Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof

Abstract

The present description relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same. More specifically, the invention relates to (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) a base resin comprising one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer. The present invention relates to a thermoplastic resin composition comprising 100 parts by weight; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight 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 more, a method for manufacturing the same, and a molded article comprising the same. According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent mechanical properties, transparency, and weather resistance, with excellent color stability and a beautiful appearance due to reduced change over time resulting from the excellent weather resistance, a method for manufacturing the same, and a molded article including the same.

Description

Technology Field

[0001] The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same. More specifically, the invention relates to a thermoplastic resin composition having excellent impact resistance, transparency, and weather resistance, with reduced change over time due to excellent weather resistance, excellent color stability, and a beautiful appearance, applicable to injection molding, extrusion molding, and calendering, a method for manufacturing the same, and a molded article comprising the same. Background Technology

[0003] Acrylic film is a representative material used as a protective finishing material due to its high transparency and weather resistance. With the trend toward premiumization, acrylic film is particularly used to coat surfaces requiring high weather resistance, such as outdoor window profiles (W / P), and coating methods include wrapping, co-extrusion, and lamination.

[0004] In general, acrylonitrile-styrene-acrylate copolymers containing alkyl (meth)acrylate compounds (hereinafter referred to as 'ASA' resins) have excellent physical properties such as processability, impact resistance, chemical resistance, and weather resistance because they do not contain ethylene-based unsaturated bonds. As a result, they are widely used in various fields, including 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 the demand for them is also rapidly increasing.

[0005] Although a product comparable to acrylic resins for finishing materials has been developed by utilizing the advantages of ASA resin, which offers superior impact strength and chemical resistance compared to acrylic film, and by supplementing its transparency, the multi-component ASA resin presents a problem regarding weather resistance. Unlike single-material acrylic film, multi-component ASA resin exhibits a change over time where the color differs from the original due to initial moisture absorption and thermal history. This phenomenon occurs due to changes in the internal refractive index of the thermoplastic resin containing ASA resin and the rearrangement of the resin's microstructure to achieve thermodynamic stabilization.

[0006] Therefore, there is a need to develop a material that can be applied as a high-quality finishing material required by the market, possessing excellent impact resistance, transparency, and weather resistance. Furthermore, due to this excellent weather resistance, changes over time are reduced, resulting in superior color stability and a beautiful appearance. Prior art literature

[0008] Korean Published Patent No. 2009-0095764 The problem to be solved

[0009] In order to solve the problems of the prior art described above, the present invention relates to a thermoplastic resin composition having excellent impact resistance, transparency, and weather resistance, and having excellent color stability and a smooth appearance due to reduced change over time resulting from the excellent weather resistance, and applicable to injection molding, extrusion molding, and calendering, a method for manufacturing the same, and a molded article containing the same.

[0010] In addition, the present invention aims to provide a method for manufacturing the above-mentioned thermoplastic resin composition.

[0011] In addition, the present invention aims to provide a molded article manufactured from the above-described thermoplastic resin composition.

[0013] The above purposes and other purposes of this description can all be achieved by the description below. means of solving the problem

[0015] To achieve the above objective, the present invention comprises: I) 100 parts by weight of a base resin comprising (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal 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 calculated by the following chemical formula 1 of 65% by weight or more. A thermoplastic resin composition is provided.

[0016] [Mathematical Formula 1]

[0017] X = {(GY) / Y} * 100

[0018] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0019] In addition, II) the present invention comprises 100 parts by weight of a base resin comprising (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; wherein, after leaving an injection molded specimen with a thickness of 3 mm for 8,000 hours according to ASTM G155-1 using a whetherometer, the degree of discoloration is measured using a colorimeter, and the change over time (△E) calculated by the following mathematical formula 4 is 3 or less.

[0020] [Mathematical Formula 4]

[0021]

[0022] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.)

[0023] III) In the above I) or II), one or more selected from the group consisting of (C) benzotriazole-based UV stabilizers, benzoate-based UV stabilizers and benzophenone-based UV stabilizers may preferably have a melting point of 100 to 200 °C.

[0024] IV) In I) to III) above, the benzotriazole-based UV stabilizer (C) may preferably be one or more selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole.

[0025] 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.

[0026] VI) In I) to V) above, the benzophenone-based UV 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 disodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid. It may be one or more selected from the group consisting of salt (2,2'-Dihydroxy-4,4'-Dimethoxybenzophenone-5,5'-Disulfonic Acid Disodium Salt).

[0027] VII) In I) to VI) above, the (D) NH type HALS-based UV stabilizer may preferably have a melting point of 60 to 120 °C.

[0028] VIII) In I) to VII) above, the (D) NH type HALS-based UV 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.

[0029] IX) In I) to VIII) above, the (a-1) graft copolymer may preferably comprise 20 to 60 weight% of alkyl acrylate rubber and 40 to 80 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it.

[0030] X) In I) to IX) above, the sum of the weights of the (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer may preferably be 15 to 80 weight% with respect to the total weight of the base resin.

[0031] XI) In I) to X) above, the sum of the weights of the (b-1) polymer and the (b-2) copolymer may preferably be 20 to 85 weight percent with respect to the total weight of the base resin.

[0032] XII) In I) to XI) above, the (b-1) (meth)acrylate alkyl ester polymer may preferably comprise one or more selected from the group consisting of (meth)acrylate methyl ester, (meth)acrylate ethyl ester, (meth)acrylate propyl ester, (meth)acrylate 2-ethylhexyl ester, (meth)acrylate decyl ester, and (meth)acrylate lauryl ester.

[0033] XIII) In I) to XII) above, the (b-2) copolymer may preferably comprise 60 to 85 weight% of an alkyl (meth)acrylate, 10 to 35 weight% of an aromatic vinyl compound, and 1 to 20 weight% of a vinyl cyanide compound.

[0034] XIV) In I) to XIII) above, the (b-1) polymer and (b-2) copolymer may preferably each have a weight-average molecular weight of 50,000 to 150,000 g / mol.

[0035] XV) In the above I) to XIV), the thermoplastic resin composition may preferably have a change over time (△E) of 3 or less, calculated by the following Equation 4 after measuring the degree of discoloration with a colorimeter after leaving an injection molded specimen with a thickness of 3 mm for 8,000 hours according to ASTM G155-1 using a whetherometer.

[0036] [Mathematical Formula 4]

[0037]

[0038] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.)

[0039] In addition, XVI) The present invention comprises 100 parts by weight of a base resin comprising (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; comprising the step of kneading and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm; wherein the (a-1) graft copolymer has an alkyl acrylate coverage (X) value calculated by the following chemical formula 1 of 65% by weight or more. A method for manufacturing a thermoplastic resin composition is provided.

[0040] [Mathematical Formula 1]

[0041] X = {(GY) / Y} * 100

[0042] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0043] Additionally, XVII) The present invention comprises 100 parts by weight of a base resin comprising (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 nm or more and less than 150 nm, and (B) one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; A method for manufacturing a thermoplastic resin composition can be provided, comprising the step of mixing and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm, including (D) more than 0.6 parts by weight and 2 parts by weight or less of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; and wherein the thermoplastic resin composition is characterized by having a change over time (△E) of 3 or less calculated by the following mathematical formula 4, after leaving an injection molded specimen with a thickness of 3 mm for 8,000 hours according to ASTM G155-1 using a whetherometer, and measuring the degree of discoloration with a colorimeter.

[0044] [Mathematical Formula 4]

[0045]

[0046] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.)

[0047] In addition, XVIII) The present invention provides a molded article characterized by comprising the thermoplastic resin compositions of I) to XV). Effects of the invention

[0049] According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent impact resistance, transparency, and weather resistance, with reduced change over time due to excellent weather resistance, excellent color stability, and a beautiful appearance, applicable to injection molding, extrusion molding, and calendering, a method for manufacturing the same, and a molded article including the same.

[0050] Furthermore, the thermoplastic resin composition of the present invention has the effect of reducing whitening during bending processes such as bending or folding by adjusting the alkyl acrylate coverage value of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50 to 120 nm to within a predetermined range. Specific details for implementing the invention

[0052] The thermoplastic resin composition, the method for manufacturing the same, and a molded article containing the same described herein will be described in detail below.

[0053] The inventors have confirmed that if a combination of one or more selected from the group consisting of 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 is included in a predetermined content ratio in a base resin comprising one or more of three types of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymers comprising rubber having different average particle sizes, and one or more of (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymers, is included, the impact resistance, transparency, and weather resistance are excellent, and color stability is improved as changes over time are reduced due to the excellent weather resistance, and it is applicable to injection molding, extrusion molding, and calendering, and furthermore, if the alkyl acrylate coverage value of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer is adjusted within a predetermined range, the occurrence of whitening during bending processing is reduced, and based on this, further research Through dedicated effort, the present invention was completed.

[0055] The thermoplastic resin composition according to the present description is described in detail as follows.

[0057] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising: (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising 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 comprising one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal 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 is characterized by having an alkyl acrylate coverage (X) value calculated by the following chemical formula 1 of 65% by weight or more. In this case, it has excellent impact resistance, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance, and it has the advantage of being applicable to injection molding, extrusion molding, and calendering.

[0058] [Mathematical Formula 1]

[0059] X = {(GY) / Y} * 100

[0060] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0062] The thermoplastic resin composition of the present invention will be described in detail below according to its components.

[0064] (a-1) An alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm

[0065] The alkyl acrylate rubber of the (a-1) graft copolymer may, for example, have an average particle size of 50 to 120 nm, preferably 50 to 110 nm, more preferably 50 to 100 nm, and more preferably 60 to 90 nm, and within this range, excellent light transmittance and glossiness can be imparted to the thermoplastic resin composition finally produced.

[0066] In this description, the average particle size can be measured using dynamic light scattering, and specifically, using a particle analyzer (product name: Nicomp 380, manufacturer: PSS), it is measured as an intensity value in Gaussian mode. As a specific measurement example, a sample is prepared by diluting 0.1 g of latex with a total solid content of 35 to 50 wt% with distilled water 1,000 to 5,000 times. The measurement method is performed by auto-dilution and measurement with a flow cell, the measurement mode is set to dynamic light scattering / intensity 300KHz / intensity-weight Gaussian Analysis, and the setting values ​​are a temperature of 23 ℃, a measurement wavelength of 632.8 nm, and a channel width of 10 μsec.

[0068] The above (a-1) graft copolymer may, for example, have an alkyl acrylate coverage (X) value calculated by the following chemical 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, and within this range, the mechanical properties, transparency and gloss are excellent, and in particular, the whitening effect is suppressed during bending processing.

[0069] [Mathematical Formula 1]

[0070] X = {(GY) / Y} * 100

[0071] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0072] In the above mathematical formula 1, the content of alkyl acrylate in the gel of the graft copolymer represents the content of alkyl acrylate in the insoluble matter collected during the process of determining the gel content described above (based on 100% by weight of the total graft copolymer added). Here, the gel content represents the content of insoluble matter based on 100% by weight of the total graft copolymer.

[0073] The content of the above alkyl acrylate is quantitatively measured through NMR (nuclear magnetic resonance) analysis or FT-IR (Fourier transform infrared spectroscopy) analysis.

[0074] In this description, NMR analysis is used unless otherwise specified 1 It refers to analysis by H NMR.

[0075] In this description, NMR analysis can be measured using methods commonly practiced in the field of the art, and specific measurement examples are as follows.

[0076] - Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe

[0077] - Measurement conditions: 1H NMR(zg30): ns=32, d1=5s, TCE-d2, at room temperature.

[0079] In this description, FT-IR analysis can be measured using methods commonly practiced in the field of this technology, and specific measurement examples are as follows.

[0080] - Equipment Name: Agilent Cary 660

[0081] - Measurement condition: ATR mode

[0083] The above gel content is calculated using the following mathematical formula 2 by adding 1 g of graft copolymer to 30 ml of acetone, stirring at room temperature for 12 hours, centrifuging to collect only the insoluble matter that does not dissolve in acetone, drying for 12 hours, and measuring the weight. As a specific measurement example, the gel content can be measured by adding 1 g of graft copolymer to 30 ml of acetone, stirring at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075), centrifuging at 18,000 rpm for 3 hours at 0°C using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble matter that does not dissolve in acetone, drying it in a forced convection oven (equipment name: Lab companion OF-12GW) at 85°C for 12 hours using a forced circulation drying method, and then measuring the weight.

[0084] [Mathematical Formula 2]

[0085] Gel content (weight%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] * 100

[0087] In this description, the alkyl acrylate coverage value is a parameter that measures the degree of dispersion of the aromatic vinyl compound-vinyl cyanide polymer grafted onto the alkyl acrylate rubber in an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer. The higher this value, the more evenly the aromatic vinyl compound-vinyl cyanide polymer is grafted onto the alkyl acrylate rubber, resulting in a uniform coating of the rubber. This leads to high gloss and transparency, as well as excellent mechanical properties, colorability, and anti-whitening characteristics. Additionally, a higher alkyl acrylate coverage value improves the homogeneity of the alkyl acrylate between the inside and outside of the graft copolymer gel, which reduces defects caused by external stress and decreases voids resulting from cracks within the graft copolymer, thereby suppressing the occurrence of whitening during bending.

[0088] The difference between the above alkyl acrylate coverage value and the above graft rate is that the alkyl acrylate coverage value is calculated from the alkyl acrylate content actually present in the graft copolymer using an NMR analyzer or FT-IR, while the graft rate is calculated from the content of the rubbery component added during polymerization.

[0090] The above (a-1) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyanide compound copolymer (shell) surrounding it.

[0091] The above (a-1) graft copolymer may, for example, comprise 20 to 60 weight% of alkyl acrylate rubber and 40 to 80 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it, based on the total weight thereof, preferably 30 to 50 weight% of alkyl acrylate rubber and 50 to 70 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it, and more preferably 40 to 50 weight% of alkyl acrylate rubber and 50 to 60 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it, and within this range, there is an effect of reducing the occurrence of whitening during bending processing, and excellent mechanical properties, gloss, transparency, and weather resistance.

[0093] The above alkyl acrylate rubber can be manufactured, for example, by emulsion polymerization of alkyl acrylate, and 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 which case the grafting efficiency is excellent, resulting in excellent mechanical properties.

[0094] The above alkyl acrylate rubber may further include, for example, an aromatic vinyl compound, in which case the chemical resistance and impact resistance are even better. The content of the aromatic vinyl compound included in the above alkyl acrylate rubber may, for example, be 0.1 to 25 weight%, preferably 2 to 23 weight%, and more preferably 5 to 20 weight% with respect to 100 weight% of the total alkyl acrylate rubber, and within this range, the impact resistance, gloss, transparency, and weather resistance are excellent without deterioration of physical properties, and the change over time is reduced due to the excellent weather resistance.

[0096] The above aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may, for example, have a weight-average molecular weight of 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, and within this range, it has excellent processability without a decrease in impact strength and has the effect of reducing whitening during bending processing.

[0097] Unless otherwise defined, the weight-average molecular weight in this description can be measured using Gel Permeation Chromatography (GPC, waters breeze). Specifically, it can be measured as a relative value to a standard polystyrene (PS) sample via Gel Permeation Chromatography (GPC, waters breeze) using Tetrahydrofuran (THF) as the eluent. In this case, as a specific measurement example, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, and the injection volume is 5 µl; the column model is 1xPLgel 10 µm MiniMix-B (250x4.6 mm) + 1xPLgel 10 µm MiniMix-B (250x4.6 mm) + 1xPLgel 10 µm MiniMix-B Guard (50x4.6 mm); the measuring instrument is an Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, the RI temperature is 35 ℃, data processing is Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

[0099] The above aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may comprise, for example, 55 to 85 weight% of an aromatic vinyl compound and 15 to 45 weight% of a vinyl cyanide compound based on the total weight thereof, preferably 60 to 80 weight% of an aromatic vinyl compound and 20 to 40 weight% of a vinyl cyanide compound, more preferably 65 to 75 weight% of an aromatic vinyl compound and 25 to 35 weight% of a vinyl cyanide compound, and within this range, it has the advantage of excellent impact resistance and weather resistance.

[0101] The above aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may preferably further include alkyl acrylate, in which case it has excellent impact resistance, weather resistance, and processability, and has the advantage of reducing whitening during bending processing.

[0102] The above aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may, for example, comprise 55 to 85 weight% of an aromatic vinyl compound, 10 to 35 weight% of a vinyl cyanide compound, and 1 to 25 weight% of an alkyl acrylate based on the total weight thereof, preferably comprises 60 to 80 weight% of an aromatic vinyl compound, 15 to 30 weight% of a vinyl cyanide compound, and 3 to 20 weight% of an alkyl acrylate, and more preferably comprises 65 to 72 weight% of an aromatic vinyl compound, 20 to 25 weight% of a vinyl cyanide compound, and 5 to 15 weight% of an alkyl acrylate, and within this range, the impact resistance and weather resistance are even better.

[0104] The above (a-1) graft copolymer can be prepared, for example, by emulsion polymerization, and in this case, it has the effect of excellent gloss and surface hardness.

[0105] The above emulsion polymerization is not particularly limited when carried out by an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and, for example, can be carried out by an emulsion graft polymerization method.

[0107] The above (a-1) graft copolymer may, for example, have a graft rate calculated by the following mathematical formula 3 of 60 to 150%, preferably 65 to 140%, more preferably 65 to 130%, even more preferably 65 to 120%, even more preferably 65 to 110%, particularly preferably 65 to 100%, and particularly more preferably 65 to 80%, and within this range, it has the advantage of excellent impact resistance and processability and reduced whitening during bending processing.

[0108] [Mathematical Formula 3]

[0109] Graft rate (%) = [Weight of grafted monomer (g) / Weight of gum (g)] * 100

[0110] (In the above mathematical formula 3, the weight (g) of the grafted monomer is the weight obtained by subtracting the weight of the rubbery substance (g) from the weight of the insoluble substance (gel) after dissolving the graft copolymer in acetone and centrifuging, and the weight of the rubbery substance (g) is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.)

[0111] The weight of the above insoluble substance (gel) is the weight measured after adding 0.5 g of (A) dry graft copolymer powder to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging to collect only the insoluble matter that does not dissolve in acetone, and drying for 12 hours, and the weight of the rubbery substance (g) is the weight (g) of the theoretical rubbery component added to 0.5 g of (A) dry graft copolymer powder.

[0112] As a specific measurement example, the weight of the insoluble substance (gel) is measured by adding 0.5 g of dry graft copolymer powder to 50 ml of acetone, stirring at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075), centrifuging the mixture at 18,000 rpm at 0 ℃ for 3 hours using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble matter that does not dissolve in acetone, drying it in a forced-circulation oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85 ℃ for 12 hours, and then measuring the result.

[0114] The above (a-1) graft copolymer may be, for example, 55 to 80 weight%, preferably 60 to 75 weight%, more preferably 65 to 70 weight% with respect to the total weight of the base resin, and within this range, there are advantages such as excellent mechanical properties, gloss and transparency, and reduced whitening during bending processing.

[0116] 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 1 to 4 carbon atoms in an alkyl group, even more preferably butyl acrylate, ethylhexyl acrylate, or a mixture thereof, and even more preferably butyl acrylate.

[0117] In the present invention, the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brovo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene, and vinyl naphthalene, preferably one or more selected from the group consisting of styrene and α-methyl styrene, more preferably styrene, in which case it has the effect of having excellent processability due to appropriate fluidity and excellent mechanical properties such as impact resistance.

[0118] In the present description, the vinyl cyanide compound may be one or more selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and preferably may be acrylonitrile.

[0120] In this description, a polymer comprising a certain compound (monomer) refers to a polymer polymerized by including that compound (monomer), wherein the monomers within the polymerized polymer originate from that compound.

[0122] (a-2) An alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm

[0123] The alkyl acrylate rubber of the above (a-2) graft copolymer may, for example, have 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, and within this range, it has the effect of having excellent mechanical properties such as impact strength.

[0125] The above (a-2) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and a shell comprising an aromatic vinyl compound and a vinyl cyanide compound surrounding it, and in this case, it has excellent mechanical properties and processability.

[0126] The above (a-2) graft copolymer may, for example, comprise 35 to 65 weight% of alkyl acrylate rubber, 20 to 55 weight% of aromatic vinyl compound, and 1 to 25 weight% of vinyl cyanide compound based on the total weight thereof, and within this range, it has excellent mechanical properties such as impact strength and transparency.

[0127] Preferably, the (a-2) graft copolymer may comprise 40 to 60 weight% of alkyl acrylate rubber, 25 to 50 weight% of an aromatic vinyl compound, and 5 to 20 weight% of a vinyl cyanide compound, and within this range, there is an effect of excellent mechanical properties such as impact strength and transparency.

[0128] More preferably, the (a-2) graft copolymer may comprise 45 to 55 weight% of alkyl acrylate rubber, 33 to 43 weight% of aromatic vinyl compound, and 10 to 15 weight% of vinyl cyanide compound, and within this range, there is an effect of excellent mechanical properties such as impact strength and transparency.

[0130] The types of alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds included in the above (a-2) graft copolymer may be within the same category as the types of alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds included in the (a-1) graft copolymer described herein.

[0131] The above (a-2) graft copolymer can be manufactured, for example, by emulsion polymerization, and in this case, it has excellent mechanical properties such as impact strength and transparency.

[0132] The above emulsion polymerization is not particularly limited when carried out by an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and, for example, can be carried out by an emulsion graft polymerization method.

[0134] The above (a-2) graft copolymer may, for example, have a graft rate calculated by the above mathematical formula 3 of 40 to 120%, preferably 45 to 100%, more preferably 45 to 80%, and within this range, have excellent mechanical properties such as impact strength and processability.

[0136] The above (a-2) graft copolymer may be, for example, 5 to 35 weight%, preferably 10 to 30 weight%, more preferably 15 to 25 weight% with respect to the total weight of the base resin, and within this range, there is an effect of excellent mechanical properties and transparency.

[0138] (a-3) An alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber with an average particle size of 80 nm or more and less than 150 nm

[0139] The alkyl acrylate rubber of the (a-3) graft copolymer may, for example, have an average particle size of 80 nm or more to less than 150 nm, preferably 90 nm or more to 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, and within this range, there is an advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0141] The above (a-3) graft copolymer may preferably comprise an alkyl acrylate rubber (core) and a shell comprising an aromatic vinyl compound and a vinyl cyanide compound surrounding it, in which case there is an advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0142] The above (a-3) graft copolymer may, for example, comprise 35 to 65 weight% of alkyl acrylate rubber, 20 to 55 weight% of aromatic vinyl compound, and 1 to 25 weight% of vinyl cyanide compound based on the total weight thereof, and within this range, it has the advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0143] Preferably, the (a-3) graft copolymer may comprise 40 to 60 weight% of alkyl acrylate rubber, 25 to 50 weight% of an aromatic vinyl compound, and 5 to 20 weight% of a vinyl cyanide compound, and within this range, there is an advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0144] More preferably, the (a-3) graft copolymer may comprise 45 to 55 weight% of alkyl acrylate rubber, 33 to 43 weight% of aromatic vinyl compound, and 10 to 15 weight% of vinyl cyanide compound, and within this range, there is an advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0146] The types of alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds included in the above (a-3) graft copolymer may be within the same category as the types of alkyl acrylate rubber, aromatic vinyl compounds, and vinyl cyanide compounds included in the (a-1) graft copolymer described herein.

[0147] The above (a-3) graft copolymer can be prepared, for example, by emulsion polymerization, and in this case, has the advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0148] The above emulsion polymerization is not particularly limited when carried out by an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and, for example, can be carried out by an emulsion graft polymerization method.

[0150] The above (a-3) graft copolymer may, for example, have a graft rate calculated by the above mathematical formula 3 of 15 to 60%, preferably 20 to 50%, more preferably 25 to 45%, and within this range, have an excellent processing dispersion with (b-1) (meth)acrylate alkyl ester polymer and (b-2) (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer.

[0152] The above (a-3) graft copolymer may be, for example, 5 to 70 weight%, preferably 10 to 65 weight%, more preferably 15 to 60 weight% with respect to the total weight of the base resin, and within this range, there is an advantage of excellent gloss and transparency and reduced whitening during bending processing.

[0154] The sum of the weights of the above (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer may be, for example, 15 to 80 weight%, preferably 15 to 75 weight%, more preferably 20 to 70 weight%, even more preferably 30 to 70 weight%, even more preferably 40 to 70 weight%, particularly preferably 50 to 70 weight%, and particularly more preferably 57 to 70 weight% with respect to the total weight of the base resin, and within this range, there is an effect of excellent mechanical properties, gloss, transparency, and processability.

[0156] The above (A) graft copolymer may be one or more selected from the group consisting of, for example, (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer, and in this case, there is an advantage of excellent mechanical properties, gloss, transparency, weather resistance, and colorability.

[0157] The above (A) graft copolymer may preferably be a (a-1) graft copolymer, in which case the mechanical properties are maintained while the gloss, transparency, and weather resistance are excellent, and the occurrence of whitening during bending processing is reduced, resulting in a beautiful appearance and excellent color stability due to reduced changes over time caused by excellent weather resistance.

[0158] The above (A) graft copolymer may preferably be a (a-2) graft copolymer, in which case it has excellent mechanical properties and weather resistance.

[0159] The above (A) graft copolymer may preferably be a (a-3) graft copolymer, in which case the mechanical properties are maintained while the gloss, transparency, and weather resistance are excellent.

[0160] The above (A) graft copolymer may preferably be a mixture of (a-2) graft copolymer and (a-3) graft copolymer, in which case the mechanical properties, gloss, and transparency are excellent, and the change over time is reduced due to excellent weather resistance.

[0161] The mixture of the above (a-2) graft copolymer and (a-3) graft copolymer may, for example, have a weight ratio (a-2:a-3) of 40:60 to 60:40, preferably 45:55 to 55:45, and within this range, mechanical properties such as impact strength, gloss, and colorability are improved.

[0162] In this description, the weight ratio of A to B refers to the weight ratio of A:B.

[0164] (b-1) Alkyl ester polymer of (meth)acrylate

[0165] The above (b-1) (meth)acrylate alkyl ester polymer may comprise, for example, one or more selected from the group consisting of (meth)acrylate methyl ester, (meth)acrylate ethyl ester, (meth)acrylate propyl ester, (meth)acrylate 2-ethylhexyl ester, (meth)acrylate decyl ester, and (meth)acrylate lauryl ester, preferably may be an alkyl methacrylate ester, an alkyl acrylate ester, or a mixture thereof, and more preferably may be a polymethyl methacrylate resin, in which case there is an advantage of excellent mechanical properties, fluidity, and transparency.

[0166] In this description, the (meth)acrylate alkyl ester polymer may mean a polymer comprising more than 85 weight%, 90 weight% or more, or 95 weight% or more of (meth)acrylate alkyl ester.

[0167] Unless otherwise specified in this description, "(meth)acrylate alkyl ester" means that both "alkyl acrylate ester" and "alkyl methacrylate ester" are possible.

[0169] The above polymethyl methacrylate resin may comprise, for example, methyl methacrylate and methyl acrylate, preferably 1 to 10 weight% of methyl acrylate, preferably 2 to 7 weight%, and within this range, it has excellent compatibility with (b-2) (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer, which has the advantage of improving gloss, fluidity, and mechanical properties.

[0171] The above (b-1) polymer may, for example, have a weight-average molecular weight of 50,000 to 150,000 g / mol, preferably 60,000 to 130,000 g / mol, more preferably 70,000 g / mol to 110,000 g / mol, and even more preferably 70,000 to 100,000 g / mol, and within this range, it has the advantage of excellent transparency, gloss, and fluidity while maintaining impact resistance.

[0173] The above (b-1) (meth)acrylate alkyl ester polymer may, for example, have a glass transition temperature of 80 to 130 °C, preferably 90 to 120 °C, and has the advantage of excellent heat resistance within this range.

[0174] In this document, the glass transition temperature can be measured using a Differential Scanning Calorimetry (DSC) in accordance with ASTM D3418, and as a specific example, it can be measured using a Q100 DSC (Differential Scanning Calorimetry) from TA Instrument at a heating rate of 10 ℃ / min.

[0176] The above (b-1) (meth)acrylate alkyl ester polymer may be, for example, 15 to 85 weight%, preferably 20 to 80 weight%, more preferably 25 to 75 weight% with respect to the total weight of the base resin, and within this range, there is an advantage of excellent transparency and gloss while maintaining mechanical properties and reducing whitening during bending processing.

[0178] The above (b-1) (meth)acrylate alkyl ester polymer can be prepared, for example, by suspension polymerization, and the suspension polymerization is not particularly limited to suspension polymerization commonly carried out in the technical field to which the present invention belongs.

[0180] (b-2) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer

[0181] The above (b-2) copolymer comprises, for example, 60 to 85 weight% of an alkyl (meth)acrylate, 10 to 35 weight% of an aromatic vinyl compound, and 1 to 20 weight% of a vinyl cyanide compound based on the total weight thereof, and within this range, it has excellent compatibility with the above (A) graft copolymer and (b-1) (meth)acrylate alkyl ester polymer, excellent mechanical properties, transparency, and gloss, and has the advantage of reducing whitening during bending processing.

[0182] Preferably, the (b-2) copolymer may comprise 65 to 80 weight% of an alkyl meth)acrylate compound, 15 to 30 weight% of an aromatic vinyl compound, and 3 to 15 weight% of a vinyl cyanide compound based on the total weight thereof, and within this range, it has excellent compatibility with the (A) graft copolymer and the (b-1) alkyl meth)acrylate polymer, excellent mechanical properties, transparency, and gloss, and has the advantage of reduced whitening during bending processing.

[0183] More preferably, the (b-2) copolymer may comprise 68 to 74 weight% of an alkyl meth)acrylate compound, 20 to 25 weight% of an aromatic vinyl compound, and 5 to 10 weight% of a vinyl cyanide compound based on the total weight thereof, and within this range, it has excellent compatibility with the (A) graft copolymer and the (b-1) alkyl meth)acrylate polymer, excellent mechanical properties, transparency, and gloss, and has the advantage of reduced whitening during bending processing.

[0185] In this description, the (meth)acrylate alkyl ester compound may be one or more selected from the group consisting of, for example, (meth)acrylate methyl ester, (meth)acrylate ethyl ester, (meth)acrylate propyl ester, (meth)acrylate 2-ethylhexyl ester, (meth)acrylate decyl ester, and (meth)acrylate lauryl ester.

[0186] The types of aromatic vinyl compounds and vinyl cyanide compounds included in the above (b-2) copolymer may be within the same category as the types of aromatic vinyl compounds and vinyl cyanide compounds included in the (a-1) graft copolymer described herein.

[0188] The above (b-2) copolymer may, for example, have a weight-average molecular weight of 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, and within this range, it has the advantage of excellent tensile strength, flexural strength, impact strength, and scratch resistance.

[0190] The above (b-2) copolymer may be, for example, 5 to 45 weight%, preferably 5 to 40 weight%, more preferably 10 to 35 weight% with respect to the total weight of the base resin, and within this range, it has the advantage of excellent compatibility with the above (b-1) (meth)acrylic acid alkyl ester polymer and excellent mechanical properties and fluidity.

[0192] The above (b-2) copolymer may be prepared by bulk polymerization, for example, and the bulk polymerization is not particularly limited to bulk polymerization commonly carried out in the technical field to which the present invention belongs.

[0194] The sum of the weights of the above (b-1) polymer and (b-2) copolymer may be, for example, 20 to 85 weight%, preferably 25 to 85 weight%, more preferably 30 to 80 weight%, even more preferably 30 to 70 weight%, even more preferably 30 to 60 weight%, particularly preferably 30 to 50 weight%, and particularly more preferably 30 to 43 weight% with respect to the total weight of the base resin, and within this range, there are advantages of excellent mechanical properties, gloss, transparency, weather resistance, and colorability.

[0196] (C) One or more selected from the group consisting of benzotriazole-based UV stabilizers, benzoate-based UV stabilizers and benzophenone-based UV stabilizers, having a molecular weight of 280 to 600 g / mol.

[0197] One or more selected from the group consisting of (C) 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, there is an advantage of having excellent impact resistance, transparency, and weather resistance, and as a result of the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance.

[0198] One or more selected from the group consisting of (C) benzotriazole-based UV stabilizers, benzoate-based UV stabilizers and benzophenone-based UV stabilizers may, for example, have a molecular weight of 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, even 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, mechanical properties, gloss, transparency, and weather resistance are excellent, and due to the excellent weather resistance, changes over time are reduced, which has the advantage of a luxurious appearance.

[0200] One or more selected from the group consisting of (C) benzotriazole-based UV stabilizers, benzoate-based UV stabilizers and benzophenone-based UV stabilizers may, for example, have a melting point of 100 to 200 ℃, preferably 110 to 200 ℃, more preferably 120 to 200 ℃, even more preferably 120 to 180 ℃, even more preferably 120 to 160 ℃, particularly preferably 125 to 150 ℃, particularly more preferably 130 to 145 ℃, and most preferably 135 to 144 ℃. Within this range, mechanical properties, gloss, transparency, and weather resistance are excellent, and due to the excellent weather resistance, changes over time are reduced, which has the advantage of a luxurious appearance.

[0201] In this description, the melting point can be measured using a Differential Scanning Calorimeter (DSC: Differential Scanning Calorimeter 2920) manufactured by TA. As a specific measurement example, the melting point can be measured by bringing the DSC to equilibrium at 0°C, raising the temperature to 180°C by increasing it at a rate of 20°C per minute, lowering it to -60°C by decreasing it at a rate of 20°C per minute, and then raising the temperature to 180°C by increasing it at a rate of 10°C per minute. Here, the melting point is obtained by taking the peak region of the endothermic curve during the second temperature increase.

[0203] The above-mentioned benzotriazole-based UV stabilizer may be, for example, one or more selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole, and preferably It may be 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234), in which case it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, so there is an advantage of having excellent color stability and a beautiful appearance.

[0205] The above-mentioned 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 excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and an aesthetic appearance.

[0207] The above-mentioned benzophenone-based UV stabilizers are, for example, 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 disodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid. It may be one or more selected from the group consisting of salts (2,2'-Dihydroxy-4,4'-Dimethoxybenzophenone-5,5'-Disulfonic Acid Disodium Salt), and preferably 4-benzyloxy-2-hydroxybenzophenone. In this case, it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, so it has the advantage of having excellent color stability and a beautiful appearance.

[0209] (D) NH-type HALS-based UV stabilizer with a molecular weight of 300 to 700 g / mol

[0210] The above (D) NH type HALS-based UV stabilizer may be, for example, more than 0.6 parts by weight and 2 parts by weight or less, preferably 0.7 to 1.7 parts by weight, more preferably 0.7 to 1.2 parts by weight per 100 parts by weight of the base resin, and within this range, there is an advantage of having excellent impact resistance, transparency and weather resistance, and as a result of the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance.

[0212] The above (D) NH type HALS-based UV stabilizer may, for example, have a molecular weight of 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, it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance.

[0213] The above (D) NH type HALS-based UV stabilizer may, for example, have a melting point of 60 to 120 ℃, preferably 65 to 110 ℃, more preferably 70 to 100 ℃, even more preferably 70 to 95 ℃, even more preferably 74 to 92 ℃, and particularly preferably 78 to 87 ℃. Within this range, it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, so it has the advantage of having excellent color stability and a beautiful appearance.

[0214] The above (D) NH type HALS-based UV stabilizer may 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, and preferably may be bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate. In this case, it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a luxurious appearance.

[0215] The above (C) UV stabilizer with a molecular weight of 280 to 600 g / mol can be used in a larger amount than, for example, the above (D) NH type HALS-based UV stabilizer, and in this case, it has excellent mechanical properties, gloss, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, so there is an advantage of excellent color stability and a luxurious appearance.

[0216] The weight ratio (C:D) of the above (C) UV stabilizer having a molecular weight of 280 to 600 g / mol and (D) NH-type HALS-based 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, mechanical properties, gloss, transparency, and weather resistance are excellent, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a luxurious appearance.

[0218] The present invention provides a combination of (C) a UV stabilizer with a molecular weight of 280 to 600 g / mol and (D) an NH-type HALS-based UV stabilizer with a molecular weight of 300 to 700 g / mol, preferably a combination of (C) a benzotriazole-based UV stabilizer with a molecular weight of 280 to 600 g / mol and (D) an NH-type HALS-based UV stabilizer with a molecular weight of 300 to 700 g / mol, more preferably a combination of (C) a benzotriazole-based UV stabilizer with a molecular weight of 280 to 600 g / mol and a melting point of 100 to 200 ℃ and (D) an NH-type HALS-based UV stabilizer with a molecular weight of 300 to 700 g / mol and a melting point of 60 to 120 ℃, thereby exhibiting excellent mechanical properties, transparency, and weather resistance, and a synergistic effect in which changes over time are reduced due to the excellent weather resistance.

[0220] Thermoplastic resin composition

[0221] The above thermoplastic resin composition may, for example, have a change over time (△E) calculated by the following mathematical formula 4, where the degree of discoloration is measured by a colorimeter after leaving an injection molded specimen with a thickness of 3 mm for 8,000 hours according to ASTM G155-1 using a weathermeter, and the change over time (△E) is 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, it has excellent mechanical properties, weather resistance, and transparency, and has the advantage of having excellent color stability and a beautiful appearance as the change over time is reduced with weather resistance.

[0222] [Mathematical Formula 4]

[0223]

[0224] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.)

[0226] The above thermoplastic resin composition may, for example, have a change over time (△E) calculated by the above mathematical formula 4, which is measured by a colorimeter after leaving an injection molded specimen with a thickness of 3 mm for 4,000 hours according to ASTM G155-1 using a weathermeter, and the degree of discoloration is 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, it has excellent mechanical properties, transparency, and weather resistance, and has the advantage of having excellent color stability and a beautiful appearance as the change over time is reduced according to weather resistance.

[0228] The above thermoplastic resin composition may, for example, 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 by a sheet with a thickness of 0.15 mm according to ASTM D1003, and within this range, it has the effect of having excellent balance of physical properties and excellent transparency and colorability.

[0230] The above thermoplastic resin composition may, for example, 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 by a sheet with a thickness of 0.15 mm according to ASTM D1003, and within this range, it has the effect of having excellent physical property balance and excellent transparency and colorability.

[0232] For example, when a sheet of the above thermoplastic resin composition with a thickness of 0.15 mm and a width of 10 cm * 10 cm is folded by hand in the MD direction (Machined direction) and TD direction (Traverse direction) and the occurrence of whitening is visually observed on the folded surface, the occurrence of whitening can be reduced. In this case, there is an advantage of excellent physical property balance, superior impact resistance and transparency, and a beautiful appearance.

[0234] The above thermoplastic resin composition has a tensile strength of 300 kgf / cm², measured in accordance with ASTM D412 under a tensile speed of 10 mm / min in the machine direction (MD) of a sheet with a thickness of, for example, 0.15 mm. 2 Ideally, 310 kgf / cm² 2 Ideally, 320 kgf / cm² 2 Ideally, 330 kgf / cm² 2 Ideally, more preferably 350 kgf / cm² 2 Above, particularly preferably 350 to 600 kgf / cm² 2 It can be, and within this range, there is an excellent balance of physical properties and an effect of excellent mechanical properties of injection molded products, extrusion molded products, and calendered products.

[0236] The above 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, even more preferably 60% or more, and particularly preferably 60 to 80%, measured in the machine direction (MD) of a sheet with a thickness of 0.15 mm according to ASTM D412. Within this range, there is an excellent balance of physical properties and an effect of excellent mechanical properties of injection molded articles, extrusion molded articles, and calendered articles.

[0238] The above thermoplastic resin composition may, for example, 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, measured in the machine direction (MD) of a sheet with a thickness of 0.15 mm according to ASTM D624 under conditions of a tensile speed of 10 mm / min, and within this range, the balance of physical properties is excellent and the mechanical properties of injection molded articles, extrusion molded articles, and calendered articles are excellent.

[0240] The above thermoplastic resin composition has a tensile strength of 230 kgf / cm² measured in accordance with ASTM D412 in the transverse direction (TD) of, for example, a sheet with a thickness of 0.15 mm under a tensile speed of 10 mm / min. 2 Ideally, 245 kgf / cm² 2 Ideally, 250 kgf / cm² 2 Above, more preferably 250 to 500 kgf / cm² 2 It can be, and within this range, there is an excellent balance of physical properties and an effect of excellent mechanical properties of injection molded products, extrusion molded products, and calendered products.

[0242] The above 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% when measured in the transverse direction (TD) of a sheet with a thickness of 0.15 mm according to ASTM D412 under conditions of a tensile speed of 10 mm / min, and within this range, there is an excellent balance of physical properties and an effect of excellent mechanical properties of injection molded articles, extrusion molded articles, and calendered articles.

[0244] The above thermoplastic resin composition may, for example, 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, even more preferably 75 kgf / cm, and particularly preferably 75 to 95 kgf / cm, measured in the transverse direction (TD) of a sheet with a thickness of 0.15 mm according to ASTM D624 under conditions of a tensile speed of 10 mm / min, and within this range, have an excellent balance of physical properties and excellent mechanical properties of injection molded articles, extrusion molded articles, and calendered articles.

[0246] The above thermoplastic resin composition may optionally further include, as needed, one or more selected from the group consisting of heat stabilizers, dyes, pigments, colorants, lubricants, release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, flame suppressants, anti-dropping 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, respectively, based on 100 parts by weight of the base resin, and within this range, the necessary physical properties are well realized without degrading the inherent physical properties of the thermoplastic resin composition described herein.

[0247] The above heat stabilizer may preferably include a primary heat stabilizer and a secondary heat stabilizer.

[0248] The above primary heat stabilizer may be, for example, a phenolic 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-hexanediolbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[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-bunyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-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, It may be one or more selected from the group consisting of 2,2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydroxycinnamoyloxy)ethoxyphenyl]propane and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, and more preferably octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate (IR1076).

[0249] The above 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, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, Tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-bunylphenol)diphosphite, tris(mono- and di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol 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, It may be one or more selected from the group consisting of 2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphophen-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphophen-6-yl}oxy]ethyl]-ethanolamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphophen, and more preferably tris(2,4-di-tert-butylphenyl) phosphite (IF168). there is.

[0250] The above lubricant may preferably be one or more selected from the group consisting of aliphatic amide-based lubricants, fatty acid ester-based lubricants, and olefin-based waxes.

[0251] The above-mentioned aliphatic amide-based lubricant may preferably be one or more selected from the group consisting of stearamide, oleamide, erucamide, ethylene bis stearamide, and ethylene bis oleamide.

[0252] The above fatty acid ester-based lubricant may preferably be one or more selected from the group consisting of fatty acid esters of alcohols or polyhydric alcohols, hydrogenated oils, butyl stearate, monoglycerides of stearate, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphate esters.

[0253] The above olefin-based wax may preferably be polyethylene wax.

[0255] Method for manufacturing a thermoplastic resin composition

[0256] A method for manufacturing a thermoplastic resin composition according to the present invention comprises: (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 mm or more to less than 150 nm; and (B) 100 parts by weight of a base resin comprising one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; comprising the step of kneading and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm; wherein the graft copolymer (a-1) is characterized by having an alkyl acrylate coverage (X) value calculated by the following chemical formula 1 of 65% by weight or more. In this case, there is an advantage that the mechanical properties, transparency, and weather resistance are excellent, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance, and it is applicable to injection molding, extrusion molding, and calendering.

[0257] [Mathematical Formula 1]

[0258] X = {(GY) / Y} * 100

[0259] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0261] The method for manufacturing the above-mentioned thermoplastic resin composition shares all the technical features of the aforementioned thermoplastic resin composition. Therefore, the description of the overlapping parts will be omitted.

[0263] The above mixing and extrusion can preferably be carried out using an extrusion mixer at 200 to 300 ℃, more preferably 210 to 260 ℃, and even more preferably 220 to 250 ℃, and within this range, stable extrusion is possible and the mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder.

[0264] The above mixing and extrusion can be performed, for example, under conditions where the screw rotation speed is 100 to 500 rpm, preferably 150 to 450 rpm, more preferably 200 to 400 rpm, and in this case, the throughput per unit time is appropriate, so the process efficiency is excellent.

[0266] The thermoplastic resin composition obtained through the above extrusion can be manufactured into pellets using, for example, a pelletizer.

[0268] The above extrusion mixer is not particularly limited to any extrusion mixer commonly used in the technical field to which the present invention belongs, and preferably may be a twin-screw extrusion mixer.

[0270] molded product

[0271] The molded article of the present invention is characterized by comprising the above-mentioned thermoplastic resin composition, and in this case, it has excellent mechanical properties, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a luxurious appearance, and has the advantage of being applicable to injection molded articles, extrusion molded articles, and calendered articles.

[0272] The above injection molded product may preferably be an automotive interior / exterior part and an electrical / electronic product part, an unpainted molded product, or a metal insert molded product, and specific examples may be a bidet control panel, a lawn robot housing and a pool clean robot housing, a door accessory, or a window frame.

[0274] The above extruded product may preferably be a film, sheet, or foil, and specifically may be a deco sheet, an outdoor building material finishing material, a roofing finishing material, an interior film, wallpaper, an edge band, VCM (Vinyl coated metal), a flooring material, PSP (Plastic-steel-Plastic) for molding, or a wrapping film.

[0276] The above calendar molded product may preferably be a film, sheet, or foil, and specifically may be a deco sheet, an outdoor building material finishing material, a roofing finishing material, an interior film, wallpaper, an edge band, VCM (Vinyl coated metal), a flooring material, PSP (Plastic-steel-Plastic) for molding, or a wrapping film.

[0278] The method for manufacturing the above-mentioned molded article preferably comprises: (A) one or more selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 80 mm or more to less than 150 nm, and (B) 100 parts by weight of a base resin comprising one or more selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol; and (D) more than 0.6 parts by weight and less than or equal to 2 parts by weight of an NH-type HALS-based UV stabilizer having a molecular weight of 300 to 700 g / mol; comprising a step of preparing an extruder by kneading and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm; and a step of preparing a molded article by molding the extruder; wherein the (a-1) graft copolymer may have an alkyl acrylate coverage (X) value calculated by the following chemical formula 1 of 65% by weight or more. In this case, it has excellent mechanical properties, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in superior color stability and a beautiful appearance, and it has the advantage of being applicable to injection molding, extrusion molding, and calendering.

[0279] [Mathematical Formula 1]

[0280] X = {(GY) / Y} * 100

[0281] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0283] The above extruded material may be in the form of pellets or plates, for example.

[0284] In this description, the plate-like form is not particularly limited to what is conventionally defined as a plate-like form in the technical field to which the present invention belongs, and may include, for example, a flat form, a sheet form, a film form, etc.

[0286] In describing the thermoplastic resin composition, the method of manufacturing the same, and the molded article described herein, it is specified that other conditions or equipment not explicitly described may be appropriately selected within the scope of practices ordinarily carried out in the industry and are not particularly limited.

[0288] Hereinafter, preferred embodiments are presented to aid in understanding the description; however, the following embodiments are merely illustrative of the description, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the description, and that such variations and modifications fall within the scope of the appended claims.

[0290] [Example]

[0291] The materials used in the following examples and comparative examples are as follows.

[0292] * (a-1-1) ASA graft copolymer comprising alkyl acrylate rubber having an average particle size of 50 to 120 nm: ASA graft copolymer having an average particle size of 70 nm of alkyl acrylate rubber prepared by emulsion polymerization (Core (rubber): 36 wt% butyl acrylate, 7 wt% styrene, Shell: 4 wt% butyl acrylate, 39.5 wt% styrene and 13.5 wt% acrylonitrile, alkyl acrylate coverage value 99 wt%, Graft rate 77%

[0293] * (a-2) ASA graft copolymer comprising alkyl acrylate rubber having an average particle size of 150 to 600 nm: ASA graft copolymer having an average particle size of 350 nm of alkyl acrylate rubber prepared by emulsion polymerization (Core (rubber): 50 wt% butyl acrylate, Shell: 37.5 wt% styrene and 12.5 wt% acrylonitrile, graft rate 50%)

[0294] * (a-3) ASA graft copolymer comprising alkyl acrylate rubber with an average particle size of 80 nm or more to less than 150 nm: ASA graft copolymer of alkyl acrylate rubber with an average particle size of 130 nm prepared by emulsion polymerization (Core (rubber): 50 wt% butyl acrylate, Shell: 37.5 wt% styrene and 12.5 wt% acrylonitrile, graft rate 35%)

[0295] * (a-1-2) ASA graft copolymer comprising alkyl acrylate rubber having an average particle size of 50 to 120 nm: alkyl acrylate rubber prepared by emulsion polymerization having an average particle size of 65 nm ASA graft copolymer (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 rate 65%)

[0296] * (b-1) PMMA resin of suspension polymerization type: polymethyl methacrylate resin (weight-average molecular weight 80,000 g / mol)

[0297] * (b-2) Bulk polymerization type SAMMA resin: Methyl methacrylate-styrene-acrylonitrile copolymer comprising 70 wt% methyl methacrylate, 22.5 wt% styrene, and 7.5 wt% acrylonitrile (weight-average molecular weight 95,000 g / mol)

[0298] * (C-1) UV234 (BASF): Benzotriazole-based UV stabilizer (2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, molecular weight 447.5 g / mol, melting point 137–141 ℃)

[0299] * (C-2) UV-P (BASF): Benzotriazole-based UV stabilizer (molecular weight 225 g / mol, melting point 128–133 ℃)

[0300] * (C-3) UV360 (BASF): Benzotriazole-based UV stabilizer (molecular weight 658.9 g / mol, melting point 195–198 ℃)

[0301] * (C-4) SONGSORB 7120 (Songwon): Benzoate-based UV stabilizer (molecular weight 438.6 g / mol, melting point 197 ℃)

[0302] * (C-5) SEESORB 105 (Shipro Kasei Kaisha): Benzophenone-based UV stabilizer (molecular weight 304.3 g / mol, melting point 122 ℃)

[0303] * (D-1) UV770 (BASF): NH-type HALS UV stabilizer (molecular weight 480 g / mol, melting point 82–85 ℃)

[0304] * (D-2) Chimassorb 994 (BASF): NH-type HALS UV stabilizer (molecular weight 2000–3100 g / mol, melting point 100–135 ℃)

[0305] * Additives

[0306] - Heat stabilizer: Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate

[0307] - Lubricant: Ethylene bis stearamide

[0309] Examples 1 to 11 and Comparative Examples 1 to 9

[0310] 0.3 parts by weight of a heat stabilizer and 0.3 parts by weight of a lubricant were fed into a twin-screw extruder along with the components and contents listed in Tables 1 and 2 below, respectively, and pellets were prepared by melt-kneading and extruding at 230°C and 150 rpm. The prepared pellets were then injected using an injection molding machine at a molding temperature of 220°C to produce specimens for measuring physical properties.

[0311] In addition, using the manufactured pellets, a sheet with a thickness of 0.15 mm was produced using a T-die extruder (ST32HS of EM Korea (Twin screw, 32T, L / D=44)) with an extrusion screw speed of 150 rpm, a temperature of 210 ℃, a three-axis roll temperature of 80 ℃, and a roll rotation speed of 1.5 m / min, and its physical properties were measured.

[0313] [Test Example]

[0314] The characteristics of the pellets or specimens prepared in Examples 1 to 11 and Comparative Examples 1 to 9 were measured by the following method, and the results are shown in Tables 1 and 2 below.

[0316] measurement method

[0317] * (a-1) Alkyl acrylate coverage value of graft copolymer (X value, weight%): Calculated using the following mathematical formula 1.

[0318] [Mathematical Formula 1]

[0319] X = {(GY) / Y} * 100

[0320] (In the above Equation 1, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.)

[0321] Here, the content of alkyl acrylate in the gel is 1 Quantitative measurements were performed using an NMR analyzer or FT-IR. The specific measurement conditions are as follows.

[0322] 1 H NMR

[0323] - Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe

[0324] - Measurement conditions: 1H NMR(zg30): ns=32, d1=5s, TCE-d2, at room temperature.

[0325] FT-IR

[0326] - Equipment Name: Agilent Cary 66

[0327] - Measurement condition: ATR mode

[0328] * Gel content (%): 1 g of graft copolymer was added to 30 ml of acetone and stirred at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075). The mixture was then centrifuged at 18,000 rpm for 3 hours at 0 ℃ using a centrifuge (Supra R30 from Hanil Science Co.) to collect only the insoluble fraction that did not dissolve in acetone. The mixture was then dried using a forced convection oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85 ℃ for 12 hours by forced circulation drying, and the weight was measured to calculate the gel content using the following mathematical formula 2.

[0329] [Mathematical Formula 2]

[0330] Gel content (%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] * 100

[0331] * Graft rate (%): 0.5 g of dry graft copolymer powder was added to 50 ml of acetone and stirred at room temperature for 12 hours. The mixture was then centrifuged to collect only the insoluble portion that did not dissolve in acetone, dried for 12 hours, and weighed. The rate was calculated using the following mathematical formula 3.

[0332] [Mathematical Formula 3]

[0333] Graft rate (%) = [Weight of grafted monomer (g) / Weight of gum (g)] * 100

[0334] (In the above mathematical formula 3, the weight (g) of the grafted monomer is the weight obtained by subtracting the weight of the rubbery substance (g) from the weight of the insoluble substance (gel) after dissolving the graft copolymer in acetone and centrifuging, and the weight of the rubbery substance (g) is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.)

[0335] Specifically, the weight of the above-mentioned insoluble substance (gel) was determined by adding 0.5 g of dry graft copolymer powder to 50 ml of acetone, stirring at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075), centrifuging the mixture at 18,000 rpm at 0 ℃ for 3 hours using a centrifuge (Supra R30 from Hanil Science Co., Ltd.), collecting only the insoluble material that did not dissolve in acetone, drying it in a forced-circulation oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85 ℃ for 12 hours, and then measuring the weight.

[0336] * Haze (%): The haze of a sheet with a thickness of 0.15 mm was measured according to ASTM D1003.

[0337] * Total light transmittance (%): The total light transmittance of a sheet with a thickness of 0.15 mm was measured according to ASTM D1003.

[0338] * Change over time (△E): Injection molded specimens with a thickness of 3 mm were left for 4,000 hours and 8,000 hours, respectively, using a whetherometer in accordance with ASTM G155-1, and the degree of discoloration was measured using a colorimeter to calculate the change over time (△E) using the following Equation 4.

[0339] [Mathematical Formula 4]

[0340]

[0341] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.)

[0342] * Anti-whitening: A sheet with a thickness of 0.15 mm and a width of 10 cm * 10 cm was folded by hand in the MD (Machined direction) and TD (Traverse direction) directions, and the occurrence of whitening on the folded surface was visually observed and evaluated according to the following criteria.

[0343] ○: No whitening occurred

[0344] △: Normal occurrence of whitening

[0345] X: Frequent occurrence of whitening

[0346] * Tensile strength (kgf / cm²) 2 ) and elongation (%): Measured for each of the length direction (Machine direction; MD) and width direction (transverse direction; TD) of a sheet with a thickness of 0.15 mm under conditions of a tensile speed of 10 mm / min in accordance with ASTM D412.

[0347] * Tear strength (kgf / cm): Measured for each of the length direction (Machine direction; MD) and width direction (transverse direction; TD) of a sheet with a thickness of 0.15 mm under conditions of a tensile speed of 10 mm / min in accordance with ASTM D624.

[0349] division Example 1 2 3 4 5 6 7 8 9 10 11 (a-1-1) ASA 70 60 70 70 70 70 70 (a-2) ASA 25 15 (a-3) ASAS 60 15 (a-1-2) ASA 70 (b-1) PMMA 30 30 30 30 30 75 40 35 30 30 30 (b-2) SAMMA 10 35 (C-1) UV234 1.5 2.0 1 2.5 1.5 1.5 1.5 1.5 1.5 (C-4) SONGSORB 7120 1.5 (C-5) SEESORB 105 1.5 (D-1) UV770 1.0 0.7 0.7 0.7 1.5 1.0 1.0 1.0 1.0 1.0 1.0 (a-1) X value of ASA (weight%) 99 99 99 99 99 - - - 77 99 99 (a-1) ASA graft rate (%) 77 77 77 77 77 - - - 65 77 77 Physical properties Total light transmittance (%) 91.4 90.9 91.4 91.1 91.2 86.7 88.8 84.3 89.8 90.9 89.2 Haze (%) 5.6 4.2 5.0 5.8 5.5 7.5 6.2 9.7 7.8 4.7 8.1 Whitening ○ ○ ○ ○ ○ X X X △ ○ ○ 4,000 hr backward change (△E) 1.07 0.98 1.25 1.21 0.98 0.93 1.28 1.46 1.17 1.92 1.70 Change over time (△E) after 8,000 hours 1.79 1.56 2.57 2.41 1.52 1.18 2.01 2.64 1.93 2.69 2.51 Tensile strength (MD, kgf / cm²) 2 ) 305 327 311 301 312 552 323 448 346 304 308 New Rate (MD, %) 70 46 68 72 69 10 32 15 44 72 65 Tear strength (MD, kgf / cm) 82 76 73 69 82 122 73 101 83 79 82 Tensile strength (TD, kgf / cm²) 2 ) 250 259 249 245 248 483 267 396 236 250 248 TD (Twisted Depth) %) 62 44 64 63 65 16 23 14 43 67 59 Tear strength (TD, kgf / cm) 66 66 64 65 67 80 58 90 76 68 65

[0351] division Comparative example 1 2 3 4 5 6 7 8 9 (a-1-1) ASA 70 70 70 70 70 70 70 70 70 (a-2) ASA (a-3) ASA (a-1-2) ASA (b-1) PMMA 30 30 30 30 30 30 30 30 30 (b-2) SAMMA (C-1) UV234 2.5 1.5 1.5 4.5 0.1 1.5 1.5 (C-2) UV-P 1.5 (C-3) UV360 1.5 (D-1) UV770 0.5 1.0 1.0 1.0 1.0 3.0 0.1 (D-2) Chimassorb994 1.0 0.5 (a-1) X value of ASA (weight%) 99 99 99 99 99 99 99 99 99 (a-1) ASA graft rate (%) 77 77 77 77 77 77 77 77 77 Physical properties Total light transmittance (%) 91.5 91.3 91.3 91.3 91.2 85.4 91.3 86.7 91.5 Haze (%) 5.5 3.3 3.4 3.2 3.7 12.7 5.5 11.3 5.3 Whitening ○ ○ ○ ○ ○ ○ ○ ○ ○ Change in 4,000 hr backwards (△E) 0.90 4.21 3.22 3.08 4.06 3.78 4.47 2.25 1.59 8,000 hr change in background (△E) 6.73 6.78 4.87 4.69 6.42 4.51 6.55 4.19 6.02 Tensile strength (MD, kgf / cm²) 2 ) 299 257 300 300 302 301 309 293 298 New Rate (MD, %) 65 59 69 70 69 72 60 73 66 Tear strength (MD, kgf / cm) 62 75 70 70 73 73 75 70 79 Tensile strength (TD, kgf / cm²) 2 ) 238 215 245 240 242 244 241 235 240 TD (Twisted Depth) %) 52 49 65 63 66 68 63 68 59 Tear strength (TD, kgf / cm) 63 63 62 63 57 69 67 62 62

[0352] (In Tables 1 and 2 above, the respective contents of (a-1-1), (a-2), (a-3), (a-1-2), (b-1), and (b-2) are weight% based on their total weight, and the respective contents of (C-1), (C-2), (C-3), (C-4), (C-5), (D-1), and (D-2) are weight parts based on 100 weight parts of the total weight of (a-1-1), (a-2), (a-3), (a-1-2), (b-1), and (b-2).)

[0354] As shown in Tables 1 to 2 above, the thermoplastic resin compositions of Examples 1 to 11 prepared according to the present invention showed excellent color stability, with light transmittance and haze equivalent to or greater than those of Comparative Examples 1 to 9, which are outside the scope of the present invention, and reduced change over time (△E) after 4,000 hours, particularly after 8,000 hours, and similar or greater tensile strength, elongation, and tear strength. Here, Examples 1 to 5, 10, and 11 containing (a-1-1) ASA graft copolymer and Example 9 containing (a-1-2) ASA graft copolymer had the effect of reducing whitening during bending processing. In addition, Examples 1 to 9 containing (C-1) benzotriazole-based UV stabilizers had a smaller change over time (△E) after 4,000 hours and a smaller change over time (△E) after 8,000 hours.

[0355] Specifically, Comparative Example 1, which did not contain (D-1) UV770, showed a large change over time (△E) after being left for 8,000 hours, while Comparative Example 2, which contained (D-2) Chimassorb994 instead of (D-1) UV770, Comparative Example 3, which contained (D-2) Chimassorb994 and a small amount of (D-1) UV770, and Comparative Examples 4 and 5, which contained (C-2) UV-P and (C-3) UV360 respectively instead of (C-1) UV234, all showed poor change over time (△E) after being left for 4,000 hours and 8,000 hours.

[0356] In addition, Comparative Examples 6 and 7, in which the content of (C-1) UV234 was outside the scope of the present invention, both showed poor changes over time (△E) after being left for 4,000 hours and 8,000 hours, respectively, and Comparative Example 6 even had poor haze and deposits occurred at the die entrance and on the sheet during sheet processing.

[0357] In addition, Comparative Example 8, which contained an excess amount of (D-1) UV770, showed poor haze and changes over time (△E) after 4,000 hours and 8,000 hours, and deposits occurred at the die entrance and on the sheet during sheet processing, while Comparative Example 9, which contained a small amount of (D-1) UV770, showed a large change over time (△E) after 8,000 hours.

[0359] In conclusion, according to the present invention, a thermoplastic resin composition comprising one or more of three types of alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymers containing rubber having a predetermined average particle size, and one or more of (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymers, and one or more selected from the group consisting of 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, was found to have excellent mechanical properties, transparency, and weather resistance, and due to the excellent weather resistance, changes over time are reduced, resulting in excellent color stability and a beautiful appearance. Furthermore, by adjusting the alkyl acrylate coverage value of the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer to within a predetermined range, the effect of reducing whitening during bending processing was also obtained.

Claims

Claim 1 (A) 100 parts by weight of a base resin comprising at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising 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 comprising at least one selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol and a melting point of 120 to 200 ℃; and (D) more than 0.6 parts by weight and less than or equal 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 is characterized by having an alkyl acrylate coverage (X) value calculated by the following Formula 1 of 65% by weight or more. [Formula 1] X = {(GY) / Y} * 100 (In Formula 1 above, G represents the gel content (weight%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (weight%) relative to the total weight of the graft copolymer.) Claim 2 delete Claim 3 A thermoplastic resin composition according to claim 1, wherein the benzotriazole-based ultraviolet stabilizer is one or more selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (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 (2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tertamethylbutyl)]-2H-benzotriazole). Claim 4 A 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. Claim 5 In claim 1, the benzophenone-based UV stabilizer comprises 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 disodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disulfonic acid. A thermoplastic resin composition characterized by being one or more selected from the group consisting of salts (2,2'-Dihydroxy-4,4'-Dimethoxybenzophenone-5,5'-Disulfonic Acid Disodium Salt). Claim 6 A thermoplastic resin composition according to claim 1, characterized in that the (D) NH type HALS-based UV stabilizer has a melting point of 60 to 120 ℃. Claim 7 A thermoplastic resin composition according to claim 1, wherein the (D) NH type HALS-based UV stabilizer is 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. Claim 8 A thermoplastic resin composition according to claim 1, wherein the (a-1) graft copolymer comprises 20 to 60 weight% of alkyl acrylate rubber and 40 to 80 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding it, based on the total weight thereof. Claim 9 A thermoplastic resin composition according to claim 1, characterized in that the sum of the weights of the (a-1) graft copolymer, (a-2) graft copolymer, and (a-3) graft copolymer is 15 to 80 weight% with respect to the total weight of the base resin. Claim 10 A thermoplastic resin composition according to claim 1, characterized in that the sum of the weights of the (b-1) polymer and the (b-2) copolymer is 20 to 85 weight% with respect to the total weight of the base resin. Claim 11 A thermoplastic resin composition according to claim 1, wherein the (b-1) (meth)acrylic acid alkyl ester polymer comprises 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. Claim 12 A thermoplastic resin composition according to claim 1, wherein the (b-2) copolymer comprises 60 to 85 weight% of an alkyl (meth)acrylate, 10 to 35 weight% of an aromatic vinyl compound, and 1 to 20 weight% of a vinyl cyanide compound. Claim 13 A thermoplastic resin composition according to claim 1, wherein the (b-1) polymer and (b-2) copolymer each have a weight-average molecular weight of 50,000 to 150,000 g / mol. Claim 14 The thermoplastic resin composition according to claim 1, characterized in that the change over time (△E) calculated by the following Equation 4 is 3 or less, after leaving an injection molded specimen with a thickness of 3 mm for 8,000 hours in accordance with ASTM G155-1 using a whetherometer and measuring the degree of discoloration with a colorimeter. [Equation 4] (In the above mathematical formula 4, L', a', and b' are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system after the specimen has been left standing, and L0, a0, and b0 are the L, a, and b values ​​measured respectively in the CIE LAB color coordinate system before standing.) Claim 15 (A) 100 parts by weight of a base resin comprising at least one selected from the group consisting of (a-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 120 nm, (a-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 150 to 600 nm, and (a-3) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising 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 comprising at least one selected from the group consisting of (b-1) an alkyl meth)acrylate ester polymer and (b-2) an alkyl meth)acrylate ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer; (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, having a molecular weight of 280 to 600 g / mol and a melting point of 120 to 200 ℃; A method for preparing a thermoplastic resin composition comprising: (D) a step of kneading and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm, wherein the graft copolymer (a-1) has an alkyl acrylate coverage (X) value calculated by the following Formula 1 is 65 wt% or more. [Formula 1] X = {(GY) / Y} * 100 (wherein in Formula 1, G represents the gel content (wt%) relative to the total weight of the graft copolymer, and Y represents the content of alkyl acrylate in the gel (wt%) relative to the total weight of the graft copolymer.) Claim 16 A molded article characterized by comprising a thermoplastic resin composition according to any one of claims 1 and 3 to 14.

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