Thermoplastic resin composition, method for producing the same, and molded article produced 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 35 to 58% by weight of an alkyl acrylate and 42 to 65% 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 alkyl-substituted styrene compound, and a vinyl cyan compound, the average particle size and refractive index of each layer of the (A) graft copolymer being 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, blackness, weather resistance, heat resistance and impact resistance, a production method thereof, and a molded article produced from the same.

Description

Technical Field

[0001] [Cross - reference to Related Applications] This application claims the benefit of priority based on Korean Patent Application No. 10 - 2022 - 0072524 filed on June 15, 2022, and all the contents disclosed in the literature of the 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 therefrom. More specifically, the present invention relates to adjusting the composition, composition ratio, and morphology of the rubber core 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 further adjusting the difference in refractive index from a matrix polymer, thereby providing a thermoplastic resin composition, a method for producing the same, and a molded article produced therefrom, which are excellent in transparency, glossiness, blackness, weather resistance, heat resistance, and impact resistance.

Background Art

[0003] Acrylate - styrene - acrylonitrile graft copolymer (hereinafter referred to as "ASA resin") does not contain unstable double bonds in the polymer, so it has very excellent weather resistance and is widely applied in various fields such as electrical and electronic components, building materials (for example, vinyl siding, etc.), extrusion profiles, and automotive parts. Recently, in the field of outdoor products, the market needs for high - value - added products having properties such as unpainted, transparent, high chroma, and special colors have been continuously increasing.

[0004] In order to achieve transparency in a graft copolymer containing a rubber core, the refractive indices of the rubber core, the graft shell, and the matrix resin must be close to each other. Further, in a resin composition containing a graft copolymer and a matrix resin, when the difference between the refractive index of the rubber core and the refractive index of the matrix resin is small, refraction and reflection of light do not occur at the interface of the graft copolymer, so the resin composition becomes transparent.

[0005] In ASA resin, which comprises 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. Due to the large difference in refractive index between the core and the shell, the resin is opaque. Furthermore, when styrene-acrylonitrile copolymer (hereinafter referred to as "SAN resin") is used as the matrix resin in ASA resin, the refractive index of the SAN resin is 1.56 to 1.58. Due to the large difference in refractive index between the ASA resin core and the SAN resin, the resin composition is opaque and has insufficient heat resistance.

[0006] Therefore, there is a need to develop resin compositions that achieve the transparency required by the market while also possessing excellent gloss, blackness, weather resistance, heat resistance, and mechanical properties, by minimizing the difference between the refractive indices of the seed, core, and shell constituting the ASA resin and the refractive index of the matrix resin. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Korean Published Patent No. 10-2006-0118156 [Overview of the project] [Problems that the invention aims to solve]

[0008] To solve the problems of the conventional technology described above, the present invention aims to provide a thermoplastic resin composition, a method for producing the same, and a molded article produced therefrom, all of which are excellent in terms of transparency, gloss, blackness, weather resistance, heat resistance, and impact resistance.

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

[0010] To achieve the above objectives, the present invention provides a thermoplastic resin composition comprising: I) (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound 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 alkyl-substituted styrene compound, and a vinyl cyanide compound, wherein the (A) graft copolymer satisfies the following formula 1, the thermoplastic resin composition has a difference in refractive index between the sol and gel measured after separation into sol and gel by stirring and centrifugation after adding acetone, a haze of 10% or less measured on a 3 mm thick injection-molded test piece in accordance with ASTM D1003, and an Izod impact strength of 10 kgf·cm / cm or more measured at room temperature on a 1 / 4" thick test piece in accordance with ASTM D256.

[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] Furthermore, the present invention provides a thermoplastic resin composition comprising: II) (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% 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 compound, and 3-15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound, and vinyl cyanide compound, wherein the (A) graft copolymer simultaneously satisfies the following formulas 1 and 2.

[0013] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0014] [Formula 2] 25 ≤ r² - r¹ ≤ 45

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

[0016] III) In I) or II) above, the (A) graft copolymer may preferably have a difference of 0.09 or less between the refractive index of the rubber core and the refractive index of the shell.

[0017] IV) In I) to III) above, the refractive index of the polymer seeds of the (A) graft copolymer may preferably be 0.012 or less in difference from the refractive index of the (B) non-graft copolymer.

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

[0019] VI) In I) to V) above, the (B) non-graft copolymer may preferably consist of 30 to 60% by weight of alkyl (meth)acrylate, 25 to 55% by weight of alkyl-substituted styrene compound, and 5 to 35% by weight of vinyl cyanide compound.

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

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

[0022] IX) In the above II) to VIII), the thermoplastic resin composition preferably may have a difference in refractive index between the sol and the gel, measured after adding acetone and separating into a sol and a gel by stirring and centrifugation, of 0.006 or less.

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

[0024] XI) In the above I) to X), the thermoplastic resin composition preferably may have a glossiness of 120 or more, measured with an injection test piece having a thickness of 3 mm at 45° in accordance with ASTM D2457.

[0025] XII) In the above II) to XI), the thermoplastic resin composition preferably may have an Izod impact strength of 10 kgf·cm / cm or more, measured with a test piece having a thickness of 1 / 4" at room temperature in accordance with ASTM D256.

[0026] Furthermore, the present invention provides a method for producing a thermoplastic resin composition comprising the steps of kneading and extruding (A) a graft copolymer comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising (A) a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% by weight of aromatic vinyl compound, surrounding the seed and polymerized with 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound, and surrounding the rubber core and polymerized with 65-82% by weight of aromatic vinyl compound, 12-30% by weight of vinyl cyanide compound, and 3-15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound, and vinyl cyanide compound, under conditions of 180-300°C and 80-400 rpm, wherein the (A) graft copolymer simultaneously satisfies the following formulas 1 and 2.

[0027] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0028] [Formula 2] 25 ≤ r² - r¹ ≤ 45

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

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

[0031] Furthermore, the present invention provides a molded article characterized by comprising the thermoplastic resin compositions described in I) to XII) above. [Effects of the Invention]

[0032] The present invention provides a thermoplastic resin composition that is excellent in heat resistance and impact resistance, as well as excellent in transparency, gloss, blackness, and weather resistance, a method for producing the same, and a molded article produced therefrom.

[0033] Furthermore, the thermoplastic resin composition of the present invention has the advantage of providing excellent impact resistance along with a beautiful appearance when applied to automotive interior materials, automotive exterior materials, building materials, home appliances, or medical components where excellent transparency, gloss, blackness, weather resistance, heat resistance, and impact resistance are required. [Modes for carrying out the invention]

[0034] The thermoplastic resin composition, its manufacturing method, and molded articles produced therefrom will be described in detail below.

[0035] The inventors have found that by adjusting the composition, composition ratio, and refractive index difference of the seed, core, and shell constituting the ASA resin to a predetermined range, and / or further reducing the refractive index difference with the matrix resin, the impact resistance, transparency, gloss, blackness, blackness, and weather resistance of a thermoplastic resin composition containing ASA resin and matrix resin can be improved while maintaining heat resistance. Based on this, they have continued their research and completed the present invention.

[0036] The thermoplastic resin composition of the present invention comprises: (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core; and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, wherein the (A) graft copolymer satisfies the following formula 1, and the thermoplastic resin composition is characterized in that, after adding acetone, the difference in refractive index between the sol and gel measured by stirring and centrifuging is 0.006 or less, the haze measured on a 3 mm thick injection-molded test piece in accordance with ASTM D1003 is 10% or less, and the Izod impact strength measured at room temperature on a 1 / 4" thick test piece in accordance with ASTM D256 is 10 kgf·cm / cm or more. In such a case, the gloss, blackness, weather resistance, and heat resistance are all excellent.

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

[0038] Furthermore, the thermoplastic resin composition of the present invention comprises (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% 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 compound, and 3-15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound, and vinyl cyanide compound, wherein the (A) graft copolymer simultaneously satisfies the following formulas 1 and 2. In such a case, there is an effect of excellent transparency, gloss, blackness, weather resistance, heat resistance, and impact resistance.

[0039] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0040] [Formula 2] 25 ≤ r² - r¹ ≤ 45

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

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

[0043] (A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer The (A) graft copolymer may, for example, be an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising a seed, a rubber core surrounding the seed, and a graft shell surrounding the rubber core. Preferably, it may include a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% 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 compound, and 3-15% by weight of alkyl acrylate. In such a case, heat resistance is ensured while transparency, gloss, blackness, weather resistance, and impact resistance are all excellent, and by introducing alkyl acrylate into the graft shell, compatibility with (B) non-graft copolymer is excellent, thus having the advantage of an excellent balance of physical properties.

[0044] seed The polymer seed of the (A) graft copolymer may, for example, be polymerized containing 35-58% by weight of alkyl acrylate and 42-65% by weight of aromatic vinyl compound, preferably 38-50% by weight of alkyl acrylate and 50-62% by weight of aromatic vinyl compound, more preferably 40-47% by weight of alkyl acrylate and 53-60% by weight of aromatic vinyl compound, and even more preferably 42-45% by weight of alkyl acrylate and 55-58% by weight of aromatic vinyl compound. In this case, the difference in refractive index with the (B) non-graft copolymer is reduced, which has the advantage of excellent transparency and gloss, as well as excellent blackness and weather resistance.

[0045] The polymer seeds of the (A) graft copolymer may, for example, have 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, blackness, and weather resistance.

[0046] In this description, the average particle size of the polymer seeds, rubber cores, and graft shells of the graft copolymer is not particularly limited, as long as it is measured by a measurement method commonly used in the art to which the present invention belongs, including electron microscopy methods such as SEM and TEM. For example, samples can be taken when the production of the polymer seeds, rubber cores, and graft shells is completed, and measured using dynamic light scattering. More specifically, the intensity value can be measured using a particle detector (product name: Nicomp380, manufacturer: PSS) in Gaussian mode. As a specific measurement example, the sample is prepared by diluting 0.1g of latex (TSC 35-50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, by appropriately diluting it so as not to deviate significantly from the intensity setpoint of 300 kHz, and placing it in a glass tube. The measurement method involves auto-dilution and measurement using a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weight Gaussian analysis, and the setting values ​​being a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0047] Rubber core The rubber core of the (A) graft copolymer may, for example, be polymerized surrounding the seed, containing 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound, preferably 80-90% by weight of alkyl acrylate and 10-20% by weight of aromatic vinyl compound, more preferably 82-88% by weight of alkyl acrylate and 12-18% by weight of aromatic vinyl compound, and even more preferably 84-87% by weight of alkyl acrylate and 13-16% by weight of aromatic vinyl compound. In this case, it is possible to achieve excellent balance of physical properties while also having excellent impact resistance, transparency, gloss, blackness, and weather resistance.

[0048] The rubber core may, for example, have an average particle size of 180 to 300 nm, preferably 200 to 280 nm, and more preferably 230 to 260 nm. Within this range, it has the effect of having excellent impact resistance while maintaining a good balance of physical properties.

[0049] Graftshell The graft shell of the (A) graft copolymer may, for example, surround the rubber core and be polymerized containing 65-82% by weight of an aromatic vinyl compound, 12-30% by weight of a vinyl cyanide compound, and 3-15% by weight of an alkyl acrylate, preferably 66-78% by weight of an aromatic vinyl compound, 14-26% by weight of a vinyl cyanide compound, and 3-13% by weight of an alkyl acrylate, more preferably 68-78% by weight of an aromatic vinyl compound, 16-22% by weight of a vinyl cyanide compound, and 5-12% by weight of an alkyl acrylate, and even more preferably 70-75% by weight of an aromatic vinyl compound, 18-21% by weight of a vinyl cyanide compound, and 6-10% by weight of an alkyl acrylate. In this case, by introducing alkyl acrylate into the graft shell, excellent compatibility with the (B) non-graft copolymer is achieved, resulting in a superior balance of physical properties and advantages such as excellent transparency, gloss, blackness, and weather resistance.

[0050] In this 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 styrene is preferred.

[0051] In this description, the vinyl cyanide compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0052] In this description, the alkyl acrylate may, for example, be an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, preferably one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, more preferably an alkyl acrylate containing an alkyl group having 1 to 4 carbon atoms, and even more preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof.

[0053] The aforementioned (A) graft copolymer satisfies both Equation 1 and Equation 2 below, for example. In this case, the difference in refractive index between (A) graft copolymer and (B) non-graft copolymer is large, reducing the thickness of the rubber core of (A) graft copolymer, resulting in excellent transparency, gloss, blackness, and weather resistance, as well as excellent impact resistance.

[0054] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0055] [Formula 2] 25 ≤ r² - r¹ ≤ 45

[0056] In the above equations 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.

[0057] The above formula 1 may preferably be 200 ≤ 2 × r² ≤ 280, more preferably 230 ≤ 2 × r² ≤ 260, and within this range, there is an effect of excellent impact resistance.

[0058] The above 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, blackness, and weather resistance.

[0059] The aforementioned r1 may also be half the average particle size of the seed, and r2 may also be half the average particle size of the core containing the seed.

[0060] The range r2-r1 refers to the thickness of the rubber core. The thinner the rubber core, the easier it is for light to pass through, resulting in improved transparency, blackness, and weather resistance.

[0061] In this description, the refractive indices of the polymer seed, rubber core, and graft shell of the graft copolymer, and (B) the refractive index of the non-graft copolymer, can be calculated using the following formula 3.

[0062] [Formula 3] RI = ΣWti × RIi Wti = Weight fraction of each component in the copolymer (%) RIi = Refractive index of the polymer components of the copolymer

[0063] 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 art to which the present invention pertains. For example, methyl methacrylate may have a refractive index of 1.49, butyl acrylate 1.46, styrene 1.592, and acrylonitrile 1.52.

[0064] The refractive index of the polymer seeds in the (A) graft copolymer may, for example, be 0.012 or less, preferably 0.007 or less, more preferably 0.004 or less, even more preferably 0.003 or less, and even more preferably 0.001 to 0.003, with the difference from the refractive index of the (B) non-graft copolymer being 0.012 or less, preferably 0.007 or less, more preferably 0.004 or less, even more preferably 0.003 or less, and even more preferably 0.001 to 0.003. Within this range, there is the advantage of excellent transparency, gloss, blackness, and weather resistance.

[0065] The difference between the refractive index of the rubber core of the (A) graft copolymer and the refractive index of the graft shell of the (A) graft copolymer may be, for example, 0.09 or less, preferably 0.070 to 0.090, more preferably 0.080 to 0.090, and even more preferably 0.083 to 0.089. Within this range, there is an effect of excellent transparency, light resistance, blackness, weather resistance, and impact resistance.

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

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

[0068] The aforementioned (A) graft copolymer may, for example, have a grafting rate of 30% or more, preferably 35-70%, and more preferably 35-60%, and within this range, it has the effect of having excellent mechanical properties such as impact resistance as well as excellent weather resistance.

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

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

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

[0072] [Formula 6] Grafting rate (%) = [Weight of grafted monomers (g) / Weight of rubbery material (g)] × 100

[0073] In the above equation 6, the weight (g) of the grafted monomer is the weight obtained by subtracting the weight (g) of the rubbery substance from the weight (g) of the insoluble substance (gel) after dissolving the graft copolymer in acetone and centrifuging it, and the weight (g) of the rubbery substance is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.

[0074] The (A) graft copolymer may contain, for example, 5 to 35% by weight of polymer seeds, preferably 10 to 30% by weight, and more preferably 15 to 25% by weight, relative to 100% by weight of the total copolymer. Within this range, there is an effect of excellent impact resistance and balance of physical properties. If the polymer seed content is below the above range, transparency, blackness, and weather resistance decrease, and if it exceeds the above range, impact resistance decreases.

[0075] The (A) graft copolymer may contain, for example, 25 to 55% by weight of rubber core, preferably 30 to 50% by weight, and more preferably 35 to 45% by weight, relative to its total weight of 100%, and within this range, there is an effect of excellent impact resistance and balance of physical properties. If the content of the rubber core is less than the above range, the rubber content will be low, and the impact reinforcement effect as a graft copolymer may decrease. If it exceeds the above range, the content of the graft shell will be low, and the rubbers may aggregate with each other during aggregation, and the compatibility with the (B) non-graft copolymer will be significantly reduced, resulting in a decrease in the impact reinforcement effect and the inability to obtain the desired degree of refractive index.

[0076] The (A) graft copolymer may contain, for example, 25 to 55% by weight of graft shells, preferably 30 to 50% by weight, and more preferably 35 to 45% by weight, based on 100% by weight of its total composition. Within this range, there is an effect of excellent impact resistance and balance of physical properties. If the content of graft shells is below the above range, the grafting efficiency decreases and the rubber aggregates, which reduces compatibility with the (B) non-graft copolymer and decreases the impact reinforcement effect. If the content of graft shells is excessive, there is a problem that the impact resistance decreases due to the relative decrease in rubber content.

[0077] The core of the rubber component may, for example, be an acrylic rubber polymerized with an alkyl acrylate, an aromatic vinyl compound, and a crosslinking agent. When a crosslinking agent is included, the gel content can be adjusted, which has the advantage of excellent impact resistance.

[0078] The polymer seed, rubber core, or both thereof may, as an example, contain one or more crosslinking agents 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 compounds represented by the following chemical formula 1.

[0079] [ka]

[0080] In the above chemical formula 1, A is independently a substituent having a vinyl group or a (meth)acrylate group, A' is a hydrogen group, 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 is independently a divalent ethyl group or a propyl group, and n is an integer from 0 to 15 or 1 to 15, preferably 0 to 5 or 1 to 5, more preferably 0 to 4 or 1 to 4.

[0081] As an example, the crosslinking agent can be used in amounts 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 monomers used in the production of the polymer seed, rubber core, and graft shell of the (A) graft copolymer.

[0082] In this description, the monomer content within a polymer may refer to the weight percentage of monomers added during the production of the polymer, or the monomer-equivalent weight percentage of the units within the polymer.

[0083] The method for producing the graft copolymer (A) may include, as an example, the steps of: i) producing a polymer seed containing 35-58% by weight of alkyl acrylate and 42-65% by weight of aromatic vinyl compound; ii) producing a rubber core containing 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound in the presence of the polymer seed; and iii) producing a graft copolymer by graft polymerization in the presence of the rubber core containing 65-82% by weight of aromatic vinyl compound, 12-30% by weight of vinyl cyanide compound and 3-15% by weight of alkyl acrylate. In this case, the product has the effect of being excellent in transparency, gloss, blackness, weather resistance and impact resistance.

[0084] The method for producing the graft copolymer (A) preferably includes the steps of: i) producing a polymer seed comprising 35-58% by weight of alkyl acrylate and 42-65% by weight of aromatic vinyl compound, an electrolyte, a crosslinking agent, an initiator, and an emulsifier; ii) producing a rubber core comprising 78-91% by weight of alkyl acrylate, 9-22% by weight of aromatic vinyl compound, a crosslinking agent, an initiator, and an emulsifier in the presence of the polymer seed; and iii) producing a graft copolymer by graft polymerization comprising 65-82% by weight of aromatic vinyl compound, 12-30% by weight of vinyl cyanide compound, 3-15% by weight of alkyl acrylate, a crosslinking agent, an initiator, and an emulsifier in the presence of the rubber core. In this case, the method has the effect of having excellent transparency, gloss, blackness, and weather resistance.

[0085] In steps i), ii), and iii), the emulsifier is not particularly limited as long as it is an emulsifier commonly used in the art to which the present invention belongs. For example, it may be one or more selected from the group consisting of C12-C18 alkyl sulfosuccinate metal salts or derivatives thereof, C12-C20 alkyl sulfate esters or derivatives thereof, C12-C20 alkyl sulfonic acid metal salts or derivatives thereof, fatty acid soaps, and rosinic acid soaps.

[0086] The C12-C18 alkyl sulfosuccinate metal salt or its derivative is preferably one or more selected from the group consisting of dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt, and dioctyl sulfosuccinate potassium salt.

[0087] The C12-C20 alkyl sulfate ester or derivative thereof, and the C12-C20 alkyl sulfonic acid metal salt or derivative thereof may preferably be one or more selected from the group consisting of sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium octadecyl sulfate, sodium oleyl sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate.

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

[0089] The rosinate soap may preferably be an abietinate.

[0090] As an example, the emulsifier can be used in amounts 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 a total of 100 parts by weight of monomers used in the production of the polymer seeds, rubber cores, and graft shells of the (A) graft copolymer.

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

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

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

[0094] The aforementioned organic peroxides are 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, and 1,1-di(t-amylperoxy)- Crohexane, ethyl 3,3-di(t-amylperoxy)-butyrate, diisopropylbenzene mono-hydroperoxide, t-amylhydroperoxide, t-butylhydroperoxide, t-butylperoxyneodecanoate, t-butylperoxypivalate, di-(3,3,5-trimethylhexanoyl)-peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,3,5-trimethylhexanoyl, t-amylperoxyneodecano Eth, t-amylperoxypivalate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-amylperoxy-2-ethylhexyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 It may be one or more selected from the group consisting of 1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di-2-ethylhexylperoxydicarbonate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, acetylperoxide, isobutylperoxide, octanoylperoxide, dibenzoylperoxide, dilauroylperoxide, 3,5,5-trimethylhexanolperoxide, and t-butylperoxyisobutyrate.

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

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

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

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

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

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

[0101] Steps i), ii), and iii) may, for example, use an oxidation-reduction catalyst in conjunction with the initiator to further accelerate the initiation reaction.

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

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

[0104] Step iii) above may include, as an example, a molecular weight modifier.

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

[0106] The molecular weight modifier may, but is not limited to, one or more selected from the group consisting of α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylenethiuram disulfide, and diisopropyl xanthogen disulfide.

[0107] In this description, 100 parts by weight of graft copolymer means 100 parts by weight of the total weight of the graft copolymer finally obtained, or, since almost all of the added monomers participate in polymerization, it may conveniently mean the combined weight of all monomers used in polymer seeds, rubber cores and graft shells, or the combined weight of all monomers added during the production of polymer seeds and rubber cores and monomers added during the production of graft shells, with 100 parts by weight as the standard.

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

[0109] The emulsion polymerization described above is not particularly limited when carried out by an emulsion polymerization method commonly used in the art to which the present invention belongs.

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

[0111] The latex of the graft copolymer (A) described above can be made into a powder through conventional processes such as flocculation, washing, and drying, for example. Specifically, it can be produced into a powder by adding a metal salt or an acid flocculant, flocculating at a temperature of 60 to 100°C, and then going through processes of maturation, dehydration, washing, and drying, but is not limited to this.

[0112] 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, relative to the total weight of the (A) graft copolymer and the (B) non-graft copolymer. Within this range, it has the effect of exhibiting excellent transparency, gloss, blackness, weather resistance, and impact resistance.

[0113] (B) Non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound and vinyl cyanide compound The (B) non-graft copolymer is a matrix resin, which may, for example, contain an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound. In this case, it has excellent compatibility with the (A) graft copolymer, ensures heat resistance, and provides the effect of excellent transparency, gloss, blackness, weather resistance, and impact resistance.

[0114] The (B) non-graft copolymer preferably contains 30-60% by weight of alkyl (meth)acrylate, 25-55% by weight of alkyl-substituted styrene compound, and 5-35% by weight of vinyl cyanide compound; more preferably, 35-55% by weight of alkyl (meth)acrylate, 30-50% by weight of alkyl-substituted styrene compound, and 15-25% by weight of vinyl cyanide compound; and even more preferably, 40-47% by weight of alkyl (meth)acrylate, 35-42% by weight of alkyl-substituted styrene compound, and 17-23% by weight of vinyl cyanide compound. Within this range, it exhibits excellent compatibility with the (A) graft copolymer, ensures heat resistance, and provides excellent transparency, gloss, blackness, weather resistance, and impact resistance.

[0115] In this description, "non-grafted" means not grafted, and more specifically, not grafted to rubber.

[0116] In this description, alkyl (meth)acrylate can be defined as including both alkyl acrylate and alkyl methacrylate.

[0117] The alkyl acrylate may, for example, be an alkyl acrylate in which the alkyl group has 1 to 15 carbon atoms, 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, 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.

[0118] The alkyl methacrylate may, for example, be an alkyl methacrylate in which the alkyl group has 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 having 1 to 4 carbon atoms, and even more preferably methyl methacrylate.

[0119] In this description, the alkyl-substituted styrene compound is, for example, one or more selected from the group consisting of α-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene, and 2,4-dimethylstyrene, and preferably α-methylstyrene, in which case it has the effect of excellent heat resistance.

[0120] The type of vinyl cyanide compound included in the (B) non-graft copolymer may be within the same category as the type of vinyl cyanide compound included in the (A) graft copolymer described herein.

[0121] The (B) non-graft copolymer may preferably be a methyl methacrylate-α-methylstyrene-acrylonitrile copolymer. In this case, the difference in refractive index with the polymer seed of the (A) graft copolymer becomes smaller, which has the advantage of excellent transparency, blackness, weather resistance, and heat resistance.

[0122] The (B) non-graft copolymer may, for example, have a weight-average molecular weight of 50,000 to 150,000 g / mol, preferably 70,000 to 130,000 g / mol, and more preferably 90,000 g / mol to 120,000 g / mol, and within this range, it has the effect of having excellent impact resistance and moldability.

[0123] In this description, unless otherwise defined, the weight-average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze). Specifically, THF (tetrahydrofuran) can be used as the eluate, and the weight-average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample via GPC. In this case, as a specific measurement example, measurements can be performed under the following conditions: 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): OECD TG 118.

[0124] The (B) non-graft copolymer may, for example, have a glass transition temperature of 110°C or higher, preferably 115°C or higher, and more preferably 115-130°C, as measured in accordance with ASTM D3418. In this case, there is the advantage of further improved heat resistance.

[0125] In this description, the glass transition temperature can be measured in accordance with ASTM D3418 using a differential scanning calorimetry (DSC, TA Instruments, Q100) at a heating rate of 10°C / min.

[0126] The (B) non-graft copolymer may, for example, have a flow index of 8 g / 10 min or more, preferably 10 g / 10 min or more, and more preferably 10 to 20 g / 10 min, measured at 220°C and under a load of 10 kg in accordance with ASTM D1238, and within this range, it has the effect of having excellent processability.

[0127] The (B) non-graft copolymer may, for example, have a refractive index of 1.52 to 1.55, preferably 1.53 to 1.54, as measured at room temperature using an Abbe refractometer in accordance with ASTM D542. Within this range, the difference in refractive index with the seed of the (A) graft copolymer is narrowed, which has the advantage of excellent transparency and gloss, as well as excellent blackness and weather resistance.

[0128] In this description, "room temperature" can refer to any single location within the range of 20±5℃.

[0129] The (B) non-graft copolymer may, for example, be produced by: i) introducing a reaction mixture containing 30-60% by weight of alkyl (meth)acrylate, 25-55% by weight of alkyl-substituted styrene compound, 5-35% by weight of vinyl cyanide compound, a solvent, and a polyfunctional group-containing organic peroxide initiator into a polymerization apparatus and polymerizing it; and ii) introducing the polymer reaction solution from step i) into a volatilization tank to separate the polymer by volatilizing the unreacted monomers and solvent.

[0130] The (B) non-graft copolymer may be produced, for example, by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and is preferably produced by bulk polymerization. The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited when performed by solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization methods that are commonly used in the art to which the present invention pertains.

[0131] The bulk polymerization in step i) above may preferably be carried out at 100 to 130°C with a residence time of 6 to 8 hours in the reactor.

[0132] The polymerization apparatus used in the polymerization reaction is not particularly limited, but a continuous polymerization apparatus in which two or more stirred-tank reactors are connected in series is preferred. In this case, the reactors are not particularly limited, but the first reactor is a stirred-tank reactor with a heat exchanger attached to the front end of the reactor, and the second reactor is an evaporative stirred-tank reactor including a stirred tank, a storage tank, a condenser, and a pressure regulating plate.

[0133] The solvent may, for example, be toluene, methyl ethyl ketone, or a mixture thereof, and is preferably toluene, in which case viscosity can be easily adjusted and the effect of suppressing a decrease in polymerization conversion rate is obtained.

[0134] The aforementioned polyfunctional group-containing organic peroxide initiator is, for example, one or more selected from the group consisting of 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-butylperoxy)2-methylcyclohexane. In this case, there is the advantage of excellent productivity and reduced thermal discoloration.

[0135] The organic peroxide initiator may, for example, be 0.05 to 0.3 parts by weight based on a total of 100 parts by weight of an alkyl-substituted styrene compound, an alkyl (meth)acrylate, and a vinyl cyanide compound, and within this range, there is an effect of increasing the polymerization conversion rate and molecular weight.

[0136] The bulk polymerization in step ii) above can be carried out in a normal volatilization tank through a normal volatilization and separation process. For example, the reaction solution (polymer reaction solution) polymerized and discharged in a continuous polymerization apparatus is put into a first volatilization tank equipped with a heat exchanger that maintains a temperature of 100-200°C and a vacuum pressure of 500-650 torr. Next, the reaction solution discharged from the first volatilization tank is put into a second volatilization tank equipped with a heat exchanger that maintains a temperature of 200-250°C and a vacuum pressure of 50 torr or less, preferably 20-30 torr, to volatilize the unreacted monomers and solvent, then condense it again and put it back in as a raw material. The polymer is then processed into pellets as it passes through a transfer pump extruder.

[0137] In this description, a polymer containing a certain compound means a polymer polymerized with that compound, and the units within the polymer originate from that compound.

[0138] The (B) non-graft copolymer is, for example, 10 to 90% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight, relative to the total weight of the (A) graft copolymer and the (B) non-graft copolymer. Within this range, it has the advantage of having excellent heat resistance, transparency, gloss, blackness, weather resistance, and impact resistance.

[0139] (C) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer with an average particle size of 50-150 nm in the rubber core. The thermoplastic resin composition may, for example, include an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having an average particle size of 50 to 150 nm for the (C) rubber core. In this case, there is an advantage of excellent compatibility with the (B) non-graft copolymer, and further improvements in transparency, gloss, blackness, and weather resistance.

[0140] The (C) graft copolymer may preferably be a graft copolymer comprising a rubber core having an average particle size of 50 to 150 nm and containing 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, containing 65 to 80% by weight of aromatic vinyl compound, 12 to 26% by weight of vinyl cyanide compound and 3 to 15% by weight of alkyl acrylate. In this case, there is an advantage that it has excellent compatibility with (B) non-graft copolymer, excellent impact resistance, and further improved transparency, gloss, blackness and weather resistance.

[0141] The (C) graft copolymer may more preferably include a rubber core having an average particle size of 70 to 130 nm and containing 80 to 90% by weight of alkyl acrylate and 10 to 20% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core, containing 67 to 78% by weight of aromatic vinyl compound, 14 to 25% by weight of vinyl cyanide compound, and 4 to 13% by weight of alkyl acrylate. In this case, there are advantages such as excellent compatibility with (B) non-graft copolymer, excellent impact resistance, and further improved transparency, gloss, blackness, and weather resistance.

[0142] The (C) graft copolymer may more preferably include a rubber core having an average particle size of 80 to 110 nm and containing 82 to 88% by weight of alkyl acrylate and 12 to 18% by weight of aromatic vinyl compound, and a graft shell surrounding the rubber core, containing 69 to 75% by weight of aromatic vinyl compound, 16 to 24% by weight of vinyl cyanide compound, and 5 to 12% by weight of alkyl acrylate. In this case, there is an advantage that the (C) graft copolymer has excellent compatibility with the (B) non-graft copolymer, excellent impact resistance, and further improved transparency, gloss, blackness, and weather resistance.

[0143] The (C) graft copolymer may, for example, consist of 30-60% by weight of rubber core and 40-70% by weight of graft shell, preferably 35-55% by weight of rubber core and 45-65% by weight of graft shell, and more preferably 40-50% by weight of rubber core and 50-60% by weight of graft shell, and within this range, it has the advantage of having excellent mechanical properties.

[0144] The types of alkyl acrylates, aromatic vinyl compounds, and vinyl cyanide compounds included in the (C) graft copolymer may be within the same category as the types of alkyl acrylates, aromatic vinyl compounds, and vinyl cyanide compounds included in the (A) graft copolymer described herein.

[0145] The method for producing the graft copolymer (C) may, as an example, include the steps of: i) producing a rubber core containing 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound; and ii) producing a graft copolymer by graft polymerization in the presence of the rubber core containing 65-80% by weight of aromatic vinyl compound, 12-26% by weight of vinyl cyanide compound and 3-15% by weight of alkyl acrylate. In this case, the method has the effect of having excellent impact resistance while also having excellent transparency, gloss, blackness, and weather resistance.

[0146] Preferably, the method for producing the (C) graft copolymer may include the steps of: i) producing a rubber core containing 78-91% by weight of alkyl acrylate, 9-22% by weight of 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 65-80% by weight of aromatic vinyl compound, 12-26% by weight of vinyl cyanide compound, 3-15% by weight of alkyl acrylate, a crosslinking agent, an initiator, and an emulsifier. In this case, the product has the effect of being excellent in transparency, gloss, blackness, and weather resistance.

[0147] The types of crosslinking agents, initiators, and emulsifiers used in steps i) and / or ii) above may be within the same category as the types of crosslinking agents, initiators, and emulsifiers used in the emulsion polymerization step of the (A) graft copolymer described herein.

[0148] 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 a total of 100% by weight of the (A) graft copolymer, (B) non-graft copolymer, and (C) graft copolymer. Within this range, there is the advantage of excellent transparency, gloss, blackness, weather resistance, and impact resistance.

[0149] The weight ratio (A:C) of the (A) graft copolymer to the (C) graft copolymer may be, for example, 5:5 to 8:2, preferably 5.5:4.5 to 7.5:2.5, more preferably 5.5:4.5 to 7:3, and even more preferably 5.5:4.5 to 6.5:3.5. Within this range, there is the advantage of even greater transparency, gloss, blackness, weather resistance, heat resistance, and impact resistance.

[0150] thermoplastic resin composition The thermoplastic resin composition is preferably subjected to stirring and centrifugation after adding acetone to separate it into an insoluble gel and a soluble sol. The difference between the refractive index of the sol and the refractive index of the gel measured is 0.006 or less, more preferably 0.004 or less, even more preferably 0.003 or less, and even more preferably 0.001 to 0.003. Within this range, there is the advantage of further improvement in transparency, gloss, blackness, and weather resistance.

[0151] In this description, the difference in refractive index between the sol and gel of a thermoplastic resin composition is determined by adding 30 g of acetone to 0.5 g of thermoplastic resin composition pellets, stirring at room temperature at 210 rpm for 12 hours (SKC-6075, Lab companion), and then centrifuging at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30, Hanil Science Co.) to separate the gel (insoluble substance that did not dissolve in acetone) from the sol (soluble substance). After drying at 85°C using a forced circulation method for 12 hours (OF-12GW, Lab companion), the refractive index of the gel and sol are measured in accordance with ASTM D542.

[0152] In this description, the refractive index is specifically measured at room temperature using an Abbe refractometer in accordance with ASTM D542.

[0153] The present invention has the effect of providing a resin composition with even better transparency, gloss, blackness, and weather resistance by controlling the difference between the refractive index of the sol and the refractive index of the gel within the aforementioned range in a thermoplastic resin composition.

[0154] The thermoplastic resin composition preferably has a haze of 10% or less, more preferably 8% or less, even more preferably 6% or less, even more preferably 5% or less, particularly preferably 1-5%, and most preferably 1-4.5%, as measured on an injection-molded test piece with a thickness of 3 mm in accordance with ASTM D1003. Within this range, there is an effect of having an excellent balance of all physical properties.

[0155] The thermoplastic resin composition preferably has a haze of 4% or less, more preferably 3% or less, even more preferably 2.5% or less, even more preferably 0.1 to 2.5%, and particularly preferably 0.5 to 2%, as measured on an extruded test piece with a thickness of 0.15 mm in accordance with ASTM D1003. Within this range, there is an effect of having an excellent balance of all physical properties.

[0156] In this description, haze was specifically measured using a haze meter (MURAKAMI HM-150) for injection-molded specimens with a thickness of 3 mm and extruded specimens with a thickness of 0.15 mm, in accordance with ASTM D1003. A smaller haze value indicates greater transparency.

[0157] The thermoplastic resin composition preferably has a gloss of 120 or higher, more preferably 130 or higher, even more preferably 130 to 160, even more preferably 130 to 150, and particularly preferably 135 to 145, as measured at 45° on an injection-molded test piece with a thickness of 3 mm in accordance with ASTM D2457, and within this range, it has the effect of having an excellent balance of physical properties.

[0158] The thermoplastic resin composition preferably has a gloss of 110 or higher, more preferably 120 or higher, even more preferably 120 to 150, even more preferably 120 to 140, and particularly preferably 125 to 135, as measured at 60° on an extruded test piece with a thickness of 0.15 mm in accordance with ASTM D2457, and within this range, it has the effect of having an excellent balance of all physical properties.

[0159] The thermoplastic resin composition preferably has an Izod impact strength of 10 kgf·cm / cm or more, more preferably 11 kgf·cm / cm or more, even more preferably 12 kgf·cm / cm or more, even more preferably 13 kgf·cm / cm or more, particularly preferably 13 to 20 kgf·cm / cm, and even more preferably 14 to 19 kgf·cm / cm, and within this range, it has the effect of having an excellent balance of all physical properties.

[0160] The thermoplastic resin composition preferably has a heat distortion temperature of 85°C or higher, more preferably 87°C or higher, even more preferably 88°C or higher, and even more preferably 88 to 100°C, measured under a load of 18.5 kgf in accordance with ASTM D648, and within this range, it has the effect of having excellent balance of physical properties and heat resistance.

[0161] The thermoplastic resin composition preferably has a Vicat softening temperature (Vicat) of 85°C or higher, more preferably 87°C or higher, even more preferably 89°C or higher, and even more preferably 89-100°C, measured in accordance with ASTM D1525 at a heating rate of 50°C / min and a load of 50N, and within this range, it has the effect of having excellent balance of physical properties and heat resistance.

[0162] The thermoplastic resin composition is preferably subjected to accelerated weathering testing using a Weather-o-meter (ATLAS Corporation, Ci4000, xenon arc lamp, quartz (inner) / S. Boro (outer) filter, irradiation dose of 0.55 W / m²). 2 After leaving the material for 3,000 hours under SAE J1960 conditions using a colorimeter (at 340 nm), the degree of discoloration is measured, and the weather resistance (△E) calculated using the following formula 7 may be 2.8 or less, more preferably 2.6 or less, even more preferably 2.4 or less, even more preferably 0.1 to 2.4, and particularly preferably 0.5 to 2.2. Within this range, there is an effect of having an excellent balance of all physical properties.

[0163] The aforementioned △E is the arithmetic mean of the L, a, and b values ​​measured in the CIE LAB color coordinate system for test specimens before and after the accelerated weathering experiment. The closer the △E value is to 0, the better the weather resistance.

[0164]

number

[0165] In the above formula 7, L', a', and b' are the L, a, and b values ​​measured in the CIE LAB color coordinate system, respectively, after the test specimen has been left for 3,000 hours under SAE J1960 conditions, while L0, a0, and b0 are the L, a, and b values ​​measured in the CIE LAB color coordinate system, respectively, before the specimen was left to stand.

[0166] The thermoplastic resin composition preferably has a blackness value of 25.5 or less, preferably 25 or less, more preferably 0 to 25, and even more preferably 5 to 24.5, as evaluated by the L value corresponding to brightness among the values ​​of the hue of the injection-molded test piece measured in the CIE LAB color coordinate system. Within this range, there is an effect of having an excellent balance of all physical properties.

[0167] In this description, the L value has a range of 0 to 100, where L=0 indicates black and L=100 indicates white.

[0168] The thermoplastic resin composition may, for example, include one or more selected from the group consisting of lubricants, antioxidants, and ultraviolet absorbers.

[0169] The lubricant may, for example, be one or more selected from the group consisting of ethylene bis-stearamide, oxidized polyethylene wax, magnesium stearate, calcium stearamide, and stearic acid, in which case the heat resistance and fluidity are improved.

[0170] The lubricant may be, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the total of (A) graft copolymer and (B) non-graft copolymer.

[0171] The antioxidant may include, for example, a phenolic antioxidant, a phosphorus-based antioxidant, or a mixture thereof. Preferably, it may be a phenolic antioxidant, in which case it has the effect of preventing oxidation due to heat during the extrusion process and having excellent mechanical properties and heat resistance.

[0172] The antioxidant may be present in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the total of (A) graft copolymer and (B) non-graft copolymer. Within this range, there is an effect of improving heat resistance while maintaining an excellent balance of physical properties.

[0173] The aforementioned ultraviolet absorber may, for example, be one or more selected from the group consisting of triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers, but is not limited thereto.

[0174] The UV absorber may be present in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the total of (A) graft copolymer and (B) non-graft copolymer. Within this range, there is an effect of improving light resistance while maintaining an excellent balance of physical properties.

[0175] The thermoplastic resin composition may further include, as an example, one or more additives selected from the group consisting of flame retardants, flame retardant auxiliary agents, fluorescent whitening agents, antistatic agents, chain extenders, mold release agents, pigments, dyes, antibacterial agents, processing aids, metal deactivators, smoke suppressants, inorganic fillers, glass fibers, friction inhibitors, and abrasion inhibitors.

[0176] As an example, the additive may be 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, of each of the (A) graft copolymer and (B) non-graft copolymer in total of 100 parts by weight. In this case, there is an effect of excellent improvement in physical properties and low manufacturing costs, thus making it economically advantageous.

[0177] The following describes a method for producing the thermoplastic resin composition of the present invention and a molded article containing the composition. The description of the method for producing the thermoplastic resin composition of the present invention and the molded article containing the composition includes all the details of the thermoplastic resin composition described above.

[0178] Method for manufacturing thermoplastic resin compositions The method for producing the thermoplastic resin composition described herein includes the steps of kneading and extruding under conditions of 180 to 300°C and 80 to 400 rpm, wherein the (A) graft copolymer comprises an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including (A) a seed polymerized with 35 to 58% by weight of alkyl acrylate and 42 to 65% 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 cyanide compound, and 3 to 15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound, and vinyl cyanide compound, wherein the (A) graft copolymer simultaneously satisfies the following formulas 1 and 2. In such a case, there is the advantage that transparency, gloss, heat resistance, and impact resistance are all excellent.

[0179] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0180] [Formula 2] 25 ≤ r² - r¹ ≤ 45

[0181] In the above equations 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.

[0182] The aforementioned kneading and extrusion steps may, for example, include an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having an average particle size of (C) rubber core of 50 to 150 nm, preferably an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising (C) a rubber core having an average particle size of 50 to 150 nm and containing 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 containing 65 to 80% by weight of aromatic vinyl compound, 12 to 26% by weight of vinyl cyanide compound and 3 to 15% by weight of alkyl acrylate. In such a case, there is an effect of greatly improving transparency, gloss, blackness and weather resistance while maintaining excellent impact resistance.

[0183] The aforementioned kneading and extrusion may be carried out, for example, through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed and has excellent compatibility.

[0184] The kneading and extrusion may, for example, be carried out within a barrel temperature range of 180 to 300°C, preferably 190 to 280°C, and more preferably 200 to 260°C. In this case, the processing rate per unit time is appropriate, sufficient melt kneading is possible, and problems such as thermal decomposition of resin components can be avoided.

[0185] The kneading and extrusion may, for example, be carried out under conditions where the screw rotation speed is 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, resulting in excellent process efficiency.

[0186] The thermoplastic resin composition obtained through the extrusion described above can, for example, be manufactured as pellets using a pelletizer.

[0187] Furthermore, the resin composition can be manufactured as molded products for various industrial fields through molding processes such as blow molding and injection molding.

[0188] molded product The molded articles described herein may, for example, contain the thermoplastic resin composition described herein, and since they exhibit excellent transparency, gloss, heat resistance, blackness, weather resistance, and impact resistance, they have the advantage of being applicable to fields where transparency is required with high quality.

[0189] The molded product may be, for example, an injection-molded product, a film, or a sheet. In this case, the thermoplastic resin composition described herein has the advantage of being able to provide products with higher quality than those required in the market for impact resistance, transparency, gloss, heat resistance, blackness, and weather resistance.

[0190] The molded product may be an automotive interior material, an automotive exterior material, a building material, a home appliance, or a medical component. In this case, it has the advantage of meeting all the requirements of the market because it is excellent in terms of transparency, gloss, heat resistance, and impact resistance.

[0191] The method for producing the molded article preferably comprises (A) a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% 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 compound and 3-15% by weight of alkyl acrylate, comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and (B The process comprises the steps of: kneading and extruding a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound under conditions of 180-300°C and 80-400 rpm to produce pellets; and injecting or extruding the produced pellets using an injection or extruder, wherein the (A) graft copolymer is characterized by simultaneously satisfying the following formulas 1 and 2, and in this case, transparency, gloss, heat resistance, blackness, weather resistance, and impact resistance are all excellent, thus providing the effect of being applicable to fields requiring these qualities with high quality.

[0192] [Formula 1] 180 ≤ 2 × r² ≤ 300

[0193] [Formula 2] 25 ≤ r² - r¹ ≤ 45

[0194] In equations 1 and 2 above, 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.

[0195] The following are preferred embodiments to aid in understanding the present invention. However, these embodiments are merely illustrative of the present invention, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the technical concept, and that such changes and modifications fall within the scope of the appended claims.

[0196] [Examples] The substances used in the examples and comparative examples are as follows: *(A) Graft copolymer: Produced in Examples 1-10 and Comparative Examples 1-11 below *(B-1) AMS T-SAN copolymer: A methyl methacrylate-α-methylstyrene-acrylonitrile copolymer comprising 42.5% by weight of methyl methacrylate, 37.5% by weight of α-methylstyrene, and 20% by weight of acrylonitrile. *(B-2)SAMMA copolymer: A non-graft copolymer of methyl methacrylate-styrene-acrylonitrile, comprising 71% by weight of methyl methacrylate, 22% by weight of styrene, and 7% by weight of acrylonitrile. *(C) Graft copolymer: A graft copolymer comprising a rubber core having an average particle size of 90 nm and comprising 85% by weight of butyl acrylate and 15% by weight of styrene, and a graft shell surrounding the rubber core, comprising 72% by weight of styrene, 20% by weight of acrylonitrile and 8% by weight of butyl acrylate (45% by weight of rubber core, and 55% by weight of graft shell) *Lubricant: SUNLUBE EBS (SUNKOO Co.) *Antioxidants: Songnox 1076 (Songwon Co.) and Irgafos 168 (BASF) *UV absorbers: Tinuvin 770 (BASF), Tinuvin P (BASF)

[0197] Example 1 A (A) acrylate-styrene-acrylonitrile graft copolymer was prepared by using 45% by weight of butyl acrylate (hereinafter referred to as "BA") and 55% by weight of styrene (hereinafter referred to as "SM") as polymer seeds, 85% by weight of BA and 15% by weight of SM as rubber cores, and 72% by weight of SM, 20% by weight of acrylonitrile (hereinafter referred to as "AN") and 8% by weight of BA as graft shells. In this case, the (A) graft copolymer consisted of 20% by weight of polymer seeds, 40% by weight of rubber cores, and 40% by weight of graft shells.

[0198] Fifty parts by weight of the manufactured (A) graft copolymer and fifty parts by weight of the (B-1) AMS T-SAN copolymer were mixed with one part by weight of lubricant, one part by weight of antioxidant, and 0.6 parts by weight of ultraviolet stabilizer. The mixture was kneaded and extruded at 220°C and 200 rpm to produce pellets. The manufactured pellets were injected at a molding temperature of 220°C to produce injection-molded test specimens for physical property measurement. The manufactured pellets were also extruded using a uniscrew film extruder under conditions of 220°C and 200 rpm to produce extruded test specimens for physical property measurement.

[0199] Examples 2-5 and 8-10 The procedure was the same as in Example 1, except that the (A) graft copolymer was replaced with the (A) graft copolymer polymerized with the components and content listed in Tables 1 and 2 below.

[0200] Example 6 The procedure was carried out in the same manner as in Example 1, except that 50 parts by weight of the (A) graft copolymer produced in Example 1 was replaced with 30 parts by weight of the (A) graft copolymer and 20 parts by weight of the (C) graft copolymer.

[0201] Example 7 The procedure was carried out in the same manner as in Example 1, except that 50 parts by weight of the (A) graft copolymer produced in Example 1 was replaced with 35 parts by weight of the (A) graft copolymer and 15 parts by weight of the (C) graft copolymer.

[0202] Comparative Examples 1-9 The procedure was the same as in Example 1, except that the (A) graft copolymer was replaced with the (A) graft copolymer polymerized with the components and content described in Tables 3 and 4 below.

[0203] Comparative Example 10 The procedure was the same as in Example 1, except that a graft copolymer was produced containing 100% by weight of BA as a polymer seed, 81% by weight of BA and 19% by weight of SM as a rubber core, and 100% by weight of methyl methacrylate (hereinafter referred to as "MMA") as a graft shell.

[0204] Comparative Example 11 The procedure was the same as in Example 1, except that (B-1)AMS T-SAN copolymer was replaced with (B-2)SAMMA copolymer.

[0205] [Example Test] The properties of the pellets and test specimens produced in Examples 1 to 10 and Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Tables 1 to 4 below. *(A) Refractive index of seed, core, and shell of graft copolymer, and (B) Refractive index of non-graft copolymer: Calculated using formula 3 below.

[0206] [Formula 3] RI = ΣWti × RIi Wti = Weight fraction of each component in the copolymer (%) RIi = Refractive index of the polymer components of the copolymer

[0207] *Average particle size (nm) of polymer seeds, rubber cores, and graft shells: Samples were taken at the completion of polymer seed production, rubber core production, and graft shell production, and measured using dynamic light scattering. Specifically, the intensity value was measured in Gaussian mode using a particle analyzer (product name: Nicomp380, manufacturer: PSS). As a specific measurement example, 0.1 g of latex with a total solids content of 35-50% by weight was prepared as a sample by diluting it 1,000-5,000 times with distilled water. The measurement method was auto-dilution and measurement in a flow cell, with the measurement mode being dynamic light scattering / intensity 300 kHz / intensity-weight Gaussian analysis, and the setting values ​​were a temperature of 23°C and a measurement wavelength of 632.8 nm.

[0208] For reference, r1 was defined as the average particle size of the seed divided by half, and r2 was defined as the average particle size of the core containing the seed divided by half.

[0209] *Izod impact strength (IMP; kgf·cm / cm): Measured at room temperature (20±5℃) using a 1 / 4" thick injection-molded specimen in accordance with ASTM D256.

[0210] *Haze (%): Haze was measured in accordance with ASTM D1003 for injection-molded specimens with a thickness of 3 mm and extruded specimens with a thickness of 0.15 mm. Lower haze indicates better transparency.

[0211] *Glossiness of injection-molded specimens: Glossiness was measured at 45° on 3mm thick injection-molded specimens in accordance with ASTM D2457.

[0212] *Glossiness of extruded specimens: Glossiness was measured at 60° on 0.15 mm thick extruded specimens in accordance with ASTM D2457.

[0213] *Thermal distortion temperature (HDT, °C): Measured under a load of 18.5 kgf in accordance with ASTM D648.

[0214] *Vicat softening point temperature (°C): Measured in accordance with ASTM D1525 at a heating rate of 50°C / min and a load of 50N.

[0215] *Difference in refractive index between sol and gel in thermoplastic resin composition: 0.5 g of thermoplastic resin composition pellets was mixed with 30 g of acetone and stirred at room temperature at 210 rpm for 12 hours (SKC-6075, Lab companion). Then, the mixture was centrifuged at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30, Hanil Science Co.) to separate the gel (insoluble substance) that did not dissolve in acetone from the sol (soluble substance). After drying at 85°C using a forced circulation method for 12 hours (OF-12GW, Lab companion), the refractive indices of each were measured at room temperature (20±5°C) using an Abbe refractometer in accordance with ASTM D542, and the difference between them was calculated.

[0216] *Weather resistance (△E): Accelerated weathering test equipment (Weather-o-meter, ATLAS, Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiation dose 0.55 W / m²) 2 After leaving the specimens for 3,000 hours under SAE J1960 conditions (at 340 nm), the degree of discoloration was measured using a colorimeter, and △E was calculated using the following formula 7. The △E below is the arithmetic mean of the L, a, and b values ​​measured in the CIE LAB color coordinate system for the test specimens before and after the accelerated weathering experiment. The closer the △E value is to 0, the better the weather resistance.

[0217]

number

[0218] In the above formula 7, L', a', and b' are the L, a, and b values ​​measured in the CIE LAB color coordinate system, respectively, after the test specimen has been left for 3,000 hours under SAE J1960 conditions, while L0, a0, and b0 are the L, a, and b values ​​measured in the CIE LAB color coordinate system, respectively, before the specimen was left to stand.

[0219] *Blackness (L): Blackness was evaluated using the L value, which corresponds to brightness, from the hue of the injection-molded test specimen measured in the CIE LAB color coordinate system. The L value ranges from 0 to 100, with L=0 indicating black and L=100 indicating white.

[0220] [Table 1]

[0221] [Table 2]

[0222] [Table 3]

[0223] [Table 4]

[0224] As shown in Tables 1 to 4 above, the thermoplastic resin compositions according to the present invention (Examples 1 to 10) were found to be superior to Comparative Examples 1 to 11 in terms of impact strength, haze, gloss, heat distortion temperature, Vicat softening point temperature, weather resistance, and blackness.

[0225] Examples 6 and 7, which included (C) graft copolymer, showed superior gloss, heat distortion temperature, and Vicat softening point temperature.

[0226] On the other hand, in Comparative Examples 1 and 2, where the composition ratio of polymer seeds in (A) graft copolymer was outside the scope of the present invention, the difference between the refractive index of the seeds in (A) graft copolymer and the refractive index of (B-1) AMS T-SAN copolymer, and / or the difference between the refractive index of the sol and gel in the thermoplastic resin composition was large, resulting in reduced haze and / or gloss, poor weather resistance, and in Comparative Example 1, a significant decrease in impact strength.

[0227] Furthermore, in Comparative Examples 3 and 4, where the composition ratio of the rubber core of the (A) graft copolymer was outside the scope of the present invention, the difference in refractive index between the sol and gel in the thermoplastic resin composition was large, resulting in reduced haze and gloss, and poor weather resistance. In Comparative Example 4, the impact strength was also significantly reduced.

[0228] Furthermore, in Comparative Examples 5 and 6, where the graft shell structure of the (A) graft copolymer fell outside the scope of the present invention, the difference in refractive index between the sol and gel in the thermoplastic resin composition was large, resulting in a decrease in haze, gloss, blackness, and weather resistance, and Comparative Example 5 also had low impact strength.

[0229] Furthermore, in Comparative Example 7, where the 2×r2 and r2-r1 of the rubber core of the graft copolymer (A) exceeded the scope of the present invention, the injection-molded test specimens exhibited poor haze, gloss, blackness, and weather resistance, and the extruded test specimens exhibited low gloss.

[0230] Furthermore, in Comparative Example 8, where the 2×r2 and r2-r1 values ​​of the rubber core of the (A) graft copolymer were below the range of the present invention, the impact strength was significantly reduced, and the blackness and weather resistance were also poor.

[0231] Furthermore, Comparative Example 9, which, like the prior art, contains styrene in the seed, butyl acrylate in the core, and styrene and acrylonitrile in the shell, had very poor haze and gloss, as well as poor blackness and weather resistance, due to the large difference in refractive index between the core and polymer seeds of (A) graft copolymer, the difference in refractive index between the polymer seeds of (A) graft copolymer and (B-1) AMS T-SAN copolymer, and the large difference in refractive index between the sol and gel in the thermoplastic resin composition.

[0232] Furthermore, Comparative Example 10, which contains butyl acrylate as the seed of the (A) graft copolymer and methyl methacrylate as the shell, had poor haze and gloss, as well as poor impact strength, blackness, and weather resistance, due to the large difference in refractive index between the seed of the (A) graft copolymer and the (B-1) AMS T-SAN copolymer, and the large difference in refractive index between the sol and gel in the thermoplastic resin composition.

[0233] Furthermore, in Comparative Example 11, in which (B-1) AMS T-SAN copolymer was replaced with (B-2) SAMMA copolymer, the difference in refractive index between the polymer seeds of (A) graft copolymer and (B-2) SAMMA copolymer was large, resulting in poor gloss, blackness, weather resistance and / or impact strength, and very low heat distortion temperature and Vicat softening point temperature.

[0234] In conclusion, in a thermoplastic resin composition comprising (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and (B) a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, it was confirmed that by adjusting the composition and composition ratio of the polymer seeds, core, and shell constituting the (A) graft copolymer within a predetermined range, and by reducing the difference between the refractive index of the core and the refractive index of the shell, and the difference between the refractive index of the polymer seeds of the (A) graft copolymer and the refractive index of the (B) non-graft copolymer, the effect of excellent transparency, gloss, and heat resistance while maintaining excellent impact resistance was confirmed.

Claims

1. (A) A graft copolymer comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound, comprising a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% 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 compound, and 3-15% by weight of alkyl acrylate, (B) A thermoplastic resin composition comprising a non-graft copolymer containing groups derived from alkyl (meth)acrylate, alkyl-substituted styrene compounds, and vinyl cyanide compounds, The (A) graft copolymer satisfies both equation 1 and equation 2 below simultaneously. The (A) graft copolymer has a difference of 0.09 or less between the refractive index of the rubber core and the refractive index of the shell. The refractive index of the polymer seeds of the (A) graft copolymer is such that the difference between it and the refractive index of the (B) non-graft copolymer is 0.012 or less. The (A) graft copolymer comprises 5 to 35% by weight of polymer seeds, 25 to 55% by weight of rubber cores, and 25 to 55% by weight of graft shells, based on a total weight of 100%. The (B) non-graft copolymer comprises 30 to 60% by weight of alkyl (meth)acrylate, 25 to 55% by weight of alkyl-substituted styrene compound, and 5 to 35% by weight of vinyl cyanide compound. The thermoplastic resin composition, after adding acetone, is stirred and centrifuged to separate it into a sol and a gel, and the difference in refractive index between the sol and the gel, as measured, is 0.006 or less. In accordance with ASTM D1003, the haze measured on a 3 mm thick injection-molded test specimen is 10% or less. A thermoplastic resin composition characterized by having an Izod impact strength of 10 kgf·cm / cm to 20 kgf·cm / cm, measured at room temperature using a 1 / 4" thick test specimen in accordance with ASTM D256. [Formula 1] 180 ≤ 2 × r² ≤ 300 [Formula 2] 25 ≤ r² - r¹ ≤ 45 (In equations 1 and 2 above, 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. The thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition comprises (A) 10 to 90% by weight of a graft copolymer and (B) 10 to 90% by weight of a non-graft copolymer.

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

4. The thermoplastic resin composition according to claim 1, characterized in that, after adding acetone, the thermoplastic resin composition is stirred and centrifuged to separate it into a sol and a gel, and the difference in refractive index between the sol and the gel, as measured, is 0.004 or less.

5. The thermoplastic resin composition according to claim 1, characterized in that the haze measured on an injection-molded test piece with a thickness of 3 mm in accordance with ASTM D1003 is 8% or less.

6. The thermoplastic resin composition according to claim 1, characterized in that the gloss level measured on an injection-molded test piece with a thickness of 3 mm at 45° in accordance with ASTM D2457 is 120 to 160.

7. The thermoplastic resin composition according to claim 1, characterized in that the Izod impact strength measured at room temperature on a 1 / 4" thick test piece in accordance with ASTM D256 is 11 kgf·cm / cm to 20 kgf·cm / cm.

8. The process comprises the steps of kneading and extruding (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising (A) a seed polymerized with 35-58% by weight of alkyl acrylate and 42-65% by weight of aromatic vinyl compound, surrounding the seed a rubber core polymerized with 78-91% by weight of alkyl acrylate and 9-22% by weight of aromatic vinyl compound, and surrounding the rubber core a graft shell polymerized with 65-82% by weight of aromatic vinyl compound, 12-30% by weight of vinyl cyanide compound, and 3-15% by weight of alkyl acrylate; and (B) a non-graft copolymer comprising groups derived from methyl methacrylate, alkyl-substituted styrene compounds, and vinyl cyanide compounds, under conditions of 180-300°C and 80-400 rpm. The (A) graft copolymer satisfies both equation 1 and equation 2 below simultaneously. The (A) graft copolymer has a difference of 0.09 or less between the refractive index of the rubber core and the refractive index of the shell. The refractive index of the polymer seeds of the (A) graft copolymer is such that the difference between it and the refractive index of the (B) non-graft copolymer is 0.012 or less. The (A) graft copolymer comprises 5 to 35% by weight of polymer seeds, 25 to 55% by weight of rubber cores, and 25 to 55% by weight of graft shells, based on a total weight of 100%. The (B) non-graft copolymer comprises 30 to 60% by weight of methyl methacrylate, 25 to 55% by weight of alkyl-substituted styrene compound, and 5 to 35% by weight of vinyl cyanide compound. Aromatic vinyl compounds include 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. The vinyl cyanide compound comprises one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile. The alkyl acrylate includes alkyl acrylates in which the alkyl group has 4 to 10 carbon atoms. A method for producing a thermoplastic resin composition, characterized in that the alkyl-substituted styrene compound comprises one or more selected from the group consisting of α-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-t-butylstyrene, and 2,4-dimethylstyrene. [Formula 1] 180 ≤ 2 × r² ≤ 300 [Formula 2] 25 ≤ r² - r¹ ≤ 45 (In equations 1 and 2 above, 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.)

9. The method for producing a thermoplastic resin composition according to claim 8, characterized in that the kneading and extrusion step includes (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer having an average particle size of 50 to 150 nm for the rubber core.

10. A molded article characterized by comprising the thermoplastic resin composition described in claim 1.

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