Thermoplastic resin composition, method for preparing same, and molded article comprising same

Abstract

The present disclosure relates to a thermoplastic resin composition, a method for preparing same, and a molded article comprising same and, more specifically, to a thermoplastic resin composition, a method for preparing same, and a molded article comprising same, the thermoplastic resin composition comprising: (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle diameter of 50 to 150 nm; (A-2) 1 to 22 wt % of an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an alkyl acrylate rubber having an average particle diameter of 150 nm (exclusive) to 600 nm (inclusive); (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer; (C) 7 to 12.5 wt % of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary agent having an average particle size of 2 μm or less. According to the present invention, a thermoplastic resin composition, a method for preparing same, and a molded article comprising same can be provided wherein the thermoplastic resin composition maintains excellent physical properties of a conventional ASA-based resin, implements high whiteness even with a reduced input amount of a white pigment, exhibits excellent thin film processability, hiding power, and glossiness, displays superior appearance quality due to the absence of protrusions on a surface, and reduces manufacturing costs.

Description

Thermoplastic resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2024-0004867, filed January 11, 2024, and Korean Patent Application No. 10-2025-0000500, filed January 2, 2025, which is hereby incorporated by reference in its entirety.

[0003] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, which maintains the excellent physical properties of a conventional ASA resin, realizes high whiteness even with a significantly reduced amount of white pigment added, has excellent thin film processability, hiding power, and gloss, has excellent appearance quality by not generating protrusions on the sheet surface, and reduces manufacturing costs.

[0004] Acrylate-styrene-acrylonitrile copolymer (hereinafter referred to as “ASA resin”) has excellent weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability, and is used in a variety of applications, including automobiles, building materials, and miscellaneous goods.

[0005] Recently, the primary color for decorative sheets used for furniture finishing has been white, with white hues being a particular trend. To achieve this white hues, the amount of expensive white pigment TiO2 in ASA resin compositions has been increasing. However, beyond a certain level, increasing the TiO2 content only marginally improves whiteness, while impact strength, durability, and surface quality deteriorate.

[0006] Accordingly, there is a need to develop a material that maintains the excellent properties of conventional ASA resin, reduces the amount of white pigment added while achieving the white color demanded by the market, and has excellent thin film processability, hiding power, gloss, and surface quality.

[0007]

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] Korean Patent Publication No. 2009-0095764

[0011] In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition having the excellent physical properties of a conventional ASA resin, realizing a high white color even with a reduced amount of expensive white pigment, having excellent thin film processability, hiding power and gloss, and having excellent appearance quality by not generating protrusions on the sheet surface, and reducing manufacturing costs.

[0012] In addition, the present invention aims to provide a method for producing the above thermoplastic resin composition.

[0013] In addition, the present invention aims to provide a molded product manufactured from the thermoplastic resin composition described above.

[0014]

[0015] The above-mentioned and other purposes of this invention can all be achieved by the invention described below.

[0016] In order to achieve the above object, I) the present invention provides a thermoplastic resin composition characterized by comprising: (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary agent having an average particle size of 2 μm or less.

[0017] II) In the above I), the (C) white pigment may be at least one selected from the group consisting of titanium oxide (TiO2), zinc oxide (ZnO), zinc sulfide (ZnS), lithopone, and lead oxide.

[0018] III) In the above I) or II), the (D) white pigment auxiliary agent may be at least one selected from the group consisting of calcium carbonate (CaCO3), talc, clay, barium sulfate (BaSO4), aluminum hydroxide (Al(OH)3), and silicon dioxide (SiO2).

[0019] IV) In the above I) to III), the (D) white pigment auxiliary agent may have a refractive index of 1.70 or less.

[0020] V) In the above I) to IV), the weight ratio (C:D) of the (C) white pigment and the (D) white pigment auxiliary agent may be 1:0.4 to 1:0.7.

[0021] VI) In the above I) to V), the (A-1) graft copolymer may comprise 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof.

[0022] VII) In the above I) to VI), the (A-2) graft copolymer may be formed by including 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof.

[0023] VIII) In the above I) to VII), the (B) aromatic vinyl compound-vinyl cyan compound copolymer may be at least one selected from the group consisting of (b-1) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and (b-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of more than 150,000 g / mol to 200,000 g / mol or less.

[0024] IX) In the above I) to VIII), the thermoplastic resin composition includes both (b-1) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and (b-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of more than 150,000 g / mol to less than 200,000 g / mol, and the weight ratio (b-1:b-2) thereof may be 2:8 to 4:6.

[0025] X) In the above I) to IX), the thermoplastic resin composition may have a whiteness (L value - b value) of 95.5 or more, calculated by measuring the L value and b value in a colorimeter SCI mode and using the difference between them.

[0026] XI) In the above I) to X), the thermoplastic resin composition may have a gloss of 82 or more measured at 60° according to ASTM D523 in a sheet having a thickness of 0.15 mm.

[0027] XII) In the above I) to XI), the thermoplastic resin composition may have an Izod impact strength of 5.3 kgf·cm / cm or more, measured using a notched injection molded specimen (thickness 1 / 4") according to ASTM D256.

[0028] In addition, XIII) The present invention provides a method for producing a thermoplastic resin composition, characterized by comprising the steps of: (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary having an average particle size of 2 ㎛ or less; and kneading and extruding under conditions of 200 to 300° C. and 100 to 500 rpm.

[0029] In addition, XIV) The present invention provides a molded article characterized by including a thermoplastic resin composition of any one of I) to XII).

[0030] According to the present invention, there is provided a thermoplastic resin composition having properties equivalent to or better than those of conventional ASA resins, realizing high whiteness even with a reduced amount of white pigment, having excellent thin film processability, hiding power and gloss, and having excellent appearance quality with no protrusions on the sheet surface, and reducing manufacturing costs by reducing the amount of white pigment, a method for producing the same, and a molded article including the same.

[0031] Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and a molded article including the same are described in detail.

[0032] The present inventors have confirmed that when a white pigment auxiliary agent having a predetermined average particle size is added to a base resin composed of two kinds of alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers including alkyl acrylate rubber having a predetermined average particle size and an aromatic vinyl compound-vinyl cyan compound copolymer, the excellent physical properties of the conventional ASA resin are maintained while reducing the amount of white pigment added to realize high whiteness, and the thin film processability, hiding power and glossiness are excellent, and the surface quality is improved because protrusions and the like do not occur on the surface of the molded product. Based on this, the inventors have devoted themselves to further research and completed the present invention.

[0033]

[0034] The thermoplastic resin composition according to this invention is examined in detail as follows.

[0035]

[0036] The thermoplastic resin composition of the present invention is characterized by comprising (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary agent having an average particle size of 2 μm or less. In this case, the excellent physical properties of the conventional ASA resin are maintained, a high white color is achieved even with a significantly reduced amount of white pigment, and the thin film processability, hiding power and gloss are excellent, and there is no occurrence of protrusions on the sheet surface, resulting in excellent appearance quality.

[0037]

[0038] Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

[0039]

[0040] (A-1) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising alkyl acrylate rubber having an average particle diameter of 50 to 150 nm

[0041] The above (A-1) graft copolymer may be, for example, 4 to 31 wt%, preferably 5 to 28 wt%, more preferably 6 to 25 wt%, and even more preferably 6 to 20 wt%, based on the total weight of the components (A-1) to (D), and within this range, the graft copolymer has properties equivalent to or greater than the excellent properties of conventional ASA resins, realizes high white color even with a reduced amount of white pigment, has excellent thin film processability, hiding power, and gloss, and has the effect of excellent appearance quality because no protrusions occur on the surface of the molded product.

[0042]

[0043] The alkyl acrylate rubber of the above (A-1) graft copolymer preferably has an average particle diameter of 60 to 140 nm, more preferably 80 to 140 nm, even more preferably 100 to 140 nm, and even more preferably 110 to 140 nm, and within this range has the advantages of excellent impact resistance, gloss, transparency, and colorability.

[0044] In this description, the average particle size can be measured using dynamic light scattering, and more specifically, it refers to the arithmetic mean particle size, i.e., the scattering intensity average particle size, in the particle size distribution measured by dynamic light scattering. Specifically, it is measured as an intensity value in Gaussian mode using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of latex with a total solid content of 35 to 50 wt% 1,000 to 5,000 times with distilled water, and the measurement method is measured using a flow cell through auto-dilution, and the measurement mode is dynamic light scattering / Intensity 300 KHz / Intensity-weight Gaussian Analysis, and the setting values ​​are temperature 23 ℃, measurement wavelength 632.8 nm, and channel width 10 μsec.

[0045]

[0046] The above (A-1) graft copolymer may preferably include an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) surrounding the core, and in this case, it has the advantage of excellent gloss, transparency, colorability, and processability while maintaining mechanical properties.

[0047] The above (A-1) graft copolymer may be, for example, composed of 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof, and has the advantage of excellent gloss, transparency, colorability, and processability while maintaining mechanical properties within this range.

[0048] Preferably, the above (A-1) graft copolymer can be formed by including 40 to 60 wt% of alkyl acrylate rubber, 25 to 50 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, and has the advantage of excellent gloss, transparency, colorability, and processability while maintaining mechanical properties within this range.

[0049] More preferably, the graft copolymer (A-1) may be formed by including 45 to 55 wt% of alkyl acrylate rubber, 33 to 43 wt% of aromatic vinyl compound, and 10 to 15 wt% of vinyl cyan compound, and has the advantage of excellent gloss, transparency, colorability, and processability while maintaining mechanical properties within this range.

[0050]

[0051] The above (A-1) graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has the advantage of excellent gloss, transparency, and colorability while maintaining mechanical properties.

[0052] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and may be performed using an emulsion graft polymerization method, for example.

[0053]

[0054] The above (A-1) graft copolymer may have a graft ratio of, for example, 15 to 60%, preferably 20 to 50%, and more preferably 25 to 45%, as calculated by the following mathematical formula 1, and has the effect of improving thin film processability within this range.

[0055] [Mathematical Formula 1]

[0056] Grafting ratio (%) = [weight of grafted monomer (g) / weight of rubber (g)] * 100

[0057] (In the above mathematical expression 1, the weight (g) of the grafted monomer is the weight (g) of the insoluble substance (gel) after dissolving the graft copolymer in acetone and centrifuging it, minus the rubber weight (g), and the rubber weight (g) is the weight (g) of the rubber component theoretically added in the graft copolymer powder.)

[0058] The weight of the above insoluble substance (gel) is the weight measured after adding 0.5 g of the graft copolymer dry powder to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging the mixture to collect only the insoluble matter that did not dissolve in acetone, drying it for 12 hours, and the rubber weight (g) is the weight (g) of the theoretical rubber component added to 0.5 g of the graft copolymer dry powder.

[0059] As a specific measurement example at this time, the weight of the insoluble substance (gel) is measured by adding 0.5 g of the graft copolymer dry powder to 50 ml of acetone, stirring at 210 rpm for 12 hours at room temperature with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075), centrifuging at 18,000 rpm at 0 ℃ for 3 hours using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble substance that has not dissolved in acetone, and drying it at 85 ℃ for 12 hours using a forced convection drying method in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW).

[0060]

[0061] In this description, thin film processability means that a sheet having a width of 1 m or more and a thickness of 0.2 mm or less can be produced with a length of 1000 m or more while maintaining a thickness deviation of within ±0.05%.

[0062]

[0063] The alkyl acrylate of the present invention may be, for example, an alkyl acrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one 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 or 8 carbon atoms, and even more preferably butyl acrylate, ethylhexyl acrylate, or a mixture thereof, and even more preferably butyl acrylate.

[0064]

[0065] The aromatic vinyl compound of the present invention may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ-bromostyrene, m-bromostyrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably at least one selected from the group consisting of styrene and α-methyl styrene, and more preferably styrene, and in this case, there is an effect of having appropriate fluidity, excellent processability, and excellent mechanical properties such as impact resistance.

[0066]

[0067] The vinyl cyanide compound of the present invention may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and preferably acrylonitrile.

[0068]

[0069] In this description, a polymer comprising a compound or monomer means a polymer polymerized including the compound or monomer, and a unit within the polymerized polymer is derived from the compound or monomer.

[0070]

[0071] (A-2) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising alkyl acrylate rubber having an average particle diameter of more than 150 nm and less than or equal to 600 nm

[0072] The above (A-2) graft copolymer may be, for example, present in an amount of 1 to 22 wt%, preferably 3 to 17 wt%, more preferably 4 to 13 wt%, and even more preferably 6 to 12 wt%, based on the total weight of components (A-1) to (D), and within this range, excellent mechanical properties, processability, and transparency are achieved.

[0073]

[0074] The alkyl acrylate rubber of the above (A-2) graft copolymer may have an average particle diameter of preferably 200 to 600 nm, more preferably 250 to 500 nm, even more preferably 300 to 470 nm, and even more preferably 330 to 430 nm, and within this range, it has excellent mechanical properties such as impact strength and processability.

[0075]

[0076] The above (A-2) graft copolymer may preferably be formed by including an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) surrounding the core, and in this case, excellent mechanical properties and processability are achieved.

[0077] The above (A-2) graft copolymer may be formed by, for example, including 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof, and within this range, it has excellent mechanical properties such as impact strength, processability, and transparency.

[0078] Preferably, the above (A-2) graft copolymer can be formed by including 40 to 60 wt% of alkyl acrylate rubber, 25 to 50 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, and within this range, excellent mechanical properties such as impact strength, processability, and transparency are achieved.

[0079] More preferably, the graft copolymer (A-2) may be formed by including 45 to 55 wt% of alkyl acrylate rubber, 33 to 43 wt% of aromatic vinyl compound, and 10 to 15 wt% of vinyl cyan compound, and within this range, excellent mechanical properties such as impact strength, processability, and transparency are achieved.

[0080]

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

[0082]

[0083] The above (A-2) graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has excellent mechanical properties such as impact strength and transparency.

[0084] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and may be performed using an emulsion graft polymerization method, for example.

[0085]

[0086] The above (A-2) graft copolymer may have a graft ratio calculated by the above mathematical formula 1 of, for example, 40 to 120%, preferably 45 to 100%, and more preferably 45 to 80%, and within this range, has excellent mechanical properties such as impact strength and processability.

[0087]

[0088] The above (A-1) graft copolymer and (A-2) graft copolymer may have, for example, an average particle diameter difference of 170 nm or more, preferably 190 nm or more, more preferably 210 nm or more, even more preferably 210 to 300 nm, and even more preferably 210 to 270 nm, and within this range, they have the advantages of excellent mechanical properties, gloss, and whiteness.

[0089]

[0090] (B) Aromatic vinyl compound-vinyl cyanide compound copolymer

[0091] The above (B) copolymer may be, for example, 55 to 77 wt%, preferably 50 to 72 wt%, more preferably 55 to 67 wt%, and even more preferably 57 to 67 wt%, based on the total weight of components (A-1) to (D), and within this range, excellent thin film processability, hiding power, and surface quality are achieved.

[0092]

[0093] The above (B) aromatic vinyl compound-vinyl cyan compound copolymer may be at least one selected from the group consisting of, for example, (b-1) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and (b-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of more than 150,000 g / mol to 200,000 g / mol, and preferably may include a (b-2) copolymer, and more preferably may include both a (b-1) copolymer and a (b-2) copolymer, in which case the thin film processability, hiding power, and surface quality are excellent.

[0094] When both the above (b-1) copolymer and the (b-2) copolymer are included, the (b-2) copolymer may be included in a greater amount than the (b-1) copolymer, and preferably, the weight ratio (b-1:b-2) thereof may be 2:8 to 4:6, more preferably 2.5:7.5 to 3.5:6.5, and even more preferably 2.7:7.3 to 3.3:6.7, and within this range, the thin film processability, hiding power, and surface quality are excellent.

[0095] The difference in weight average molecular weight between the above (b-1) copolymer and (b-2) copolymer may be, for example, 30,000 to 70,000 g / mol, preferably 35,000 to 65,000 g / mol, more preferably 40,000 to 60,000 g / mol, and within this range, excellent thin film processability, hiding power, and surface quality are achieved.

[0096]

[0097] In this description, the weight average molecular weight (Mw) can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection amount is 5 ㎕, the column model is 1xPLgel 10 μm MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 μm MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 μm MiniMix-B Guard (50 x 4.6 mm), the measuring device is Agilent 1200 series system, the refractive index detector: Agilent G1362 RID, the RI temperature is 35 ℃, the data processing is Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

[0098]

[0099] The above (b-1) copolymer may preferably have a weight average molecular weight of 110,000 to 140,000 g / mol, more preferably 110,000 to 130,000 g / mol, and within this range, has excellent mechanical properties, surface quality, and thin film processability.

[0100]

[0101] The above (b-1) copolymer may be, for example, composed of 60 to 85 wt% of an aromatic vinyl compound and 15 to 40 wt% of a vinyl cyan compound based on the total weight thereof, preferably 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound, more preferably 72 to 80 wt% of an aromatic vinyl compound and 20 to 28 wt% of a vinyl cyan compound, and within this range, excellent mechanical properties, surface quality, and thin film processability are achieved.

[0102]

[0103] The above (b-1) copolymer is preferably a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin) or a mixture thereof, more preferably a styrene-acrylonitrile copolymer (SAN resin), in which case the mechanical properties, surface quality and thin film processability are excellent.

[0104]

[0105] The above (b-2) copolymer may preferably have a weight average molecular weight of 160,000 to 190,000 g / mol, more preferably 160,000 to 180,000 g / mol, and within this range, has excellent mechanical properties, surface quality, and thin film processability.

[0106]

[0107] The above (b-2) copolymer may be, for example, composed of 55 to 80 wt% of an aromatic vinyl compound and 20 to 45 wt% of a vinyl cyan compound based on the total weight thereof, preferably 60 to 75 wt% of an aromatic vinyl compound and 25 to 40 wt% of a vinyl cyan compound, more preferably 63 to 71 wt% of an aromatic vinyl compound and 29 to 37 wt% of a vinyl cyan compound, and within this range, excellent mechanical properties, surface quality, and thin film processability are achieved.

[0108]

[0109] The above (b-2) copolymer is preferably a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin) or a mixture thereof, more preferably a styrene-acrylonitrile copolymer (SAN resin), in which case the mechanical properties, surface quality and thin film processability are excellent.

[0110]

[0111] The types of aromatic vinyl compounds and vinyl cyan compounds included in the above (B) aromatic vinyl compound-vinyl cyan compound copolymer may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds included in the (A-1) graft copolymer of the present disclosure.

[0112]

[0113] The above (B) copolymer can be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and preferably bulk polymerization.

[0114] The above solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are not particularly limited as long as they are performed using the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization methods commonly performed in the technical field to which the present invention belongs.

[0115]

[0116] (C) white pigment

[0117] The above (C) white pigment may be, for example, 7 to 12.5 wt%, preferably 8 to 12 wt%, more preferably 9 to 12 wt%, and even more preferably 10 to 11.5 wt%, based on the total weight of the (A-1) to (D) components, and within this range, it implements a white color in a small amount, has excellent impact resistance, thin film processability, hiding power, and surface quality, and has the effect of reducing manufacturing costs.

[0118]

[0119] The above (C) white pigment may be, for example, at least one selected from the group consisting of titanium oxide (TiO2), zinc oxide (ZnO), zinc sulfide (ZnS), lithopone, and lead oxide, preferably titanium oxide (TiO2), zinc oxide (ZnO), or a mixture thereof, more preferably titanium oxide (TiO2), and in this case, it implements a white color in a small amount, has excellent impact resistance, thin film processability, hiding power, and surface quality, and has the effect of reducing manufacturing costs.

[0120]

[0121] The above (C) white pigment may have, for example, an average particle size of 0.1 to 2 ㎛, preferably 0.2 to 1.5 ㎛, more preferably 0.4 to 1 ㎛, and even more preferably 0.4 to 0.7 ㎛, in which case it can realize white color in a small amount, has excellent impact resistance, thin film processability, hiding power, and surface quality, and has the effect of reducing manufacturing costs.

[0122] In this description, the average particle size can be measured by sedimentation particle size analysis using Stokes' law according to ASTM B761, and as a specific example, can be measured using SediGraph III Plus 5125 equipment.

[0123]

[0124] The above (C) white pigment may have, for example, a refractive index of 2 to 3, preferably 2.2 to 2.9, more preferably 2.4 to 2.8, and even more preferably 2.6 to 2.8, and has the advantage of excellent hiding power and surface quality within this range.

[0125] In this description, the refractive index can be measured at room temperature using a known method, i.e., generally an Abbe Refractometer according to ASTM D542.

[0126] In this description, room temperature may be a point within the range of 20 ± 5 ℃.

[0127]

[0128] The above (C) white pigment may be, for example, a white pigment coated with a surface treatment agent, and preferably may be surface-coated with aluminum or silicon-aluminum, in which case the compatibility and dispersibility with the white pigment auxiliary agent are improved, so that there is an advantage of excellent hiding power and surface quality.

[0129] The surface treatment agent may be, for example, present in an amount of 0 to 5 wt%, preferably 0.1 to 4.5 wt%, more preferably 1 to 4 wt%, even more preferably 2 to 4 wt%, and even more preferably 3 to 4 wt%, based on 100 wt% of the total surface-treated white pigment, and within this range, compatibility with the white pigment auxiliary agent is improved, thereby providing the advantage of excellent hiding power and surface quality.

[0130]

[0131] (D) White pigment auxiliary agent having an average particle size of 2 ㎛ or less

[0132] The above (D) white pigment auxiliary agent having an average particle size of 2 ㎛ or less may be, for example, 3.5 to 8 wt%, preferably 3.5 to 7 wt%, more preferably 4 to 6 wt%, and even more preferably 4.5 to 5.5 wt%, based on the total weight of the components (A-1) to (D), and within this range, while maintaining the excellent physical properties of the conventional ASA resin, a synergistic effect with the white pigment is exhibited, so that even if the amount of white pigment input is reduced, a high white color is realized, and thin film processability, hiding power, and glossiness are excellent, and there is no occurrence of protrusions on the sheet surface, so that the appearance quality is excellent and the manufacturing cost is reduced.

[0133]

[0134] The above (D) white pigment auxiliary agent may be, for example, at least one selected from the group consisting of calcium carbonate (CaCO3), talc, clay, barium sulfate (BaSO4), aluminum hydroxide (Al(OH)3), and silicon dioxide (SiO2), and preferably may be calcium carbonate (CaCO3). In this case, there is an advantage in that a high white color is realized while reducing the amount of white pigment added, thin film processability, hiding power, and surface quality are excellent, and manufacturing costs are reduced.

[0135]

[0136] The above (D) white pigment auxiliary agent may have an average particle size of preferably 1.5 ㎛ or less, more preferably 0.1 to 1.5 ㎛, still more preferably 0.3 to 1.3 ㎛, still more preferably 0.4 to 1.2 ㎛, particularly preferably 0.5 to 1.1 ㎛, and still more preferably 0.6 to 1.0 ㎛, and within this range, it has the advantage of realizing high whiteness while reducing the amount of white pigment added, and of excellent thin film processability, hiding power, and surface quality, and of reducing manufacturing costs.

[0137]

[0138] The above (D) white pigment auxiliary agent may have a refractive index of, for example, 1.70 or less, preferably 1.0 to 1.70, more preferably 1.30 to 1.70, and even more preferably 1.50 to 1.70, and within this range, it has the advantage of excellent hiding power and surface quality.

[0139]

[0140] The weight ratio (C:D) of the above (C) white pigment and the above (D) white pigment auxiliary agent may preferably be 1:0.4 to 1:0.7, more preferably 1:0.4 to 1:0.6, and within this range, the amount of white pigment input can be reduced while realizing a high white color, and there is an advantage of excellent thin film processability, hiding power and surface quality, and reducing manufacturing costs.

[0141]

[0142] The total amount of the above (C) white pigment and the above (D) white pigment auxiliary agent may be, for example, 12 to 19 wt%, preferably 13 to 18 wt%, and more preferably 14 to 17 wt%, based on the total weight of the components (A-1) to (D), and within this range, there is an advantage of realizing a high white color while reducing the amount of white pigment added, and of having excellent thin film processability, hiding power, and surface quality, and of reducing manufacturing costs.

[0143]

[0144] thermoplastic resin composition

[0145] The thermoplastic resin composition preferably has a whiteness (L value - b value) calculated by measuring the L value and b value in a colorimeter SCI mode and calculating the difference between them of 95.5 or more, more preferably 95.5 to 99.5, and has the advantage of realizing a high whiteness while having excellent physical property balance within this range.

[0146] In this description, whiteness (L value - b value) refers to the values ​​of L value and b value measured in the colorimeter SCI mode using a specimen manufactured without adding pigments or dyes such as blue colorant. The lower the whiteness (L value - b value), the more pigments or dyes such as blue colorant must be added to achieve whiteness, which results in deterioration of mechanical properties, durability, etc.

[0147] The L value measured in the colorimeter SCI mode has a value from 0 to 100, and the closer it is to 0, the blacker it is, and the closer it is to 100, the whiter it is. The b value is closer to yellow as the +b value increases, and the closer it is to blue as the -b value increases. In the b value measured in the colorimeter SCI mode, there are whites with high +b values ​​and whites with high -b values, and the closer the b value is to 0, the more luxurious it is and is preferred in the market.

[0148] Since the conventional ASA resin composition has a high +b value measured by the colorimeter SCI mode, a pigment or dye such as blue colorant is added to lower the b value and make it close to 0. However, as the amount added increases, the L value also decreases, resulting in poor whiteness and reduced durability. Therefore, the higher the whiteness calculated by the difference between the L value and the b value, the more luxurious whiteness can be realized with a small amount of blue colorant or a pigment or dye, and there is an advantage of excellent appearance quality because no protrusions occur on the sheet surface.

[0149] In addition, the present invention has the advantage of maintaining the excellent physical properties of a conventional ASA resin while maintaining the L value of the thermoplastic resin composition at a high level and making the b value close to 0 by adding a white pigment auxiliary agent having an average particle size of 2 ㎛ or less together with the white pigment.

[0150]

[0151] The thermoplastic resin composition may preferably have a gloss of 82 or more, more preferably 84 or more, and even more preferably 84 to 100, measured at 60° according to ASTM D523 in the form of a sheet having a thickness of 0.15 mm, and has the advantage of having an excellent balance of physical properties and a luxurious appearance within this range.

[0152]

[0153] The thermoplastic resin composition may preferably have an Izod impact strength of 5.3 kgf·cm / cm or more, more preferably 5.7 kgf·cm / cm or more, even more preferably 6.0 kgf·cm / cm or more, and still more preferably 6.0 to 9.0 kgf·cm / cm, as measured by a notched injection molded specimen (thickness 1 / 4") according to ASTM D256, and within this range, has excellent physical property balance, and has the advantage of excellent mechanical properties and trimming properties that enable cutting in a desired direction and have a clean cut surface when cutting a sheet.

[0154]

[0155] The thermoplastic resin composition may preferably have a melt index of 7.5 g / 10 min or more, more preferably 8.0 g / 10 min or more, still more preferably 8.0 to 20 g / 10 min, and still more preferably 8.0 to 15 g / 10 min, measured at 220° C. and under a 10 kg load according to ASTM D1238, and within this range, has the advantage of excellent physical property balance and excellent processability and thin film processability.

[0156]

[0157] The thermoplastic resin composition is preferably 0.8 m thick on the sheet surface. 2 When observing the range with the naked eye, there is no occurrence of protrusions, and therefore, the appearance quality is excellent.

[0158] In this description, sheet refers to all sheets, films or foils unless otherwise specified.

[0159]

[0160] The thermoplastic resin composition can preferably be produced in a sheet having a width of 1 m or more and a thickness of 0.2 mm or less with a length of 1000 m or more while maintaining a thickness deviation of within ±0.05%, and thus has the advantage of excellent thin film processability.

[0161]

[0162] The thermoplastic resin composition may optionally contain one or more selected from the group consisting of heat stabilizers, dyes, pigments (excluding white pigments), colorants, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, inhibitors, anti-dripping agents, anti-friction agents, and anti-wear agents, for example, 0.001 to 20 parts by weight, 0.01 to 15 parts by weight, 0.05 to 10 parts by weight, 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight, based on 100 parts by weight of the total of components (A-1) to (D), and within this range, the thermoplastic resin composition of the present invention has the effect of well implementing the required properties without lowering the original properties.

[0163]

[0164] The above heat stabilizer may preferably include a primary heat stabilizer and a secondary heat stabilizer.

[0165] The above primary heat stabilizer may be, for example, a phenol-based heat stabilizer, preferably 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediolbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-t-butylphenol)terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, It may be at least one selected from the group consisting of 2,2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, and more preferably octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate (IR1076).

[0166] The above secondary heat stabilizer may be, for example, a phosphorus-based heat stabilizer, and preferably, bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, Tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol)diphosphite, tris(mono- and di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tris[4,4'-isopropylidenebis(2-t-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butylphenol)bis(nonylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, It may be at least one selected from the group consisting of 2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphepine-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine, and more preferably, it may be tris(2,4-di-tert-butylphenyl) phosphite (IF168). there is.

[0167]

[0168] In addition to the above heat stabilizer, the remaining dyes, etc. are not particularly limited as long as they are dyes commonly used in the technical field to which the present invention belongs.

[0169]

[0170] Method for producing a thermoplastic resin composition

[0171] The method for producing a thermoplastic resin composition of the present invention is characterized by including the steps of kneading and extruding under conditions of 200 to 300° C. and 100 to 500 rpm, comprising: (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary having an average particle size of 2 μm or less. In this case, it has the excellent properties of conventional ASA resins, implements high white color even with a reduced amount of white pigment, has excellent thin film processability, hiding power and gloss, and has the effect of reducing manufacturing costs by not generating protrusions on the sheet surface, resulting in excellent appearance quality.

[0172]

[0173] The method for manufacturing the above thermoplastic resin composition shares all the technical characteristics of the thermoplastic resin composition described above. Therefore, a description of the overlapping portions will be omitted.

[0174]

[0175] The above mixing and extrusion can preferably be performed using an extruder at a temperature of 200 to 300°C, more preferably 210 to 270°C, and even more preferably 220 to 250°C, and within this range, stable extrusion is possible and the mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder.

[0176] The above mixing and extrusion can be performed under conditions where the screw rotation speed is, for example, 100 to 500 rpm, preferably 150 to 450 rpm, and more preferably 200 to 400 rpm, in which case the processing amount per unit time is appropriate, resulting in excellent process efficiency.

[0177]

[0178] The thermoplastic resin composition obtained through the above extrusion can be manufactured into pellets using, for example, a pelletizer.

[0179]

[0180] The above extruder is not particularly limited as long as it is an extruder commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extruder.

[0181]

[0182] molded products

[0183] The molded article of the present invention is characterized by including the thermoplastic resin composition, and in this case, the physical properties are equivalent to or better than the excellent physical properties of conventional ASA resins, white color is realized even with a reduced amount of white pigment, thin film processability, hiding power and gloss are excellent, and the appearance quality is excellent because no protrusions occur on the surface, and the manufacturing cost is reduced.

[0184]

[0185] The above-mentioned molded product may preferably be a film, sheet, or foil, and specifically may be a decorative sheet for furniture finishing, an outdoor building material finishing material, a roofing finishing material, an interior film, wallpaper, an edge band, VCM (Vinyl coated metal), a flooring material, PSP (Plastic-steel-Plastic) for molding, or a film for wrapping.

[0186]

[0187] The method for manufacturing the above-mentioned molded product preferably comprises the steps of: (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary having an average particle size of 2 ㎛ or less; mixing and extruding under conditions of 200 to 300° C. and 100 to 500 rpm to manufacture an extrudate; And a step of molding the extruded product to manufacture a molded product; may include. In this case, the excellent physical properties of the conventional ASA resin are maintained, and a white color is realized even with a reduced amount of white pigment, and the thin film processability, hiding power, and glossiness are excellent, and the appearance quality is excellent because there is no occurrence of protrusions on the sheet surface, and the manufacturing cost is reduced.

[0188]

[0189] The extrudate may be, for example, in the form of pellets or plates.

[0190] In this description, the plate shape is not particularly limited as long as it is defined as a plate shape commonly in the technical field to which the present invention belongs, and may include, for example, a flat shape, a sheet shape, a film shape, a foil shape, etc.

[0191]

[0192] In describing the thermoplastic resin composition, the manufacturing method thereof, and the molded product of the present invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0193]

[0194] Hereinafter, preferred examples are presented to help understand the present disclosure; however, the following examples are merely illustrative of the present disclosure, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0195]

[0196] [Example]

[0197] The materials used in the following examples and comparative examples are as follows.

[0198] * (A-1) ASA graft copolymer comprising alkyl acrylate rubber having an average particle size of 50 to 150 nm: ASA graft copolymer of alkyl acrylate rubber having an average particle size of 130 nm, manufactured by an emulsion polymerization method (rubber (core): 50 wt% of butyl acrylate, shell: 37.5 wt% of styrene and 12.5 wt% of acrylonitrile, graft ratio: 35%)

[0199] * (A-2) ASA graft copolymer comprising alkyl acrylate rubber having an average particle size of 150 nm to 600 nm: ASA graft copolymer of alkyl acrylate rubber having an average particle size of 350 nm, manufactured by an emulsion polymerization method (rubber (core): 50 wt% of butyl acrylate, shell: 37.5 wt% of styrene and 12.5 wt% of acrylonitrile, graft ratio: 50%)

[0200] * (b-1) Aromatic vinyl compound-vinyl cyanide compound copolymer: SAN resin with Mw of 120,000 g / mol (73 wt% styrene and 27 wt% acrylonitrile)

[0201] * (b-2) Aromatic vinyl compound-vinyl cyanide compound copolymer: SAN resin with Mw of 170,000 g / mol (70 wt% styrene and 30 wt% acrylonitrile)

[0202] * (C) White pigment

[0203] - (C-1) Aluminum-coated TiO2 (TiO2 96.6 wt% and aluminum coating agent 3.4 wt%, average particle size: 0.46 ㎛, refractive index: 2.76)

[0204] - (C-2) Aluminum-coated TiO2 (TiO2 97.0 wt% and aluminum coating agent 3.0 wt%, average particle size: 0.49 ㎛, refractive index: 2.76)

[0205] - (C-3) Silicon-aluminum coated TiO2 (TiO2 96.1 wt% and silicon-aluminum coating agent 3.9 wt%, average particle size: 0.52 ㎛, refractive index: 2.76)

[0206] * (D) White pigment auxiliary agent

[0207] - (D-1) CaCO3 with an average particle size of 0.6 ㎛ (refractive index: 1.59)

[0208] - (D-2) CaCO3 with an average particle size of 0.75 ㎛ (refractive index: 1.59)

[0209] - (D-3) CaCO3 with an average particle size of 1.0 ㎛ (refractive index: 1.59)

[0210] - (D-4) CaCO3 with an average particle size of 5.0 ㎛ (refractive index: 1.59)

[0211]

[0212] Examples 1 to 7 and Comparative Examples 1 to 9

[0213] The ingredients and contents described in Tables 1 and 2 below were each fed into a twin-screw extruder and melt-mixed and extruded at 230°C and 150 rpm to produce pellets. The produced pellets were injection-molded at 230°C to produce injection-molded specimens.

[0214] Additionally, the pellets were extruded into a film at 220°C to produce a sheet with a thickness of 0.15 mm.

[0215]

[0216] [Example Exam]

[0217] The properties of the pellets, injection molded specimens, or sheets manufactured in Examples 1 to 7 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0218]

[0219] measurement method

[0220] * Melt index (g / 10min): Measured at 220℃ and under a 10 kg load according to ASTM D1238.

[0221] * Impact strength (kgf·cm / cm): Izod impact strength was measured using notched injection molded specimens (1 / 4" thick) according to ASTM D256.

[0222] * Gloss: Measured at 60° according to ASTM D523 on sheets with a thickness of 0.15 mm.

[0223] * Protrusion: 0.8 m on the surface of the extruded sheet 2The occurrence of protrusions within the range was visually observed, and if there were no protrusions, they were marked with an “X”, and if there were protrusions, they were marked with an “○”.

[0224] * Whiteness (L value - b value): The L value and b value were measured in the colorimeter SCI mode for a thermoplastic resin composition that did not contain pigments or dyes such as blue colorant, and the difference between them (L value - b value) was calculated. The higher the whiteness (L value - b value), the higher the whiteness.

[0225]

[0226] Classification (weight%) Example 1234567 (A-1) ASA6176625178 (A-2) ASA12912124813 (b-1) SAN17181721 (b-2) SAN67426767374242 (C-1) TiO2 2.5465832 (C-2) TiO2 6332.530.56 (C-3) TiO2 1.5312.57.53 (D-1) CaCO35 (D-2) CaCO35 (D-3) CaCO355555 (D-4) CaCO3 Properties Flow Index (g / 10min) 8.0 10.9 8.0 7.7 9.18.2 16.5 Impact Strength (kgf cm / cm) 6.2 6.3 5.5 6.7 5.4 6.15.7 Gloss 88.5 86.28 3.19 3.28 5.3 86.88 3.0 Bump Occurrence XXXXXXX Whiteness (L value - b value) 95.6 95.695.5 95.7 95.695.995.5

[0227] Classification (weight%) Comparison Example 123456789 (A-1) ASA6172518161538117 (A-2) ASA12849884318 (b-1) SAN171818161542.55317 (b-2) SAN6742374640.53841 (C-1) TiO2 158233.343.51.54 (C-2) TiO2 37843.52.53 (C-3) TiO2 73.223.568 (D-1) CaCO3 (D-2) CaCO3 (D-3) CaCO3 6514552 (D-4) CaCO3 5 Water Fluidity index (g / 10min) 9.4 10.17.6 11.99.88.6 18.123.29.6 Impact strength (kgf·cm / cm) 8.05.04.7 9.03.22.5 16.73 6.66.7 Glossiness 94.4 79.997.68 5.284.768.27 5.95 0.690.7 Protrusion occurrence X○XXXXXXXX Whiteness (L value - b value) 95.5 95.195.790.495.795.094.693.794.4

[0228] As shown in Tables 1 to 2 above, the thermoplastic resin compositions of Examples 1 to 7 according to the present invention have excellent processability due to excellent fluidity index even when the (C) TiO2 content is reduced compared to Comparative Examples 1 to 9, have an Izod impact strength of 5.3 kgf·cm / cm or more, have excellent trimming properties in which the sheet is cut in a desired direction and has a clean cut surface, have no protrusions on the sheet surface, have excellent gloss, have excellent surface quality, and have a high whiteness, which reduces manufacturing costs.

[0229]

[0230] On the other hand, Comparative Example 1, which added an excess of (C) TiO2 and did not add a white pigment auxiliary agent (D), had a similar whiteness level despite using an excess of (C) TiO2 compared to Examples 1 to 7.

[0231] In addition, Comparative Example 2 including (D-4) CaCO3, in which the average particle size of the white pigment auxiliary agent (D) was outside the range of the present invention, had protrusions on the sheet surface, resulting in poor surface quality and low whiteness (L value - b value).

[0232] In addition, Comparative Example 3, in which (C) TiO2 was added in excess and (D) no white pigment auxiliary agent was added, had low impact strength and poor trimming properties, and expensive TiO2 had to be added in excess to achieve the whiteness level of the example, which significantly increased the manufacturing cost.

[0233] In addition, it was found that Comparative Example 4, which included a small amount of (C) TiO2, had poor whiteness (L value - b value), and thus a large amount of pigment or dye such as blue colorant had to be used to achieve whiteness.

[0234] In addition, Comparative Example 5 containing an excessive amount of (C) TiO2 and Comparative Example 6 containing an excessive amount of (D-3) CaCO3 had low impact strength and poor trimmability, and in particular, Comparative Example 6 had a reduced glossiness.

[0235] In addition, Comparative Examples 7 and 8, in which the content of (A-1) graft copolymer and (B) copolymer, or the content of (A-2) graft copolymer was outside the range of the present invention, had a reduced gloss and poor whiteness (L value-b value).

[0236] In addition, Comparative Example 9, which contained (C) an excessive amount of TiO2 and (D) a small amount of CaCO3, had poor whiteness (L value - b value).

[0237]

[0238] In conclusion, it was confirmed that when a white pigment auxiliary agent having a predetermined average particle size is added to a base resin composed of two kinds of alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers including an alkyl acrylate rubber having a predetermined average particle size according to the present invention and an aromatic vinyl compound-vinyl cyan compound copolymer, the excellent physical properties of the conventional ASA resin are maintained, a high white color is realized even with a reduced amount of white pigment added, and thin film processability, hiding power, and gloss are excellent, and the appearance quality is excellent because no protrusions are generated on the sheet surface, and the manufacturing cost is reduced.

Claims

1. (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm; (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of more than 150 nm and less than or equal to 600 nm; (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer; (C) 7 to 12.5 wt% of white pigment; and (D) characterized by comprising 3.5 to 8 wt% of a white pigment auxiliary agent having an average particle size of 2 ㎛ or less; Thermoplastic resin composition.

2. In paragraph 1, The above (C) white pigment is characterized by being at least one selected from the group consisting of titanium oxide (TiO2), zinc oxide (ZnO), zinc sulfide (ZnS), lithopone, and lead oxide. Thermoplastic resin composition.

3. In paragraph 1, The above (D) white pigment auxiliary agent is characterized by being at least one selected from the group consisting of calcium carbonate (CaCO3), talc, clay, barium sulfate (BaSO4), aluminum hydroxide (Al(OH)3), and silicon dioxide (SiO2). Thermoplastic resin composition.

4. In paragraph 1, The above (D) white pigment auxiliary agent is characterized by having a refractive index of 1.70 or less. Thermoplastic resin composition.

5. In paragraph 1, The above (C) white pigment and the above (D) white pigment auxiliary agent are characterized in that the weight ratio (C:D) is 1:0.4 to 1:0.

7. Thermoplastic resin composition.

6. In paragraph 1, The above (A-1) graft copolymer is characterized in that it comprises 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof. Thermoplastic resin composition.

7. In paragraph 1, The above (A-2) graft copolymer is characterized in that it comprises 35 to 65 wt% of alkyl acrylate rubber, 20 to 55 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound based on the total weight thereof. Thermoplastic resin composition.

8. In paragraph 1, The above (B) aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that it is at least one selected from the group consisting of (b-1) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and (b-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of more than 150,000 g / mol to 200,000 g / mol or less. Thermoplastic resin composition.

9. In paragraph 8, The thermoplastic resin composition comprises both (b-1) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g / mol and (b-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of more than 150,000 g / mol to less than 200,000 g / mol, and is characterized in that the weight ratio (b-1:b-2) thereof is 2:8 to 4:

6. Thermoplastic resin composition.

10. In paragraph 1, The thermoplastic resin composition is characterized in that the whiteness (L value - b value) calculated by measuring the L value and b value in the colorimeter SCI mode and calculating the difference between them is 95.5 or higher. Thermoplastic resin composition.

11. In paragraph 1, The thermoplastic resin composition is characterized by having a gloss of 82 or more as measured at 60° according to ASTM D523 in the form of a sheet having a thickness of 0.15 mm. Thermoplastic resin composition.

12. In paragraph 1, The thermoplastic resin composition is characterized in that the Izod impact strength measured using a notched injection molded specimen (1 / 4" thick) according to ASTM D256 is 5.3 kgf·cm / cm or more. Thermoplastic resin composition.

13. (A-1) 4 to 31 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 50 to 150 nm, (A-2) 1 to 22 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of more than 150 nm to 600 nm or less, and (B) 55 to 77 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, (C) 7 to 12.5 wt% of a white pigment; and (D) 3.5 to 8 wt% of a white pigment auxiliary agent having an average particle size of 2 ㎛ or less; characterized by comprising a step of mixing and extruding under conditions of 200 to 300° C. and 100 to 500 rpm. A method for producing a thermoplastic resin composition.

14. A thermoplastic resin composition comprising any one of claims 1 to 12. Molded product.