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 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 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, a vinyl cyan compound, and an imide compound; wherein the average particle size and refractive index of each layer of the (A) graft copolymer 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, heat resistance, 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. 10-2022-0072523, 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 that is excellent in transparency, gloss, heat resistance, 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, and by adjusting 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, and the resin is opaque due to the large difference in refractive index between the core and the shell. 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, and the difference in refractive index between the ASA resin core and the SAN resin is large, resulting in a resin composition that is opaque and has insufficient heat resistance.

[0006] Therefore, there is a need to develop a resin composition that has excellent gloss, heat resistance, weather resistance, and mechanical properties while realizing transparency by approximating the differences in refractive index between 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, heat resistance, 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] In order to achieve the above object, the present invention also 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, a vinyl cyanide compound, and an imide 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 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 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, a vinyl cyan compound, and an imide 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 (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.)

[0015] III) In I) or II), the thermoplastic resin composition preferably 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 containing 50 to 69% by weight of an alkyl acrylate and 31 to 50% by weight of an aromatic vinyl compound; a rubber core surrounding the seed polymerized containing 81 to 88% by weight of an alkyl acrylate and 12 to 19% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized containing 66 to 78% by weight of an aromatic vinyl compound, 14 to 26% by weight of a vinyl cyan compound, and 3 to 13% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyan compound, and an imide compound; and the (A) graft copolymer can simultaneously satisfy the above formula 1 and formula 2.

[0016] IV) In the above I) to III), 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] V) In the above I) to IV), 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] VI) In I) to V), the (A) graft copolymer preferably contains 5 to 35% by weight of polymer seed, 25 to 55% by weight of rubber core, and 25 to 55% by weight of graft shell, relative to a total of 100% by weight.

[0019] VII) In the above I) to VI), the (B) non-graft copolymer may preferably contain 60 to 90% by weight of alkyl (meth)acrylate, 3 to 33% by weight of aromatic vinyl compound, 0.1 to 20% by weight of vinyl cyanide compound, and 0.1 to 20% by weight of imide compound.

[0020] VIII) In the above I) to VII), the imide-based compound in the non-graft copolymer (B) may preferably be at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

[0021] IX) In the above I) to VIII), 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.

[0022] X) In the above I) to IX), 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.

[0023] XI) In the above II) to X), 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 may be 0.006 or less.

[0024] XII) In the above II) to XI), 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.

[0025] XIII) In the above I) to XII), 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.

[0026] XIV) In the above II) to XIII), 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.

[0027] 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, a vinyl cyan compound, and an imide compound; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyan compound, and an imide compound; wherein the graft copolymer (A) simultaneously satisfies the following formulas 1 and 2:

[0028] [Formula 1] 180≦2×r2≦300

[0029] [Formula 2] 25≦r2-r1≦45

[0030] 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.

[0031] The method for producing the thermoplastic resin composition preferably includes the steps of: (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 containing 50 to 69% by weight of an alkyl acrylate and 31 to 50% by weight of an aromatic vinyl compound; a rubber core surrounding the seed polymerized containing 81 to 88% by weight of an alkyl acrylate and 12 to 19% by weight of an aromatic vinyl compound; and a graft shell surrounding the rubber core polymerized containing 66 to 78% by weight of an aromatic vinyl compound, 14 to 26% by weight of a vinyl cyan compound, and 3 to 13% by weight of an alkyl acrylate; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyan compound, and an imide compound, at 180 to 300°C and 80 to 400 rpm, wherein the graft copolymer (A) can simultaneously satisfy the above formula (1) and formula (2).

[0032] XVII) In the above XV) or XVI), the kneading and extruding step may preferably include (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.

[0033] The present invention also provides XVIII) a molded article comprising the thermoplastic resin composition of any one of I) to XIV). [Effects of the Invention]

[0034] The present invention has the effect of providing a thermoplastic resin composition that is excellent in heat resistance and impact resistance, as well as in transparency, gloss, and weather resistance, a method for producing the same, and a molded article produced from the same.

[0035] 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 and heat resistance as well as beautiful appearance. DETAILED DESCRIPTION OF THE INVENTION

[0036] The thermoplastic resin composition of the present invention, its production method, and molded articles produced therefrom will be described in detail below.

[0037] The present inventors have confirmed that in order to improve the transparency, gloss, heat resistance, 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 constituting 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 impact resistance, transparency, gloss, and weather resistance while maintaining heat resistance. Based on this, the inventors have continued their research and have completed the present invention.

[0038] The thermoplastic resin composition of the present invention comprises: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound 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, a vinyl cyanide compound, and an imide compound, wherein the graft copolymer (A) satisfies the following mathematical formula 1:

[0039] [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.)

[0040] 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, a vinyl cyan compound, and an imide compound, wherein the graft copolymer (A) simultaneously satisfies the following formulas 1 and 2. In this case, the composition exhibits excellent transparency, gloss, heat resistance, weather resistance, and impact resistance.

[0041] [Formula 1] 180≦2×r2≦300

[0042] [Formula 2] 25≦r2-r1≦45

[0043] 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.

[0044] The thermoplastic resin composition of the present invention will be described in detail below, by constituent.

[0045] (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 graft copolymer comprising a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core. Preferably, the graft copolymer comprises a seed polymerized with 45-72% by weight of alkyl acrylate and 28-55% by weight of aromatic vinyl compound, a rubber core surrounding the seed polymerized with 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core polymerized with 65-82% by weight of aromatic vinyl compound, 12-30% by weight of vinyl cyanide, and 3-15% by weight of alkyl acrylate. This provides excellent transparency, gloss, weather resistance, and impact resistance while maintaining heat resistance. The incorporation of alkyl acrylate into the graft shell provides excellent compatibility with the (B) non-graft copolymer, resulting in a well-balanced physical property profile.

[0046] 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 69% by weight of alkyl acrylate and 31 to 50% by weight of aromatic vinyl compound, more preferably 54 to 66% by weight of alkyl acrylate and 34 to 46% by weight of aromatic vinyl compound, and even more preferably 57 to 63% by weight of alkyl acrylate and 37 to 43% by weight of aromatic vinyl compound. In this case, the difference in refractive index with the non-graft copolymer (B) is reduced, resulting in excellent transparency and gloss.

[0047] 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, and weather resistance.

[0048] 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.

[0049] 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, and even more preferably 0.001 to 0.006. Within this range, there are advantages such as excellent transparency, gloss, and weather resistance.

[0050] Rubber Core For example, the rubber core of the graft copolymer (A) 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 effective in terms of transparency, gloss, weather resistance, and impact resistance.

[0051] 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.

[0052] 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.

[0053] 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 0.088 or less, even more preferably 0.070 to 0.088, and even more preferably 0.080 to 0.088. Within this range, the effect of excellent transparency, gloss, weather resistance, and impact resistance can be achieved.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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 and gloss as well as excellent impact resistance.

[0058] [Formula 1] 180≦2×r2≦300

[0059] [Formula 2] 25≦r2-r1≦45

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] The r2-r1 represents the thickness of the rubber core, and the thinner the rubber core, the easier it is for light to pass through, resulting in improved transparency.

[0065] 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.

[0066] [Formula 3] RI=ΣWti×RIi Wti = weight fraction (%) of each component in the copolymer RIi = refractive index of each component polymer of the copolymer

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] [Formula 4] Gel content (wt%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] × 100

[0073] [Formula 5] Swelling index = Weight of insoluble matter after centrifugation and before drying (g) / Weight of insoluble matter after centrifugation and after drying (g)

[0074] [Formula 6] Graft rate (%) = [weight of grafted monomer (g) / weight of rubber (g)] × 100

[0075] In Equation 6, the weight (g) of the grafted monomer is the weight (g) of the insoluble material (gel) obtained after dissolving the graft copolymer in acetone and centrifuging the resulting solution, minus the weight (g) of the rubbery material, and the weight (g) of the rubbery material is the weight (g) of the rubbery component theoretically added to the graft copolymer powder.

[0076] 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.

[0077] In this description, normal temperature may be a point within the range of 20±5°C.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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:

[0082] [ka]

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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 a rubber core containing 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, heat resistance, and impact resistance.

[0087] 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, weather resistance, heat resistance, and impact resistance.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] The rosin acid soap may preferably be an abietic acid salt.

[0093] 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.

[0094] In the steps i), ii) and iii), the initiator is not particularly limited, but a radical initiator can be preferably used.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] For example, step iii) may include a molecular weight regulator.

[0108] 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.

[0109] 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.

[0110] In this description, 100 parts by weight of the graft copolymer refers to 100 parts by weight of the total weight of the final graft copolymer, or it can refer to the combined weight of all the monomers used in the polymer seed, rubber core, and graft shell, since almost all of the added monomers participate in the polymerization, or the combined weight of all the monomers added during the preparation of the polymer seed and rubber core and the graft shell, based on 100 parts by weight.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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, heat resistance, and impact resistance are all excellent.

[0116] (B) A non-graft copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyanide compound, and an imide-based compound. The (B) non-graft copolymer is a matrix resin, and may, for example, comprise an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyan compound, and an imide-based compound, and may preferably comprise 60 to 90% by weight of an alkyl (meth)acrylate, 3 to 33% by weight of an aromatic vinyl compound, 0.1 to 20% by weight of a vinyl cyan compound, and 0.1 to 20% by weight of an imide-based compound. In this case, the non-graft copolymer has excellent compatibility with the (A) graft copolymer, and while heat resistance is ensured, it has the effect of providing excellent transparency, gloss, weather resistance, and impact resistance.

[0117] The (B) non-graft copolymer may more preferably comprise 65 to 85% by weight of alkyl (meth)acrylate, 8 to 28% by weight of aromatic vinyl compound, 0.1 to 15% by weight of vinyl cyan compound, and 1 to 15% by weight of imide compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the (A) graft copolymer, and exhibits excellent heat resistance, weather resistance, transparency, gloss, and impact resistance.

[0118] The (B) non-graft copolymer may more preferably comprise 70 to 80% by weight of alkyl (meth)acrylate, 13 to 23% by weight of an aromatic vinyl compound, 0.1 to 10% by weight of a vinyl cyan compound, and 2 to 10% by weight of an imide compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the (A) graft copolymer, and exhibits excellent heat resistance, weather resistance, transparency, gloss, and impact resistance.

[0119] More preferably, the (B) non-graft copolymer may contain 72 to 77% by weight of alkyl (meth)acrylate, 15 to 20% by weight of aromatic vinyl compound, 0.5 to 5% by weight of vinyl cyan compound, and 3 to 9% by weight of imide compound. Within these ranges, the non-graft copolymer (B) has excellent compatibility with the (A) graft copolymer, and exhibits excellent heat resistance, weather resistance, transparency, gloss, and impact resistance.

[0120] In this description, "ungrafted" means not grafted, and more specifically, not grafted to a rubber.

[0121] In the present description, the imide-based compound is, for example, one or more selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, and is preferably N-phenylmaleimide, which has the effect of providing excellent heat resistance and an excellent balance of physical properties.

[0122] In this description, alkyl (meth)acrylate can be defined to include both alkyl acrylates and alkyl methacrylates.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] The non-graft copolymer (B) may preferably be an N-phenylmaleimide-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, as well as excellent heat resistance and weather resistance.

[0127] The non-graft copolymer (B) may have a weight average molecular weight of, for example, 50,000 to 150,000 g / mol, preferably 70,000 to 130,000 g / mol, and more preferably 90,000 to 120,000 g / mol. Within this range, the copolymer has the effect of providing excellent impact resistance and moldability.

[0128] 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.

[0129] The non-graft copolymer (B) may have, for example, a glass transition temperature of 110°C or higher, preferably 115°C or higher, measured in accordance with ASTM D3418, which has the effect of improving heat resistance.

[0130] In this description, the glass transition temperature can be measured in accordance with ASTM D3418 using a differential scanning calorimetry (DSC, manufactured by TA Instruments, model Q100) at a heating rate of 10°C / min.

[0131] The non-graft copolymer (B) may have a flow index of 8 g / 10 min or more, preferably 10 g / 10 min or more, measured at 220°C under a load of 10 kg in accordance with ASTM D1238, for example. When the flow index is within this range, excellent processability is achieved.

[0132] The refractive index of the non-graft copolymer (B), as measured at room temperature using an Abbe refractometer in accordance with ASTM D542, may be, for example, 1.5 to 1.525, preferably 1.51 to 1.52. Within this range, the difference in refractive index between the non-graft copolymer (B) and the seed copolymer (A) becomes small, resulting in excellent transparency and gloss.

[0133] The (B) non-graft copolymer may be produced, for example, by polymerizing a polymerization solution obtained by mixing 100 parts by weight of a monomer mixture containing 60 to 90% by weight of alkyl (meth)acrylate, 3 to 33% by weight of an aromatic vinyl compound, 0.1 to 20% by weight of a vinyl cyan compound, and 0.1 to 20% by weight of an imide-based compound with 15 to 40 parts by weight of a reaction solvent and 0.01 to 1 part by weight of an initiator.

[0134] The reaction solvent may be, for example, one or more selected from the group consisting of ethylbenzene, toluene, methyl ethyl ketone, and xylene, and may be preferably toluene. In this case, it is easy to adjust the viscosity and has the effect of suppressing a decrease in the polymerization conversion rate.

[0135] The reaction solvent may be, for example, 25 to 40 parts by weight, preferably 30 to 40 parts by weight, based on 100 parts by weight of the monomer mixture. Within this range, there is an effect of preventing an excessive increase in viscosity and a decrease in conversion rate and molecular weight.

[0136] Examples of initiators used in the production of the (B) non-graft copolymer include tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexane)propane, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, and t-butylperoxyisopropyl monocarbonate. isopropylmonocarbonate, t-butyl peroxy 2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, dicumylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexaneThe peroxide may be one or more selected from the group consisting of 5-bis(t-butyl peroxy)hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, and di-t-amyl peroxide, and preferably tert-butylperoxy-2-ethylhexanoate, which facilitates the polymerization reaction and thereby improves impact resistance and weather resistance.

[0137] The initiator may be, for example, 0.01 to 1 part by weight, 0.01 to 0.5 parts by weight, or preferably 0.01 to 0.4 parts by weight, relative to 100 parts by weight of the monomer mixture. Within this range, the polymerization reaction is facilitated, thereby maintaining excellent levels of mechanical properties and heat resistance.

[0138] The polymerization in the step of preparing the non-graft copolymer (B) can be carried out, for example, by continuously feeding the polymerization solution into a continuous reactor at a rate of 7 to 20 kg / hr, preferably 10 to 15 kg / hr, at a temperature of 130 to 160°C, preferably 140 to 150°C. In this case, the particle stability of the copolymer is improved compared to the case of adding the copolymer all at once, and the internal structure of the particles is made uniform, thereby resulting in excellent mechanical properties and heat resistance.

[0139] In this description, "continuous polymerization" refers to a process in which materials participating in polymerization are continuously fed into a reactor, the polymerized product is continuously discharged, and unreacted monomers are recovered and reused using a volatilization process.

[0140] The (B) non-graft copolymer may be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization. The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited as long as they are solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization commonly performed in the technical field to which the present invention pertains, respectively.

[0141] 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, there are advantages in that the transparency, gloss, and impact resistance are all excellent.

[0142] 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.

[0143] (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 are advantages in that the compatibility with (B) the non-graft copolymer is excellent, and the weather resistance, transparency, and gloss are further improved.

[0144] 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 weather resistance, transparency, and gloss are further improved.

[0145] The (C) graft copolymer more preferably has an average particle size of 70 to 130 nm and can comprise 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 weather resistance, transparency, and gloss are further improved.

[0146] 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 weather resistance, transparency, and gloss are further improved.

[0147] 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.

[0148] 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.

[0149] 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 weather resistance, transparency, and gloss.

[0150] 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 impact resistance, weather resistance, transparency, and gloss.

[0151] 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.

[0152] 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 weather resistance, transparency, gloss, and impact resistance are all excellent.

[0153] 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 7:3, and more preferably 5.5:4.5 to 6.5:3.5. Within this range, there are advantages such as even better transparency, gloss, heat resistance, weather resistance, and impact resistance.

[0154] 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 weather resistance, transparency, and gloss are further improved.

[0155] 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.

[0156] In this description, the refractive index is measured at room temperature using an Abbe refractometer, specifically in accordance with ASTM D542.

[0157] 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.

[0158] 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, and most preferably 0.5 to 2.4%, 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.

[0159] 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, and particularly preferably 0.5 to 1.7%, 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.

[0160] 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.

[0161] The thermoplastic resin composition preferably has a gloss, measured at 45° using a 3 mm thick injection test piece in accordance with ASTM D2457, of 122 or more, more preferably 130 or more, even more preferably 135 or more, still more preferably 138 or more, and particularly preferably 138 to 160. Within these ranges, there is an effect of achieving an excellent balance of all physical properties.

[0162] The thermoplastic resin composition preferably has a gloss of 110 or more, more preferably 120 or more, even more preferably 125 or more, still more preferably 130 or more, and particularly preferably 130 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.

[0163] 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, and even more preferably 14 to 18 kgf·cm / cm, as measured at room temperature using a ¼-inch thick test piece in accordance with ASTM D256. A range within this range provides the effect of achieving an excellent balance of all physical properties.

[0164] The thermoplastic resin composition may preferably have a heat distortion temperature of 90°C or higher, more preferably 92°C or higher, even more preferably 92 to 100°C, and even more preferably 92 to 97°C, as measured under a load of 18.5 kgf in accordance with ASTM D648. Within this range, the composition has the effect of exhibiting excellent balance of physical properties and heat resistance.

[0165] The thermoplastic resin composition may preferably have a Vicat softening temperature (Vicat) measured in accordance with ASTM D1525 at a heating rate of 50°C / min under a load of 50 N of 97°C or higher, more preferably 100°C or higher, even more preferably 100 to 110°C, and even more preferably 100 to 105°C. Within this range, the thermoplastic resin composition has the effect of exhibiting excellent balance of physical properties and heat resistance.

[0166] 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 2.8 or less, more preferably 2.6 or less, even more preferably 2.5 or less, even more preferably 2.3 or less, and particularly preferably 0.1 to 2.3. Within this range, there is an effect that all physical properties are well balanced.

[0167] 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.

[0168]

number

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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).

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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, a vinyl cyan compound, and an imide-based compound, wherein the graft copolymer (A) simultaneously satisfies the following formulas 1 and 2. In this case, the composition has the advantages of excellent transparency, gloss, heat resistance, weather resistance, and impact resistance.

[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 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.

[0184] The kneading and extrusion step may, for example, include (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 preferably (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 wt % of an alkyl acrylate and 9 to 22 wt % of an aromatic vinyl compound, and a graft shell surrounding the rubber core and comprising 65 to 80 wt % of an aromatic vinyl compound, 14 to 25 wt % of a vinyl cyanide compound, and 3 to 15 wt % of an alkyl acrylate. In this case, the impact resistance is excellent, while transparency, gloss, heat resistance, and weather resistance are significantly improved.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] The thermoplastic resin composition obtained through the extrusion may be produced as pellets using, for example, a pelletizer.

[0189] 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.

[0190] Molded product The molded article described herein may, for example, contain the thermoplastic resin composition described herein, and has excellent transparency, gloss, heat resistance, weather resistance, and impact resistance, and therefore has the effect of being applicable with high quality in fields where transparency is required.

[0191] 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 a higher quality than the quality required in the market in terms of impact resistance, heat resistance, weather resistance, transparency, and gloss.

[0192] 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, heat resistance, weather resistance, and impact resistance.

[0193] The method for producing the molded article preferably includes the steps of: (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 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; a non-graft copolymer comprising a vinyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyan compound, and an imide-based compound; and a step of kneading and extruding the mixture at 180 to 300°C and 80 to 400 rpm to produce pellets; and injecting or extruding the produced pellets using an injector or extruder. The graft copolymer (A) is characterized by simultaneously satisfying the following formulas 1 and 2. In this case, the graft copolymer (A) has excellent transparency, gloss, heat resistance, weather resistance, and impact resistance, and is therefore applicable with high quality to fields where high transparency and gloss are required.

[0194] [Formula 1] 180≦2×r2≦300

[0195] [Formula 2] 25≦r2-r1≦45

[0196] 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.

[0197] 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.

[0198] [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) Non-graft copolymer: PMI-T-MS copolymer containing 75% by weight of methyl methacrylate, 18% by weight of styrene, 1% by weight of acrylonitrile, and 6% by weight of N-phenylmaleimide (weight average molecular weight: 100,000 g / mol, glass transition temperature: 120°C, flow index: 11 g / 10 min) *(B-2) Non-graft copolymer: SAN copolymer containing 73% by weight of styrene and 27% by weight of acrylonitrile *(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)

[0199] 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.

[0200] 50 parts by weight of the prepared (A) graft copolymer and 50 parts by weight of (B-1) PMI-T-MS 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.

[0201] 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.

[0202] 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.

[0203] Example 6 The same procedure as in Example 1 was carried out, except that the 50 parts by weight of the (A) graft copolymer produced in Example 1 was changed to 35 parts by weight of the (A) graft copolymer and 15 parts by weight of the (C) graft copolymer.

[0204] 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.

[0205] Comparative Example 10 The same procedure as in Example 1 was carried out, except that (B-1) PMI-T-MS copolymer was changed to (B-2) SAN copolymer.

[0206] Comparative Example 11 Transparent acrylonitrile-butadiene-styrene resin (LG Chemical, TR557) was injected to prepare injection specimens for measuring physical properties.

[0207] [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.

[0208] [Formula 3] RI=ΣWti×RIi Wti = weight fraction (%) of each component in the copolymer RIi = refractive index of each component polymer of the copolymer

[0209] *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.

[0210] 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.

[0211] *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.

[0212] *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.

[0213] *Gloss of injection test piece: Gloss was measured at 45° on a 3mm thick injection test piece in accordance with ASTM D2457.

[0214] *Gloss of extruded specimen: Gloss was measured at 60° on an extruded specimen with a thickness of 0.15 mm in accordance with ASTM D2457.

[0215] *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.

[0216] *Heat distortion temperature (HDT, °C): Measured in accordance with ASTM D648 under a load of 18.5 kgf.

[0217] *Vicat softening point temperature (Vicat, °C): Measured in accordance with ASTM D1525 under a heating rate of 50 °C / min and a load of 50 N

[0218] *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 2 After leaving the test piece 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 equation 7. The following ΔE is the arithmetic mean value of the L, a, and b values ​​measured on the test piece using the CIE LAB color coordinate system before and after the accelerated weathering experiment, and the closer the ΔE value is to 0, the better the weather resistance.

[0219]

number

[0220] 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.

[0221] [Table 1]

[0222] [Table 2]

[0223] [Table 3]

[0224] [Table 4]

[0225] 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, gloss, and weather resistance compared to Comparative Examples 1 to 11.

[0226] Here, Examples 5 and 6 containing the graft copolymer (C) were excellent in impact resistance and heat resistance, and also in haze, gloss and weather resistance.

[0227] On the other hand, in Comparative Examples 1 and 2, in which the composition ratio of the polymer seed of (A) graft copolymer was outside the range of the present invention, the difference in refractive index between the seed of (A) graft copolymer and the PMI-T-MS copolymer (B-1), and the difference in refractive index between the sol and gel in the thermoplastic resin composition were large, so that the haze and gloss of both the injection test piece and the extrusion test piece were low, and the weather resistance was poor. Comparative Example 1 also had low impact strength.

[0228] 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 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, so the haze and gloss of both the injection test piece and the extrusion test piece were low, and the weather resistance was poor. Comparative Example 4 also had low impact strength.

[0229] 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 the 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 reduced, and the weather resistance was poor.

[0230] 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 gloss of the injection test piece and extrusion test piece were reduced.

[0231] Furthermore, in 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, the impact strength was significantly reduced.

[0232] In addition, Comparative Example 9, which contains only butyl acrylate in the seed and core and styrene and acrylonitrile in the shell as in the conventional technology, had significantly low 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 large difference in refractive index between the polymer seed of (A) graft copolymer and the (B-1) PMI-T-MS copolymer, and the large difference in refractive index between the sol and gel in the thermoplastic resin composition.

[0233] In addition, in Comparative Example 10, in which the PMI-T-MS copolymer (B-1) was changed to the SAN copolymer (B-2), the difference in refractive index between the polymer seed of the graft copolymer (A) and the SAN copolymer (B-2) and the difference in refractive index between the sol and gel in the thermoplastic resin composition were large, so that the haze and gloss were significantly reduced in both the injection test piece and the extrusion test piece, and the heat distortion temperature, Vicat softening point temperature, and weather resistance were poor.

[0234] Furthermore, Comparative Example 11, which was a transparent acrylonitrile-butadiene-styrene resin, was extremely poor in weather resistance, heat distortion temperature, and Vicat softening point temperature.

[0235] In conclusion, it has been confirmed that the present invention provides excellent transparency and gloss while also providing excellent impact resistance, heat resistance, and weather resistance, by adjusting the composition, composition ratio, and refractive index difference of the polymer seed, core, and shell constituting (A) alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer within a predetermined range and narrowing the difference between the refractive index of the polymer seed of (A) graft copolymer and that of (B) non-graft copolymer.

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 methyl methacrylate, an aromatic vinyl compound, a vinyl cyan compound, and a group derived from an imide compound, 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 imide-based compound is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; The graft copolymer (A) simultaneously satisfies the following formula 1 and formula 2, and the graft copolymer (A) contains 5 to 35 wt % of a polymer seed, 25 to 55 wt % of a rubber core, and 25 to 55 wt % of a graft shell, relative to a total of 100 wt % of the graft copolymer: the non-graft copolymer (B) contains 60 to 90% by weight of methyl methacrylate, 3 to 33% by weight of an aromatic vinyl compound, 0.1 to 20% by weight of a vinyl cyan compound, and 0.1 to 20% by weight of an imide-based compound; The thermoplastic resin composition is characterized in that the difference in refractive index between the sol and gel, which are separated by adding acetone, stirring, and centrifuging, is 0.006 or less; the haze, measured using a 3 mm thick injection specimen according to ASTM D1003, is 10% or less; and the Izod impact strength, measured using a ¼ inch thick specimen according to ASTM D256 at room temperature, is 10 kgf cm / cm to 18 kgf cm / cm. [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 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.

7. 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 a 3 mm thick injection test piece in accordance with ASTM D2457.

8. 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 18 kgf cm / cm, measured at room temperature using a ¼" thick test piece in accordance with ASTM D256.

9. (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 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 methyl methacrylate, an aromatic vinyl compound, a vinyl cyanide compound, and groups derived from an imide-based compound, under conditions of 180 to 300°C and 80 to 400 rpm, 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 60 to 90% by weight of methyl methacrylate, 3 to 33% by weight of an aromatic vinyl compound, 0.1 to 20% by weight of a vinyl cyan compound, and 0.1 to 20% by weight of an imide-based compound; 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 imide-based compound is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; and the graft copolymer (A) simultaneously satisfies the following mathematical formulas 1 and 2: [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.)

10. 10. The method for producing a thermoplastic resin composition according to claim 9, 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.

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

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