than 200 nm and not more than 500 nm and containing an alkyl acrylate compound; and an aromatic vinyl compound-vinyl cyan compound copolymer shell surrounding the alkyl acrylate rubber core and containing an aromatic vinyl compound and a vinyl cyan compound. In this case, there are advantages such as even more excellent moldability, impact strength, tensile strength, and heat resistance.

[0141] The (C) graft copolymer may be included in an amount of, for example, 0 to 12 parts by weight, specifically 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 2 to 8 parts by weight, based on 100 parts by weight of the total of the (A) graft copolymer and the (B) recycled polystyrene. Within this range, there are advantages such as excellent fluidity and gloss without deterioration of other physical properties.

[0142] The average particle size of the alkyl acrylate rubber core contained in the (C) graft copolymer may be, for example, more than 200 nm and not more than 500 nm, preferably 205 to 500 nm, more preferably 210 to 490 nm, even more preferably 250 to 450 nm, and even more preferably 300 to 430 nm. In this case, there are advantages in that the moldability, impact strength, tensile strength, and heat resistance are all excellent.

[0143] The (C) graft copolymer may, for example, contain 30 to 70% by weight of the alkyl acrylate rubber core and 30 to 70% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer shell relative to its total weight, preferably 35 to 65% by weight of the alkyl acrylate rubber core and 35 to 65% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer shell, and more preferably 40 to 60% by weight of the alkyl acrylate rubber core and 40 to 60% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer shell, in which case the copolymer has the advantages of excellent moldability, impact strength, tensile strength and heat resistance.

[0144] The aromatic vinyl compound-vinyl cyan compound copolymer shell contained in the graft copolymer (C) may, for example, contain 50 to 99% by weight of the aromatic vinyl compound and 1 to 50% by weight of the vinyl cyan compound, preferably 60 to 90% by weight of the aromatic vinyl compound and 10 to 40% by weight of the vinyl cyan compound, and more preferably 65 to 80% by weight of the aromatic vinyl compound and 20 to 35% by weight of the vinyl cyan compound. In this case, the advantages of excellent moldability, impact strength, and gloss are obtained.

[0145] The alkyl acrylate, aromatic vinyl compound, and vinyl cyanide compound contained in the graft copolymer (C) can be appropriately selected from the ranges mentioned for the graft copolymer (A).

[0146] The graft copolymer (C) can be produced by, for example, a production method commonly applied in the technical field to which the present invention pertains, and commercially available products can also be used as long as they comply with the definition of the present invention.

[0147] (D) Light stabilizer The thermoplastic resin composition may contain, for example, (D) a light stabilizer. Specifically, the light stabilizer may be contained in an amount of 0.1 to 7 parts by weight, preferably 0.3 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 1 to 2 parts by weight, based on 100 parts by weight of the total of the (A) graft copolymer and the (B) matrix resin. Within this range, there is an advantage that the weather resistance is further improved without deteriorating other physical properties.

[0148] The (D) light stabilizer may include, for example, one or more selected from the group consisting of triazine-based compounds, benzophenone-based compounds, benzotriazole-based compounds, indole-based compounds, quinolinone-based compounds, benzoate-based compounds, cyanoacrylate-based compounds, and amine-based compounds. Preferably, the (D) light stabilizer may be a benzotriazole-based UV absorber or an amine-based compound. In this case, the light stabilizer has an excellent balance of physical properties and further improved light resistance.

[0149] Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 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-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-octyloxyphenyl)-1,3,5-triazine -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 )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol.

[0150] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4- The compound may be one or more selected from the group consisting of methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0151] Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-2'-hydroxy-3',2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenyl-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy The compound may be one or more selected from the group consisting of 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 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.

[0152] The indole-based ultraviolet absorber may be, for example, 2-[(1-methyl-2-phenyl-1H-indol-3-yl)methylene]propanedinitrile.

[0153] The quinolinone ultraviolet absorber may be, for example, 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

[0154] The benzoate-based ultraviolet absorber may be, for example, one or more 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.

[0155] The cyanoacrylate-based ultraviolet absorber may be, for example, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate, or a mixture thereof.

[0156] The amine-based UV absorber may be, for example, a hindered amine light stabilizer (HALS), and preferably, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, or bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate. , bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, condensation products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2 ,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene linear or cyclic condensation products of hexanediamine with 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 with epichlorohydrin, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,The compound may be one or more selected from the group consisting of bis(2,2,6,6-tetramethyl-4-piperidinyl)imino, and preferably bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

[0157] thermoplastic resin composition The thermoplastic resin composition contains the (A) graft copolymer and the (B) matrix resin. In this case, the inclusion of recycled resins provides the advantages of being environmentally friendly and of being excellent in all of moldability, impact strength, tensile strength, heat resistance, and colorability.

[0158] As an example, the thermoplastic resin composition may contain the (A) graft copolymer, the (B) matrix resin, and one or more selected from the group consisting of the (C) graft copolymer and the (D) light stabilizer. In this case, there are advantages such as further excellent molding processability, impact strength, and gloss.

[0159] As an example, the thermoplastic resin composition may contain, relative to 100 parts by weight of the total of the (A) graft copolymer and the (B) matrix resin, 0 to 12 parts by weight or 0.1 to 12 parts by weight of the (C) graft copolymer; and 0 to 7 parts by weight or 0.1 to 7 parts by weight of the (D) light stabilizer. In this case, the inclusion of recycled resins offers the advantages of being environmentally friendly and of being excellent in all of moldability, impact strength, tensile strength, heat resistance, and colorability.

[0160] The thermoplastic resin composition may have a heat distortion temperature (HDT) of 82°C or higher, preferably 82 to 120°C, more preferably 82 to 115°C, and even more preferably 83 to 110°C, as measured under a load of 18.5 kgf in accordance with ASTM D 648, and specifically may have a HDT of 87 to 110°C or 88 to 105°C. Within this range, there is an advantage that the heat resistance is further improved without any deterioration in other physical properties.

[0161] The thermoplastic resin composition has, for example, a tensile strength of 400 kgf / cm2 measured at room temperature at a speed of 50 mm / min in accordance with ASTM D 638. 2 or more, preferably 400 to 530 kgf / cm 2 , more preferably 400 to 520 kgf / cm 2 , and more preferably 400 to 510 kgf / cm 2 A specific example is 405 to 520 kgf / cm 2 , or 410~510kgf / cm 2 Within this range, there is an advantage that the tensile strength is further improved without deteriorating other physical properties.

[0162] For example, the thermoplastic resin composition may have a flow index of 6 g / 10 min or more, preferably 6 to 30 g / 10 min, more preferably 6 to 25 g / 10 min, and even more preferably 6 to 22 g / 10 min, as measured in accordance with ASTM D1238 at a temperature of 230°C under a load of 10 kg. A flow index within this range has the advantage of providing even better moldability without any deterioration in other physical properties.

[0163] For example, the thermoplastic resin composition may have an impact strength of 10 kgf·cm / cm or more, preferably 10 to 30 kgf·cm / cm, more preferably 10 to 25 kgf·cm / cm, and even more preferably 10 to 20 kgf·cm / cm, as measured at room temperature and at a thickness of 1 / 4 inch in accordance with ASTM D1238. Within this range, there is an advantage that the impact strength is even better without deteriorating other physical properties.

[0164] In this description, normal temperature may be a point within the range of 23±3°C.

[0165] For example, the thermoplastic resin composition may have a colorability C / S value derived from the L and b values ​​measured in accordance with the CIE Lab method of 103 or more, preferably 103 to 120, more preferably 103 to 115, and even more preferably 103 to 110. Within this range, there is an advantage that the colorability is further improved without deteriorating other physical properties.

[0166] In this description, color strength is measured using an X-lite Color-eye 7000A device under a UV D65 light source at a 10° Degree Observer angle in accordance with the CIE Lab method, and L and b values ​​are obtained in the Reflectance Mode according to the CIE Lab method in accordance with the Munsell System. The measured L and b values ​​are then automatically calculated as a color strength (C / S) value based on a formula incorporated in the software for Propalett Paint / Plastics Formulation Platinum 5.2.5.1 by GretagMacbeth LLC. Here, the C / S value is based on 100, and a value greater than 100 indicates excellent color strength, with the higher the value, the better the color strength.

[0167] For reference, in the CIE LAB color coordinate system, L is expressed as a number from 0 to 100, with values ​​closer to 0 indicating black and values ​​closer to 100 indicating white, the a value indicating the red-green value, and the b value indicating the yellow-blue value.

[0168] Method for producing thermoplastic resin composition The thermoplastic resin composition of the present invention comprises a step of kneading and extruding (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber core having an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyan compound copolymer shell, and (B) a matrix resin, under conditions of 180 to 300°C and 100 to 400 rpm, wherein the copolymer shell of the (A) graft copolymer comprises, relative to its total weight, 85 to 99% by weight of the aromatic vinyl compound and 1 to 15% by weight of the vinyl cyan compound, and has a weight-average molecular weight of 100,000 to 400,000 g / mol, and the (B) matrix resin comprises, relative to its total weight, 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide. In this case, the inclusion of recycled resins offers the advantages of being environmentally friendly and of being excellent in moldability, impact strength, tensile strength, heat resistance, and colorability.

[0169] For example, the kneading and extruding step may include kneading and extruding at least one selected from the group consisting of (A) a graft copolymer, (B) a matrix resin, and (C) a graft copolymer and (D) a light stabilizer. In this case, the resulting composition has the advantages of excellent moldability, impact strength, tensile strength, heat resistance, and colorability.

[0170] The kneading and extruding steps may be performed using, for example, one or more selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer. Using the extruder, the composition may be uniformly mixed and then extruded to obtain, for example, a pellet-shaped thermoplastic resin composition. In this case, there is an effect of preventing deterioration in mechanical properties and heat resistance and achieving excellent appearance quality.

[0171] The kneading and extrusion steps may be carried out, for example, at a cylinder temperature of the extruder within a range of 180 to 300°C, preferably 210 to 290°C, and more preferably 220 to 280°C. In this case, the processing amount per unit time is appropriate, and melt-kneading is sufficiently carried out, which has the advantage of preventing deterioration of physical properties such as thermal decomposition.

[0172] The kneading and extrusion may be carried out, for example, under conditions where the screw rotation speed is 100 to 400 rpm, preferably 110 to 350 rpm, and more preferably 120 to 270 rpm. In this case, the processing amount per unit time is appropriate, which has the advantage of excellent process efficiency.

[0173] The thermoplastic resin composition may optionally further contain one or more other additives selected from the group consisting of lubricants, heat stabilizers, pigments, release agents, antistatic agents, antibacterial agents, processing aids, smoke suppressants, anti-dripping agents, anti-friction agents, and anti-wear agents in an amount of 0.01 to 10 parts by weight, 0.05 to 7 parts by weight, 0.1 to 5 parts by weight, 0.3 to 4.5 parts by weight, or 0.3 to 4 parts by weight, based on 100 parts by weight of the total of the (A) graft copolymer and the (B) matrix resin. Within this range, there is an advantage that the desired physical properties of the thermoplastic resin composition described herein are well achieved without decreasing the intended physical properties.

[0174] The lubricant may be, for example, one or more selected from the group consisting of fatty acid amide compounds, montan waxes, silicone oils, and olefin waxes, preferably olefin waxes, and more preferably polyethylene waxes. In this case, not only are the molding processability and mold releasability excellent, but also the friction and noise resistance properties can be further improved.

[0175] The fatty acid amide compound may be, for example, at least one selected from the group consisting of stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxy stearamide), erucamide, oleamide, and ethylene bis oleamide.

[0176] The montan wax may be, for example, a montan wax, a montan ester wax, or a mixture thereof.

[0177] The silicone oil may be, for example, one or more selected from the group consisting of dimethyl silicone oil, methyl hydrogen silicone oil, ester-modified silicone oil, hydroxy silicone oil, carbinol-modified silicone oil, vinyl silicone oil, and silicone acrylate.

[0178] The olefin wax may be, for example, an oxidized polyethylene wax, a polyethylene wax, a polypropylene wax, or a mixture thereof.

[0179] The heat stabilizer may include, for example, a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, or a mixture thereof, and preferably 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.

[0180] Examples of the phenolic heat stabilizer include N,N'-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydrocinnamamide], The hydroxybenzyl group may be one or more selected from the group consisting of 3,5-di-t-butyl-4-hydroxybenzyl phosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate. In this case, the heat resistance can be significantly improved while maintaining a high balance of physical properties.

[0181] Examples of the phosphorus-based heat stabilizer include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, and monooctyl diphenyl phosphite. The phosphate group may be one or more selected from the group consisting of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, stearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, and trimethyl phosphate.

[0182] The pigment may be an inorganic pigment or an organic pigment.

[0183] The organic pigment may be, for example, one or more selected from the group consisting of perinone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, indigo pigments, dioxazine pigments, quinacridone pigments, methane pigments, quinoline pigments, isoindolinone pigments, and phthalone pigments.

[0184] The inorganic pigment may be, for example, one or more selected from the group consisting of ultramarine pigments, titanium dioxide, zinc sulfide, tetracyclic zinc, iron oxide, and carbon black.

[0185] The release agent may be, for example, one or more selected from the group consisting of glycerin stearate, polyethylene tetrastearate, etc., but is not limited thereto.

[0186] The antistatic agent may be, for example, one or more of anionic surfactants, nonionic surfactants, etc., but is not limited thereto.

[0187] The anti-dripping 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 (polymethyl methacrylate) (PTFE / PMMA), polyamide, polysilicon, and a TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymer, preferably at least one selected from the group consisting of PTFE / SAN and PTFE / PMMA, more preferably PTFE / SAN. The PTFE / SAN and PTFE / PMMA may be mixed in a weight ratio of 1:0.5 to 1.5, respectively, and in one example, in a weight ratio of 1:1.

[0188] The antibacterial agent, processing aid, smoke suppressant, anti-friction agent, anti-wear agent, etc. are not particularly limited as long as they are commonly used in the technical field to which the present invention pertains.

[0189] molded product The molded article described herein is characterized by containing the thermoplastic resin composition of the present invention. In this case, the inclusion of recycled resins provides the advantages of being environmentally friendly and of being excellent in moldability, impact strength, tensile strength, and heat resistance.

[0190] Even though the molded product contains recycled resin, it has physical properties equivalent to or better than those of conventional virgin resin-based thermoplastic resins, and therefore can be applied without additional processing to various fields where conventional virgin resin-based ASA-based thermoplastic resin compositions are used, such as interior and exterior materials for buildings, interior and exterior materials for automobiles, ships, and leisure and sporting goods.

[0191] As a preferred example, the molded article has a heat distortion temperature (HDT) of 82°C or more measured under a load of 18.5 kgf according to ASTM D 648, a flow index of 6 g / 10 min or more measured under a load of 10 kg at a temperature of 230°C according to ASTM D 1238, an impact strength of 10 kgf·cm / cm or more measured at room temperature and at a thickness of 1 / 4 inch according to ASTM D 256, and a tensile strength of 400 kgf / cm or more measured at room temperature and at a speed of 50 mm / min according to ASTM D 638. 2 As described above, the colorability measured under the above conditions is excellent at 103 or more, and therefore has the advantage of being applicable to fields where excellent moldability, impact strength, tensile strength, heat resistance, and colorability are all required.

[0192] The molded article may be manufactured by a method commonly used in the technical field to which the present invention pertains. For example, the molded article may be manufactured by 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 melt-kneaded product or pellets of the thermoplastic resin composition according to the present invention as a raw material. In this case, the size, thickness, shape, etc. of the molded article may be appropriately adjusted depending on the intended use.

[0193] The molded article can be preferably produced by injecting a melt blend or pellets of the thermoplastic resin composition according to the present invention using an injector at a barrel temperature of 180 to 300°C. The molded article thus produced has the advantage of being applicable to fields where gloss, moldability, and impact strength are all required.

[0194] In describing the thermoplastic resin composition, its manufacturing method, and molded articles described herein, other conditions, equipment, etc. not explicitly described can be appropriately selected within the range commonly used in the art, and are not particularly limited.

[0195] Preferred examples are presented below to aid in understanding the present invention. However, the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical idea of ​​the present invention. Naturally, such changes and modifications also fall within the scope of the appended claims.

[0196] [Example] The materials used in the following examples and comparative examples are as follows. (A) ASA graft copolymer: an ASA graft copolymer comprising a butyl acrylate seed polymer; a butyl acrylate rubber core; and a styrene-acrylonitrile copolymer shell; wherein the average particle size of the seed and core particles, the composition and weight average molecular weight of the shell, etc. satisfy the conditions set forth in Table 1 below (the seed polymer is contained in an amount of 7 wt %, the rubber core in an amount of 43 wt %, and the copolymer shell in an amount of 50 wt %, based on the total weight of the (A) ASA graft copolymer).

[0197] [Table 1] (In Table 1, A-9 does not contain a vinyl cyanide compound, but for ease of comparison, it is classified as (A) ASA graft copolymer, AN means acrylonitrile, Mw means weight average molecular weight, and the AN content of the shell means the weight % of AN relative to the total weight of the shell.)

[0198] (B) Matrix resin: (B-1) Recycled PS resin (non-foamed PS) with Mw 240,000 g / mol (B-2) Recycled EPS resin with Mw of 165,000 g / mol (B-3) Virgin GPPS (LG Chem 25SPI) with a molecular weight of 275,000 g / mol (B-4) PPO: Poly(2,6-dimethyl-1,4-phenylene) oxide (Bluestar LXR035) having an intrinsic viscosity of 0.32 dl / g and a flow index of 28 g / 10 min measured at 220°C under a load of 10 kg in accordance with ASTM D1238. (B-5) SAN resin (LG Chem 82TR SAN) (C) Large particle size ASA resin (LG Chem SA927) containing a butyl acrylate rubber core with an average particle size of 380-500 nm

[0199] Examples 1 to 13 and Comparative Examples 1 to 10 The components (A) to (C) were mixed in the amounts shown in Table 2 below using a super mixer, and extruded into pellets using a twin-screw extruder (screw diameter 26 mm, L / D = 40) under extrusion conditions of a cylinder temperature of 260°C and a screw rotation speed of 200 rpm.

[0200] The prepared thermoplastic resin composition pellets were dried at 80°C for 2 hours or more, and then injection-molded in an injector under the conditions of a barrel temperature of 230°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to prepare test specimens for measuring physical properties. The test specimens were left at room temperature for 48 hours or more, and then the physical properties were measured.

[0201] [Test example] The physical properties of the test specimens prepared in the examples and comparative examples were measured by the following methods, and the results are shown in Table 3 below. *Flow index (g / 10 min): In accordance with ASTM D1238, the weight (g) of the resin that flowed out after melting for 10 minutes at a temperature of 220°C under a load of 10 kg was measured. *Izod impact strength (kgf·cm / cm): Measured at room temperature using 1 / 4" thick injection specimens in accordance with ASTM D256. *Tensile strength (kgf / cm 2 ): Measured at room temperature on 1 / 8" thick injection specimens at a rate of 50 mm / min in accordance with ASTM D 638. *Heat distortion temperature (°C): HDT was measured under a load of 18.5 kgf in accordance with ASTM D648. *Color Strength (C / S): Measurements were made in accordance with the CIE Lab method using an X-lite Color-eye 7000A under a UV D65 light source at a 10° degree observer angle. The L and b values ​​were measured in the Reflectance Mode according to the CIE Lab method in accordance with the Munsell System. The C / S (Color Strength) value was calculated from the measured L and b values ​​using a formula built into the Propalett Paint / Plastics Formulation Platinum 5.2.5.1 software from GretagMacbeth LLC. Here, C / S is based on 100, and better color strength indicates a value greater than 100.

[0202] [Table 2]

[0203] [Table 3]

[0204] Referring to Tables 1 to 3, in the case of Examples 1 to 13 according to the present invention, even though they contain recycled PS, the flow index, impact strength, tensile strength, heat distortion temperature and colorability were equal to or better than those of the comparative examples, confirming that they were all excellent in moldability, mechanical rigidity, heat resistance and colorability.

[0205] On the other hand, in Comparative Examples 1 to 5, in which ASA was used in which the average particle size of the alkyl acrylate rubber contained in the (A) graft copolymer, the content of acrylonitrile contained in the copolymer shell, and the weight-average molecular weight of the copolymer shell were outside the ranges of the present invention, the flow index, impact strength, tensile strength, and / or colorability were reduced, and in Comparative Example 6, in which only GPPS was used instead of PPO as the matrix resin, the mechanical rigidity and heat resistance were significantly reduced. Meanwhile, in Comparative Example 9, even when the recycled resin content was reduced and the ASA content was increased without using PPO, the flow, tensile strength, and heat resistance were poor, confirming that this is not suitable as a replacement for conventional non-recycled resin compositions.

[0206] In addition, Comparative Example 7, which contained an excessive amount of PPO, showed reduced moldability and colorability, despite the recycled resin content being approximately 15% by weight, about half that of the Examples, and Comparative Example 8, which had an insufficient PPO content, showed reduced mechanical rigidity and heat resistance.On the other hand, in Comparative Example 10, although the recycled resin ratio in the total weight of the composition was at the same level as the Examples, the total matrix resin content and the ratios of the components constituting the matrix resin were outside the ranges of the present invention, resulting in a significant reduction in impact strength.

Claims

1. (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber core having an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyanide compound copolymer shell; (B) a matrix resin; the copolymer shell of the graft copolymer (A) comprises, based on the total weight of the graft copolymer, 85 to 99% by weight of an aromatic vinyl compound and 1 to 15% by weight of a vinyl cyan compound, and has a weight average molecular weight of 100,000 to 400,000 g / mol; The (B) matrix resin is a thermoplastic resin composition characterized in that it contains 50 to 90 wt% of recycled polystyrene and 8 to 50 wt% of polyarylene oxide, with the total being 100 wt%.

2. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 20 to 60% by weight of the graft copolymer (A) and 40 to 80% by weight of the matrix resin (B), relative to 100% by weight in total of the graft copolymer (A) and the matrix resin (B).

3. The thermoplastic resin composition according to claim 1, wherein the (A) graft copolymer comprises 40 to 70% by weight of an alkyl acrylate rubber core and 30 to 60% by weight of a copolymer shell, based on a total of 100% by weight of the graft copolymer.

4. The thermoplastic resin composition according to claim 1, wherein the graft copolymer (A) comprises, relative to a total of 100% by weight, 1 to 20% by weight of a polymer seed comprising at least one compound selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, and vinyl cyan compounds, 35 to 65% by weight of an alkyl acrylate rubber core, and 30 to 60% by weight of a copolymer shell.

5. The thermoplastic resin composition according to claim 1, wherein the recycled polystyrene comprises any one selected from the group consisting of recycled non-expanded polystyrene, recycled expanded polystyrene, and mixtures thereof.

6. The thermoplastic resin composition according to claim 1, wherein the recycled polystyrene has a weight average molecular weight of 100,000 to 350,000 g / mol.

7. The thermoplastic resin composition according to claim 1 , wherein the matrix resin (B) further contains virgin polystyrene.

8. 2. The thermoplastic resin composition according to claim 1, wherein the matrix resin (B) further comprises 1 to 15% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 75 to 95% by weight of an aromatic vinyl compound and 5 to 25% by weight of a vinyl cyan compound.

9. The thermoplastic resin composition according to claim 1, characterized in that it comprises (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber core having an average particle size of more than 200 nm and not more than 500 nm, and an aromatic vinyl compound-vinyl cyan compound copolymer shell.

10. The thermoplastic resin composition according to claim 9, wherein the (C) graft copolymer is contained in an amount of 0.1 to 12 parts by weight based on 100 parts by weight of the total of the (A) graft copolymer and the (B) matrix resin.

11. The thermoplastic resin composition according to claim 1, characterized in that it comprises 0.1 to 7 parts by weight of (D) a light stabilizer based on a total of 100 parts by weight of the (A) graft copolymer and the (B) matrix resin.

12. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a heat distortion temperature (HDT) of 82°C or higher, measured under a load of 18.5 kgf in accordance with ASTM D 648.

13. The thermoplastic resin composition has a tensile strength of 400 kgf / cm measured at a speed of 50 mm / min in accordance with ASTM D 638. ２ The thermoplastic resin composition according to claim 1, characterized in that

14. (A) an alkyl acrylate-vinyl cyanide compound graft copolymer having an alkyl acrylate rubber core with an average particle size of 60 to 200 nm and an aromatic vinyl compound-vinyl cyanide compound copolymer shell, and (B) a matrix resin, and kneading and extruding the mixture under conditions of 180 to 300°C and 100 to 400 rpm; A method for producing a thermoplastic resin composition, characterized in that the copolymer shell of the graft copolymer (A) comprises, relative to its total weight, 85 to 99% by weight of an aromatic vinyl compound and 1 to 15% by weight of a vinyl cyan compound, and has a weight-average molecular weight of 100,000 to 400,000 g / mol, and the matrix resin (B) comprises, relative to its total weight, 50 to 90% by weight of recycled polystyrene and 8 to 50% by weight of polyarylene oxide.

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

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