Thermoplastic resin composition, its manufacturing method and molded article manufactured therefrom

Abstract

The present invention relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition comprising: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the alkyl acrylate-aromatic vinyl compound graft copolymer comprising a seed polymerized containing 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound; a rubber core surrounding the seed and polymerized containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core and polymerized containing 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; wherein the average particle size and refractive index of each layer of the graft copolymer (A) are appropriately adjusted, a manufacturing method thereof, and a molded article manufactured therefrom. The present invention has the effect of providing a thermoplastic resin composition excellent in all of transparency, gloss, weather resistance and impact resistance, a production method thereof and a molded article produced therefrom.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0072522, filed on June 15, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article produced from the same. More specifically, the present invention relates to a thermoplastic resin composition having excellent transparency, gloss, weather resistance, and impact resistance by adjusting the composition and composition ratio of each layer of a graft copolymer having a structure of a polymer seed, a rubber core surrounding the seed, and a graft shell surrounding the core, as well as the morphology of the rubber core, and further adjusting the difference in refractive index from the matrix polymer, as well as a method for producing the same and a molded article produced from the same. [Background technology]

[0003] Acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as "ASA resin") has excellent weather resistance because it does not contain unstable double bonds within the polymer, and is therefore widely used in various fields such as electrical and electronic parts, building materials (e.g., vinyl siding), extrusion profiles, and automotive parts. Recently, in the field of outdoor products, there has been a continuous increase in market demand for high-value-added products with properties such as unpainted, transparency, high saturation, and special colors.

[0004] In order to realize transparency in a graft copolymer containing a rubber core, the refractive indexes of the rubber core, the graft shell, and the matrix resin must be close to each other. Furthermore, in a resin composition containing a graft copolymer and a matrix resin, if the difference between the refractive indexes of the rubber core and the matrix resin is small, refraction and reflection of light do not occur at the interface of the graft copolymer, making the resin composition transparent.

[0005] In an ASA resin comprising a butyl acrylate rubber core and a styrene-acrylonitrile copolymer shell, the refractive index of the butyl acrylate rubber is 1.46, and the refractive index of the styrene-acrylonitrile copolymer is 1.56 to 1.58, so the difference in refractive index between the core and shell is large, making the resin opaque. Furthermore, when a styrene-acrylonitrile copolymer (hereinafter referred to as "SAN resin") is used as the matrix resin for the ASA resin, the refractive index of the SAN resin is 1.56 to 1.58, so the resin composition is opaque, because the refractive index of the SAN resin is 1.56 to 1.58, so the difference in refractive index between the ASA resin core and the SAN resin is large.

[0006] Therefore, there is a need to develop a resin composition that achieves transparency while also having excellent gloss and mechanical properties and further improved weather resistance by reducing the difference between the refractive index of each of the seed, core, and shell that make up the ASA resin and the refractive index of the matrix resin. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent Publication No. 10-2006-0118156 Summary of the Invention [Problem to be solved by the invention]

[0008] In order to solve the above-mentioned problems of the prior art, an object of the present invention is to provide a thermoplastic resin composition having excellent transparency, gloss, weather resistance, and impact resistance, a method for producing the same, and a molded article produced from the same.

[0009] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0010] To achieve the above object, the present invention provides I) a thermoplastic resin composition comprising: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer, the graft copolymer comprising a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound, wherein the graft copolymer (A) satisfies the following mathematical formula 1:

[0011] [Formula 1] 180≦2×r2≦300 (In the above formula 1, r2 is the thickness (nm) from the center of the graft copolymer to the core.)

[0012] The present invention also provides II) a thermoplastic resin composition comprising: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising: a seed polymerized containing 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound; a rubber core surrounding the seed polymerized containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized containing 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; wherein the graft copolymer (A) simultaneously satisfies the following formula 1 and formula 2:

[0013] [Formula 1] 180≦2×r2≦300

[0014] [Formula 2] 25≦r2-r1≦45

[0015] In the above formulas 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the rubber core.

[0016] III) In the above I) or II), the graft copolymer (A) may preferably have a difference in refractive index between the rubber core and the shell of 0.093 or less.

[0017] IV) In the above I) to III), the difference between the refractive index of the polymer seed of the graft copolymer (A) and the refractive index of the non-graft copolymer (B) may preferably be 0.015 or less.

[0018] V) In the above I) to IV), the (A) graft copolymer may preferably contain 5 to 35% by weight of seeds, 25 to 55% by weight of rubber cores, and 25 to 55% by weight of graft shells, relative to a total of 100% by weight.

[0019] VI) In the above I) to V), the (B) non-graft copolymer may preferably contain 55 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound.

[0020] VII) In the above I) to VI), the thermoplastic resin composition may preferably contain 10 to 90% by weight of (A) the graft copolymer and 10 to 90% by weight of (B) the non-graft copolymer.

[0021] VIII) In the above I) to VII), the thermoplastic resin composition may preferably contain (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core with an average particle size of 50 to 150 nm.

[0022] IX) In the above II) to VIII), the thermoplastic resin composition may preferably be added with acetone, followed by stirring and centrifuging to separate the composition into a sol and a gel, and the difference in refractive index between the sol and the gel measured may be 0.006 or less.

[0023] X) In the above II) to IX), the thermoplastic resin composition may preferably have a haze of 10% or less as measured on an injection molded specimen having a thickness of 3 mm in accordance with ASTM D1003.

[0024] XI) In the above I) to X), the thermoplastic resin composition may preferably have a gloss of 122 or more as measured at 45° using an injection molded specimen having a thickness of 3 mm in accordance with ASTM D2457.

[0025] XII) In the above II) to XI), the thermoplastic resin composition may preferably have an Izod impact strength of 10 kgf cm / cm or more, measured at room temperature using a ¼ inch thick test piece in accordance with ASTM D256.

[0026] The present invention also provides a method for producing a thermoplastic resin composition, comprising the steps of: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the method comprising: a seed polymerized containing 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound; a rubber core surrounding the seed polymerized containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized containing 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, the graft copolymer simultaneously satisfying the following formulas 1 and 2:

[0027] [Formula 1] 180≦2×r2≦300

[0028] [Formula 2] 25≦r2-r1≦45

[0029] In the above formulas 1 and 2, r1 is the thickness (nm) from the center of the graft copolymer to the seed, and r2 is the thickness (nm) from the center of the graft copolymer to the core.

[0030] XIV) In the above XIII), the kneading and extruding step may preferably include (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core average particle size of 50 to 150 nm.

[0031] The present invention also provides XV) a molded article comprising the thermoplastic resin composition of any one of I) to XII). [Effects of the Invention]

[0032] The present invention has the effect of providing a thermoplastic resin composition that is excellent in impact resistance as well as transparency, gloss and weather resistance, a method for producing the same, and a molded article produced from the same.

[0033] In addition, the thermoplastic resin composition of the present invention is useful for automobile interior and exterior materials, building materials, home appliances, and medical parts, which require high transparency, gloss, and weather resistance, and has the advantage of imparting excellent impact resistance as well as beautiful appearance. DETAILED DESCRIPTION OF THE INVENTION

[0034] The thermoplastic resin composition of the present invention, its production method, and molded articles produced therefrom will be described in detail below.

[0035] The present inventors have confirmed that in order to improve the transparency, gloss, weather resistance, and impact resistance of a thermoplastic resin composition containing an ASA resin and a matrix resin, the structure, composition ratio, and / or difference in refractive index of the seed, core, and shell that make up the ASA resin are adjusted to within a predetermined range, and / or the difference in refractive index with the matrix resin is narrowed, thereby significantly improving the transparency, gloss, and weather resistance while maintaining excellent impact resistance. Based on this, the inventors have continued their research and have completed the present invention.

[0036] The thermoplastic resin composition of the present invention comprises: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer, the graft copolymer comprising a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound, wherein the graft copolymer (A) satisfies the following mathematical formula 1:

[0037] [Formula 1] 180≦2×r2≦300 (In the above formula 1, r2 is the thickness (nm) from the center of the graft copolymer to the core.)

[0038] The thermoplastic resin composition of the present invention comprises: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a seed polymerized with 45 to 72% by weight of alkyl acrylate and 28 to 55% by weight of aromatic vinyl compound; a rubber core surrounding the seed polymerized with 78 to 91% by weight of alkyl acrylate and 9 to 22% by weight of aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized with 65 to 82% by weight of aromatic vinyl compound, 12 to 30% by weight of vinyl cyan compound, and 3 to 15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, wherein the graft copolymer (A) simultaneously satisfies the following formulas 1 and 2. In this case, the composition exhibits excellent transparency, gloss, weather resistance, and impact resistance.

[0039] [Formula 1] 180≦2×r2≦300

[0040] [Formula 2] 25≦r2-r1≦45

[0041] In the above formulas 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.

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

[0043] (A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer The (A) graft copolymer may be, for example, an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core. Preferably, the (A) graft copolymer may include a seed polymerized with 45 to 72% by weight of alkyl acrylate and 28 to 55% by weight of aromatic vinyl compound, a rubber core surrounding the polymer seed and polymerized with 78 to 91% by weight of alkyl acrylate and 9 to 22% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core and polymerized with 65 to 82% by weight of aromatic vinyl compound, 12 to 30% by weight of vinyl cyanide compound, and 3 to 15% by weight of alkyl acrylate. In this case, the graft copolymer has excellent transparency, gloss, weather resistance, and impact resistance. The introduction of alkyl acrylate into the graft shell provides excellent compatibility with the (B) non-graft copolymer, resulting in an excellent balance of physical properties.

[0044] seed The polymer seed of the graft copolymer (A) may be polymerized containing, for example, 45 to 72% by weight of alkyl acrylate and 28 to 55% by weight of aromatic vinyl compound, preferably 50 to 70% by weight of alkyl acrylate and 30 to 50% by weight of aromatic vinyl compound, more preferably 57 to 67% by weight of alkyl acrylate and 33 to 43% by weight of aromatic vinyl compound, and even more preferably 62 to 67% by weight of alkyl acrylate and 33 to 38% by weight of aromatic vinyl compound. In this case, the difference in refractive index between the graft copolymer (A) and the non-graft copolymer (B) is reduced, resulting in excellent transparency, gloss, and weather resistance.

[0045] The polymer seeds of the graft copolymer (A) may have, for example, an average particle size of 120 to 220 nm, preferably 150 to 190 nm. Within this range, the final thermoplastic resin composition can be imparted with excellent impact resistance, fluidity, transparency, gloss, and weather resistance.

[0046] In this description, the average particle size of the polymer seed, rubber core, and graft shell of the graft copolymer may be measured by a method commonly used in the technical field to which the present invention pertains, including electron microscopy using SEM, TEM, etc., and is not particularly limited thereto. For example, samples may be taken at the completion of the preparation of the polymer seed, the preparation of the rubber core, and the preparation of the graft shell, and the measurements may be made using dynamic light scattering. More specifically, the measurements may be made using a particle size analyzer (product name: Nicomp380, manufacturer: PSS) in Gaussian mode, as intensity values. As a specific measurement example, 0.1 g of sample latex (TSC 35-50 wt%) is diluted 1,000-5,000 times with deionized or distilled water, i.e., diluted appropriately so as not to deviate significantly from the intensity setpoint of 300 kHz, and placed in a glass tube. The measurement method is auto-dilution and measurement is performed using a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis, and the settings are a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0047] The difference between the refractive index of the polymer seed of the graft copolymer (A) and the refractive index of the non-graft copolymer (B) may be, for example, 0.015 or less, preferably 0.01 or less, more preferably 0.008 or less, even more preferably 0.006 or less, even more preferably 0.004 or less, and particularly preferably 0.001 to 0.004. Within this range, there are advantages such as excellent transparency, gloss, and weather resistance.

[0048] Rubber Core For example, the rubber core of the (A) graft copolymer may surround the seed and be polymerized containing 78 to 91% by weight of alkyl acrylate and 9 to 22% by weight of aromatic vinyl compound, preferably 81 to 88% by weight of alkyl acrylate and 12 to 19% by weight of aromatic vinyl compound, more preferably 84 to 88% by weight of alkyl acrylate and 12 to 16% by weight of aromatic vinyl compound. In this case, the rubber core has an excellent balance of physical properties, and is excellent in impact resistance, transparency, gloss, and weather resistance.

[0049] The rubber core may have an average particle size of, for example, 180 to 300 nm, preferably 200 to 280 nm, and more preferably 230 to 260 nm. Within this range, the rubber core has the effect of achieving excellent balance of physical properties and excellent impact resistance.

[0050] Graft Shell The graft shell of the (A) graft copolymer may, for example, surround the rubber core and be polymerized with 65 to 82 wt% aromatic vinyl compound, 12 to 30 wt% vinyl cyanide compound, and 3 to 15 wt% alkyl acrylate, preferably 66 to 78 wt% aromatic vinyl compound, 14 to 26 wt% vinyl cyanide compound, and 3 to 13 wt% alkyl acrylate, more preferably 68 to 78 wt% aromatic vinyl compound, 16 to 22 wt% vinyl cyanide compound, and 5 to 12 wt% alkyl acrylate, and even more preferably 70 to 75 wt% aromatic vinyl compound, 18 to 21 wt% vinyl cyanide compound, and 6 to 10 wt% alkyl acrylate. In this case, the introduction of alkyl acrylate into the graft shell provides excellent compatibility with the (B) non-graft copolymer, resulting in an excellent balance of physical properties, including transparency, gloss, and weather resistance.

[0051] The difference between the refractive index of the rubber core of the graft copolymer (A) and the refractive index of the graft shell of the graft copolymer (A) may be, for example, 0.093 or less, preferably 0.090 or less, more preferably 0.070 to 0.090, even more preferably 0.080 to 0.090, and even more preferably 0.082 to 0.088. Within this range, the transparency, gloss, weather resistance, and impact resistance are all excellent.

[0052] In the present description, the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably styrene.

[0053] In the present description, the vinyl cyanide compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, and preferably acrylonitrile.

[0054] In the present description, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and may be preferably one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, more preferably an alkyl acrylate containing an alkyl group having 1 to 4 carbon atoms, and even more preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof.

[0055] For example, the (A) graft copolymer simultaneously satisfies the following formula 1 and formula 2. In this case, the thickness of the rubber core of the (A) graft copolymer, which has a large difference in refractive index from the (B) non-graft copolymer, is reduced, resulting in excellent transparency, gloss, weather resistance, and impact resistance.

[0056] [Formula 1] 180≦2×r2≦300

[0057] [Formula 2] 25≦r2-r1≦45

[0058] In the above formulas 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.

[0059] The formula 1 may preferably be 200≦2×r2≦280, more preferably 230≦2×r2≦260, and within this range, the effect of excellent impact resistance is obtained.

[0060] The formula 2 may preferably be 30≦r2−r1≦40, more preferably 32≦r2−r1≦37, and within this range, there is an effect of excellent transparency.

[0061] The r1 may also be the average particle size of the seeds divided by half, and the r2 may also be the average particle size of the cores containing the seeds divided by half.

[0062] The r2-r1 represents the thickness of the rubber core, and the thinner the thickness of the rubber core, the easier it is for light to pass through, resulting in improved transparency and gloss.

[0063] In this description, the refractive index of each of the polymer seed, rubber core, and graft shell of the graft copolymer, and the refractive index of the non-graft copolymer (B) can be calculated by the following Equation 3.

[0064] [Formula 3] RI=ΣWti×RIi Wti = weight fraction (%) of each component in the copolymer RIi = refractive index of each component polymer of the copolymer

[0065] In this description, the refractive index of each component of the copolymer, i.e., the monomer polymer, is not particularly limited as long as it is a value generally accepted in the technical field to which the present invention pertains. For example, methyl methacrylate may have a refractive index of 1.49, butyl acrylate may have a refractive index of 1.46, styrene may have a refractive index of 1.592, and acrylonitrile may have a refractive index of 1.52.

[0066] The graft copolymer (A) may have a gel content of, for example, 70 to 98% by weight, preferably 80 to 95% by weight, and more preferably 82 to 92% by weight. Within this range, the copolymer has the effect of exhibiting excellent mechanical properties such as impact resistance.

[0067] The graft copolymer (A) may have a swelling index of, for example, 2.5 to 10, preferably 3 to 7, and more preferably 4 to 6. Within this range, the graft copolymer has the effect of exhibiting excellent weather resistance while also exhibiting excellent mechanical properties such as impact resistance.

[0068] The graft copolymer (A) may have a graft ratio of, for example, 30% or more, preferably 35 to 70%, and more preferably 35 to 60%. Within this range, the copolymer has the effect of exhibiting excellent weather resistance while also exhibiting excellent mechanical properties such as impact resistance.

[0069] The gel content, swelling index, and graft ratio described herein can be calculated by adding 30 g of acetone to 0.5 g of graft copolymer powder, stirring at 210 rpm at room temperature for 12 hours (SKC-6075, Lab Companion), centrifuging the mixture at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30, Hanil Science), collecting only the insoluble matter that did not dissolve in acetone, drying it at 85°C for 12 hours using a forced circulation method (OF-12GW, Lab Companion), and measuring its weight, and then calculating the values ​​using the following Equations 4, 5, and 6.

[0070] [Formula 4] Gel content (wt%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] × 100

[0071] [Formula 5] Swelling index = Weight of insoluble matter after centrifugation and before drying (g) / Weight of insoluble matter after centrifugation and after drying (g)

[0072] [Formula 6] Graft rate (%) = [weight of grafted monomer (g) / weight of rubber (g)] × 100 (In Equation 6, the weight (g) of the grafted monomer is the weight (g) of the insoluble substance (gel) obtained after dissolving the graft copolymer in acetone and centrifuging the solution, minus the weight (g) of the rubbery substance, and the weight (g) of the rubbery substance is the weight (g) of the rubbery component theoretically added to the graft copolymer powder.)

[0073] In this description, normal temperature may be a point within the range of 20±5°C.

[0074] The graft copolymer (A) may contain, for example, 5 to 35% by weight, preferably 10 to 30% by weight, and more preferably 15 to 25% by weight of the polymer seeds relative to the total weight of the copolymer (A). Within this range, the polymer seeds have the effect of providing excellent impact resistance and a good balance of physical properties. If the content of the polymer seeds is less than this range, the transparency decreases, and if it exceeds this range, the impact resistance decreases.

[0075] The (A) graft copolymer may contain, for example, 25 to 55 wt %, preferably 30 to 50 wt %, and more preferably 35 to 45 wt % of the rubber core relative to the total weight of the (A) graft copolymer. Within this range, the impact resistance and balance of physical properties are excellent. If the rubber core content is less than this range, the rubber content will be low, and the impact reinforcement effect of the graft copolymer may be reduced. If the rubber core content is more than this range, the graft shell content will be low, and the rubbers may aggregate during aggregation. This significantly reduces compatibility with the (B) non-graft copolymer, resulting in a reduced impact reinforcement effect and an inability to obtain the desired refractive index.

[0076] The (A) graft copolymer may contain, for example, 25 to 55 wt %, preferably 30 to 50 wt %, and more preferably 35 to 45 wt % of the graft shell relative to the total 100 wt % of the copolymer, and within this range, excellent impact resistance and a good balance of physical properties can be achieved. If the content of the graft shell is less than this range, the graft efficiency decreases, causing the rubber to aggregate, which reduces compatibility with the (B) non-graft copolymer and reduces the impact reinforcement effect. However, if the content of the graft shell is excessive, the relative decrease in the rubber content causes a problem of reduced impact resistance.

[0077] The core of the rubber component may be, for example, an acrylic rubber polymerized with alkyl acrylate, an aromatic vinyl compound, and a crosslinking agent. When a crosslinking agent is included, the gel content can be controlled, and there are advantages in that the impact resistance is excellent.

[0078] The polymer seed, the rubber core, or both may contain, as a crosslinking agent, one or more selected from the group consisting of divinylbenzene, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, aryl acrylate, aryl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, triallyl isocyanurate, triarylamine, diallylamine, and a compound represented by the following Chemical Formula 1:

[0079] [ka]

[0080] In the above chemical formula 1, A' is independently a substituent having a vinyl group or a (meth)acrylate group; A' is a hydrogen atom, a substituent having a vinyl group, an alkyl group having 1 to 30 carbon atoms, an allylalkyl group having 5 to 24 carbon atoms, an arylamine group having 5 to 24 carbon atoms, or an allyl group having 6 to 30 carbon atoms; R's are independently a divalent ethyl group or a propyl group; and n is an integer of 0 to 15 or 1 to 15, preferably 0 to 5 or 1 to 5, and more preferably 0 to 4 or 1 to 4.

[0081] For example, the crosslinking agent may be used in an amount of 0.001 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on a total of 100 parts by weight of the monomers used in producing the polymer seed, rubber core, and graft shell of the (A) graft copolymer.

[0082] In this description, the content of a monomer in a polymer may refer to the weight % of the monomer added when the polymer is produced, or the weight % of the unit in the polymer converted to the monomer.

[0083] The method for producing the graft copolymer (A) may, for example, include the steps of: i) producing a polymer seed containing 45 to 72 wt% of an alkyl acrylate and 28 to 55 wt% of an aromatic vinyl compound; ii) producing a rubber core containing 78 to 91 wt% of an alkyl acrylate and 9 to 22 wt% of an aromatic vinyl compound in the presence of the polymer seed; and iii) graft polymerizing 65 to 82 wt% of an aromatic vinyl compound, 12 to 30 wt% of a vinyl cyanide compound, and 3 to 15 wt% of an alkyl acrylate in the presence of the rubber core to produce a graft copolymer. In this case, the graft copolymer has excellent transparency, gloss, weather resistance, and impact resistance.

[0084] The method for producing the graft copolymer (A) preferably includes the steps of: i) producing a polymer seed containing 45 to 72% by weight of an alkyl acrylate, 28 to 55% by weight of an aromatic vinyl compound, an electrolyte, a crosslinking agent, an initiator, and an emulsifier; ii) producing a rubber core in the presence of the polymer seed containing 78 to 91% by weight of an alkyl acrylate, 9 to 22% by weight of an aromatic vinyl compound, a crosslinking agent, an initiator, and an emulsifier; and iii) producing a graft copolymer by graft polymerization in the presence of the rubber core containing 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyanide compound, 3 to 15% by weight of an alkyl acrylate, a crosslinking agent, an initiator, and an emulsifier. In this case, the graft copolymer has excellent transparency, gloss, and weather resistance.

[0085] In steps i), ii), and iii), the emulsifier is not particularly limited as long as it is an emulsifier commonly used in the technical field to which the present invention pertains, and may be, for example, one or more selected from the group consisting of a metal salt of alkyl sulfosuccinate having 12 to 18 carbon atoms or a derivative thereof, an alkyl sulfate ester having 12 to 20 carbon atoms or a derivative thereof, a metal salt of alkyl sulfonate having 12 to 20 carbon atoms or a derivative thereof, a fatty acid soap, and a rosin acid soap.

[0086] The metal salt of alkyl sulfosuccinate having 12 to 18 carbon atoms or a derivative thereof may preferably be at least one selected from the group consisting of dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt, and dioctyl sulfosuccinate potassium salt.

[0087] The alkyl sulfate ester having 12 to 20 carbon atoms or a derivative thereof, and the metal alkyl sulfonate having 12 to 20 carbon atoms or a derivative thereof may preferably be one or more selected from the group consisting of sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium octadecyl sulfate, sodium oleyl sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate.

[0088] The fatty acid soap may preferably be one or more selected from the group consisting of sodium salts or potassium salts of oleic acid, stearic acid, lauric acid, and mixed fatty acids.

[0089] The rosin acid soap may preferably be an abietic acid salt.

[0090] As an example, the emulsifier can be used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 1 to 3 parts by weight, based on 100 parts by weight in total of the monomers used in producing the polymer seed, rubber core, and graft shell of the (A) graft copolymer.

[0091] In the steps i), ii) and iii), the initiator is not particularly limited, but a radical initiator can be preferably used.

[0092] The radical initiator may be, for example, one or more selected from the group consisting of inorganic peroxides, organic peroxides, peroxyketal peroxides, peroxycarbonate peroxides, and azo compounds.

[0093] The inorganic peroxide may preferably be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide.

[0094] The organic peroxides include t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, di-t-amyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)-cyclohexane, 1,1-di(t-amylperoxy)-cyclohexane, and 1,1-di(t-amylperoxy)-cyclohexane. Cyclohexane, ethyl 3,3-di(t-amylperoxy)-butyrate, diisopropylbenzene mono-hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, di-(3,3,5-trimethylhexanoyl)-peroxide, t-butyl peroxy-2-ethylhexanoate, t-butylperoxy-3,3,5-trimethylhexanoyl, t-amyl peroxyneodecanoate ester, t-amyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxy-2-ethylhexyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1 The peroxide may be one or more selected from the group consisting of 1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, di-2-ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutyl peroxy neodecanoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxyisobutyrate.

[0095] The peroxyketal peroxide may preferably be one or more selected from the group consisting of 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, ethyl-3,3-di(t-butylperoxy)butyrate, and ethyl-3,3-di(t-amylperoxy)butyrate.

[0096] The peroxycarbonate peroxide may preferably be at least one selected from the group consisting of dicumyl peroxide, di(t-butylperoxy)-m / p-diisopropylbenzene, 2,5-dimethyl-2,5-(t-butylperoxy)hexane, t-butylcumyl peroxide, dialkyl peroxides such as 2,5-methyl-2,5-(t-butylperoxy)hexyne-3, t-butylperoxy 2-ethylhexyl monocarbonate, and t-butylperoxybenzoate.

[0097] The azo compound may preferably be at least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate (butyrate).

[0098] In at least one of steps i), ii), and iii), an activator may be used together with the polymerization initiator to promote the initiation reaction of the peroxide.

[0099] The activator is not particularly limited as long as it is an activator commonly used in the technical field to which the present invention pertains.

[0100] The activator may be added in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the total graft copolymer, and within this range, there is an advantage that a high degree of polymerization can be achieved.

[0101] In steps i), ii) and iii), for example, an oxidation-reduction catalyst may be used together with the initiator to further promote the initiation reaction.

[0102] The oxidation-reduction catalyst may be, for example, one or more selected from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediaminetetraacetate, and preferably may be a mixture of sodium pyrophosphate, dextrose, and ferrous sulfide, but is not limited thereto.

[0103] In step i), the electrolyte may be, for example, one or more selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO4, Na2S2O7, K3P2O7, K3PO4, Na3PO4, and Na2HPO4, but is not limited thereto.

[0104] For example, step iii) may include a molecular weight regulator.

[0105] The amount of the molecular weight modifier may be, for example, 0.01 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total graft copolymer. Within this range, a polymer having the desired molecular weight can be easily produced.

[0106] The molecular weight modifier may be, for example, at least one selected from the group consisting of α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanthogen disulfide, but is not limited thereto.

[0107] In this description, 100 parts by weight of the graft copolymer means 100 parts by weight of the total weight of the final graft copolymer, or, since almost all of the added monomers participate in the polymerization, it can conveniently mean the combined weight of all the monomers used in the polymer seed, rubber core, and graft shell, or the combined weight of all the monomers added during the preparation of the polymer seed and rubber core and the monomers added during the preparation of the graft shell, which is 100 parts by weight.

[0108] The graft copolymer (A) may be produced by emulsion polymerization, for example, and in this case, it has the effect of being excellent in chemical resistance, weather resistance, fluidity, tensile strength, and impact strength.

[0109] The emulsion polymerization is not particularly limited as long as it is an emulsion polymerization method commonly used in the technical field to which the present invention pertains.

[0110] The polymerization temperature during the emulsion polymerization is not particularly limited, but may be, for example, 50 to 85°C, and preferably 60 to 80°C.

[0111] The latex of the graft copolymer (A) may be powdered through, for example, conventional processes such as coagulation, washing, and drying. Specifically, the latex may be coagulated at a temperature of 60 to 100°C by adding a metal salt or an acid coagulant, and then aged, dehydrated, washed, and dried, resulting in a powdered product, but is not limited thereto.

[0112] The amount of the (A) graft copolymer is, for example, 10 to 90% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight, based on the total weight of the (A) graft copolymer and the (B) non-graft copolymer. Within this range, the transparency, gloss, weather resistance, and impact resistance are all excellent.

[0113] (B) A non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound. The (B) non-graft copolymer is a matrix resin, and for example, comprises an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, preferably 55 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the (A) graft copolymer, and exhibits excellent transparency, gloss, weather resistance, and impact resistance.

[0114] The non-graft copolymer (B) preferably contains 60 to 80% by weight of alkyl (meth)acrylate, 15 to 30% by weight of aromatic vinyl compound, and 1 to 15% by weight of vinyl cyan compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the graft copolymer (A), and exhibits excellent transparency, gloss, and impact resistance.

[0115] The (B) non-graft copolymer more preferably contains 65 to 75% by weight of alkyl (meth)acrylate, 20 to 25% by weight of aromatic vinyl compound, and 5 to 10% by weight of vinyl cyan compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the (A) graft copolymer, and exhibits excellent transparency, gloss, weather resistance, and impact resistance.

[0116] In this description, "ungrafted" means not grafted, and more specifically, not grafted to a rubber.

[0117] In this description, alkyl (meth)acrylate can be defined to include both alkyl acrylates and alkyl methacrylates.

[0118] The alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and may be 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, and may be preferably an alkyl acrylate containing an alkyl group having 1 to 4 carbon atoms, and more preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof.

[0119] The alkyl methacrylate may be, for example, an alkyl methacrylate having an alkyl group with 1 to 15 carbon atoms, preferably one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, more preferably an alkyl methacrylate containing an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl methacrylate.

[0120] The types of aromatic vinyl compounds and vinyl cyan compounds contained in the non-graft copolymer (B) may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds contained in the graft copolymer (A) described herein.

[0121] The non-graft copolymer (B) may preferably be a methyl methacrylate-styrene-acrylonitrile copolymer. In this case, the difference in refractive index between the graft copolymer (A) and the polymer seed becomes small, resulting in excellent transparency and gloss.

[0122] The non-graft copolymer (B) may have a weight average molecular weight of, for example, 50,000 to 150,000 g / mol, preferably 60,000 to 130,000 g / mol, and more preferably 70,000 to 100,000 g / mol. Within this range, the copolymer has the effect of providing excellent impact resistance and moldability.

[0123] In this description, unless otherwise specified, the weight average molecular weight can be measured using GPC (gel permeation chromatography, water breeze), and specifically, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using THF (tetrahydrofuran) as an eluent. In this case, as a specific measurement example, the following conditions can be used: solvent: THF, column temperature: 40°C, flow rate: 0.3 ml / min, sample concentration: 20 mg / ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35°C, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): Measurement can be performed under the conditions of OECD TG 118.

[0124] The (B) non-graft polymer may be produced, for example, by the steps of: i) mixing 25 to 35 parts by weight of a reaction medium with 100 parts by weight of a monomer mixture containing 10 to 35% by weight of an aromatic vinyl compound, 55 to 85% by weight of an alkyl (meth)acrylate, and 1 to 20% by weight of a vinyl cyan compound to produce a reaction mixture; ii) adding 0.005 to 0.05 parts by weight of a bifunctional organic peroxide initiator to the reaction mixture of step i) relative to 100 parts by weight of the reaction mixture; and iii) polymerizing the mixture to which the initiator of step ii) has been added.

[0125] The polymerization in the step iii) can be preferably carried out by a method in which polymerization is carried out at 110 to 140°C for 2 to 4 hours, and then polymerization is further carried out at 120 to 160°C for 2 to 4 hours.

[0126] In step i), the reaction medium may be, for example, one or more selected from the group consisting of ethylbenzene, toluene, and xylene, and is preferably toluene.

[0127] In step ii), the bifunctional organic peroxide initiator may be, for example, one or more selected from the group consisting of cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-butylperoxy)2-methylcyclohexane. In this case, the advantages of excellent productivity and reduced thermal discoloration are obtained.

[0128] The step iii) may include, for example, an antioxidant, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight in total of the aromatic vinyl compound, alkyl (meth)acrylate, and vinyl cyan compound.

[0129] The non-graft copolymer (B) may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, preferably bulk polymerization. The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization may be any of the solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization methods commonly used in the technical field to which the present invention pertains, and are not particularly limited.

[0130] The non-graft copolymer (B) is, for example, 10 to 90% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight, based on the total weight of the graft copolymer (A) and the non-graft copolymer (B). Within this range, the copolymer has the advantages of excellent transparency, gloss, weather resistance, and impact resistance.

[0131] In this description, a polymer comprising a certain compound means a polymer that is polymerized containing that compound, and the monomers in the polymer are derived from that compound.

[0132] (C) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer having an average particle size of the rubber core of 50 to 150 nm As an example, the thermoplastic resin composition may contain (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having an average particle size of the rubber core of 50 to 150 nm. In this case, there is an advantage that the compatibility with (B) the non-graft copolymer is excellent, and the transparency, gloss, and weather resistance are further improved.

[0133] The (C) graft copolymer may preferably be a graft copolymer having an average particle size of 50 to 150 nm, comprising a rubber core containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core and containing 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate. In this case, there are advantages in that the compatibility with the (B) non-graft copolymer is excellent, the impact resistance is excellent, and the transparency, gloss, and weather resistance are further improved.

[0134] The (C) graft copolymer more preferably has an average particle size of 70 to 130 nm and can include a rubber core containing 80 to 90% by weight of an alkyl acrylate and 10 to 20% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core and containing 67 to 77% by weight of an aromatic vinyl compound, 14 to 22% by weight of a vinyl cyan compound, and 5 to 12% by weight of an alkyl acrylate. In this case, there are advantages in that the compatibility with the (B) non-graft copolymer is excellent, the impact resistance is excellent, and the transparency, gloss, and weather resistance are further improved.

[0135] The (C) graft copolymer more preferably has an average particle size of 80 to 110 nm and can comprise a rubber core containing 82 to 88% by weight of an alkyl acrylate and 12 to 18% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core and containing 70 to 75% by weight of an aromatic vinyl compound, 17 to 22% by weight of a vinyl cyan compound, and 5 to 10% by weight of an alkyl acrylate. In this case, there are advantages in that the compatibility with the (B) non-graft copolymer is excellent, the impact resistance is excellent, and the transparency, gloss, and weather resistance are further improved.

[0136] The (C) graft copolymer may, for example, have a rubber core of 30 to 60% by weight and a graft shell of 40 to 70% by weight, preferably a rubber core of 35 to 55% by weight and a graft shell of 45 to 65% by weight, and more preferably a rubber core of 40 to 50% by weight and a graft shell of 50 to 60% by weight, and within these ranges, there is an advantage in that the mechanical properties are excellent.

[0137] The types of alkyl acrylate, aromatic vinyl compound, and vinyl cyan compound contained in the (C) graft copolymer may be within the same category as the types of alkyl acrylate, aromatic vinyl compound, and vinyl cyan compound contained in the (A) graft copolymer described herein.

[0138] The method for producing the graft copolymer (C) can include, for example, the steps of: i) producing a rubber core containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound; and ii) graft polymerizing, in the presence of the rubber core, 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate to produce a graft copolymer. In this case, the graft copolymer has excellent impact resistance, transparency, gloss, and weather resistance.

[0139] The method for producing the graft copolymer (C) preferably includes the steps of: i) producing a rubber core containing 78 to 91% by weight of an alkyl acrylate, 9 to 22% by weight of an aromatic vinyl compound, a crosslinking agent, an initiator, and an emulsifier; and ii) producing a graft copolymer by graft polymerization in the presence of the rubber core containing 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, 3 to 15% by weight of an alkyl acrylate, a crosslinking agent, an initiator, and an emulsifier. In this case, the graft copolymer has excellent transparency, gloss, and weather resistance.

[0140] The types of crosslinking agent, initiator, and emulsifier used in the steps i) and / or ii) may be within the same category as the types of crosslinking agent, initiator, and emulsifier used in the emulsion polymerization step of the graft copolymer (A) described herein.

[0141] The total weight of the (A) graft copolymer and the (C) graft copolymer may be, for example, 10 to 90% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight, based on 100% by weight of the total of the (A) graft copolymer, the (B) non-graft copolymer, and the (C) graft copolymer. Within this range, there are advantages in that the transparency, gloss, weather resistance, and impact resistance are all excellent.

[0142] The weight ratio (A:C) of the (A) graft copolymer to the (C) graft copolymer may be, for example, 5:5 to 8:2, preferably 5.5:4.5 to 7.5:2.5, more preferably 5.5:4.5 to 7:3, and even more preferably 5.5:4.5 to 6.5:3.5. Within this range, there are advantages such as even greater transparency, gloss, heat resistance, and impact resistance.

[0143] thermoplastic resin composition The thermoplastic resin composition is preferably prepared by adding acetone, followed by stirring and centrifuging to separate the composition into an insoluble gel and a soluble sol. The difference in refractive index between the sol and the gel measured is preferably 0.006 or less, more preferably 0.004 or less, even more preferably 0.003 or less, even more preferably 0.002 or less, and particularly preferably 0.001 to 0.002. Within this range, there is an advantage that the transparency, gloss, and weather resistance are further improved.

[0144] In this description, the difference in refractive index between the sol and gel of a thermoplastic resin composition is measured by adding 0.5 g of thermoplastic resin composition pellets to 30 g of acetone and stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab Companion). The mixture is then centrifuged at 18,000 rpm for 3 hours at 0°C using a centrifuge (Supra R30, Hanil Science) to separate the insoluble gel from the soluble sol. The mixture is then dried at 85°C for 12 hours using a forced circulation system (OF-12GW, Lab Companion), and the refractive index of the gel and sol are measured according to ASTM D542.

[0145] In this description, the refractive index is measured at room temperature using an Abbe refractometer, specifically in accordance with ASTM D542.

[0146] The present invention has the effect of providing a thermoplastic resin composition having even more excellent transparency and gloss by controlling the difference between the refractive index of the sol and the refractive index of the gel within the above range.

[0147] The thermoplastic resin composition may preferably have a haze of 10% or less, more preferably 7% or less, even more preferably 5% or less, even more preferably 3% or less, particularly preferably 2.6% or less, particularly more preferably 2.4% or less, most preferably 2.1% or less, and most particularly preferably 0.5 to 2.1%, as measured on an injection test piece having a thickness of 3 mm in accordance with ASTM D1003. Within this range, there is an effect of achieving an excellent balance of all physical properties.

[0148] The thermoplastic resin composition preferably has a haze of 3% or less, more preferably 2.5% or less, even more preferably 2% or less, still more preferably 1.7% or less, particularly preferably 1.5% or less, and particularly preferably 0.5 to 1.5%, as measured on an extruded test piece having a thickness of 0.15 mm in accordance with ASTM D1003. Within this range, the composition has the effect of achieving an excellent balance of all physical properties.

[0149] In this description, the haze is specifically measured using a haze meter (MURAKAMI HM-150) for a 3 mm thick injection test piece and a 0.15 mm thick extrusion test piece in accordance with ASTM D1003, and the smaller the haze value, the more transparent the film.

[0150] The thermoplastic resin composition preferably has a gloss of 122 or more, more preferably 130 or more, even more preferably 140 or more, still more preferably 145 or more, and particularly preferably 145 to 160, as measured at 45° using an injection test piece having a thickness of 3 mm in accordance with ASTM D2457. Within this range, the composition has the effect of having an excellent balance of physical properties.

[0151] The thermoplastic resin composition preferably has a gloss of 120 or more, more preferably 130 or more, even more preferably 135 or more, and still more preferably 135 to 155, as measured at 60° on an extruded test piece having a thickness of 0.15 mm in accordance with ASTM D2457. Within this range, the composition has the effect of achieving an excellent balance of all physical properties.

[0152] The thermoplastic resin composition may preferably have an Izod impact strength of 10 kgf·cm / cm or more, more preferably 12 kgf·cm / cm or more, even more preferably 14 kgf·cm / cm or more, still more preferably 16 kgf·cm / cm or more, and particularly preferably 16 to 20 kgf·cm / cm, as measured at room temperature using a ¼-inch thick test piece in accordance with ASTM D256. A value within this range has the effect of providing an excellent balance of all physical properties.

[0153] The thermoplastic resin composition is preferably subjected to an accelerated weathering test using a Weather-o-meter (ATLAS, Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiance 0.55 W / m 2 After leaving the composition for 3,000 hours under the conditions of SAE J1960 using a color difference meter (at 340 nm), the degree of discoloration is measured using a color difference meter, and the weather resistance (ΔE) calculated by the following mathematical formula 7 may be 2.7 or less, more preferably 2.5 or less, even more preferably 2.3 or less, and even more preferably 0.1 to 2.3. Within this range, there is an effect that all physical properties are well balanced.

[0154] The ΔE is the arithmetic mean value of the L, a, and b values ​​measured on the test piece before and after the accelerated weathering experiment using the CIE LAB color coordinate system, and the closer the ΔE value is to 0, the better the weather resistance is.

[0155]

number

[0156] In Equation 7, L', a', and b' are the L, a, and b values ​​measured in the CIE LAB color coordinate system after the test piece was left to stand for 3,000 hours under the conditions of SAE J1960, and L0, a0, and b0 are the L, a, and b values ​​measured in the CIE LAB color coordinate system before the test piece was left to stand.

[0157] The thermoplastic resin composition may include, for example, one or more selected from the group consisting of a lubricant, an antioxidant, and an ultraviolet absorber.

[0158] The lubricant may be, for example, one or more selected from the group consisting of ethylene bisstearamide, oxidized polyethylene wax, magnesium stearate, calcium stearamide, and stearic acid, which has the effect of improving heat resistance and fluidity.

[0159] The amount of the lubricant may be, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, relative to 100 parts by weight in total of the graft copolymer (A) and the non-graft copolymer (B).

[0160] The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, or a mixture thereof, and is preferably a phenol-based antioxidant. In this case, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0161] The antioxidant may be present in an amount of, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, relative to 100 parts by weight of the total of (A) the graft copolymer and (B) the non-graft copolymer. Within this range, the heat resistance is improved while the physical properties are well balanced.

[0162] The UV absorber may be, for example, one or more selected from the group consisting of triazine-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoate-based UV absorbers, and cyanoacrylate-based UV absorbers, but is not limited thereto.

[0163] The amount of the ultraviolet absorber may be, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, relative to 100 parts by weight of the total of (A) the graft copolymer and (B) the non-graft copolymer. Within this range, the effect of improving light resistance while achieving an excellent balance of physical properties is achieved.

[0164] The thermoplastic resin composition may further include, for example, one or more additives selected from the group consisting of flame retardants, flame retardant aids, fluorescent brighteners, antistatic agents, chain extenders, release agents, pigments, dyes, antibacterial agents, processing aids, metal deactivators, smoke suppressants, inorganic fillers, glass fibers, antifriction agents, and antiwear agents.

[0165] For example, the additives may be present in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of (A) the graft copolymer and (B) the non-graft copolymer. In this case, the additives are effective in improving physical properties and are economically advantageous due to low production costs.

[0166] The following describes a method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition. The description of the method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition includes all of the above-mentioned thermoplastic resin compositions.

[0167] Method for producing thermoplastic resin composition The method for producing a thermoplastic resin composition described herein includes the steps of kneading and extruding (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including a seed polymerized with 45 to 72% by weight of alkyl acrylate and 28 to 55% by weight of aromatic vinyl compound, a rubber core surrounding the seed polymerized with 78 to 91% by weight of alkyl acrylate and 9 to 22% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core polymerized with 65 to 82% by weight of aromatic vinyl compound, 12 to 30% by weight of vinyl cyan compound, and 3 to 15% by weight of alkyl acrylate, at 180 to 300°C and 80 to 400 rpm, and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, wherein the graft copolymer (A) simultaneously satisfies the following formulas 1 and 2. This provides the advantages of excellent transparency, gloss, and impact resistance.

[0168] [Formula 1] 180≦2×r2≦300

[0169] [Formula 2] 25≦r2-r1≦45

[0170] In the above formulas 1 and 2, r1 is the thickness (nm) from the center of the graft copolymer to the polymer seed, and r2 is the thickness (nm) from the center of the graft copolymer to the rubber core.

[0171] The kneading and extruding step preferably includes (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core with an average particle size of 50 to 150 nm, and more preferably includes (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core with an average particle size of 50 to 150 nm and comprising 78 to 91% by weight of alkyl acrylate and 9 to 22% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core and comprising 65 to 80% by weight of aromatic vinyl compound, 14 to 25% by weight of vinyl cyanide compound, and 3 to 15% by weight of alkyl acrylate. In such a case, the impact resistance is excellent, while the transparency and gloss are significantly improved.

[0172] The kneading and extrusion may be performed using, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, which has the effect of uniformly dispersing the composition and providing excellent compatibility.

[0173] The kneading and extrusion may be carried out, for example, at a barrel temperature within a range of 180 to 300°C, preferably 190 to 280°C, and more preferably 200 to 260°C. In this case, the processing amount per unit time is appropriate, sufficient melt-kneading is possible, and problems such as thermal decomposition of the resin component are not caused.

[0174] The kneading and extrusion may be carried out under conditions where the screw rotation speed is, for example, 80 to 400 rpm, preferably 100 to 300 rpm, and more preferably 150 to 250 rpm. In this case, the processing amount per unit time is appropriate, which has the effect of providing excellent process efficiency.

[0175] The thermoplastic resin composition obtained through the extrusion may be produced as pellets using, for example, a pelletizer.

[0176] Furthermore, the resin composition can be manufactured into molded articles for various industrial fields through molding processes such as a blow process and an injection process.

[0177] Molded product The molded article described herein may, for example, contain the thermoplastic resin composition described herein, and has excellent transparency, gloss, weather resistance, and impact resistance, and therefore has the effect of being applicable with high quality in fields where transparency is required.

[0178] The molded article may be, for example, an injection-molded article, a film, or a sheet. In this case, the thermoplastic resin composition described herein has the advantage of being able to provide impact resistance, transparency, weather resistance, and gloss that are higher than those required in the market.

[0179] The molded article may be an automobile interior material, an automobile exterior material, a building material, a home appliance, or a medical part, and in this case, it has the advantage of satisfying all of the requirements required in the market since it has excellent transparency, gloss, weather resistance, and impact resistance.

[0180] The method for producing the molded article preferably includes the steps of: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including a seed polymerized containing 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound; a rubber core surrounding the seed polymerized containing 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized containing 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyanide compound, and 3 to 15% by weight of an alkyl acrylate. and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; and kneading and extruding the resulting mixture under conditions of 180 to 300°C and 80 to 400 rpm to produce pellets. The resulting pellets are then injecting or extruding using an injector or extruder. The (A) graft copolymer is characterized by simultaneously satisfying the following formulas 1 and 2. In this case, the resulting copolymer has excellent transparency, gloss, weather resistance, and impact resistance, and is therefore applicable with high quality to fields where transparency is required.

[0181] [Formula 1] 180≦2×r2≦300

[0182] [Formula 2] 25≦r2-r1≦45

[0183] In the above formulas 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the rubber core.

[0184] Preferred examples are presented below to aid in understanding the present invention. However, the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical idea of ​​the present invention. Naturally, such changes and modifications also fall within the scope of the appended claims.

[0185] [Example] The materials used in the examples and comparative examples are as follows. *(A) Graft copolymer: Produced in Examples 1 to 10 and Comparative Examples 1 to 10 below *(B-1) SAMMA copolymer: a non-graft copolymer of methyl methacrylate-styrene-acrylonitrile comprising 71% by weight of methyl methacrylate, 22% by weight of styrene, and 7% by weight of acrylonitrile. *(B-2) SAN copolymer: non-graft copolymer of styrene and acrylonitrile (styrene 73% by weight, acrylonitrile 27% by weight) *(C) Graft copolymer: A graft copolymer (45% by weight of rubber core and 55% by weight of graft shell) containing a rubber core having an average particle size of 90 nm and containing 85% by weight of butyl acrylate and 15% by weight of styrene, and a graft shell surrounding the rubber core and consisting of 72% by weight of styrene, 20% by weight of acrylonitrile, and 8% by weight of butyl acrylate. *Lubricant: SUNLUBE EBS (SUNKOO) *Antioxidants: Songnox 1076 (Songwon) and Irgafos 168 (BASF) *UV absorber: Tinuvin 770 (BASF), Tinuvin P (BASF)

[0186] Example 1 (A) acrylate-styrene-acrylonitrile graft copolymer was prepared using 60 wt% butyl acrylate (BA) and 40 wt% styrene (SM) as the polymer seed, 87 wt% BA and 13 wt% SM as the rubber core, and 72 wt% SM, 20 wt% acrylonitrile (AN), and 8 wt% BA as the graft shell. The (A) graft copolymer consisted of 20 wt% polymer seed, 40 wt% rubber core, and 40 wt% graft shell.

[0187] 50 parts by weight of the prepared (A) graft copolymer and 50 parts by weight of the (B-1) SAMMA copolymer were mixed with 1 part by weight of lubricant, 1 part by weight of antioxidant, and 0.6 parts by weight of UV stabilizer, and the mixture was kneaded and extruded at 220°C and 200 rpm to prepare pellets. The prepared pellets were extruded at a molding temperature of 220°C to prepare injection specimens for measuring physical properties, and the prepared pellets were extruded using a single-screw film extruder at 220°C and 200 rpm to prepare extrusion specimens for measuring physical properties.

[0188] Examples 2 to 4 and 7 to 10 The same procedure as in Example 1 was carried out, except that the graft copolymer (A) in Example 1 was changed to a graft copolymer (A) polymerized with the components and contents shown in Tables 1 and 2 below.

[0189] Example 5 The same procedure as in Example 1 was carried out, except that 50 parts by weight of the (A) graft copolymer produced in Example 1 was changed to 30 parts by weight of the (A) graft copolymer and 20 parts by weight of the (C) graft copolymer.

[0190] Example 6 The same procedure as in Example 1 was carried out, except that the 50 parts by weight of the graft copolymer (A) produced in Example 1 was changed to 35 parts by weight of the graft copolymer (A) and 15 parts by weight of the graft copolymer (C).

[0191] Comparative Examples 1 to 9 The same procedure as in Example 1 was carried out, except that the graft copolymer (A) in Example 1 was changed to a graft copolymer (A) polymerized with the components and contents shown in Tables 3 and 4 below.

[0192] Comparative Example 10 The same procedure as in Example 1 was carried out, except that (B-1) SAMMA copolymer was changed to (B-2) SAN copolymer.

[0193] Comparative Example 11 Transparent acrylonitrile-butadiene-styrene resin (LG Chemical, TR557) was injected to prepare injection specimens for measuring physical properties.

[0194] [Test example] The properties of the pellets and test pieces produced in Examples 1 to 10 and Comparative Examples 1 to 11 were measured by the following methods, and the results are shown in Tables 1 to 4 below. *(A) Refractive index of the seed, core, and shell of the graft copolymer, and (B) refractive index of the non-graft copolymer: calculated using the following formula 3.

[0195] [Formula 3] RI=ΣWti×RIi Wti = weight fraction (%) of each component in the copolymer RIi = refractive index of each component polymer of the copolymer

[0196] *Average particle size (nm) of polymer seeds, rubber cores, and graft shells: Samples were taken upon completion of the polymer seed, rubber core, and graft shell production, and measured using dynamic light scattering. Specifically, intensity values ​​were measured in Gaussian mode using a particle size analyzer (product name: Nicomp380, manufacturer: PSS). As a specific measurement example, 0.1 g of latex with a total solids content of 35-50 wt% was diluted 1,000-5,000 times with distilled water to prepare a sample. The measurement method was auto-dilution and measurement was performed using a flow cell. The measurement mode was dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis, with the temperature and wavelength settings being 23°C and 632.8 nm.

[0197] For reference, r1 was determined by dividing the average particle size of the seeds in half, and r2 was determined by dividing the average particle size of the cores including the seeds in half.

[0198] *Izod impact strength (IMP; kgf·cm / cm): Measured at room temperature (20±5°C) using 1 / 4" thick injection test specimens in accordance with ASTM D256.

[0199] *Haze (%): Haze was measured in accordance with ASTM D1003 for a 3 mm thick injection test piece and a 0.15 mm thick extrusion test piece. The lower the haze, the better the transparency.

[0200] *Gloss of injection test piece: Gloss was measured at 45° on a 3mm thick injection test piece in accordance with ASTM D2457.

[0201] *Gloss of extruded specimen: Measured at 60° on 0.15 mm thick extruded specimens in accordance with ASTM D2457.

[0202] *Refractive index difference between sol and gel in thermoplastic resin composition: 0.5 g of thermoplastic resin composition pellets were added to 30 g of acetone and stirred at 210 rpm for 12 hours (SKC-6075, Lab Companion). The mixture was then centrifuged at 18,000 rpm for 3 hours at 0°C using a centrifuge (Supra R30, Hanil Science) to separate the insoluble gel from the soluble sol. The mixture was then dried at 85°C for 12 hours using a forced circulation system (OF-12GW, Lab Companion). The refractive index of each was measured at room temperature (20±5°C) using an Abbe refractometer according to ASTM D542, and the difference between the two was calculated.

[0203] *Weather resistance (△E): Accelerated weather resistance test equipment (Weather-o-meter, ATLAS, Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiance 0.55W / m 2After leaving the specimens for 3,000 hours under the conditions of SAE J1960 using a chromatic aberration detector (at 340 nm), the degree of discoloration was measured using a color difference meter, and ΔE was calculated using the following formula 7. The following ΔE is the arithmetic mean value of the L, a, and b values ​​measured on the test specimens before and after the accelerated weathering experiment using the CIE LAB color coordinate system, and the closer the ΔE value is to 0, the better the weather resistance.

[0204]

number

[0205] In Equation 7, L', a', and b' are the L, a, and b values ​​measured in the CIE LAB color coordinate system after the test piece was left to stand for 3,000 hours under the conditions of SAE J1960, and L0, a0, and b0 are the L, a, and b values ​​measured in the CIE LAB color coordinate system before the test piece was left to stand.

[0206] [Table 1]

[0207] [Table 2]

[0208] [Table 3]

[0209] [Table 4]

[0210] As shown in Tables 1 to 4, it was confirmed that the thermoplastic resin compositions of the present invention (Examples 1 to 10) were superior in impact strength, haze, weather resistance, and gloss compared to Comparative Examples 1 to 11.

[0211] Here, Examples 5 and 6 containing the graft copolymer (C) were excellent in impact strength, as well as in haze, gloss and weather resistance.

[0212] On the other hand, in Comparative Examples 1 and 2, in which the composition ratio of the polymer seed of the graft copolymer (A) was outside the range of the present invention, the difference in refractive index between the seed and the SAMMA copolymer (B-1), and the difference in refractive index between the sol and gel in the thermoplastic resin composition were large, so that both the injection test pieces and the extrusion test pieces showed reduced haze, gloss, and weather resistance, and Comparative Example 1 also showed low impact strength.

[0213] In addition, in Comparative Examples 3 and 4, in which the composition ratio of the rubber core of the (A) graft copolymer was outside the range of the present invention, the difference in refractive index between the rubber core and the graft shell of the (A) graft copolymer and / or the difference in refractive index between the sol and the gel in the thermoplastic resin composition was large, so that the haze and gloss of both the injection test piece and the extrusion test piece were reduced, and the weather resistance was low, and Comparative Example 4 also had poor impact strength.

[0214] In addition, in Comparative Examples 5 and 6, in which the structure of the graft shell of the (A) graft copolymer was outside the range of the present invention, the difference in refractive index between the sol and gel in the thermoplastic resin composition and / or the difference in refractive index between the rubber core and the graft shell of the (A) graft copolymer was large, and therefore the haze and gloss of both the injection test pieces and the extrusion test pieces were low, and the weather resistance was also low.

[0215] In addition, in Comparative Example 7, in which 2×r2 and r2−r1 of the rubber core of the (A) graft copolymer were outside the range of the present invention, the haze and / or gloss of the injection test piece and extrusion test piece decreased.

[0216] Furthermore, Comparative Example 8, in which 2×r2 and r2−r1 of the rubber core of the graft copolymer (A) were below the ranges of the present invention, had a significantly low impact strength.

[0217] In addition, Comparative Example 9, in which the seed and core contained only butyl acrylate and the shell contained styrene and acrylonitrile as in the conventional technology, had poor haze and gloss in both the injection test piece and the extrusion test piece due to the large difference in refractive index between the core and shell of (A) graft copolymer, the difference in refractive index between the polymer seed of (A) graft copolymer and (B-1) SAMMA copolymer, and the difference in refractive index between the sol and gel in the thermoplastic resin composition.

[0218] In addition, in Comparative Example 10, in which (B-1) SAMMA copolymer was changed to (B-2) SAN copolymer, the difference in refractive index between the polymer seed of (A) graft copolymer and (B-2) SAN copolymer was large, and therefore the haze and gloss decreased in both the injection test piece and the extrusion test piece, and the weather resistance was extremely poor.

[0219] Furthermore, Comparative Example 11, which was a transparent acrylonitrile-butadiene-styrene resin, had very poor weather resistance.

[0220] In conclusion, it has been confirmed that the present invention provides excellent impact resistance, transparency, and glossiness when the structure and composition ratio of the polymer seed, core, and shell constituting the (A) alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer are adjusted within a predetermined range, and the difference between the refractive index of the core and the refractive index of the shell, and the difference between the refractive index of the polymer seed of the (A) graft copolymer and the refractive index of the (B) non-graft copolymer are narrowed.

Claims

1. (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising a seed polymerized with 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound, a rubber core surrounding the seed polymerized with 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core polymerized with 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyanide compound, and 3 to 15% by weight of an alkyl acrylate; (B) a non-graft copolymer containing a group derived from an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, The alkyl acrylate includes an alkyl acrylate having an alkyl group having 1 to 15 carbon atoms, the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene; the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile; The graft copolymer (A) simultaneously satisfies the following formula 1 and formula 2: The graft copolymer (A) contains, relative to a total of 100% by weight, 5 to 35% by weight of a polymer seed, 25 to 55% by weight of a rubber core, and 25 to 55% by weight of a graft shell; the non-graft copolymer (B) contains 55 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound; The thermoplastic resin composition is added with acetone, and then stirred and centrifuged to separate it into a sol and a gel, and the difference in refractive index between the sol and the gel is measured and is 0.006 or less; The haze measured on a 3 mm thick injection test piece in accordance with ASTM D1003 is 10% or less; A thermoplastic resin composition having an Izod impact strength of 10 kgf cm / cm to 20 kgf cm / cm, measured at room temperature using a 1 / 4" thick test piece in accordance with ASTM D256. [Formula 1] 180≦2×r2≦300 [Formula 2] 25≦r2−r1≦45 (In the above formulas 1 and 2, r1 is the thickness (nm) from the center of the graft copolymer to the seed, and r2 is the thickness (nm) from the center of the graft copolymer to the core.)

2. 2. The thermoplastic resin composition according to claim 1, wherein the difference between the refractive index of the rubber core and the refractive index of the shell of the graft copolymer (A) is 0.093 or less.

3. The thermoplastic resin composition according to claim 1, wherein the difference between the refractive index of the polymer seed of the graft copolymer (A) and the refractive index of the non-graft copolymer (B) is 0.015 or less.

4. The thermoplastic resin composition according to claim 1, characterized in that it comprises 10 to 90% by weight of (A) a graft copolymer and 10 to 90% by weight of (B) a non-graft copolymer.

5. The thermoplastic resin composition according to claim 1, characterized in that it contains (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core with an average particle size of 50 to 150 nm.

6. 2. The thermoplastic resin composition according to claim 1, wherein the difference in refractive index between the sol and the gel measured by adding acetone, stirring, and centrifuging the mixture is 0.004 or less.

7. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a haze of 7% or less as measured on an injection molded specimen having a thickness of 3 mm in accordance with ASTM D1003.

8. The thermoplastic resin composition according to claim 1, characterized in that the gloss of the thermoplastic resin composition is 122 to 160 as measured at 45° using an injection test piece having a thickness of 3 mm in accordance with ASTM D2457.

9. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an Izod impact strength of 12 kgf cm / cm to 20 kgf cm / cm, measured at room temperature using a ¼" thick test piece in accordance with ASTM D256.

10. (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising a seed polymerized from 45 to 72% by weight of an alkyl acrylate and 28 to 55% by weight of an aromatic vinyl compound, a rubber core surrounding the seed polymerized from 78 to 91% by weight of an alkyl acrylate and 9 to 22% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core polymerized from 65 to 82% by weight of an aromatic vinyl compound, 12 to 30% by weight of a vinyl cyanide compound, and 3 to 15% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising groups derived from methyl methacrylate, an aromatic vinyl compound, and a vinyl cyanide compound, the ... The alkyl acrylate includes an alkyl acrylate having an alkyl group having 4 to 10 carbon atoms, the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene; the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile; The graft copolymer (A) simultaneously satisfies the following formula 1 and formula 2: The graft copolymer (A) contains, relative to a total of 100% by weight, 5 to 35% by weight of a polymer seed, 25 to 55% by weight of a rubber core, and 25 to 55% by weight of a graft shell; A method for producing a thermoplastic resin composition, characterized in that the non-graft copolymer (B) contains 55 to 85% by weight of methyl methacrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound. [Formula 1] 180≦2×r2≦300 [Formula 2] 25≦r2−r1≦45 (In the above formulas 1 and 2, r1 is the thickness (nm) from the center of the graft copolymer to the seed, and r2 is the thickness (nm) from the center of the graft copolymer to the core.)

11. The method for producing a thermoplastic resin composition according to claim 10, wherein the kneading and extruding step includes (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having a rubber core with an average particle size of 50 to 150 nm.

12. A molded article comprising the thermoplastic resin composition according to claim 1.

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