Thermoplastic resin composition and article manufactured using the same

Abstract

(A) 30 to 40 weight% of a butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) 20 to 40 weight% of a first aromatic vinyl compound-vinyl cyanide compound copolymer having a glass transition temperature (Tg) of 107 to 110°C; and (C) 20 to 50 weight% of a second aromatic vinyl compound-vinyl cyanide compound copolymer having a non-linear structure; with respect to 100 weight parts of a base resin comprising (D) 15 to 25 weight parts of a bromine-based flame retardant; and (E) 2 to 6 weight parts of a third aromatic vinyl compound-vinyl cyanide compound copolymer having a weight-average molecular weight of 3,000,000 to 6,000,000 g / mol, a molded article made therefrom is provided.

Description

Technology Field

[0001] The invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. Background Technology

[0002] Styrene-based resins, represented by acrylonitrile-butadiene-styrene copolymer (ABS) resin, are widely used in automobiles, home appliances, and OA equipment due to their excellent moldability, mechanical properties, appearance, and secondary processability.

[0003] Molded products made using styrene-based resins can be widely applied to various products requiring painting or non-painting, for example, interior and exterior materials for automobiles.

[0004] Recently, there has been a trend in Europe and elsewhere to further strengthen flame retardant standards for automotive interior and exterior materials as a measure to prevent casualties caused by fire accidents involving vehicles such as buses and trucks. Accordingly, a new flame retardant standard, ECE R 118, for automotive interior and exterior materials requiring higher flame retardancy and impact resistance compared to existing standards has recently been announced in Europe.

[0005] Therefore, for use in automotive interior and exterior materials, there is a need to develop materials capable of maintaining high levels of flame retardancy, high impact resistance, and heat resistance, in addition to moldability such as sheet extrusion characteristics. The problem to be solved

[0006] A thermoplastic resin composition having excellent sheet extrusion characteristics, flame retardancy, heat resistance, and impact resistance is provided.

[0007] Another embodiment provides a molded article manufactured from the thermoplastic resin composition. means of solving the problem

[0008] According to one embodiment, a thermoplastic resin composition is provided comprising (A) 30 to 40 weight% of a butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) 20 to 40 weight% of a first aromatic vinyl compound-vinyl cyanide compound copolymer having a glass transition temperature (Tg) of 107 to 110°C; and (C) 20 to 50 weight% of a second aromatic vinyl compound-vinyl cyanide compound copolymer having a non-linear structure, with respect to 100 weight parts of a base resin, (D) 15 to 25 weight parts of a brominated flame retardant; and (E) 2 to 6 weight parts of a third aromatic vinyl compound-vinyl cyanide compound copolymer having a weight-average molecular weight of 3,000,000 to 6,000,000 g / mol.

[0009] The above (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer may have a core-shell structure comprising a core made of a butadiene-based rubbery polymer and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0010] The average particle size of the above butadiene-based rubbery polymer may be 200 to 400 nm.

[0011] The above (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).

[0012] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may comprise 55 to 80 weight% of an aromatic vinyl compound-derived component and 20 to 45 weight% of a vinyl cyanide-derived component based on 100 weight%.

[0013] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may have a weight-average molecular weight of 80,000 to 300,000 g / mol.

[0014] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may have an oligomer content of less than 0.4 weight% based on 100 weight%.

[0015] In the above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer, the aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0016] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may have a weight-average molecular weight of 200,000 to 500,000 g / mol.

[0017] In the above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer, the aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0018] The above (D) bromine-based flame retardant may contain 60% or more of bromine based on 100% by weight.

[0019] The above (D) brominated flame retardant may be 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

[0020] In the above (E) third aromatic vinyl compound-vinyl cyanide compound copolymer, the aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0021] According to one embodiment, the thermoplastic resin composition may further include at least one additive selected from nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes.

[0022] According to another embodiment, a molded article manufactured from the above-described thermoplastic resin composition is provided.

[0023] The above molded product has a Charpy impact strength of 35 kJ / m² measured on a 4 mm thick specimen according to ISO 179. 2 It could be more than that.

[0024] The above molded product may have a flame retardancy of V-1 grade or higher when measured on a 3.2 mm thick specimen according to UL-94 standards.

[0025] The above molded product may have an elongation of 30% or more when measured on a 3.2 mm thick specimen according to ASTM D638.

[0026] The above molded product may have a Vicat softening temperature (VST) of 94°C or higher as measured according to ISO 306 standards. Effects of the invention

[0027] A thermoplastic resin composition having excellent sheet extrusion characteristics, flame retardancy, heat resistance, and impact resistance, and a molded article using the same can be provided.

[0028] In addition, the thermoplastic resin composition according to one embodiment and the molded article using the same exhibit excellent flame retardancy, impact resistance, heat resistance, and sheet extrusion characteristics, and can be widely applied to various products used as painted or unpainted products, and in particular, can be usefully applied to applications such as automotive interior / exterior materials. Specific details for implementing the invention

[0029] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0030] Unless specifically stated otherwise in this specification, "copolymer" means block copolymer, random copolymer, and graft copolymer, and "copolymer" means block copolymer, random copolymer, and graft copolymer.

[0031] Unless specifically stated otherwise in this specification, the average particle size of a rubbery polymer refers to the volume-average diameter and means the Z-average particle size measured using dynamic light scattering analysis equipment.

[0032] Unless specifically stated otherwise in this specification, the weight-average molecular weight is measured by dissolving a powder sample in a suitable solvent, such as tetrahydrofuran (THF), and then using Agilent Technologies’ 1200 series Gel Permeation Chromatography (GPC) (using Shodex’s polystyrene as the standard sample).

[0033] A thermoplastic resin composition according to one embodiment comprises, for every 100 parts by weight of a base resin comprising (A) 30 to 40 weight% of a butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) 20 to 40 weight% of a first aromatic vinyl compound-vinyl cyanide compound copolymer having a glass transition temperature (Tg) of 107 to 110°C; and (C) 20 to 50 weight% of a second aromatic vinyl compound-vinyl cyanide compound copolymer having a non-linear structure, (D) 15 to 25 parts by weight of a bromine-based flame retardant; and (E) 2 to 6 parts by weight of a third aromatic vinyl compound-vinyl cyanide compound copolymer having a weight-average molecular weight of 3,000,000 to 6,000,000 g / mol.

[0034] Hereinafter, each component included in the above thermoplastic resin composition will be described in detail.

[0035] (A) Butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer

[0036] In one embodiment, the (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer imparts excellent impact resistance to the thermoplastic resin composition.

[0037] In one embodiment, the (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer may have a core-shell structure comprising a core made of a butadiene-based rubbery polymer and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0038] The above (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer can be prepared by adding an aromatic vinyl compound and a vinyl cyanide compound to a butadiene-based rubbery polymer and graft polymerizing through a conventional polymerization method such as emulsion polymerization or bulk polymerization.

[0039] With respect to 100 weight% of the above (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer, the butadiene-based rubbery polymer core may be included in an amount of 40 to 65 weight%. Meanwhile, the shell may contain the aromatic vinyl compound and the vinyl cyanide compound in a weight ratio of 8:2 to 6:4.

[0040] The butadiene-based rubbery polymer can be selected from the group consisting of butadiene rubbery polymer, butadiene-styrene rubbery polymer, butadiene-acrylonitrile rubbery polymer, butadiene-acrylate rubbery polymer, and mixtures thereof.

[0041] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0042] The vinyl cyanide compound mentioned above may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.

[0043] The average particle size of the butadiene-based rubbery polymer may be 200 to 400 nm, for example, 200 to 250 nm, for example, 200 to 300 nm, for example, 200 to 350 nm, or for example, 250 to 400 nm. When the above range is satisfied, the thermoplastic resin composition may exhibit excellent impact resistance and appearance characteristics.

[0044] In one embodiment, the butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).

[0045] The above (A) butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer may be included in an amount of, for example, 30 to 40 weight%, for example, 30 to 35 weight%, for example, 35 to 40 weight% with respect to 100 weight% of the base resin. Within the above weight range, the thermoplastic resin composition may exhibit excellent impact resistance.

[0046] (B) First aromatic vinyl compound-vinyl cyanide compound copolymer

[0047] In one embodiment, the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer can improve the heat resistance of the thermoplastic resin composition and maintain compatibility between the components at a certain level.

[0048] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may have an oligomer content of less than 0.4% by weight based on 100% by weight. When the oligomer content is within the above range, the generation of volatile organic compounds (VOCs) can be minimized and the glass transition temperature can be increased.

[0049] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may have a glass transition temperature of 107 to 110°C. The heat resistance of the thermoplastic resin composition may be improved within the above glass transition temperature range.

[0050] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may have a weight-average molecular weight of 80,000 g / mol or more, for example 85,000 g / mol or more, for example 90,000 g / mol or more, for example 300,000 g / mol or less, for example 200,000 g / mol or less, for example 80,000 to 300,000 g / mol, for example 80,000 to 200,000 g / mol.

[0051] In one embodiment, the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer can be prepared by using conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization of the aromatic vinyl compound and the vinyl cyanide compound.

[0052] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0053] The vinyl cyanide compound mentioned above may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.

[0054] The above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the aromatic vinyl compound-derived component in, for example, 55 weight% or more, 60 weight% or more, 65 weight% or more, 70 weight% or more, or 75 weight% or more, and 80 weight% or less, 75 weight% or less, 70 weight% or less, 65 weight% or less, or 60 weight% or less, and may contain, for example, 55 to 80 weight%, for example, 60 to 75 weight%.

[0055] In addition, the above (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the vinyl cyanide compound-derived component in, for example, 20 weight% or more, 25 weight% or more, 30 weight% or more, 35 weight% or more, or 40 weight% or more, and 45 weight% or less, 40 weight% or less, 35 weight% or less, 30 weight% or less, or 25 weight% or less, and may contain, for example, 20 to 45 weight%, for example, 25 to 40 weight%.

[0056] In one embodiment, the aromatic vinyl compound-vinyl cyanide compound copolymer in the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0057] In one embodiment, the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer may be 20 to 40 weight%, for example 20 to 35 weight%, for example 20 to 30 weight%, for example 25 to 40 weight%, based on 100 weight% of the base resin. Within the above weight range, the thermoplastic resin composition may exhibit excellent moldability and mechanical properties.

[0058] (C) Second aromatic vinyl compound-vinyl cyanide compound copolymer

[0059] In one embodiment, the (C) second aromatic vinyl compound-vinyl cyanide compound copolymer enables obtaining a sheet of uniform thickness when manufacturing a molded article through sheet extrusion molding.

[0060] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may have a non-linear structure.

[0061] Among the commonly used butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound copolymer resin compositions, acrylonitrile-butadiene-styrene (ABS) resin compositions are mainly used for injection molding, but when extruded into sheets, there is a problem in that the stretching characteristics are poor, resulting in variations in sheet thickness. To improve this problem, the stretching characteristics can be improved by using a styrene-based copolymer resin with a high weight-average molecular weight among the ABS resin compositions, but when the sheet thickness becomes thin or the size of the molded product increases, sufficient stretching characteristics are not exhibited, and thus the variation in sheet thickness is not improved.

[0062] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer overcomes these problems and can provide a thermoplastic resin composition with improved moldability suitable for molding processes such as sheet extrusion molding and vacuum molding by significantly improving elongation characteristics through a non-linear structure. In one embodiment, when the above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer is included in the thermoplastic resin composition, a sheet of uniform thickness can be obtained when manufacturing a molded article through sheet extrusion molding.

[0063] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may have a weight-average molecular weight of, for example, 200,000 to 500,000 g / mol, for example, 250,000 to 500,000 g / mol, for example, 300,000 to 500,000 g / mol, for example, 300,000 to 500,000 g / mol. Within the above weight-average molecular weight range, excellent moldability may be achieved during sheet extrusion molding.

[0064] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer can be prepared by using an aromatic vinyl compound and a vinyl cyanide compound through conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

[0065] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0066] The vinyl cyanide compound mentioned above may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.

[0067] The above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the aromatic vinyl compound-derived component in, for example, 55 weight% or more, 60 weight% or more, 65 weight% or more, 70 weight% or more, or 75 weight% or more, and 80 weight% or less, 75 weight% or less, 70 weight% or less, 65 weight% or less, or 60 weight% or less, and may contain, for example, 55 to 80 weight%, for example, 60 to 75 weight%.

[0068] In addition, the above (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the vinyl cyanide compound-derived component in, for example, 20 weight% or more, 25 weight% or more, 30 weight% or more, 35 weight% or more, or 40 weight% or more, and 45 weight% or less, 40 weight% or less, 35 weight% or less, 30 weight% or less, or 25 weight% or less, and may contain, for example, 20 to 45 weight%, for example, 25 to 40 weight%.

[0069] In one embodiment, in the (C) second aromatic vinyl compound-vinyl cyanide compound copolymer, the aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0070] In one embodiment, the (C) second aromatic vinyl compound-vinyl cyanide compound copolymer may be 20 to 50 weight%, for example 25 to 50 weight%, for example 20 to 45 weight%, based on 100 weight% of the base resin. Within the above weight range, the thermoplastic resin composition may exhibit excellent sheet extrusion moldability.

[0071] (D) Brominated flame retardant

[0072] In one embodiment, the (D) bromine-based flame retardant can impart flame retardancy to the thermoplastic resin composition.

[0073] The above (D) bromine-based flame retardant may contain 60% by weight or more of bromine based on 100% by weight. In the above weight% range, the flame retardancy of the thermoplastic resin composition may be excellent, and the impact resistance of the thermoplastic resin composition may also be improved.

[0074] The above (D) brominated flame retardant may be 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, but is not limited thereto.

[0075] The above (D) brominated flame retardant may be included in an amount of 15 to 25 parts by weight per 100 parts by weight of the base resin ((A)+(B)+(C)). Within the above weight range, the flame retardancy and impact resistance of the thermoplastic resin composition may be excellent, and unpleasant odors that may occur from the addition of the flame retardant may be minimized.

[0076] (E) 3rd aromatic vinyl compound-vinyl cyanide compound copolymer

[0077] In one embodiment, the (E) third aromatic vinyl compound-vinyl cyanide compound copolymer can further improve the performance of the thermoplastic resin composition, such as sheet extrusion characteristics, heat resistance, and impact resistance.

[0078] The above (E) third aromatic vinyl compound-vinyl cyanide compound copolymer may have a weight-average molecular weight of, for example, 3,000,000 to 6,000,000 g / mol, for example, 4,000,000 to 6,000,000 g / mol, for example, 3,000,000 to 5,000,000 g / mol.

[0079] The above (E) third aromatic vinyl compound-vinyl cyanide compound copolymer can be prepared by using an aromatic vinyl compound and a vinyl cyanide compound through conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

[0080] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0081] The vinyl cyanide compound mentioned above may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.

[0082] The above (E) third aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the aromatic vinyl compound-derived component in, for example, 55 weight% or more, 60 weight% or more, 65 weight% or more, 70 weight% or more, or 75 weight% or more, and 80 weight% or less, 75 weight% or less, 70 weight% or less, 65 weight% or less, or 60 weight% or less, and may contain, for example, 55 to 80 weight%, for example, 60 to 75 weight%.

[0083] In addition, the above (E) third aromatic vinyl compound-vinyl cyanide compound copolymer may contain, based on 100 weight%, the vinyl cyanide compound-derived component, for example, 20 weight% or more, 25 weight% or more, 30 weight% or more, 35 weight% or more, or 40 weight% or more, and 45 weight% or less, 40 weight% or less, 35 weight% or less, 30 weight% or less, or 25 weight% or less, and may contain, for example, 20 to 45 weight%, for example, 25 to 40 weight%.

[0084] In one embodiment, in the (E) third aromatic vinyl compound-vinyl cyanide compound copolymer, the aromatic vinyl compound-vinyl cyanide compound copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0085] In one embodiment, the (E) third aromatic vinyl compound-vinyl cyanide compound copolymer may be included in an amount of 2 to 6 parts by weight, for example, 3 to 5 parts by weight, per 100 parts by weight of the base resin. Within the above weight range, performance characteristics such as sheet extrusion properties, heat resistance, and impact resistance of the thermoplastic resin composition may be improved.

[0086] (F) Additives

[0087] In addition to the above components (A) to (E), the thermoplastic resin composition according to one embodiment may further include one or more additives necessary for balancing the properties without causing degradation of other properties while enabling excellent sheet extrusion properties, flame retardancy, and impact resistance, or depending on the final use of the thermoplastic resin composition.

[0088] Specifically, the above additives may include nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, dyes, etc., and these may be used alone or in combination of two or more.

[0089] These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less per 100 parts by weight of the base resin, but are not limited thereto.

[0090] The thermoplastic resin composition according to the present invention can be manufactured by a known method for manufacturing a thermoplastic resin composition.

[0091] Meanwhile, another embodiment provides a molded article manufactured using a thermoplastic resin composition according to one embodiment. The molded article can be manufactured using the thermoplastic resin composition by various methods known in the art, such as extrusion molding.

[0092] The Charpy impact strength of the above molded product, measured on a 4 mm thick specimen according to ISO 179, is, for example, 35 kJ / m 2 Above, for example, 37 kJ / m² 2 It could be more than that.

[0093] The above molded product may have a flame retardancy of V-1 grade or higher when measured on a 3.2 mm thick specimen according to UL-94 standards.

[0094] The above molded article may have an elongation of, for example, 30% or more, for example, 35% or more, for example, 40% or more, measured on a 3.2 mm thick specimen according to ASTM D638 standards.

[0095] The above molded product may have a Vicat softening temperature (VST) measured according to ISO 306 standards of, for example, 94°C or higher, for example, 95°C or higher.

[0096] As such, the above-mentioned molded product possesses excellent sheet extrusion characteristics, flame retardancy, heat resistance, and impact resistance, and can be advantageously used in various electrical and electronic components, building materials, sports equipment, and automotive interior / exterior parts.

[0097] Preferred embodiments of the present invention are described below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited by the following embodiments.

[0098] Examples

[0099] The thermoplastic resin compositions of the examples and comparative examples were each prepared according to the component content ratios listed in Table 1 below.

[0100] In Table 1, (A), (B), and (C) are included in the base resin and are expressed as weight% based on the total weight of the base resin, and (D) and (E) are added to the base resin and are expressed as weight parts per 100 weight parts of the base resin.

[0101] The components listed in Table 1 were quantitatively and continuously fed into the feed section (barrel temperature: approximately 220°C) of a twin-screw extruder (L / D = 44, diameter = 35 mm) and then extruded / processed to produce a thermoplastic resin composition in the form of pellets. Subsequently, the thermoplastic resin composition pellets were dried at approximately 80°C for approximately 2 hours, and then sheets with thicknesses of 3.2 mm and 4 mm were produced using a sheet extrusion machine (National) at a barrel temperature of approximately 210°C, and these were cut into the shape of specimens for physical property evaluation to produce specimens for physical property evaluation.

[0102] division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) 35 35 35 35 35 35 35 (B1) 30 30 30 - 30 - - (B2) - - - 25 - - 30 (C1) 35 35 35 40 - 35 35 (C2) - - - - 35 30 - (D1) 21 21 - - 21 - 21 (D2) - - 25 25 - 25 - (E) 3 5 3 - - 3 3

[0103] The description of each component listed in Table 1 above is as follows.

[0104] (A) Butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer

[0105] An acrylonitrile-butadiene-styrene graft copolymer (Lotte Chemical Co., Ltd.) was used, comprising a core (average particle size: about 250 nm) made of butadiene rubbery polymer at about 58 wt% and a shell formed by graft polymerization of acrylonitrile and styrene (acrylonitrile:styrene weight ratio = about 2.5: about 7.5) onto the core.

[0106] (B) First aromatic vinyl compound-vinyl cyanide compound copolymer

[0107] (B1) copolymerized from a monomer mixture comprising about 28 wt% acrylonitrile and about 72 wt% styrene, having a weight-average molecular weight of about 110,000 g / mol, a glass transition temperature of about 108°C, and an oligomer content of about 0.3 wt% Styrene-acrylonitrile copolymer (Lotte Chemical Co.) was used.

[0108] (B2) An α-methylstyrene-styrene-acrylonitrile copolymer (Lotte Chemical Co., Ltd.) was used, having a weight-average molecular weight of about 160,000 g / mol and a glass transition temperature of about 116°C, copolymerized from a monomer mixture comprising about 27 wt% acrylonitrile, about 54 wt% α-methylstyrene, and about 19 wt% styrene.

[0109] (C) Second aromatic vinyl compound-vinyl cyanide compound copolymer

[0110] (C1) A styrene-acrylonitrile copolymer with a weight-average molecular weight of about 390,000 g / mol, copolymerized from a monomer mixture containing about 29 wt% acrylonitrile and about 71 wt% styrene (Lotte Chemical Co., Ltd.) was used.

[0111] (C2) A weight-average molecular weight of about 130,000 g / mol copolymerized from a monomer mixture comprising about 28 wt% acrylonitrile and about 72 wt% styrene A linear structure styrene-acrylonitrile copolymer (Lotte Chemical Co.) was used.

[0112] (D) Brominated flame retardant

[0113] (D1) 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (ICL Industrial Products, product name: FR-245) with a bromine content of about 63 wt% was used.

[0114] (D2) A brominated epoxy oligomer resin (Kukdo Chemical Co., YDB-406) with a bromine content of about 58 wt% was used.

[0115] (E) An aromatic vinyl compound-vinyl cyanide compound copolymer with a weight-average molecular weight of about 5,000,000 g / mol (Zibo Hauxing Additives) was used.

[0117] Physical property evaluation

[0118] The experimental results are shown in Table 2 below.

[0119] (1) Impact resistance (unit: kJ / m 2 ): A 4 mm thick sheet extrusion was cut into a specimen shape for measuring Charpy impact strength according to ISO 179, and then the Charpy impact strength was measured according to ISO 179.

[0120] (2) Elongation (Unit: %): A sheet extrusion product with a thickness of 3.2 mm was cut into a specimen shape for measuring tensile strength according to ASTM D638, and the elongation until the specimen fractured was measured under a tensile speed condition of 5 mm / min according to ASTM D638.

[0121] (3) Flame retardancy (unit: grade): A 3.2 mm thick sheet extrusion product was cut into a specimen shape for measuring flame retardancy according to UL-94 standards, and the flame retardancy grade was measured according to the UL-94 vertical test.

[0122] (4) Heat resistance (unit: ℃): The Vicat softening temperature (VST) of a 4 mm thick sheet extrusion molded product was measured according to ISO 306 B50 under conditions of a 5 kg load and a heating rate of 50℃ / hr.

[0123] (5) Appearance: The surface of a 3.2 mm thick sheet extrusion molded product specimen was observed using a microscope. Specifically, the number of appearance defects, such as foreign matter and pinholes, present within a standard area of ​​100 mm (width) x 100 mm (height) x 3.2 mm (thickness) was measured and evaluated according to the following criteria.

[0124] Excellent: No external defects observed

[0125] Excellent: 10 or fewer appearance defects observed

[0126] Normal: 10 to 20 appearance defects observed

[0127] Poor: 20 or more appearance defects observed

[0128] division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Impact resistance 36 38 30 25 35 35 28 Shin Yul 40 50 30 30 25 40 20 flame retardant V-1 V-1 V-1 V-1 V-1 V-1 V-1 heat resistance 96 95 95 98 97 93 98 appearance Very excellent excellence excellence Bad commonly Very excellent Very excellent

[0129] From Tables 1 and 2, it can be confirmed that by using (A) a butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer, (B) a first aromatic vinyl compound-vinyl cyanide compound copolymer having a glass transition temperature (Tg) of 107°C to 110°C, (C) a second aromatic vinyl compound-vinyl cyanide compound copolymer having a non-linear structure, (D) a bromine-based flame retardant, and (E) a third aromatic vinyl compound-vinyl cyanide compound copolymer having a weight-average molecular weight of 3,000,000 to 6,000,000 g / mol in the amounts according to one embodiment as in Examples 1 and 2, a thermoplastic resin composition having excellent impact resistance, flame retardancy, sheet extrusion characteristics (stretching characteristics), heat resistance, and appearance characteristics, and a molded article using the same can be provided.

[0130] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the appended claims are also included within the scope of the present invention.

Claims

Claim 1 A thermoplastic resin composition comprising (A) 30 to 40 weight% of a butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) 20 to 40 weight% of a first aromatic vinyl compound-vinyl cyanide compound copolymer having a glass transition temperature (Tg) of 107 to 110°C; and (C) 20 to 50 weight% of a second aromatic vinyl compound-vinyl cyanide compound copolymer having a non-linear structure, with respect to 100 weight parts of a base resin, (D) 15 to 25 weight parts of a brominated flame retardant; and (E) 2 to 6 weight parts of a third aromatic vinyl compound-vinyl cyanide compound copolymer having a weight-average molecular weight of 3,000,000 to 6,000,000 g / mol. Claim 2 A thermoplastic resin composition according to claim 1, wherein (A) the butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer is a core-shell structure comprising a core made of a butadiene-based rubbery polymer and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core. Claim 3 A thermoplastic resin composition according to claim 2, wherein the average particle size of the butadiene-based rubbery polymer is 200 to 400 nm. Claim 4 A thermoplastic resin composition according to claim 1, wherein (A) the butadiene-based rubber-modified aromatic vinyl compound-vinyl cyanide compound graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer (g-ABS). Claim 5 A thermoplastic resin composition according to claim 1, wherein the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer comprises 55 to 80 weight% of an aromatic vinyl compound-derived component and 20 to 45 weight% of a vinyl cyanide compound-derived component based on 100 weight%. Claim 6 In claim 1, the thermoplastic resin composition wherein the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer has a weight-average molecular weight of 80,000 to 300,000 g / mol. Claim 7 A thermoplastic resin composition according to claim 1, wherein the (B) first aromatic vinyl compound-vinyl cyanide compound copolymer has an oligomer content of less than 0.4 weight% based on 100 weight%. Claim 8 A thermoplastic resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyanide compound copolymer in (B) the first aromatic vinyl compound-vinyl cyanide compound copolymer is a styrene-acrylonitrile copolymer. Claim 9 A thermoplastic resin composition according to claim 1, wherein the (C) second aromatic vinyl compound-vinyl cyanide compound copolymer has a weight-average molecular weight of 200,000 to 500,000 g / mol. Claim 10 A thermoplastic resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyanide compound copolymer in the (C) second aromatic vinyl compound-vinyl cyanide compound copolymer is a styrene-acrylonitrile copolymer. Claim 11 In claim 1, the above (D) bromine-based flame retardant is a thermoplastic resin composition containing 60% by weight or more of bromine based on 100% by weight. Claim 12 A thermoplastic resin composition according to claim 1, wherein the (D) brominated flame retardant is 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine. Claim 13 A thermoplastic resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyanide compound copolymer in the (E) third aromatic vinyl compound-vinyl cyanide compound copolymer is a styrene-acrylonitrile copolymer. Claim 14 A thermoplastic resin composition according to claim 1, further comprising at least one additive selected from nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes. Claim 15 A molded article manufactured from a thermoplastic resin composition of any one of claims 1 to 14. Claim 16 In paragraph 15, the above-mentioned molded article has a Charpy impact strength of 35 kJ / m² measured on a 4 mm thick specimen according to ISO 179. 2 Lee Sang-in, molded product. Claim 17 In paragraph 15, the above-mentioned molded article is a molded article having a flame retardancy of V-1 grade or higher as measured on a 3.2 mm thick specimen according to UL-94 standards. Claim 18 In Clause 15, the above-mentioned molded article is a molded article having an elongation of 30% or more as measured on a 3.2 mm thick specimen according to ASTM D638. Claim 19 In Clause 15, the above-mentioned molded article is a molded article having a Vicat softening temperature of 94°C or higher as measured according to ISO 306 standards.

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