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

Abstract

The present disclosure relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, and more specifically, to a thermoplastic resin composition comprising at least one selected from the group consisting of (A) (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, the composition comprising: (b-2) 100 parts by weight of a base resin containing one or more selected from the group consisting of (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymers; (C) 0.5 to 3.5 parts by weight of one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers, each having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value of 65% by weight or more. According to the present invention, there are provided a thermoplastic resin composition which has excellent mechanical properties, transparency, and weather resistance, and which exhibits reduced change over time due to the excellent weather resistance, excellent color stability, and a beautiful appearance; a method for producing the same; 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. 10-2022-0135356 filed on October 20, 2022, and Korean Patent Application No. 10-2023-0108416, refiled on August 18, 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. More specifically, the present invention relates to a thermoplastic resin composition that is excellent in impact resistance, transparency, and weather resistance, and that exhibits reduced change over time due to the excellent weather resistance, has excellent color stability, and has a beautiful appearance, and is applicable to any of injection molding, extrusion molding, and calendar molding, a method for producing the same, and a molded article containing the same. [Background technology]

[0003] Acrylic film is a highly transparent and weather-resistant material that is typically used as a finishing material to protect materials. As the market becomes more sophisticated, acrylic film is increasingly used to coat the surfaces of outdoor window profiles (W / Ps), which require particularly high weather resistance. Coating methods include wrapping, co-extrusion, and lamination.

[0004] In general, acrylonitrile-styrene-acrylate copolymers (hereinafter referred to as "ASA" resins) containing alkyl (meth)acrylate compounds have excellent physical properties such as processability, impact resistance, chemical resistance, and weather resistance due to the absence of ethylenically unsaturated bonds, and are therefore widely used in various fields such as construction materials, interior and exterior materials for vehicles such as automobiles and motorcycles, electrical and electronic products, as well as ships, leisure goods, and gardening supplies, and demand for them is rapidly increasing.

[0005] ASA resin has the advantages of superior impact strength and chemical resistance compared to acrylic film, and complements its transparency to develop products with a similar level to acrylic resin for finishing materials. However, compared to acrylic film, which is a single material, ASA resin is a multi-component system, and its weather resistance has the problem of changing over time, resulting in a difference in color from its original color due to initial moisture absorption and heat history. This phenomenon occurs due to changes in the internal refractive index of thermoplastic resins, including ASA resin, and rearrangement of the resin's microstructure as it is thermodynamically stabilized.

[0006] Therefore, there is a need to develop a material that can be used as a high-quality finishing material required in the market, has excellent impact resistance, transparency, and weather resistance, and has excellent weather resistance that reduces changes over time, has excellent color stability, and provides a beautiful appearance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent Publication No. 10-2009-0095764 Summary of the Invention [Problem to be solved by the invention]

[0008] In order to solve the above-mentioned problems of the prior art, the present disclosure aims to provide a thermoplastic resin composition that is excellent in impact resistance, transparency, and weather resistance, and that exhibits reduced deterioration over time due to its excellent weather resistance, has excellent color stability, and has a beautiful appearance, and that can be used in any of injection molding, extrusion molding, and calender molding.

[0009] Another object of the present disclosure is to provide a method for producing the thermoplastic resin composition.

[0010] Another object of the present disclosure is to provide a molded article produced from the thermoplastic resin composition.

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

[0012] In order to achieve the above object, I) the present disclosure provides a polymerizable composition comprising (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester polymer. (a) 100 parts by weight of a base resin containing one or more selected from the group consisting of acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymers; (c) 0.5 to 3.5 parts by weight of one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers, each having a molecular weight of 280 to 600 g / mol; and (d) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value of 65% by weight or more, calculated by the following mathematical formula 1:

[0013] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0014] Furthermore, II) the present disclosure relates to a polymerizable composition comprising (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) an alkyl (meth)acrylate. and (b-2) 100 parts by weight of a base resin containing at least one selected from the group consisting of an alkyl ester polymer and (b-3) a copolymer of an alkyl (meth)acrylate compound, an aromatic vinyl compound, and a vinyl cyan compound; (C) 0.5 to 3.5 parts by weight of at least one selected from the group consisting of a benzotriazole-based UV stabilizer, a benzoate-based UV stabilizer, and a benzophenone-based UV stabilizer having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; wherein a 3 mm thick injection molded specimen is left for 8,000 hours using a weatherometer in accordance with ASTM G155-1, and the degree of discoloration is measured with a color difference meter, and the change over time (ΔE) calculated by the following formula 4 is 3 or less.

[0015]

number

[0016] III) In I) or II), the (C) one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers may preferably have a melting point of 100 to 200°C.

[0017] IV) In I) to III), the benzotriazole-based UV stabilizer may preferably be one or more selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole.

[0018] V) In I) to IV) above, the benzoate-based UV stabilizer may preferably be 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, or a mixture thereof.

[0019] VI) In the above I) to V), the benzophenone-based ultraviolet stabilizer is preferably 2-hydroxy-4-octoxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid disodium salt. Salt).

[0020] VII) In the above I) to VI), the (D) NH type HALS ultraviolet stabilizer may preferably have a melting point of 60 to 120°C.

[0021] VIII) In the above I) to VII), the (D) NH type HALS ultraviolet stabilizer may preferably be one or more selected from the group consisting of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

[0022] IX) In the above I) to VIII), the (a-1) graft copolymer may preferably contain, relative to its total weight, 20 to 60% by weight of alkyl acrylate rubber and 40 to 80% by weight of the aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it.

[0023] X) In the above I) to IX), the total weight of the (a-1) graft copolymer, the (a-2) graft copolymer, and the (a-3) graft copolymer may preferably be 15 to 80% by weight based on the total weight of the base resin.

[0024] XI) In the above I) to X), the total weight of the (b-1) polymer and the (b-2) copolymer may preferably be 20 to 85% by weight based on the total weight of the base resin.

[0025] XII) In the above I) to XI), the (b-1) (meth)acrylic acid alkyl ester polymer may preferably comprise one or more selected from the group consisting of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

[0026] XIII) In the above I) to XII), the (b-2) copolymer may preferably contain 60 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound.

[0027] XIV) In the above I) to XIII), the (b-1) polymer and the (b-2) copolymer may each preferably have a weight average molecular weight of 50,000 to 150,000 g / mol.

[0028] XV) In the above I) to XIV), the thermoplastic resin composition may preferably be such that a 3 mm thick injection molded specimen is left for 8,000 hours using a weatherometer in accordance with ASTM G155-1, and then the degree of discoloration is measured with a color difference meter, and the change in color over time (ΔE) calculated by the following Equation 4 is 3 or less.

[0029]

number

[0030] XVI) The present disclosure also provides a polymerizable composition comprising (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound- The present invention provides a method for producing a thermoplastic resin composition, comprising: (a) 100 parts by weight of a base resin containing one or more selected from the group consisting of vinyl cyanide compound copolymers; (C) 0.5 to 3.5 parts by weight of one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers, each having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; and kneading and extruding the resulting mixture at 200 to 300°C and 100 to 500 rpm, wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value of 65% by weight or more, as calculated by the following mathematical formula 1:

[0031] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0032] XVII) The present disclosure also provides a polymerizable composition comprising (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester polymer. and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; and (E) kneading and extruding the resulting mixture at 200 to 300°C and 100 to 500 rpm to produce a thermoplastic resin composition. The thermoplastic resin composition is characterized in that a 3 mm thick injection test piece is left for 8,000 hours using a weatherometer in accordance with ASTM G155-1, and the degree of discoloration of the resulting thermoplastic resin composition is measured using a color difference meter, and the change in color over time (ΔE) calculated using the following Equation 4 is 3 or less.

[0033]

number

[0034] Furthermore, XVIII) the present invention provides a molded article comprising the thermoplastic resin composition of any one of I) to XV). [Effects of the Invention]

[0035] The present invention has the effect of providing a thermoplastic resin composition that is excellent in impact resistance, transparency, and weather resistance, and that exhibits reduced change over time due to the excellent weather resistance, has excellent color stability, and has a beautiful appearance, and is applicable to any of injection molding, extrusion molding, and calendar molding; a method for producing the same; and a molded article containing the same.

[0036] Furthermore, the thermoplastic resin composition of the present invention has the effect of reducing the occurrence of whitening during bending processes such as bending and folding by adjusting the alkyl acrylate coverage value of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing the alkyl acrylate rubber having an average particle size of 50 to 120 nm to within a predetermined range. DETAILED DESCRIPTION OF THE INVENTION

[0037] The thermoplastic resin composition of the present invention, its production method, and molded articles containing the same will be described in detail below.

[0038] The present inventors have found that when a base resin containing one or more of three alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymers containing rubbers having different average particle sizes and one or more of a (meth)acrylic acid alkyl ester polymer and a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer is combined with one or more benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers having a predetermined molecular weight and an NH-type HALS-based UV stabilizer in a predetermined content ratio, the resulting resin exhibits excellent impact resistance, transparency, and weather resistance, and the excellent weather resistance reduces deterioration over time and improves color stability, making it suitable for injection molding, extrusion molding, and calendar molding. Furthermore, when the alkyl acrylate coverage of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer is adjusted within a predetermined range, the occurrence of whitening during bending is reduced. Based on this finding, the inventors continued their research and completed the present invention.

[0039] The thermoplastic resin composition according to the present invention will be described in detail below.

[0040] The thermoplastic resin composition of the present invention comprises (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) an (meth)acrylic acid alkyl ester polymer and (b-2) (a-1) graft copolymer (a-2) is characterized in that it comprises: (a) 100 parts by weight of a base resin containing one or more selected from the group consisting of (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymers; (c) 0.5 to 3.5 parts by weight of one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers, each having a molecular weight of 280 to 600 g / mol; and (d) more than 0.6 to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value of 65% by weight or greater, calculated by the following Equation 1: In this case, the graft copolymer has excellent impact resistance, transparency, and weather resistance, and the excellent weather resistance reduces deterioration over time, resulting in excellent color stability and a beautiful appearance, and is applicable to all of injection molding, extrusion molding, and calendar molding.

[0041] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0042] The thermoplastic resin composition of the present invention will be described in detail below, by constituent.

[0043] (a-1) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber having an average particle size of 50 to 120 nm The alkyl acrylate rubber of the (a-1) graft copolymer may have, for example, an average particle size of 50 to 120 nm, preferably 50 to 110 nm, more preferably 50 to 100 nm, and even more preferably 60 to 90 nm. Within this range, excellent light transmittance and gloss can be imparted to the finally produced thermoplastic resin composition.

[0044] In this description, the average particle size can be measured using dynamic light scattering. Specifically, it is measured as an intensity value in Gaussian mode using a particle size analyzer (product name: Nicomp380, manufacturer: PSS). As a specific measurement example, a sample is prepared by diluting 0.1 g of latex with a total solids content of 35-50 wt% 1,000-5,000 times with distilled water. The measurement method is auto-dilution followed by measurement using a flow cell. The measurement mode is dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis, with the following settings: temperature 23°C, measurement wavelength 632.8 nm, and channel width 10 μsec.

[0045] For example, the (a-1) graft copolymer may have an alkyl acrylate coverage (X) value calculated by the following mathematical formula 1 of 65% by weight or more, preferably 75% by weight or more, more preferably 85% by weight or more, even more preferably 85 to 140% by weight, and even more preferably 95 to 120% by weight. Within this range, the graft copolymer has excellent mechanical properties, transparency, and gloss, and is particularly effective in suppressing whitening during bending processing.

[0046] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0047] In Equation 1, the alkyl acrylate content in the gel of the graft copolymer refers to the alkyl acrylate content in the insoluble matter (based on 100% by weight of the total graft copolymer added) collected during the process of determining the gel content. Here, the gel content refers to the content of the insoluble matter based on 100% by weight of the total graft copolymer.

[0048] The content of the alkyl acrylate is quantitatively measured by NMR (nuclear magnetic resonance) analysis or FT-IR (Fourier transform infrared spectroscopy) analysis.

[0049] In this description, unless otherwise specified, NMR analysis is 1 H NMR analysis.

[0050] In this description, NMR analysis can be performed using a method commonly used in this technical field, and a specific example of the measurement is as follows. -Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe -Measurement conditions: 1 H NMR(zg30): ns=32, d1=5s, TCE-d2, at room temp.

[0051] In this description, FT-IR analysis can be measured using a method commonly used in this technical field, and a specific measurement example is as follows. -Equipment name: Agilent Cary 660 -Measurement conditions: ATR mode

[0052] The gel content can be calculated using Equation 2 below: 1 g of graft copolymer is added to 30 ml of acetone, stirred at room temperature for 12 hours, centrifuged, and the insoluble matter that did not dissolve in acetone is collected and dried for 12 hours, and then weighed. Specifically, the gel content can be calculated using Equation 2 below: 1 g of graft copolymer is added to 30 ml of acetone, stirred at room temperature for 12 hours using an orbital shaker (Lab companion SKC-6075) at 210 rpm, centrifuged for 3 hours using a centrifuge (Hanil Scientific Co., Ltd. Supra R30) at 0°C for 18,000 rpm, and the insoluble matter that did not dissolve in acetone is collected and dried for 12 hours using a forced convection oven (Lab companion OF-12GW) at 85°C using a forced circulation drying method.

[0053] [Formula 2] Gel content (wt%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] × 100

[0054] In this description, the alkyl acrylate coverage value is a parameter that measures the degree of dispersion of the aromatic vinyl compound-vinyl cyan compound polymer grafted onto the alkyl acrylate rubber in an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer. The higher this value, the more uniformly the aromatic vinyl compound-vinyl cyan compound polymer is grafted onto the alkyl acrylate rubber, surrounding the rubber uniformly, resulting in higher gloss and transparency, as well as excellent mechanical properties, colorability, and anti-whitening properties. Furthermore, the higher the alkyl acrylate coverage value, the more uniform the alkyl acrylate is between the inside and outside of the graft copolymer gel, reducing defects caused by external stress. This also reduces voids due to cracks within the graft copolymer, thereby suppressing whitening during bending.

[0055] The difference between the alkyl acrylate coverage value and the graft ratio is that the alkyl acrylate coverage value is calculated from the content of alkyl acrylate actually present in the graft copolymer using an NMR analyzer or FT-IR, while the graft ratio is calculated from the content of the rubber component added during polymerization.

[0056] The (a-1) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding the alkyl acrylate rubber.

[0057] The (a-1) graft copolymer may, for example, comprise, based on its total weight, 20 to 60% by weight of alkyl acrylate rubber and 40 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer surrounding it, preferably 30 to 50% by weight of alkyl acrylate rubber and 50 to 70% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer surrounding it, and more preferably 40 to 50% by weight of alkyl acrylate rubber and 50 to 60% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer surrounding it. Within these ranges, the graft copolymer has excellent mechanical properties, gloss, transparency, and weather resistance, and is less likely to whiten during bending.

[0058] For example, the alkyl acrylate rubber may be prepared by emulsion polymerization of alkyl acrylate, or preferably by emulsion polymerization of a mixture of alkyl acrylate, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent. In this case, the alkyl acrylate rubber has excellent grafting efficiency and therefore excellent mechanical properties.

[0059] For example, the alkyl acrylate rubber may further contain an aromatic vinyl compound, which has the effect of providing even better chemical resistance and impact resistance. The content of the aromatic vinyl compound in the alkyl acrylate rubber may be, for example, 0.1 to 25 wt%, preferably 2 to 23 wt%, and more preferably 5 to 20 wt%, based on 100 wt% of the total weight of the alkyl acrylate rubber. Within this range, the alkyl acrylate rubber has excellent impact resistance, gloss, transparency, and weather resistance without any deterioration in physical properties, and the excellent weather resistance reduces deterioration over time.

[0060] The aromatic vinyl compound-vinyl cyan compound copolymer (shell) may have a weight average molecular weight of, for example, 40,000 to 120,000 g / mol, preferably 50,000 to 110,000 g / mol, and more preferably 60,000 to 110,000 g / mol. Within this range, excellent processability is achieved without a decrease in impact strength, and whitening during bending processing is reduced.

[0061] In this description, unless otherwise specified, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, water breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using THF (tetrahydrofuran) as an eluent. In this specific measurement example, the solvent is THF, the column temperature is 40°C, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection volume is 5 μL, the column model is 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), the measuring equipment is an Agilent 1200 series system, the refractive index detector is an Agilent G1362 RID, the RI temperature is 35°C, the data is processed by Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under the conditions of OECD TG 118.

[0062] The aromatic vinyl compound-vinyl cyan compound copolymer (shell) may contain, for example, 55 to 85% by weight of the aromatic vinyl compound and 15 to 45% by weight of the vinyl cyan compound, preferably 60 to 80% by weight of the aromatic vinyl compound and 20 to 40% by weight of the vinyl cyan compound, more preferably 65 to 75% by weight of the aromatic vinyl compound and 25 to 35% by weight of the vinyl cyan compound, based on the total weight of the copolymer. Within these ranges, the copolymer has the advantage of being excellent in impact resistance and weather resistance.

[0063] The aromatic vinyl compound-vinyl cyan compound copolymer (shell) may preferably further contain alkyl acrylate, which has the advantages of excellent impact resistance, weather resistance, and processability, and reduced whitening during bending.

[0064] The aromatic vinyl compound-vinyl cyan compound copolymer (shell) may contain, for example, 55 to 85% by weight of the aromatic vinyl compound, 10 to 35% by weight of the vinyl cyan compound, and 1 to 25% by weight of the alkyl acrylate, based on the total weight of the copolymer, preferably 60 to 80% by weight of the aromatic vinyl compound, 15 to 30% by weight of the vinyl cyan compound, and 3 to 20% by weight of the alkyl acrylate, and more preferably 65 to 72% by weight of the aromatic vinyl compound, 20 to 25% by weight of the vinyl cyan compound, and 5 to 15% by weight of the alkyl acrylate. Within these ranges, the impact resistance and weather resistance are further improved.

[0065] The (a-1) graft copolymer may be prepared by emulsion polymerization, for example, and in this case, it has the effect of providing excellent gloss and surface hardness.

[0066] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and may be, for example, an emulsion graft polymerization method.

[0067] The graft ratio of the (a-1) graft copolymer, calculated by the following mathematical formula 3, may be, for example, 60 to 150%, preferably 65 to 140%, more preferably 65 to 130%, even more preferably 65 to 120%, still more preferably 65 to 110%, particularly preferably 65 to 100%, and particularly more preferably 65 to 80%. Within this range, there are advantages such as excellent impact resistance and processability, and reduced whitening during bending processing.

[0068] [Formula 3] Graft rate (%) = [weight of grafted monomer (g) / weight of rubber (g)] × 100 (In Equation 3, the weight (g) of the grafted monomer is the weight (g) of the insoluble substance (gel) obtained after dissolving the graft copolymer in acetone and centrifuging the solution, minus the weight (g) of the rubbery substance, and the weight (g) of the rubbery substance is the weight (g) of the rubbery component theoretically added to the graft copolymer powder.)

[0069] The weight of the insoluble material (gel) was measured after adding 0.5 g of dry powder of (A) graft copolymer to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging the mixture, and collecting only the insoluble matter that did not dissolve in acetone, which was then dried for 12 hours. The weight (g) of the rubbery substance was the theoretical weight (g) of the rubbery component added to 0.5 g of dry powder of (A) graft copolymer.

[0070] As a specific measurement example, the weight of the insoluble material (gel) is measured by adding 0.5 g of dry powder of the graft copolymer to 50 ml of acetone, stirring the mixture at 210 rpm for 12 hours using an orbital shaker (Lab companion SKC-6075) at room temperature, and then centrifuging the mixture at 18,000 rpm for 3 hours using a centrifuge (Hanil Scientific Supra R30) at 0°C. The insoluble material that did not dissolve in acetone is then collected and dried in a forced convection oven (Lab companion OF-12GW) at 85°C for 12 hours using a forced circulation drying method.

[0071] The (a-1) graft copolymer may be, for example, 55 to 80% by weight, preferably 60 to 75% by weight, and more preferably 65 to 70% by weight, based on the total weight of the base resin. Within this range, the mechanical properties, gloss, and transparency are excellent, and the occurrence of whitening during bending processing is reduced.

[0072] 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 butyl acrylate, ethylhexyl acrylate, or a mixture thereof, and even more preferably butyl acrylate.

[0073] In this description, the aromatic vinyl compound may be, for example, one or more compounds selected from the group consisting of styrene, α-methylstyrene, ο-methylstyrene, ρ-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, ο-bromostyrene, ρ-bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably one or more compounds selected from the group consisting of styrene and α-methylstyrene, more preferably styrene, which has appropriate fluidity and therefore excellent processability and mechanical properties such as impact resistance.

[0074] In the present description, the vinyl cyanide compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and preferably acrylonitrile.

[0075] In this description, a polymer comprising a certain compound (monomer) means a polymer that is polymerized containing that compound (monomer), and the units in the polymerized polymer are derived from that compound.

[0076] (a-2) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber having an average particle size of 150 to 600 nm The alkyl acrylate rubber of the (a-2) graft copolymer may have, for example, an average particle size of 150 to 600 nm, preferably 200 to 600 nm, more preferably 250 to 500 nm, even more preferably 300 to 470 nm, and even more preferably 330 to 430 nm. Within this range, excellent mechanical properties such as impact strength can be achieved.

[0077] The (a-2) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and a shell surrounding the core, the shell containing an aromatic vinyl compound and a vinyl cyanide compound. In this case, the graft copolymer has excellent mechanical properties and processability.

[0078] The (a-2) graft copolymer may contain, for example, 35 to 65% by weight of alkyl acrylate rubber, 20 to 55% by weight of aromatic vinyl compound, and 1 to 25% by weight of vinyl cyanide compound, based on the total weight of the graft copolymer. Within these ranges, the copolymer has the effect of exhibiting excellent mechanical properties such as impact strength and transparency.

[0079] Preferably, the (a-2) graft copolymer may contain 40 to 60% by weight of alkyl acrylate rubber, 25 to 50% by weight of aromatic vinyl compound, and 5 to 20% by weight of vinyl cyanide compound. Within these ranges, the copolymer has the effect of exhibiting excellent mechanical properties such as impact strength and transparency.

[0080] More preferably, the (a-2) graft copolymer may contain 45 to 55% by weight of alkyl acrylate rubber, 33 to 43% by weight of aromatic vinyl compound, and 10 to 15% by weight of vinyl cyanide compound. Within these ranges, excellent mechanical properties such as impact strength and transparency can be obtained.

[0081] The types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (a-2) graft copolymer may be within the same category as the types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (a-1) graft copolymer of the present invention.

[0082] The (a-2) graft copolymer may be prepared by emulsion polymerization, for example, and in this case, it has the effect of being excellent in mechanical properties such as impact strength and transparency.

[0083] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and may be, for example, an emulsion graft polymerization method.

[0084] The (a-2) graft copolymer may have a graft ratio calculated by the above-mentioned formula 3 of, for example, 40 to 120%, preferably 45 to 100%, more preferably 45 to 80%, and within this range, the copolymer has the effect of exhibiting excellent mechanical properties such as impact strength and excellent processability.

[0085] The (a-2) graft copolymer may be, for example, 5 to 35% by weight, preferably 10 to 30% by weight, and more preferably 15 to 25% by weight, based on the total weight of the base resin. Within this range, the effect of excellent mechanical properties and transparency is achieved.

[0086] (a-3) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm The alkyl acrylate rubber of the (a-3) graft copolymer may have, for example, an average particle size of 80 nm or more and less than 150 nm, preferably 90 nm or more and less than 150 nm, more preferably 91 to 140 nm, even more preferably 101 to 140 nm, and even more preferably 111 to 140 nm. Within this range, there are advantages in that the mechanical properties are maintained while the gloss, transparency, and colorability are excellent.

[0087] The (a-3) graft copolymer may preferably comprise an alkyl acrylate rubber (core) surrounded by a shell containing an aromatic vinyl compound and a vinyl cyan compound. In this case, the graft copolymer has advantages of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0088] The (a-3) graft copolymer may, for example, contain 35 to 65% by weight of alkyl acrylate rubber, 20 to 55% by weight of aromatic vinyl compound, and 1 to 25% by weight of vinyl cyan compound, based on the total weight of the copolymer. Within these ranges, the copolymer has the advantages of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0089] Preferably, the (a-3) graft copolymer may contain 40 to 60% by weight of alkyl acrylate rubber, 25 to 50% by weight of aromatic vinyl compound, and 5 to 20% by weight of vinyl cyan compound. Within these ranges, the mechanical properties are maintained while the copolymer has the advantages of excellent gloss, transparency, and colorability.

[0090] More preferably, the (a-3) graft copolymer may contain 45 to 55% by weight of alkyl acrylate rubber, 33 to 43% by weight of aromatic vinyl compound, and 10 to 15% by weight of vinyl cyan compound. Within these ranges, the mechanical properties are maintained while the copolymer has excellent gloss, transparency, and colorability.

[0091] The types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (a-3) graft copolymer may be within the same category as the types of alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyan compound contained in the (a-1) graft copolymer of the present invention.

[0092] The (a-3) graft copolymer may be prepared by emulsion polymerization, for example. In this case, the graft copolymer has advantages of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0093] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains, and may be, for example, an emulsion graft polymerization method.

[0094] The graft copolymer (a-3) may have a graft ratio calculated by the above-mentioned mathematical formula 3 of 15 to 60%, preferably 20 to 50%, and more preferably 25 to 45%, for example. Within this range, there is an effect of excellent processing dispersion with the (b-1) (meth)acrylic acid alkyl ester polymer and the (b-2) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer.

[0095] The (a-3) graft copolymer may be, for example, 5 to 70% by weight, preferably 10 to 65% by weight, and more preferably 15 to 60% by weight, based on the total weight of the base resin. Within this range, the resin has the advantages of excellent gloss and transparency and reduced whitening during bending.

[0096] The total weight of the (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer may be, for example, 15 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight, even more preferably 30 to 70% by weight, even more preferably 40 to 70% by weight, particularly preferably 50 to 70% by weight, and especially more preferably 57 to 70% by weight, relative to the total weight of the base resin. Within this range, excellent mechanical properties, gloss, transparency, and processability are achieved.

[0097] The (A) graft copolymer may be, for example, one or more selected from the group consisting of (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer. In this case, there are advantages such as excellent mechanical properties, gloss, transparency, weather resistance, and colorability.

[0098] The (A) graft copolymer may preferably be the (a-1) graft copolymer, which has excellent gloss, transparency, and weather resistance while maintaining mechanical properties, reduces whitening during bending processing, resulting in a beautiful appearance, and reduces deterioration over time due to excellent weather resistance, resulting in significantly excellent color stability.

[0099] The (A) graft copolymer may preferably be the (a-2) graft copolymer, in which case there is an effect of excellent mechanical properties and weather resistance.

[0100] The (A) graft copolymer may preferably be the (a-3) graft copolymer, in which case there is an effect of maintaining mechanical properties while achieving excellent gloss, transparency and weather resistance.

[0101] The (A) graft copolymer may preferably be a mixture of the (a-2) graft copolymer and the (a-3) graft copolymer. In this case, the graft copolymer has excellent mechanical properties, gloss, and transparency, and its excellent weather resistance reduces deterioration over time.

[0102] The blend of the graft copolymer (a-2) and the graft copolymer (a-3) may have a weight ratio (a-2:a-3) of 40:60 to 60:40, preferably 45:55 to 55:45, for example. Within this range, mechanical properties such as impact strength, gloss, and colorability are improved.

[0103] In this description, the weight ratio of A to B means the weight ratio of A:B.

[0104] (b-1) (Meth)acrylic acid alkyl ester polymer The (b-1) (meth)acrylic acid alkyl ester polymer may, for example, comprise one or more selected from the group consisting of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester, and may preferably be a methacrylic acid alkyl ester, an acrylic acid alkyl ester, or a mixture thereof, and more preferably be a polymethyl methacrylate resin, which has the advantages of excellent mechanical properties, fluidity, and transparency.

[0105] In this description, a (meth)acrylic acid alkyl ester polymer can mean a polymer comprising more than 85 wt%, 90 wt% or more, or 95 wt% or more of a (meth)acrylic acid alkyl ester.

[0106] In this description, unless otherwise specified, "(meth)acrylic acid alkyl ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" are possible.

[0107] The polymethyl methacrylate resin may contain, for example, methyl methacrylate and methyl acrylate, and preferably contains 1 to 10% by weight, more preferably 2 to 7% by weight, of methyl acrylate. Within this range, the compatibility with (b-2) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer is excellent, resulting in improved gloss, fluidity, and mechanical properties.

[0108] The (b-1) polymer may have a weight-average molecular weight of, for example, 50,000 to 150,000 g / mol, preferably 60,000 to 130,000 g / mol, more preferably 70,000 to 110,000 g / mol, and even more preferably 70,000 to 100,000 g / mol. Within this range, there are advantages in that the polymer has excellent transparency, gloss, and fluidity while maintaining impact resistance.

[0109] The (b-1) (meth)acrylic acid alkyl ester polymer may have a glass transition temperature of, for example, 80 to 130°C, preferably 90 to 120°C, and within this range, it has the advantage of being excellent in heat resistance.

[0110] In this description, the glass transition temperature can be measured using a differential scanning calorimetry (DSC) in accordance with ASTM D3418, and specifically, can be measured using a TA Instruments Q100 differential scanning calorimeter at a heating rate of 10°C / min.

[0111] The (b-1) (meth)acrylic acid alkyl ester polymer may be, for example, 15 to 85% by weight, preferably 20 to 80% by weight, and more preferably 25 to 75% by weight, based on the total weight of the base resin. Within this range, the mechanical properties are maintained, while the transparency and gloss are excellent, and the occurrence of whitening during bending processing is reduced.

[0112] The (b-1) (meth)acrylic acid alkyl ester polymer may be prepared by, for example, suspension polymerization, and the suspension polymerization is not particularly limited as long as it is suspension polymerization commonly performed in the technical field to which the present invention belongs.

[0113] (b-2) (Meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer The (b-2) copolymer, for example, contains, relative to its total weight, 60 to 85% by weight of alkyl (meth)acrylate, 10 to 35% by weight of aromatic vinyl compound, and 1 to 20% by weight of vinyl cyan compound. Within these ranges, the copolymer has advantages such as excellent compatibility with the (A) graft copolymer and the (b-1) (meth)acrylic acid alkyl ester polymer, excellent mechanical properties, transparency, and gloss, and reduced whitening during bending processing.

[0114] Preferably, the (b-2) copolymer may contain, relative to its total weight, 65 to 80% by weight of a (meth)acrylic acid alkyl ester compound, 15 to 30% by weight of an aromatic vinyl compound, and 3 to 15% by weight of a vinyl cyan compound. Within these ranges, the copolymer has the advantages of excellent compatibility with the (A) graft copolymer and the (b-1) (meth)acrylic acid alkyl ester polymer, excellent mechanical properties, transparency, and gloss, and reduced whitening during bending processing.

[0115] More preferably, the (b-2) copolymer may comprise, relative to its total weight, 68 to 74% by weight of a (meth)acrylic acid alkyl ester compound, 20 to 25% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyan compound. Within these ranges, the copolymer has the advantages of excellent compatibility with the (A) graft copolymer and the (b-1) (meth)acrylic acid alkyl ester polymer, excellent mechanical properties, transparency, and gloss, and reduced whitening during bending.

[0116] In the present description, the (meth)acrylic acid alkyl ester compound may be, for example, one or more selected from the group consisting of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

[0117] The types of aromatic vinyl compounds and vinyl cyan compounds contained in the copolymer (b-2) may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds contained in the graft copolymer (a-1) described herein.

[0118] The (b-2) copolymer may have a weight-average molecular weight of, for example, 50,000 to 150,000 g / mol, preferably 60,000 to 130,000 g / mol, more preferably 70,000 to 120,000 g / mol, and even more preferably 80,000 to 110,000 g / mol. Within this range, the copolymer has the advantages of excellent tensile strength, flexural strength, impact strength, and scratch resistance.

[0119] The (b-2) copolymer may be, for example, 5 to 45% by weight, preferably 5 to 40% by weight, and more preferably 10 to 35% by weight, based on the total weight of the base resin. Within this range, the copolymer has the advantages of excellent compatibility with the (b-1) (meth)acrylic acid alkyl ester polymer, and excellent mechanical properties and flowability.

[0120] The (b-2) copolymer may be prepared by bulk polymerization, for example. The bulk polymerization is not particularly limited as long as it is a bulk polymerization commonly performed in the technical field to which the present invention pertains.

[0121] The total weight of the (b-1) polymer and the (b-2) copolymer may be, for example, 20 to 85% by weight, preferably 25 to 85% by weight, more preferably 30 to 80% by weight, even more preferably 30 to 70% by weight, even more preferably 30 to 60% by weight, particularly preferably 30 to 50% by weight, and especially more preferably 30 to 43% by weight, relative to the total weight of the base resin. Within this range, there are advantages such as excellent mechanical properties, gloss, transparency, weather resistance, and colorability.

[0122] (C) one or more ultraviolet stabilizers selected from the group consisting of benzotriazole-based ultraviolet stabilizers, benzoate-based ultraviolet stabilizers, and benzophenone-based ultraviolet stabilizers, each having a molecular weight of 280 to 600 g / mol; The (C) one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers may be, for example, 0.5 to 3.5 parts by weight, preferably 1 to 3 parts by weight, more preferably 1 to 2.6 parts by weight, and even more preferably 1.5 to 2.2 parts by weight, per 100 parts by weight of the base resin. Within this range, the composition has the advantages of excellent impact resistance, transparency, and weather resistance, as well as reduced change over time due to the excellent weather resistance, excellent color stability, and a beautiful appearance.

[0123] The (C) one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers may have a molecular weight of, for example, 280 to 600 g / mol, preferably 300 to 600 g / mol, more preferably 300 to 550 g / mol, even more preferably 300 to 500 g / mol, still more preferably 350 to 500 g / mol, particularly preferably 400 to 500 g / mol, particularly more preferably 420 to 470 g / mol, and most preferably 440 to 455 g / mol. Within this range, the composition has the advantages of excellent mechanical properties, gloss, transparency, and weather resistance, as well as reduced deterioration over time due to the excellent weather resistance, resulting in a luxurious appearance.

[0124] The (C) one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers may have a melting point of, for example, 100 to 200°C, preferably 110 to 200°C, more preferably 120 to 200°C, even more preferably 120 to 180°C, still more preferably 120 to 160°C, particularly preferably 125 to 150°C, particularly more preferably 130 to 145°C, and most preferably 135 to 144°C. Within this range, the composition has the advantages of excellent mechanical properties, gloss, transparency, and weather resistance, and the excellent weather resistance reduces deterioration over time, resulting in a luxurious appearance.

[0125] In this description, the melting point can be measured using a differential scanning calorimeter (DSC) manufactured by TA Corporation (2920). As a specific measurement example, the melting point can be measured by equilibrating the DSC at a temperature of 0°C, increasing the temperature by 20°C per minute to 180°C, decreasing the temperature by 20°C per minute to -60°C, and then increasing the temperature by 10°C per minute to 180°C. Here, the melting point can be measured by measuring the peak region of the endothermic curve during the second temperature increase.

[0126] Examples of the benzotriazole-based UV stabilizer include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole. [1-methyl-1-phenylethyl]-2H-benzotriazole), and preferably 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234). In this case, the resin has the advantages of excellent mechanical properties, gloss, transparency, and weather resistance, and the excellent weather resistance reduces change over time, resulting in excellent color stability and a beautiful appearance.

[0127] The benzoate-based UV stabilizer may be, for example, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, or a mixture thereof, and preferably 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate. In this case, it has advantages such as excellent mechanical properties, gloss, transparency, and weather resistance, as well as reduced deterioration over time due to excellent weather resistance, excellent color stability, and beautiful appearance.

[0128] Examples of the benzophenone-based UV stabilizer include 2-hydroxy-4-octoxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid disodium salt. Salt), and preferably 4-benzyloxy-2-hydroxybenzophenone. In this case, the resin has advantages of excellent mechanical properties, gloss, transparency, and weather resistance, and also has excellent color stability and beautiful appearance, with reduced change over time due to the excellent weather resistance.

[0129] (D) NH type HALS UV stabilizer with a molecular weight of 300 to 700 g / mol The (D) NH type HALS-based UV stabilizer may be, for example, more than 0.6 parts by weight and not more than 2 parts by weight, preferably 0.7 to 1.7 parts by weight, and more preferably 0.7 to 1.2 parts by weight, per 100 parts by weight of the base resin. Within this range, the composition has the advantages of excellent impact resistance, transparency, and weather resistance, as well as reduced change over time due to the excellent weather resistance, excellent color stability, and a beautiful appearance.

[0130] The (D) NH type HALS-based UV stabilizer may have a molecular weight of, for example, 300 to 700 g / mol, preferably 350 to 650 g / mol, more preferably 400 to 600 g / mol, even more preferably 450 to 550 g / mol, and even more preferably 460 to 510 g / mol. Within this range, the composition has excellent mechanical properties, gloss, transparency, and weather resistance, and the excellent weather resistance reduces deterioration over time, resulting in excellent color stability and a beautiful appearance.

[0131] The (D) NH type HALS-based ultraviolet stabilizer may have a melting point of, for example, 60 to 120°C, preferably 65 to 110°C, more preferably 70 to 100°C, even more preferably 70 to 95°C, even more preferably 74 to 92°C, and particularly preferably 78 to 87°C. Within this range, the composition has excellent mechanical properties, gloss, transparency, and weather resistance, and the excellent weather resistance reduces deterioration over time, resulting in excellent color stability and a beautiful appearance.

[0132] The (D) NH type HALS UV stabilizer may be, for example, one or more selected from the group consisting of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. In this case, it has the advantages of excellent mechanical properties, gloss, transparency, and weather resistance, as well as reduced change over time due to excellent weather resistance, excellent color stability, and a luxurious appearance.

[0133] The (C) UV stabilizer having a molecular weight of 280 to 600 g / mol may be used in a larger amount than the (D) NH type HALS UV stabilizer, for example. In this case, the (C) UV stabilizer has advantages such as excellent mechanical properties, gloss, transparency, and weather resistance, as well as reduced deterioration over time due to its excellent weather resistance, excellent color stability, and a luxurious appearance.

[0134] The weight ratio (C:D) of the (C) UV stabilizer having a molecular weight of 280 to 600 g / mol to the (D) NH type HALS UV stabilizer may be, for example, 1.3:1 to 3.2:1, preferably 1.5:1 to 3.0:1, more preferably 2.0:1 to 3.0:1, and even more preferably 2.5:1 to 3.0:1. Within this range, the composition has the advantages of excellent mechanical properties, gloss, transparency, and weather resistance, as well as reduced deterioration over time due to the excellent weather resistance, excellent color stability, and a luxurious appearance.

[0135] The present invention provides a combination of (C) an ultraviolet stabilizer having a molecular weight of 280 to 600 g / mol and (D) an NH-type HALS-based ultraviolet stabilizer having a molecular weight of 300 to 700 g / mol, preferably a combination of (C) a benzotriazole-based ultraviolet stabilizer having a molecular weight of 280 to 600 g / mol and (D) an NH-type HALS-based ultraviolet stabilizer having a molecular weight of 300 to 700 g / mol, and more preferably a combination of (C) a benzotriazole-based ultraviolet stabilizer having a molecular weight of 280 to 600 g / mol and a melting point of 100 to 200°C and (D) an NH-type HALS-based ultraviolet stabilizer having a molecular weight of 300 to 700 g / mol and a melting point of 60 to 120°C, which not only provides excellent mechanical properties, transparency, and weather resistance, but also exhibits a synergistic effect of reducing deterioration over time due to the excellent weather resistance.

[0136] thermoplastic resin composition For example, the thermoplastic resin composition may have a change in color over time (ΔE) calculated by the following Equation 4, where a 3 mm thick injection test piece is left for 8,000 hours using a weatherometer in accordance with ASTM G155-1, and then the degree of discoloration is measured using a color difference meter. The change in color over time (ΔE) may be 3 or less, preferably 2.5 or less, more preferably 2 or less, even more preferably 1.8 or less, even more preferably 1.6 or less, and particularly preferably 0.1 to 1.6. Within this range, the thermoplastic resin composition has advantages such as excellent mechanical properties, weather resistance, and transparency, as well as reduced change over time due to excellent weather resistance, excellent color stability, and a beautiful appearance.

[0137]

number

[0138] For example, the thermoplastic resin composition may have a change in color over time (ΔE) calculated by Equation 4, as determined by using a weatherometer to measure the degree of discoloration of a 3 mm thick injection molded specimen in accordance with ASTM G155-1 for 4,000 hours, and the change in color over time (ΔE) may be 2 or less, preferably 1.6 or less, more preferably 1.3 or less, even more preferably 1.0 or less, and even more preferably 0.1 to 1.0. Within this range, the thermoplastic resin composition has advantages such as excellent mechanical properties, transparency, and weather resistance, as well as reduced change over time due to the excellent weather resistance, excellent color stability, and a beautiful appearance.

[0139] For example, the thermoplastic resin composition may have a haze of 10% or less, preferably 8% or less, more preferably 6% or less, and even more preferably 0.1 to 6%, as measured on a sheet having a thickness of 0.15 mm in accordance with ASTM D1003. Within this range, the composition has the effect of having an excellent balance of physical properties, transparency, and colorability.

[0140] For example, the thermoplastic resin composition may have a total light transmittance of 80% or more, preferably 85% or more, more preferably 90% or more, and even more preferably 90 to 120%, as measured on a sheet having a thickness of 0.15 mm in accordance with ASTM D1003. Within this range, the composition has the effect of having an excellent balance of physical properties, transparency, and colorability.

[0141] For example, when a 10 cm x 10 cm sheet of the thermoplastic resin composition having a thickness of 0.15 mm is manually folded in the machined direction (MD) and the traverse direction (TD), the occurrence of whitening on the folded surface is visually observed. As a result, the occurrence of whitening can be reduced. In this case, the thermoplastic resin composition has advantages of excellent balance of physical properties, excellent impact resistance and transparency, and beautiful appearance.

[0142] The thermoplastic resin composition has, for example, a tensile strength of 300 kgf / cm2 measured in the machine direction (MD) of a sheet having a thickness of 0.15 mm at a pulling rate of 10 mm / min in accordance with ASTM D412. 2 or more, preferably 310 kgf / cm 2 More preferably, 320 kgf / cm 2 More preferably, 330 kgf / cm 2 More preferably, 350 kgf / cm 2 More preferably, 350 to 600 kgf / cm 2 Within this range, the physical properties are well balanced, and the injection molded, extrusion molded and calender molded articles have excellent mechanical properties.

[0143] For example, the thermoplastic resin composition may have an elongation of 10% or more, preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, still more preferably 60% or more, and particularly preferably 60 to 80%, as measured in the machine direction (MD) of a 0.15 mm thick sheet at a tensile speed of 10 mm / min in accordance with ASTM D412. Within this range, the composition has an excellent balance of physical properties, and the mechanical properties of injection-molded products, extrusion-molded products, and calender-molded products are excellent.

[0144] For example, the thermoplastic resin composition may have a tear strength of 67 kgf / cm or more, preferably 72 kgf / cm or more, more preferably 80 kgf / cm or more, even more preferably 90 kgf / cm or more, and even more preferably 90 to 130 kgf / cm, as measured in the machine direction (MD) of a 0.15 mm thick sheet at a tensile speed of 10 mm / min in accordance with ASTM D624. Within this range, the thermoplastic resin composition has an excellent balance of physical properties, and the mechanical properties of injection-molded products, extrusion-molded products, and calender-molded products are excellent.

[0145] The thermoplastic resin composition has, for example, a tensile strength of 230 kgf / cm when measured in the transverse direction (TD) of a sheet having a thickness of 0.15 mm at a pulling rate of 10 mm / min in accordance with ASTM D412. 2 More than 245kgf / cm, preferably 245kgf / cm 2 More preferably, 250 kgf / cm 2 More preferably, 250 to 500 kgf / cm 2 Within this range, the physical properties are well balanced, and the injection molded, extrusion molded and calender molded articles have excellent mechanical properties.

[0146] For example, the thermoplastic resin composition may have an elongation of 14% or more, preferably 20% or more, more preferably 30% or more, even more preferably 40% or more, even more preferably 50% or more, and particularly preferably 50 to 75%, as measured in the transverse direction (TD) of a 0.15 mm thick sheet at a tensile speed of 10 mm / min in accordance with ASTM D412. Within this range, the composition has an excellent balance of physical properties, and the mechanical properties of injection-molded, extrusion-molded, and calender-molded articles are excellent.

[0147] For example, the thermoplastic resin composition may have a tear strength of 55 kgf / cm or more, preferably 60 kgf / cm or more, more preferably 65 kgf / cm or more, even more preferably 70 kgf / cm or more, still more preferably 75 kgf / cm, and particularly preferably 75 to 95 kgf / cm, when measured in the transverse direction (TD) of a 0.15 mm thick sheet at a pulling rate of 10 mm / min in accordance with ASTM D624. Within this range, the thermoplastic resin composition has an excellent balance of physical properties, and the mechanical properties of injection-molded articles, extrusion-molded articles, and calender-molded articles are excellent.

[0148] The thermoplastic resin composition may optionally further contain one or more additives selected from the group consisting of heat stabilizers, dyes, pigments, colorants, lubricants, release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, anti-dripping agents, anti-friction agents, and anti-wear agents, in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 part by weight, based on 100 parts by weight of the base resin. Within these ranges, the desired physical properties can be achieved without deteriorating the inherent physical properties of the thermoplastic resin composition described herein.

[0149] The heat stabilizer may preferably include a primary heat stabilizer and a secondary heat stabilizer.

[0150] The primary heat stabilizer may be, for example, a phenol-based heat stabilizer, and preferably, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediol bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene bis-[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxy hydroxybenzyl) isocyanurate, 2,2'-methylenebis(4-methyl-6-t-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2,2-bis[4-(2-3,5-di-t-butyl-4- The alkyl ester may be one or more selected from the group consisting of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid stearyl ester, and more preferably octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (IR1076).

[0151] The secondary heat stabilizer may be, for example, a phosphorus-based heat stabilizer, and preferably, bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, diphenyl phosphite, Tearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, tris(mono- and di-mixed nonylphenyl) phosphite, hydrogenated 4,4'-isopropylidene Distearyl diphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris[4,4'-isopropylidenebis(2-t-butylphenol)]phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butylphenol)bis(nonylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl Phosphite, 2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphepin-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyl-dibenz[d,f][1.3.2]-dioxaphosphepin-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepin-6-yl}oxy]ethyl]-ethanamine.The compound may be one or more selected from the group consisting of 2,4-dioxaphosphepines, and more preferably tris(2,4-di-tert-butylphenyl)phosphite (IF168).

[0152] The lubricant may preferably be one or more selected from the group consisting of an aliphatic amide-based lubricant, a fatty acid ester-based lubricant, and an olefin-based wax.

[0153] The aliphatic amide lubricant may be preferably one or more selected from the group consisting of stearamide, oleamide, erucamide, ethylene bis stearamide, and ethylene bis oleamide.

[0154] The fatty acid ester-based lubricant may preferably be at least one selected from the group consisting of fatty acid esters of alcohols or polyhydric alcohols, hardened oils, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphate esters.

[0155] The olefin wax may preferably be a polyethylene wax.

[0156] Method for producing thermoplastic resin composition The method for producing the thermoplastic resin composition of the present invention includes mixing (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester copolymer. (C) 0.5 to 3.5 parts by weight of at least one UV stabilizer having a molecular weight of 280 to 600 g / mol, selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers; and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; and kneading and extruding the resulting mixture at 200 to 300°C and 100 to 500 rpm, wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value of 65% by weight or more, calculated by the following Equation 1: In this case, the resin composition has advantages such as excellent mechanical properties, transparency, and weather resistance, and the excellent weather resistance reduces changes over time, resulting in excellent color stability, a beautiful appearance, and applicability to any of injection molding, extrusion molding, and calendar molding.

[0157] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0158] The method for producing the thermoplastic resin composition shares all the technical features of the thermoplastic resin composition described above, and therefore, a description of the overlapping parts will be omitted.

[0159] The kneading and extrusion can be preferably carried out using an extrusion kneader at 200 to 300°C, more preferably 210 to 260°C, and even more preferably 220 to 250°C, within which stable extrusion is possible and excellent kneading effects can be achieved. At this time, the temperature is the temperature set in the cylinder.

[0160] The kneading and extrusion may be carried out under conditions where the screw rotation speed is, for example, 100 to 500 rpm, preferably 150 to 450 rpm, and more preferably 200 to 400 rpm. In this case, the processing amount per unit time is appropriate, which has the effect of providing excellent process efficiency.

[0161] The thermoplastic resin composition obtained through the extrusion may be made into pellets using, for example, a pelletizer.

[0162] The extrusion kneader is not particularly limited as long as it is an extrusion kneader commonly used in the technical field to which the present invention pertains, and is preferably a twin-screw extrusion kneader.

[0163] Molded product The molded article described herein is characterized by containing the thermoplastic resin composition, and in this case, has the advantages of being excellent in mechanical properties, transparency, and weather resistance, and in that the excellent weather resistance reduces changes over time, the color stability is excellent, and the appearance is luxurious, and it can be applied to any of injection-molded articles, extrusion-molded articles, and calendar-molded articles.

[0164] The injection molded product may be preferably an automobile interior / exterior part, an electrical / electronic product part, an unpainted molded product, or a metal insert molded product, and specific examples thereof may include a bidet control panel, a lawn robot housing, a pool cleaning robot housing, a door accessory, or a window frame.

[0165] The extrusion product may preferably be a film, sheet, or foil, and specifically may be a deco sheet, an exterior building finish, a roof finish, an interior film, wallpaper, an edge band, VCM (Vinyl coated metal), flooring, PSP (Plastic-steel-Plastic) for molding, or a wrapping film.

[0166] The calendered product may preferably be a film, sheet, or foil, and specifically may be a deco sheet, an outdoor building material finish, a roof finish, an interior film, wallpaper, an edge band, VCM (Vinyl coated metal), a flooring material, a PSP (Plastic-steel-Plastic) for molding, or a wrapping film.

[0167] The method for producing the molded article preferably includes mixing (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound graft copolymer. and (C) 0.5 to 3.5 parts by weight of at least one UV stabilizer having a molecular weight of 280 to 600 g / mol, selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers; and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; kneading and extruding the resulting mixture under conditions of 200 to 300°C and 100 to 500 rpm to produce an extrudate; and molding the extrudate to produce a molded product, wherein the (a-1) graft copolymer may have an alkyl acrylate coverage (X) value of 65% by weight or more, calculated by the following Equation 1: In this case, the resin composition has advantages such as excellent mechanical properties, transparency, and weather resistance, and the excellent weather resistance reduces changes over time, leading to excellent color stability and a beautiful appearance, and being applicable to any of injection molding, extrusion molding, and calendar molding.

[0168] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0169] The extrudate may be in the form of pellets or plates, for example.

[0170] In this description, the plate-like shape is not particularly limited as long as it is defined as a normal plate-like shape in the technical field to which the present invention belongs, and examples thereof include a flat shape, a sheet shape, a film shape, etc.

[0171] 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.

[0172] Below, preferred examples are presented to help understand the present description, but the following examples are merely illustrative of the present description, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present description, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0173] [Example] The materials used in the following examples and comparative examples are as follows. *(a-1-1) ASA graft copolymer containing alkyl acrylate rubber with an average particle size of 50 to 120 nm: ASA graft copolymer with an average particle size of 70 nm of alkyl acrylate rubber produced by emulsion polymerization (Core (rubber): butyl acrylate 36 wt%, styrene 7 wt%, Shell: butyl acrylate 4 wt%, styrene 39.5 wt%, and acrylonitrile 13.5 wt%, alkyl acrylate coverage value 99 wt%, graft ratio 77%) *(a-2) ASA graft copolymer containing alkyl acrylate rubber with an average particle size of 150 to 600 nm: ASA graft copolymer with an average particle size of 350 nm of alkyl acrylate rubber produced by emulsion polymerization (core (rubber): butyl acrylate 50% by weight, shell: styrene 37.5% by weight and acrylonitrile 12.5% ​​by weight, graft ratio 50%) *(a-3) ASA graft copolymer containing alkyl acrylate rubber with an average particle size of 80 nm or more and less than 150 nm: ASA graft copolymer with an average particle size of 130 nm of alkyl acrylate rubber produced by emulsion polymerization (core (rubber): butyl acrylate 50 wt%, shell: styrene 37.5 wt% and acrylonitrile 12.5 wt%, graft ratio 35%) *(a-1-2) ASA graft copolymer containing alkyl acrylate rubber with an average particle size of 50 to 120 nm: ASA graft copolymer with an average particle size of 65 nm of alkyl acrylate rubber produced by emulsion polymerization (Core (rubber): butyl acrylate 43 wt%, styrene 3 wt%, Shell: butyl acrylate 4 wt%, styrene 37.5 wt%, and acrylonitrile 12.5 wt%, alkyl acrylate coverage value 77 wt%, graft ratio 65%) *(b-1) PMMA resin by suspension polymerization: Polymethyl methacrylate resin (weight average molecular weight 80,000 g / mol) *(b-2) Bulk polymerization SAMMA resin: methyl methacrylate-styrene-acrylonitrile copolymer (weight average molecular weight 95,000 g / mol) containing 70% by weight of methyl methacrylate, 22.5% by weight of styrene, and 7.5% by weight of acrylonitrile. *(C-1) UV234 (BASF): Benzotriazole-based UV stabilizer (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, molecular weight 447.5 g / mol, melting point 137-141°C) *(C-2) UV-P (BASF): Benzotriazole-based UV stabilizer (molecular weight 225g / mol, melting point 128-133℃) *(C-3) UV360 (BASF): Benzotriazole-based UV stabilizer (molecular weight 658.9 g / mol, melting point 195-198°C) *(C-4) SONGSORB 7120 (Songwon): Benzoate-based UV stabilizer (molecular weight 438.6 g / mol, melting point 197°C) *(C-5) SEESORB 105 (Shipro Kasei Kaisha): Benzophenone-based UV stabilizer (molecular weight 304.3 g / mol, melting point 122°C) *(D-1) UV770 (BASF): NH type HALS UV stabilizer (molecular weight 480 g / mol, melting point 82-85°C) *(D-2) Chimassorb 994 (BASF): NH type HALS UV stabilizer (molecular weight 2000-3100 g / mol, melting point 100-135°C) *Additives -Heat stabilizer: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate - Lubricant: Ethylene bisstearamide

[0174] Examples 1 to 11 and Comparative Examples 1 to 9 The components and contents shown in Tables 1 and 2 below were added to a twin-screw extruder along with 0.3 parts by weight of a heat stabilizer and 0.3 parts by weight of a lubricant, and the mixture was melt-mixed and extruded at 230°C and 150 rpm to prepare pellets. The pellets were then extruded at a molding temperature of 220°C using an injector to prepare test specimens for measuring physical properties.

[0175] In addition, the produced pellets were used to prepare a sheet having a thickness of 0.15 mm using a T-die extruder (ST32HS (Twin screw, 32T, L / D=44) manufactured by EM Co., Ltd., Korea) at an extrusion screw speed of 150 rpm, a temperature of 210°C, a three-screw roll temperature of 80°C, and a roll rotation speed of 1.5 m / min, and the physical properties were measured.

[0176] [Test example] The properties of the pellets or test pieces produced in Examples 1 to 11 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0177] Measurement method *(a-1) Alkyl acrylate coverage value of graft copolymer (X value, % by weight): Calculated using the following formula 1.

[0178] [Formula 1] X = {(GY) / Y} × 100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

[0179] Here, the content of alkyl acrylate in the gel is 1 Quantitative measurements were made using an NMR analyzer or FT-IR under the following specific measurement conditions: 1 H NMR -Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe -Measurement conditions: 1 H NMR(zg30): ns=32, d1=5s, TCE-d2, at room temp. FT-IR -Equipment name: Agilent Cary 66 -Measurement conditions: ATR mode

[0180] *Gel content (%): 1 g of graft copolymer was added to 30 ml of acetone and stirred at room temperature using an orbital shaker (Lab companion SKC-6075) at 210 rpm for 12 hours. This was then centrifuged at 18,000 rpm for 3 hours using a centrifuge (Hanil Scientific Supra R30) at 0°C. Only the insoluble matter that did not dissolve in acetone was collected and dried in a forced convection oven (Lab companion OF-12GW) at 85°C for 12 hours using a forced circulation drying method. The weight was then measured and the gel content was calculated using the following formula 2.

[0181] [Formula 2] Gel content (%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] × 100

[0182] * Graft rate (%): 0.5 g of dry powder of the graft copolymer was added to 50 ml of acetone, stirred at room temperature for 12 hours, centrifuged, and only the insoluble matter that did not dissolve in acetone was collected, dried for 12 hours, and then weighed and calculated using the following formula 3.

[0183] [Formula 3] Graft rate (%) = [weight of grafted monomer (g) / weight of rubber (g)] × 100 (In Equation 3, the weight (g) of the grafted monomer is the weight (g) of the insoluble substance (gel) obtained after dissolving the graft copolymer in acetone and centrifuging the solution, minus the weight (g) of the rubbery substance, and the weight (g) of the rubbery substance is the weight (g) of the rubbery component theoretically added to the graft copolymer powder.)

[0184] Specifically, the weight of the insoluble material (gel) was measured by adding 0.5 g of dry powder of the graft copolymer to 50 ml of acetone, stirring the mixture at 210 rpm for 12 hours using an orbital shaker (Lab companion SKC-6075) at room temperature, and then centrifuging the mixture at 18,000 rpm for 3 hours using a centrifuge (Hanil Scientific Supra R30) at 0°C. The insoluble material that did not dissolve in acetone was collected and dried in a forced convection oven (Lab companion OF-12GW) at 85°C for 12 hours using a forced circulation drying method, followed by weighing.

[0185] *Haze (%): The haze of a sheet having a thickness of 0.15 mm was measured in accordance with ASTM D1003.

[0186] *Total light transmittance (%): The total light transmittance of a sheet having a thickness of 0.15 mm was measured in accordance with ASTM D1003.

[0187] *Change over time (△E): Using a weatherometer, 3mm thick injection test pieces were left for 4,000 hours and 8,000 hours in accordance with ASTM G155-1, and then the degree of discoloration was measured with a color difference meter, and the change over time (△E) was calculated using the following formula 4.

[0188]

number

[0189] *Whitening resistance: A 10cm x 10cm sheet with a thickness of 0.15mm was folded by hand in the machined direction (MD) and traverse direction (TD), and the occurrence of whitening on the folded surface was visually observed and evaluated according to the following criteria. ○: No whitening occurs △: Whitening is normal ×: Whitening occurs frequently

[0190] *Tensile strength (kgf / cm 2 ) and elongation (%): Measured in the machine direction (MD) and transverse direction (TD) of a 0.15 mm thick sheet at a tension speed of 10 mm / min in accordance with ASTM D412.

[0191] *Tear strength (kgf / cm): Measured in accordance with ASTM D624 for a 0.15 mm thick sheet in both the machine direction (MD) and transverse direction (TD) at a pulling rate of 10 mm / min.

[0192] [Table 1]

[0193] [Table 2] (In Tables 1 and 2, the contents of (a-1-1), (a-2), (a-3), (a-1-2), (b-1) and (b-2) are in weight percent based on the total weight of these, and the contents of (C-1), (C-2), (C-3), (C-4), (C-5), (D-1) and (D-2) are in parts by weight based on 100 parts by weight of the total weight of (a-1-1), (a-2), (a-3), (a-1-2), (b-1) and (b-2).)

[0194] As shown in Tables 1 and 2, the thermoplastic resin compositions of Examples 1 to 11 prepared according to the present invention had comparable or better total light transmittance and haze than Comparative Examples 1 to 9, which were outside the scope of the present invention. Furthermore, the change in ΔE (ΔE) over time after 4,000 hours of storage, especially after 8,000 hours of storage, was reduced, demonstrating excellent color stability. The tensile strength, elongation, and tear strength were comparable or superior. Examples 1 to 5, 10, and 11 containing the ASA graft copolymer (a-1-1) and Example 9 containing the ASA graft copolymer (a-1-2) also showed reduced whitening during bending. Furthermore, Examples 1 to 9 containing the benzotriazole-based UV stabilizer (C-1) showed even less change in ΔE (ΔE) over time after 4,000 hours of storage and after 8,000 hours of storage.

[0195] Specifically, Comparative Example 1, which did not contain (D-1) UV770, showed a large change over time (ΔE) after being left to stand for 8,000 hours, while Comparative Example 2, which contained (D-2) Chimassorb 994 instead of (D-1) UV770, Comparative Example 3, which contained (D-2) Chimassorb 994 and a small amount of (D-1) UV770, and Comparative Examples 4 and 5, which contained (C-2) UV-P and (C-3) UV360 instead of (C-1) UV234, respectively, showed poor changes over time (ΔE) after being left to stand for 4,000 hours and 8,000 hours.

[0196] In addition, Comparative Examples 6 and 7, in which the content of (C-1) UV234 was outside the range of the present invention, showed poor changes over time (ΔE) after being left for 4000 hours and 8000 hours, respectively. Comparative Example 6 also showed poor haze, and deposits occurred at the die entrance and on the sheet during sheet processing.

[0197] Furthermore, Comparative Example 8, which contained an excessive amount of (D-1) UV770, not only exhibited poor haze and poor aging (ΔE) after being left for 4,000 and 8,000 hours, but also generated deposits at the die entrance and on the sheet during sheet processing. Comparative Example 9, which contained a small amount of (D-1) UV770, exhibited a large aging (ΔE) after being left for 8,000 hours.

[0198] In conclusion, a thermoplastic resin composition comprising a base resin containing one or more of three alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymers containing a rubber having a predetermined average particle size, and one or more of a (meth)acrylic acid alkyl ester polymer and a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer, and a predetermined molecular weight and containing one or more of a benzotriazole-based UV stabilizer, a benzoate-based UV stabilizer, and a benzophenone-based UV stabilizer in a predetermined content ratio, and an NH-type HALS-based UV stabilizer, has been confirmed to have excellent mechanical properties, transparency, and weather resistance, as well as excellent weather resistance, which reduces deterioration over time, resulting in excellent color stability and a beautiful appearance. Furthermore, when the alkyl acrylate coverage of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer is adjusted within a predetermined range, the occurrence of whitening during bending processing is also reduced.

Claims

1. (A) at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm; and (B) 100 parts by weight of a base resin containing at least one selected from the group consisting of (b-1) a (meth)acrylic acid alkyl ester polymer and (b-2) a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer; (C) 0.5 to 3.5 parts by weight of at least one ultraviolet stabilizer having a molecular weight of 280 to 600 g / mol and selected from the group consisting of benzotriazole-based ultraviolet stabilizers, benzoate-based ultraviolet stabilizers, and benzophenone-based ultraviolet stabilizers; (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH type HALS ultraviolet stabilizer having a molecular weight of 300 to 700 g / mol; The (a-1) graft copolymer has an alkyl acrylate coverage (X) value calculated by the following equation 1 of 65% by weight or more. [Formula 1] X={(G-Y) / Y}×100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

2. The thermoplastic resin composition according to claim 1, wherein the (C) at least one selected from the group consisting of a benzotriazole-based UV stabilizer, a benzoate-based UV stabilizer, and a benzophenone-based UV stabilizer has a melting point of 100 to 200°C.

3. 2. The thermoplastic resin composition according to claim 1, wherein the benzotriazole-based UV stabilizer is at least one selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234) and 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole.

4. 2. The thermoplastic resin composition according to claim 1, wherein the benzoate-based UV stabilizer is 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, or a mixture thereof.

5. The benzophenone-based ultraviolet stabilizer includes 2-hydroxy-4-octoxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid. 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid disodium salt (2,2'-Dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid disodium salt).

6. 2. The thermoplastic resin composition according to claim 1, wherein the (D) NH-type HALS ultraviolet stabilizer has a melting point of 60 to 120°C.

7. The thermoplastic resin composition according to claim 1, wherein the (D) NH-type HALS ultraviolet stabilizer is at least one selected from the group consisting of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate.

8. The thermoplastic resin composition according to claim 1, wherein the (a-1) graft copolymer comprises, based on its total weight, 20 to 60% by weight of alkyl acrylate rubber and 40 to 80% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the alkyl acrylate rubber.

9. The thermoplastic resin composition according to claim 1, wherein the total weight of the graft copolymer (a-1), the graft copolymer (a-2), and the graft copolymer (a-3) is 15 to 80% by weight based on the total weight of the base resin.

10. The thermoplastic resin composition according to claim 1, wherein the total weight of the (b-1) polymer and the (b-2) copolymer is 20 to 85% by weight based on the total weight of the base resin.

11. The thermoplastic resin composition according to claim 1, wherein the (meth)acrylic acid alkyl ester polymer (b-1) comprises at least one selected from the group consisting of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

12. The thermoplastic resin composition according to claim 1, wherein the copolymer (b-2) comprises 60 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound.

13. The thermoplastic resin composition according to claim 1, wherein the (b-1) polymer and the (b-2) copolymer each have a weight average molecular weight of 50,000 to 150,000 g / mol.

14. The thermoplastic resin composition according to claim 1, wherein a 3 mm thick injection molded specimen is left for 8,000 hours in accordance with ASTM G155-1 using a weatherometer, and then the degree of discoloration is measured using a color difference meter. The change in color over time (ΔE) calculated using Equation 4 below is 3 or less: [Equation 1] (In Equation 4, L', a', and b' are the L, a, and b values ​​measured in the CIE LAB color coordinate system after the test piece is left to stand, respectively, and L ０ , a ０ , b ０ are the L, a, and b values ​​measured in the CIE LAB color coordinate system before standing.

15. (A) one or more selected from the group consisting of (a-1) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers containing alkyl acrylate rubbers having an average particle size of 50 to 120 nm, (a-2) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers containing alkyl acrylate rubbers having an average particle size of 150 to 600 nm, and (a-3) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers containing alkyl acrylate rubbers having an average particle size of 80 nm or more but less than 150 nm, and (B) (b-1) (meth)acrylic acid alkyl ester polymers and and (b-2) 100 parts by weight of a base resin containing one or more selected from the group consisting of (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymers; (C) 0.5 to 3.5 parts by weight of one or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers, and benzophenone-based UV stabilizers, each having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and not more than 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; and kneading and extruding the mixture under conditions of 200 to 300°C and 100 to 500 rpm, The (a-1) graft copolymer has an alkyl acrylate coverage (X) value calculated by the following Equation 1 of 65% by weight or more. [Formula 1] X={(G-Y) / Y}×100 (In the above formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel relative to the total weight of the graft copolymer.)

16. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 14.

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