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

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article comprising the same. According to the present invention, a conventional transparent ABS-based resin can be replaced, chemical resistance to a detergent containing an alcohol or a disinfectant containing cyclopentane can be improved, and transparency can be excellent.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10 - 2023 - 0140052, filed on October 19, 2023, with the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference. Technical field

[0003] The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article including the same, and more particularly, to a thermoplastic resin composition capable of providing chemical resistance to detergents or disinfectants including alcohol and achieving excellent transparency, a method for preparing the thermoplastic resin composition, and a molded article including the thermoplastic resin composition. Background art

[0004] Vinyl cyanide compound - conjugated diene rubber - aromatic vinyl compound graft copolymers (hereinafter referred to as "ABS - type resins") have the rigidity and chemical resistance of acrylonitrile, the secondary processability and mechanical strength of butadiene and styrene, and an aesthetically pleasing appearance, and thus have been applied to various fields such as automotive supplies, electrical / electronic products, and office equipment.

[0005] By introducing an alkyl methacrylate into the ABS - type resin, the ABS - type resin is applied to products that require transparency. In the case of these transparent ABS - based resins, there is a problem of whitening due to poor chemical resistance to detergents or disinfectants.

[0006] Therefore, there is a need to develop a thermoplastic resin composition that can be used to replace conventional transparent ABS materials, has chemical resistance to detergents or disinfectants including alcohol, and provides transparency.

[0007] [Related technical literature]

[0008] [Patent literature]

[0009] Chinese Patent Application Publication No. 114316112 Summary of the invention

[0010] Technical problem

[0011] Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a thermoplastic resin composition and a method for preparing the thermoplastic resin composition, which can achieve an excellent physical property balance between chemical resistance to detergents or disinfectants including alcohol and transparency.

[0012] Another object of the present invention is to provide a molded article manufactured using the thermoplastic resin composition.

[0013] The above and other objects can be achieved by the present invention described below.

[0014] Technical solution

[0015] I) According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle size of 50 nm to 120 nm; 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 nm to 300 nm; and 43% to 57% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), wherein, based on 100% by weight in total of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), it contains 80% by weight or less of an alkyl methacrylate compound, and contains (A-1) and (A-2) in a weight ratio of 1:0.8 to 1:3.1 (A-1:A-2).

[0016] II) According to I), based on 100% by weight in total of (A) and (B), the content of the acrylic graft copolymer (A-1) can be 15% to 25% by weight.

[0017] III) According to I) or II), based on 100% by weight in total of the acrylic graft copolymer (A-1), it may contain 30% to 70% by weight of an acrylate rubber polymer having an average particle size of 50 nm to 120 nm, 30% to 50% by weight of an aromatic vinyl compound, and 10% to 30% by weight of a vinyl cyanide compound.

[0018] IV) According to I) to III), based on 100% by weight in total of (A) and (B), the content of the acrylic graft copolymer (A-2) can be 25% to 35% by weight.

[0019] V) According to I) to IV), the total amount of (A-1) and (A-2) can be 43% to 57% by weight.

[0020] VI) According to I) to V), based on 100% by weight in total of the acrylic graft copolymer (A-2), it may contain 30% to 70% by weight of an acrylate rubber polymer having an average particle size of 50 nm to 120 nm, 30% to 50% by weight of an aromatic vinyl compound, and 10% to 30% by weight of a vinyl cyanide compound.

[0021] VII) Based on I) to VI), based on a total of 100% by weight of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), it may contain 60% to 80% by weight of the alkyl methacrylate compound, 10% to 30% by weight of the aromatic vinyl compound, and 5% to 15% by weight of the vinyl cyanide compound.

[0022] VIII) According to I) to VII), the weight average molecular weight of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) may be from 90,000 g / mol to 200,000 g / mol.

[0023] IX) According to I) to VIII), the thermoplastic resin composition may be an alcohol - resistant thermoplastic resin composition.

[0024] The thermoplastic resin composition can be used for household / electrical appliances products, kitchen utensils or bathroom products.

[0025] X) According to I) to IX), when a 3 - mm thick sheet is immersed in a 70% aqueous isopropyl alcohol solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and when the transparency is measured according to ASTM D1003, and when the transparency before immersion is measured according to ASTM D1003, the transparency retention of the thermoplastic resin composition calculated based on the transparency before immersion and the transparency after immersion can be 2.5 or less.

[0026] XI) According to I) to X), the tensile strength of the thermoplastic resin composition measured at 50 mm / min according to ASTM D638 can be 300 kg / cm² or more.

[0027] XII) According to another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising melt - kneading and extruding the following materials: 5% to 25% by weight of an acrylic graft copolymer (A - 1) containing an acrylate rubber polymer with an average particle size of 50 nm to 120 nm; 25% to 37% by weight of an acrylic graft copolymer (A - 2) containing an acrylate rubber polymer with an average particle size of 150 nm to 300 nm; and 43% to 57% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), wherein, based on a total of 100% by weight of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), it contains 80% by weight or less of the alkyl methacrylate compound; and (A - 1) and (A - 2) are included in a weight ratio of 1:0.8 to 1:3.1 (A - 1:A - 2).

[0028] XIII) According to yet another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising melt-kneading and extruding the following materials: 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle size of 50 nm to 120 nm; 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 nm to 300 nm; and 43% to 57% by weight of a methacrylic acid alkyl ester compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), wherein, based on a total of 100% by weight of the methacrylic acid alkyl ester compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B), it contains 80% by weight or less of the methacrylic acid alkyl ester compound; and when a 3 mm thick sheet is immersed in a 70% aqueous isopropyl alcohol solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and the transparency is measured according to ASTM D1003, and when the transparency before immersion is measured according to ASTM D1003, the transparency retention of the thermoplastic resin composition calculated based on the transparency before immersion and the transparency after immersion is 2.5 or less.

[0029] XIV) According to yet another aspect of the present invention, there is provided a molded article comprising the above thermoplastic resin composition.

[0030] XV) According to XIV), the molded article may be a product exposed to a detergent or disinfectant containing alcohol.

[0031] XVI) According to XIV), the molded article may be a transparent container or a transparent component.

[0032] Advantageous Effects

[0033] The thermoplastic resin composition according to the present invention provides an excellent balance of physical properties between chemical resistance to detergents or disinfectants containing alcohol and transparency.

[0034] That is, the molded article manufactured using the thermoplastic resin composition according to the present invention has excellent chemical resistance to detergents or disinfectants containing alcohol and excellent transparency.

[0035] Therefore, the thermoplastic resin composition according to the present invention and the molded article manufactured using the same can be applied to transparent containers and transparent components of household appliances that are repeatedly exposed to detergents or disinfectants containing alcohol. Detailed Description

[0036] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0037] The terms and words used in this specification and the appended claims should not be construed as limited to their ordinary or dictionary meanings, but should be construed to have meanings and concepts that match the technical spirit of the present invention, so as to describe the present invention in the best way.

[0038] The present inventors have confirmed that in a copolymer of an alkyl methacrylate compound - an aromatic vinyl compound - a vinyl cyanide compound, by controlling the content of the alkyl methacrylate compound and including an acrylic graft copolymer in an appropriate mixing ratio, a physical property balance between chemical resistance to a detergent containing alcohol or a disinfectant containing cyclopentane and transparency has been achieved. Based on these findings, the present inventors have conducted further research to complete the present invention.

[0039] Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.

[0040] (A) Acrylic graft copolymer

[0041] The acrylic graft copolymer (A) may include an acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle size of 50 nm to 120 nm; and an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 nm to 300 nm.

[0042] For example, the acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle size of 50 nm to 120 nm and the acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 nm to 300 nm may be included in a weight ratio (A:B) of 1:0.8 to 1:3.1, preferably 1:0.9 to 1:2.7, more preferably 1:1 to 1:2.4. In this case, chemical resistance to a detergent containing alcohol or a disinfectant containing cyclopentane can be provided, and excellent transparency can be achieved.

[0043] (A-1) Acrylic graft copolymer

[0044] The acrylic graft copolymer (A-1) is a small-particle-size acrylic graft copolymer, which has the effect of improving chemical resistance to alcohols such as whitening resistance.

[0045] The acrylic graft copolymer (A-1) may contain an acrylate rubber polymer having an average particle size preferably of 50 nm to 120 nm, more preferably of 60 nm to 120 nm, and further preferably of 80 nm to 110 nm. Within this range, mechanical strength such as impact strength can be excellent.

[0046] In the present invention, the average particle size is measured by dynamic light scattering method. Specifically, the average particle size is measured in Gaussian mode using a Nicomp 380 particle size analyzer (manufacturer: PSS). As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (total solid content: 35 wt% to 50 wt%) 1000 to 5000 times with distilled water. Then, using an automatically diluted flow cell, the average particle size of the sample is measured in the measurement mode of dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis. At this time, the set values are as follows: temperature: 23 °C, measurement wavelength: 632.8 nm, channel width: 10 μsec.

[0047] For example, based on 100 wt% in total, the acrylic graft copolymer (A-1) may contain 30 wt% to 70 wt% of an acrylate rubber polymer, 30 wt% to 50 wt% of an aromatic vinyl compound, and 10 wt% to 30 wt% of a vinyl cyanide compound, preferably 32 wt% to 65 wt% or 32 wt% to 60 wt% of an acrylate rubber polymer, 30 wt% to 50 wt% or 40 wt% to 45 wt% of an aromatic vinyl compound, and 12 wt% to 30 wt% or 20 wt% to 26 wt% of a vinyl cyanide compound. Within this range, the chemical resistance to alcohols such as whitening resistance can be excellent.

[0048] In the present invention, a polymer containing a certain compound means a polymer prepared by polymerizing the compound, and the units in the polymer are derived from the compound.

[0049] The acrylate rubber polymer may include an acrylic acid alkyl ester compound.

[0050] In the present invention, the acrylic acid alkyl ester compound may include an acrylic acid alkyl ester containing an alkyl group having 1 to 15 carbon atoms, preferably one or more selected from 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 acrylic acid alkyl ester containing a linear alkyl group having 1 to 4 carbon atoms, still more preferably butyl acrylate.

[0051] In the present invention, for example, the aromatic vinyl compound may include one or more selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably one or more selected from styrene and α-methylstyrene, and still more preferably styrene. In this case, due to appropriate fluidity, processability and mechanical properties such as impact resistance can be excellent.

[0052] In the present invention, for example, the vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0053] For example, the acrylic graft copolymer (A-1) can be prepared by emulsion polymerization. In this case, mechanical strengths such as impact strength can be excellent.

[0054] The emulsion polymerization can be carried out using an emulsion polymerization method generally practiced in the technical field to which the present invention pertains, without particular limitation. For example, an emulsion graft polymerization method can be used.

[0055] For example, the weight average molecular weight of the acrylic graft copolymer (A-1) can be 50,000 g / mol to 200,000 g / mol, preferably 60,000 g / mol to 200,000 g / mol, more preferably 60,000 g / mol to 150,000 g / mol, and still more preferably 60,000 g / mol to 80,000 g / mol.

[0056] In the present invention, the weight average molecular weight can be measured by gel permeation chromatography (GPC, Waters Breeze) using tetrahydrofuran (THF) as an eluent. In this case, the weight average molecular weight is obtained as a relative value with respect to a polystyrene (PS) standard sample. Specifically, the weight average molecular weight is the weight average molecular weight (Mw) based on polystyrene conversion by gel permeation chromatography (GPC, PL GPC220, Agilent Technologies).

[0057] Specifically, the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 1%, and 10 μL of the dissolved sample was injected into a gel permeation chromatograph (GPC) at a flow rate of 0.3 mL / min. At this time, analysis was performed at a sample concentration of 2.0 mg / mL (100 μL injection) at 30°C. In this case, two columns (PLmixed B, Waters Co.) were connected in series, and an RI detector (2414, Agilent Waters Co.) was used. At this time, measurement was performed at 40°C, and data was processed using ChemStation.

[0058] In the present invention, unless otherwise defined, % represents weight %.

[0059] For example, the grafting degree of the acrylic acid graft copolymer (A-1) can be 25% to 70%, preferably 40% to 70% or 25% to 55%.

[0060] In the present invention, when measuring the grafting degree, acetone was added to 1 g of the dried graft polymer powder, and then stirred at room temperature for 24 hours. Then, centrifugation was performed to separate the insoluble matter insoluble in acetone, followed by drying. Then, the weight of the insoluble matter was measured. The measured value was substituted into Equation 1 below to calculate the grafting degree.

[0061] [Equation 1]

[0062] Grafting degree (%) = [weight of grafting compound (g) / weight of rubber (g)] × 100

[0063] - Weight of grafting compound (g): The graft copolymer was impregnated in acetone, vibrated for 24 hours with a vibrator (trade name: SI-600R, manufacturer: Lab Companion) to dissolve the separated graft copolymer, centrifuged at 14,000 rpm for 1 hour using a centrifuge, and dried at 140°C using a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) to obtain insoluble matter (gel). Then, the weight of the graft monomer was obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter.

[0064] - Weight of rubber (g): The weight (parts by weight) of the rubber (core) theoretically added to the graft copolymer powder.

[0065] For example, based on a total of 100% by weight of (A-1), (A-2) and (B), the content of the acrylic acid graft copolymer (A-1) can be 5% to 25% by weight, preferably 10% to 25% by weight, more preferably 15% to 25% by weight. Within this range, chemical resistance to detergents including alcohol or disinfectants including cyclopentane can be imparted to the thermoplastic resin composition, and excellent transparency can be achieved.

[0066] The acrylic graft copolymer (A-1) can be a commercially available material as long as it meets the definition of the present invention.

[0067] (A-2) Acrylic graft copolymer

[0068] The acrylic graft copolymer (A-2) is a large-particle-size acrylic graft copolymer and has the effect of improving mechanical strengths such as impact strength.

[0069] The acrylic graft copolymer (A-2) may contain an acrylate rubber polymer having an average particle size preferably of 150 nm to 300 nm, more preferably of 180 nm to 300 nm, and still more preferably of 200 nm to 300 nm. Within this range, mechanical strengths such as impact strength can be excellent.

[0070] In the present invention, the average particle size is measured by the dynamic light scattering method. Specifically, the average particle size is measured using a Nicomp 380 particle size analyzer (manufacturer: PSS) in the Gaussian mode. As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (total solid content: 35 wt% to 50 wt%) 1000 to 5000 times with distilled water. Then, using an automatically diluted flow cell, the average particle size of the specimen is measured in the measurement mode of dynamic light scattering / intensity 300 kHz / intensity-weighted Gaussian analysis. At this time, the set values are as follows: temperature: 23°C, measurement wavelength: 632.8 nm, channel width: 10 μsec.

[0071] For example, based on its total 100 wt%, the acrylic graft copolymer (A-2) may contain 30 wt% to 70 wt% of an acrylate rubber polymer, 30 wt% to 50 wt% of an aromatic vinyl compound, and 10 wt% to 30 wt% of a vinyl cyanide compound, preferably 32 wt% to 65 wt% or 32 wt% to 60 wt% of an acrylate rubber polymer, 35 wt% to 50 wt% or 40 wt% to 45 wt% of an aromatic vinyl compound, and 12 wt% to 30 wt% or 20 wt% to 26 wt% of a vinyl cyanide compound. Within this range, mechanical strengths such as impact strength can be excellent.

[0072] The acrylate rubber polymer may include an acrylic alkyl ester compound.

[0073] The types of the acrylic alkyl ester compound, the aromatic vinyl compound, and the vinyl cyanide compound are as described in the description of the acrylic graft copolymer (A-1).

[0074] For example, the acrylic graft copolymer (A-2) can be prepared by emulsion polymerization. In this case, mechanical strengths such as impact strength and chemical resistance to alcohol such as whitening resistance can be excellent.

[0075] The emulsion polymerization can be carried out by the emulsion polymerization methods commonly practiced in the technical field to which the present invention pertains, without particular limitation. For example, the emulsion graft polymerization method can be used.

[0076] For example, the weight-average molecular weight of the acrylic acid graft copolymer (A-2) can be from 90,000 g / mol to 200,000 g / mol, preferably from 100,000 g / mol to 200,000 g / mol, more preferably from 100,000 g / mol to 150,000 g / mol, still more preferably from 110,000 g / mol to 140,000 g / mol. In this case, mechanical strengths such as impact strength can be excellent.

[0077] For example, the acrylic acid graft copolymer (A-2) can have a grafting degree of 25% to 70%, preferably 40% to 70% or 25% to 55%.

[0078] In the present invention, when measuring the grafting degree, acetone is added to 1 g of the dried graft polymer powder, and then stirred at room temperature for 24 hours. Then, centrifugation is carried out to separate the insoluble matter insoluble in acetone, followed by drying. Then, the weight of the insoluble matter is measured. The measured value is substituted into the following Equation 1 to calculate the grafting degree.

[0079] [Equation 1]

[0080] Grafting degree (%) = [Weight of grafting compound (g) / Weight of rubber (g)] × 100

[0081] - Weight of grafting compound (g): The graft copolymer is impregnated in acetone, vibrated for 24 hours with a vibrator (trade name: SI-600R, manufacturer: Lab Companion) to dissolve the separated graft copolymer, centrifuged at 14,000 rpm for 1 hour using a centrifuge, and dried at 140 °C for 2 hours using a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) to obtain the insoluble matter (gel). Then, the weight of the graft monomer is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter.

[0082] - Weight of rubber (g): The weight (parts by weight) of the rubber (core) theoretically added in the graft copolymer powder

[0083] For example, based on (A-1), (A-2) and (B) which make up the thermoplastic resin composition in a total of 100% by weight, the content of the acrylic graft copolymer (A-2) can be 25% to 37% by weight, preferably 25% to 38% by weight, more preferably 25% to 35% by weight. Within this range, chemical resistance to detergents containing alcohols or disinfectants containing cyclopentane can be imparted to the thermoplastic resin composition, and excellent transparency can be achieved.

[0084] The acrylic graft copolymer (A-2) can be a commercially available material as long as it meets the definition of the present invention.

[0085] (B) Alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer

[0086] The alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can provide a physical property balance between chemical resistance to detergents containing alcohols and isopropyl alcohol or disinfectants containing cyclopentane and transparency.

[0087] For example, based on its total of 100% by weight, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can contain 80% by weight or less of the alkyl methacrylate compound. As specific examples, 60% to 80% by weight of the alkyl methacrylate compound, 10% to 30% by weight of the aromatic vinyl compound, and 5% to 15% by weight of the vinyl cyanide compound, preferably 65% to 80% or 68% to 80% by weight of the alkyl methacrylate compound, 15% to 30% or 15% to 25% by weight of the aromatic vinyl compound, and 5% to 15% or 5% to 10% by weight of the vinyl cyanide compound. Within this range, mechanical properties such as tensile strength can be excellent.

[0088] The alkyl methacrylate compound can be selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, and decyl methacrylate. The alkyl methacrylate compound is preferably methyl methacrylate.

[0089] The types of the aromatic vinyl compound and the vinyl cyanide compound are as described in the description of the acrylic graft copolymer (A-1).

[0090] For example, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can be prepared by bulk polymerization. In this case, mechanical strengths such as impact strength can be excellent.

[0091] The bulk polymerization of the present invention can be carried out using a bulk polymerization method commonly practiced in the technical field to which the present invention pertains, without particular limitation.

[0092] For example, the weight - average molecular weight of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can be from 50,000 g / mol to 200,000 g / mol, preferably from 60,000 g / mol to 200,000 g / mol, more preferably from 60,000 g / mol to 150,000 g / mol, and still more preferably from 100,000 g / mol to 150,000 g / mol.

[0093] For example, based on a total of 100% by weight of (A - 1), (A - 2), and (B), the content of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can be from 43% by weight to 57% by weight, preferably from 43% by weight to 55% by weight, and more preferably from 45% by weight to 55% by weight. Within this range, chemical resistance to detergents containing alcohol or disinfectants containing cyclopentane can be imparted to the thermoplastic resin composition, and excellent transparency can be achieved.

[0094] The alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) can be a commercially available material as long as the material meets the definition of the present invention.

[0095] Thermoplastic resin composition

[0096] The thermoplastic resin composition may further contain additives.

[0097] For example, the additives can include one or more selected from lubricants, heat stabilizers, ultraviolet stabilizers, fluorescent brighteners, pigments, dyes, processing aids, metal deactivators, friction reducers, and anti - wear agents.

[0098] For example, based on a total of 100 parts by weight of (A - 1), (A - 2), and (B) constituting the thermoplastic resin composition, the content of each additive can be from 0.01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight, and more preferably from 0.1 to 3 parts by weight. In this case, the desired properties can be effectively achieved without degrading the inherent properties of the thermoplastic resin composition of the present invention.

[0099] For example, the lubricant may include one or more selected from alkyl acrylate lubricants, styrene-acrylonitrile copolymers having a weight average molecular weight of 30,000 g / mol to 70,000 g / mol, ethylene copolymers, olefin waxes, and aliphatic amide compounds, preferably one or more selected from alkyl acrylate lubricants, styrene-acrylonitrile copolymers having a weight average molecular weight of 30,000 g / mol to 70,000 g / mol, and olefin waxes, and more preferably alkyl acrylate lubricants. In this case, the physical property balance, scratch resistance, and appearance quality may be excellent.

[0100] As another example, based on 100 parts by weight in total of (A-1), (A-2), and (B) constituting the thermoplastic resin composition, the content of the lubricant may be 0.1 to 3 parts by weight, preferably 0.5 to 2.5 parts by weight, and more preferably 0.7 to 2.2 parts by weight. Within this range, the impact resistance and fluidity may be excellent.

[0101] The alkyl acrylate lubricant may preferably include one or more selected from poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate). In this case, the formation of mold fouling is suppressed, so that the appearance of the molded article may be attractive and high gloss may be achieved.

[0102] The alkyl acrylate lubricant is not particularly limited as long as it follows the definition of the present invention. The alkyl acrylate lubricant may be prepared directly or a commercially available product may be used.

[0103] The weight average molecular weight of the styrene-acrylonitrile copolymer may preferably be 40,000 g / mol to 67,000 g / mol, more preferably 50,000 g / mol to 65,000 g / mol, and still more preferably 55,000 g / mol to 65,000 g / mol. Within this range, the fluidity can be improved, thereby improving the processability and appearance quality.

[0104] For example, the styrene-acrylonitrile copolymer may have a melt flow index (190 °C, 5 kg) of 20 g / 10 min to 60 g / 10 min, preferably 25 g / 10 min to 55 g / 10 min, as measured according to ISO1133. Within this range, the impact strength, fluidity, and appearance quality may be excellent.

[0105] For example, as measured according to ASTM D648, the heat distortion temperature of the styrene-acrylonitrile copolymer may be 82 °C to 90 °C, preferably 84 °C to 88 °C. Within this range, the impact strength, fluidity, and appearance quality may be excellent.

[0106] For example, the ethylene copolymer may include one or more selected from an ethylene / 1-butene copolymer and an ethylene / n-butyl acrylate / carbon monoxide terpolymer. In this case, the heat resistance, fluidity, and appearance quality may be excellent.

[0107] For example, the olefin wax may include one or more selected from polyethylene wax and polypropylene wax, preferably polyethylene wax. In this case, the heat resistance, fluidity, and appearance quality may be excellent.

[0108] For example, the aliphatic amide compound may include one or more selected from stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bisoleamide, preferably ethylene bis(stearamide). In this case, the impact strength, fluidity, and appearance quality may be excellent.

[0109] As another example, based on a total of 100 parts by weight of (A-1), (A-2), and (B) constituting the thermoplastic resin composition, the content of the heat stabilizer may be 0.1 to 2 parts by weight, more preferably 0.2 to 1.5 parts by weight. Within this range, the heat resistance can be improved.

[0110] For example, the heat stabilizer may include one or more selected from phenolic heat stabilizers, phosphite heat stabilizers, and thioether heat stabilizers, preferably one or more selected from phenolic heat stabilizers and phosphite heat stabilizers.

[0111] For example, the phenolic heat stabilizer may include one or more selected from tetramethylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0112] For example, the phosphite heat stabilizer may be tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0113] For example, the thioether heat stabilizer may include one or more selected from dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl mercaptoacetate, butyl mercaptoacetate, octyl mercaptoacetate, and thiocresol.

[0114] As another example, based on 100 total parts by weight of (A-1), (A-2) and (B) constituting the thermoplastic resin composition, the content of the ultraviolet stabilizer may be 0.1 to 3 parts by weight, more preferably 0.5 to 1.5 parts by weight. In this case, weather resistance can be improved.

[0115] For example, the ultraviolet stabilizer may include a hindered amine light stabilizer (HALS), preferably selected from 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-methyl-2-cycloundecyl-1-oxo-3,8-diaza-4-oxaspiro[4,5]decane and epichlorohydrin, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino], more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(2H-benzotriazol-2-yl)-4-(-(1,1,3,3-tetramethylbutyl)phenol, poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino] or a mixture thereof, even more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino] or a mixture thereof. In this case, the impact resistance and fluidity can be excellent, and the weather resistance can be greatly improved.

[0116] For example, the pigment may be carbon black.

[0117] As another example, based on a total of 100 parts by weight of (A-1), (A-2), and (B) constituting the thermoplastic resin composition, the content of the pigment may be 0.5 to 5 parts by weight, preferably 1 to 4.5 parts by weight, and more preferably 2 to 4.5 parts by weight. Within this range, the balance of physical properties and coloring properties can be excellent.

[0118] For example, the thermoplastic resin composition contains 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle diameter of 50 nm to 120 nm; 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle diameter of 150 nm to 300 nm; and 43% to 57% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B). Based on a total of 100% by weight, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) contains 80% by weight or less of the alkyl methacrylate compound, and (A-1) and (A-2) are contained in a weight ratio (A-1:A-2) of 1:0.8 to 1:3.1. In this case, chemical resistance to detergents including alcohol or disinfectants including cyclopentane can be imparted to the thermoplastic resin composition, and excellent transparency can be achieved.

[0119] For example, when a sample is fixed using an ESCR 2% jig, then covered with gauze, a 70% aqueous isopropyl alcohol solution is applied to the gauze, left for 1 hour, and then the gauze is removed, no microcracks are observed in the thermoplastic resin composition.

[0120] Here, the specimen may be an injection specimen that can be used to measure tensile strength and the like.

[0121] For example, when a 3 mm thick sheet is immersed in a 70% aqueous isopropyl alcohol solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and the transparency is measured according to ASTM D1003, and when the transparency before immersion is measured according to ASTM D1003, the thermoplastic resin composition may have a transparency retention of 2.5 or less, preferably 1.2 to 2.4, which is calculated based on the transparency before immersion and the transparency after immersion. Within this range, the transparency can be excellent without affecting the mechanical strength.

[0122] For example, the thermoplastic resin composition may have a tensile strength measured at 50 mm / min according to ASTM D638 of 300 kg / cm² or more, or 300 kg / cm² to 400 kg / cm². Within this range, the mechanical strength and transparency may be excellent, and the chemical resistance to detergents containing alcohol or disinfectants containing cyclopentane may be excellent.

[0123] For example, the thermoplastic resin composition may have an impact strength of 10 kg / cm² or more, preferably 10 kg / cm² to 20 kg / cm², as measured using D256 on a 1 / 4-inch sample under notched cantilever conditions. Within this range, the mechanical strength and transparency may be excellent, and the chemical resistance to detergents containing alcohol or disinfectants containing cyclopentane may be excellent.

[0124] As a preferred example, the thermoplastic resin composition comprises 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer having an average particle size of 50 nm to 120 nm; 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 nm to 300 nm; and 43% to 57% by weight of a methacrylic acid alkyl ester compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B). Based on 100% by weight of its total amount, the methacrylic acid alkyl ester compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) contains 80% by weight or less of the methacrylic acid alkyl ester compound. When a 3-mm thick sheet is immersed in a 70% aqueous isopropyl alcohol solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and the transparency is measured according to ASTM D1003. When the transparency before immersion is measured according to ASTM D1003, the thermoplastic resin composition has a transparency retention rate of 2.5 or less, which is calculated based on the transparency before immersion and the transparency after immersion. In this case, chemical resistance to detergents containing alcohol or disinfectants containing cyclopentane can be imparted to the thermoplastic resin composition, and excellent transparency can be achieved.

[0125] Method for preparing a thermoplastic resin composition

[0126] For example, the method for preparing the thermoplastic resin composition of the present invention includes the steps of melt-kneading and extruding the following components: 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer with an average particle size of 50 nm to 120 nm, 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer with an average particle size of 150 nm to 300 nm, and 43% to 57% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B); wherein, based on 100% by weight of its total amount, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) contains 80% by weight or less of the alkyl methacrylate compound. In this case, it can replace the conventional transparent ABS material, and can improve the chemical resistance to detergents including alcohol or disinfectants including cyclopentane, and can achieve excellent transparency.

[0127] Preferably, (A-1) and (A-2) can be included in a weight ratio (A-1:A-2) of 1:0.8 to 1:3.1.

[0128] When the extrusion step is a process of manufacturing an extruded product using an extruder, the extrusion step is not limited. For example, the extrusion step can be carried out at a temperature of 200°C to 300°C, preferably 220°C to 260°C. Within this range, stable extrusion is possible, and the mixing effect can be excellent. At this time, the temperature corresponds to the temperature set in the cylinder.

[0129] Any extruder commonly used in the technical field to which the present invention pertains can be used for the present invention without any particular limitation. Preferably, a twin-screw extruder can be used.

[0130] The method may include the step of injecting an extruded product manufactured by the method for preparing the thermoplastic resin composition. In this case, a molded product having both chemical resistance and impact strength can be easily manufactured.

[0131] For example, the injection can be carried out at an injection temperature of 220°C to 280°C, preferably 230°C to 270°C. Within this range, an injection-molded product requiring a complex design can be easily manufactured. At this time, the injection temperature corresponds to the temperature set in the cylinder.

[0132] In addition, the injection can be carried out at an injection pressure of 70 bar to 90 bar, preferably 75 bar to 85 bar. Within this range, an injection-molded product requiring a complex design can be easily manufactured.

[0133] In addition, the injection can be carried out at a holding pressure of 35 bar to 60 bar, preferably 40 bar to 55 bar. Within this range, an injection-molded product requiring a complex design can be easily manufactured.

[0134] As a preferred example, the method for preparing the thermoplastic resin composition of the present invention includes the steps of melt-kneading and extruding the following components: 5% to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylate rubber polymer with an average particle size of 50 nm to 120 nm, 25% to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer with an average particle size of 150 nm to 300 nm, and 43% to 57% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B); wherein, based on 100% by weight of its total amount, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound copolymer (B) includes 80% by weight or less of an alkyl methacrylate compound; and (A-1) and (A-2) are included in a weight ratio (A-1:A-2) of 1:0.8 to 1:3.1. In this case, instead of conventional transparent ABS materials, the chemical resistance to detergents containing alcohols or disinfectants containing cyclopentane can be improved, and excellent transparency can be achieved.

[0135] The method for preparing the thermoplastic resin composition shares all the technical features of the above thermoplastic resin composition. Therefore, the description of the repeated parts is omitted.

[0136] Molded article

[0137] For example, the molded article of the present invention contains the thermoplastic resin composition of the present invention. In this case, compared with the conventional thermoplastic resin composition, the chemical resistance to detergents containing alcohols or disinfectants containing cyclopentane can be improved, and excellent transparency can be achieved.

[0138] The molded article can be a product repeatedly exposed to detergents containing alcohols or disinfectants containing cyclopentane, that is, an alcohol-resistant product.

[0139] In addition, the molded article can be a transparent container or a transparent component for household appliances.

[0140] When describing the thermoplastic resin composition of the present invention, its preparation method, and the molded article containing it, it should be noted that other conditions or equipment not explicitly described herein can be appropriately selected within the range commonly implemented in the art, without particular limitation.

[0141] Hereinafter, the present invention will be described in more detail with reference to the following preferred embodiments. However, these embodiments are provided for illustrative purposes only and should not be construed as limiting the scope and spirit of the present invention. In addition, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention, and these changes and modifications are also within the scope of the appended claims.

[0142] Example

[0143] The materials used in the examples and comparative examples are as follows.

[0144] *(A) Acrylic graft copolymer

[0145] (A-1) ASA graft copolymer containing acrylate rubber with an average particle size of 100 nm (butyl acrylate: 40 wt%, styrene: 46.5 wt%, acrylonitrile: 13.5 wt%, weight average molecular weight: 70,000 g / mol, melt flow rate (MI): 2 g / 10 min)

[0146] (A-2) ASA graft copolymer containing acrylate rubber with an average particle size of 250 nm (butyl acrylate: 40 wt%, styrene: 46.5 wt%, acrylonitrile: 13.5 wt%, weight average molecular weight: 110,000 g / mol, melt flow rate (MI): 1 g / 10 min

[0147] *(B) Copolymer of alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide compound (methyl methacrylate: 65 wt%, styrene: 25 wt%, acrylonitrile: 10 wt%, weight average molecular weight: 120,000 g / mol)

[0148] *(C) ABS graft copolymer containing diene rubber with an average particle size of 100 nm (butadiene: 50 wt%, methyl methacrylate: 35 wt%, styrene: 12.5 wt%, acrylonitrile: 2.5 wt%, weight average molecular weight: 80,000 g / mol)

[0149] *(D) ABS graft copolymer containing diene rubber with an average particle size of 250 nm (butadiene: 50 wt%, methyl methacrylate: 35 wt%, styrene: 12.5 wt%, acrylonitrile: 2.5 wt%, weight average molecular weight: 100,000 g / mol)

[0150] * Additive 1: Antioxidant IR 1010

[0151] * Additive 2: Antioxidant PEP-8

[0152] * Additive 3: Lubricant stearic acid

[0153] Examples 1 to 3 and Comparative Examples 1 to 8

[0154] According to the contents shown in Table 1, the components shown in Table 1 were introduced into a twin-screw extruder. In addition, the addition amount of each additive was 0.15 parts by weight relative to a total of 100 parts by weight of (A-1), (A-2), (B), and (C). Then, pellets were produced using the twin-screw extruder at a barrel temperature of 240°C. Further, the obtained pellets were injection-molded using an injection molding machine at a barrel temperature of 230°C to produce samples for measuring impact strength and tensile strength.

[0155] In addition, the pellets obtained by extruding the samples for measuring physical properties (for measuring transparency retention and chemical resistance) were extruded at 220°C to 260°C using an extruder to produce an extruded sheet having a width, length, and thickness of 13 mm × 80 mm × 3 mm.

[0156] Test Example

[0157] The properties of the samples produced in Examples 1 to 3 and Comparative Examples 1 to 8 were measured by the following methods, and the results are shown in Table 1 below.

[0158] Measurement method:

[0159] * Transparency retention (ΔHz): A 3-mm thick sheet was immersed in a 70% aqueous isopropyl alcohol solution for 24 hours. The sheet was taken out of the solution and left for 30 minutes. The transparency was measured according to ASTM D1003, and the transparency before immersion was also measured according to ASTM D1003. The transparency retention was calculated based on the transparency before immersion and the transparency after immersion.

[0160] * Impact strength (kg / cm·cm): The notched Izod impact strength was measured on a 1 / 4-inch sample according to ASTM D256.

[0161] * Chemical resistance: Cyclopentane was placed on the extruded pellets using an ESCR (environmental stress crack resistance) 1.0% jig for 5 minutes, and then the occurrence of cracking was confirmed. When no cracks appeared, it was rated as "no cracks". In the case where fine cracks occurred on the side, it was evaluated as "fine cracks". In the case where multiple horizontal through-cracks occurred, it was evaluated as "cracks".

[0162] * Tensile strength (kg / cm·cm): The tensile strength was measured at 50 mm / min according to ASTM D638.

[0163] [Table 1]

[0164]

[0165] As shown in Table 1, Examples 1 to 3 according to the present invention exhibit mechanical strength equal to or superior to Comparative Examples 1 to 8. However, in the case of Examples 1 to 3, transparency retention and chemical resistance are excellent compared to Comparative Examples 1 to 8.

[0166] Therefore, when the thermoplastic resin composition according to the present invention is applied to a transparent container or transparent component of a household appliance, mechanical strength can be maintained, a physical property balance between transparency retention and chemical resistance can be ensured, and thus product reliability can be greatly improved.

[0167] On the other hand, in the case of Comparative Example 1 where an excessive amount of acrylic graft copolymer (A-2) is used, the transparency is poor compared to Example 1.

[0168] In addition, in the case of Comparative Example 2 where an excessive amount of acrylic graft copolymer (A-1) and a small amount of acrylic graft copolymer (A-2) are used, the impact strength is poor compared to Example 1.

[0169] Furthermore, in the case of Comparative Example 3 where acrylic graft copolymer (A-1) is not included and an excessive amount of acrylic graft copolymer (A-2) is used, the transparency is significantly reduced compared to Example 1.

[0170] In addition, in the case of Comparative Example 4 where acrylic graft copolymer (A-2) is not included and an excessive amount of acrylic graft copolymer (A-1) is used, the impact strength is significantly reduced compared to Example 1.

[0171] In addition, in the case of Comparative Example 5 where an excessive amount of alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (B) is used, microcracks are observed compared to Example 1, indicating poor chemical resistance.

[0172] In addition, in the case of Comparative Example 6 where a small amount of alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (B) is used, the tensile strength is very poor compared to Example 1.

[0173] In addition, in the case of Comparative Example 7 where acrylic graft copolymer (A-1) is not included and diene graft copolymer (C) is added in a corresponding amount, the transparency and chemical resistance are very poor compared to Example 1, and the impact strength is also reduced.

[0174] In addition, in the case of Comparative Example 8 where acrylic graft copolymer (A-1) is not included and diene graft copolymer (D) is added in a corresponding amount, the transparency and chemical resistance are very poor compared to Example 1.

[0175] In summary, in the thermoplastic resin composition according to the present invention, by adjusting the content of the alkyl methacrylate compound within a predetermined range in the copolymer of an alkyl methacrylate compound - an aromatic vinyl compound - a vinyl cyanide compound and adding an acrylic graft copolymer containing rubbers having different average particle diameters within a predetermined range, due to the combined synergistic effect thereof, transparency equal to or superior to that of conventional transparent ABS resins is provided, and the transparency retention and chemical resistance are greatly improved. Therefore, the thermoplastic resin composition is suitable for transparent containers or transparent components of household appliances repeatedly exposed to detergents or disinfectants.

Claims

1. A thermoplastic resin composition, comprising: 5 to 25% by weight of an acrylic graft copolymer (A-1) containing an acrylic ester rubber polymer having an average particle size of 50 to 120 nm; 25 to 37% by weight of an acrylic graft copolymer (A-2) containing an acrylate rubber polymer having an average particle size of 150 to 300 nm; and 43 to 57% by weight of an alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B), in, The alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B) contains 80% by weight or less of the alkyl methacrylate compound, based on 100% by weight in total, and (A-1) and (A-2) are contained in a weight ratio (A-1:A-2) of 1:0.8 to 1:3.

1.

2. The thermoplastic resin composition according to claim 1, wherein The content of the acrylic graft copolymer (A-1) is 15 to 25 wt % based on 100 wt % in total of (A) and (B).

3. The thermoplastic resin composition according to claim 1, wherein The acrylic graft copolymer (A-1) comprises 30 to 70 wt % of an acrylic ester rubber polymer having an average particle diameter of 50 to 120 nm, 30 to 50 wt % of an aromatic vinyl compound, and 10 to 30 wt % of a vinyl cyanide compound, based on 100 wt % in total of all components constituting the acrylic graft copolymer (A-1).

4. The thermoplastic resin composition according to claim 1, wherein The content of the acrylic graft copolymer (A-2) is 25 to 35 wt % based on 100 wt % in total of (A) and (B).

5. The thermoplastic resin composition according to claim 1, wherein The acrylic graft copolymer (A-2) comprises 30 to 70 wt % of an acrylic ester rubber polymer having an average particle size of 50 to 120 nm, 30 to 50 wt % of an aromatic vinyl compound and 10 to 30 wt % of a vinyl cyanide compound, based on 100 wt % in total.

6. The thermoplastic resin composition according to claim 1, wherein The alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B) comprises 60 to 80 wt % of an alkyl methacrylate compound, 10 to 30 wt % of an aromatic vinyl compound and 5 to 15 wt % of a vinyl cyanide compound, based on 100 wt % in total, or has a weight average molecular weight of 90,000 to 200,000 g / mol.

7. The thermoplastic resin composition according to claim 1, wherein When a 3 mm thick sheet is immersed in a 70% isopropyl alcohol aqueous solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and the transparency is measured according to ASTM D1003, and when the transparency before immersion is measured according to ASTM D1003, the thermoplastic resin composition has a transparency retention calculated based on the transparency before immersion and the transparency after immersion of 2.5 or less.

8. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition has a tensile strength of 300 kg / cm.cm or more measured according to ASTM D638.

9. A method for preparing a thermoplastic resin composition, comprising melt-kneading and extruding the following materials: 5 wt % to 25 wt % of an acrylic graft copolymer (A-1) comprising an acrylic ester rubber polymer having an average particle size of 50 nm to 120 nm; 25 wt % to 37 wt % of an acrylic graft copolymer (A-2) comprising an acrylic ester rubber polymer having an average particle size of 150 nm to 300 nm; and 43 wt % to 57 wt % of an alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B), in, The alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B) contains 80% by weight or less of the alkyl methacrylate compound based on 100% by weight in total; and (A-1) and (A-2) are contained in a weight ratio (A-1:A-2) of 1:0.8 to 1:3.

1.

10. A method for preparing a thermoplastic resin composition, comprising melt-kneading and extruding the following materials: 5 wt % to 25 wt % of an acrylic graft copolymer (A-1) comprising an acrylic ester rubber polymer having an average particle diameter of 50 nm to 120 nm; 25 wt % to 37 wt % of an acrylic graft copolymer (A-2) comprising an acrylic ester rubber polymer having an average particle diameter of 150 nm to 300 nm; and 43 wt % to 57 wt % of an alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B), in, The alkyl methacrylate compound-aromatic vinyl compound-vinyl cyanide compound copolymer (B) contains 80% by weight or less of the alkyl methacrylate compound based on 100% by weight in total; and When a 3 mm thick sheet is immersed in a 70% isopropyl alcohol aqueous solution for 24 hours, the sheet is taken out of the solution and left for 30 minutes, and the transparency is measured according to ASTM D1003, and when the transparency before immersion is measured according to ASTM D1003, the thermoplastic resin composition has a transparency retention calculated based on the transparency before immersion and the transparency after immersion of 2.5 or less.

11. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 8.

12. The molded article according to claim 11, wherein The molded article is a transparent container or a transparent part.

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