Thermoplastic resin composition and molded article formed therefrom

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a thermoplastic polyurethane resin having a Shore D hardness of about 60-65 and a refractive index of about 1.562-1.565; about 105-135 parts by weight of an aromatic vinyl-vinyl cyanide-based copolymer resin; and about 20-40 parts by weight of a glycidyl(meth)acrylate-modified aromatic vinyl-based copolymer resin consisting of a methyl methacrylate-derived component, an aromatic vinyl-based monomer-derived component, a vinyl cyanide-based monomer-derived component, and a glycidyl(meth)acrylate-derived component. The thermoplastic resin composition has excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, and moldability, an excellent balance between the aforementioned physical properties, and the like.

Description

Thermoplastic resin composition and molded article formed therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, moldability, and a balance of these physical properties, and a molded article formed therefrom.

[0002]

[0003] Since the COVID-19 pandemic, there has been an increasing need for the development of chemical-resistant transparent materials related to the advancement of detergents. Furthermore, with the expansion of the Chinese vacuum cleaner market and the diversification of dry and wet vacuum cleaner models, the chemical resistance performance required by each company is becoming more sophisticated.

[0004] During the detergent immersion evaluation, a whitening phenomenon was observed in rubber-modified aromatic vinyl copolymer resin materials such as MABS, and it was confirmed that polystyrene resin and aromatic vinyl copolymer resin materials were brittle, making commercialization difficult. Additionally, while polymethyl methacrylate resin did not exhibit whitening, it was confirmed that its chemical resistance and other properties deteriorated.

[0005] Therefore, there is a need to develop a thermoplastic resin composition that exhibits excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, moldability, and a balance of these physical properties without such problems.

[0006] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2010-0078429, etc.

[0007]

[0008] The objective of the present invention is to provide a thermoplastic resin composition having excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, moldability, and a balance of these physical properties.

[0009] Another objective of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0010] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0011]

[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a thermoplastic polyurethane resin having a Shore D hardness of about 60 to about 65 and a refractive index of about 1.562 to about 1.565; about 105 to about 135 parts by weight of an aromatic vinyl-vinyl cyanide copolymer resin; and about 20 to about 40 parts by weight of a glycidyl (meth)acrylate modified aromatic vinyl copolymer resin composed of a methyl methacrylate-derived component, an aromatic vinyl monomer-derived component, a vinyl cyanide monomer-derived component, and a glycidyl (meth)acrylate-derived component.

[0013] 2. In the above 1 embodiment, the thermoplastic polyurethane resin may have a weight-average molecular weight of about 100,000 to about 250,000 g / mol.

[0014] 3. In the above 1 or 2 embodiments, the aromatic vinyl-vinyl cyanide copolymer resin may have a weight-average molecular weight of about 50,000 to about 300,000 g / mol.

[0015] 4. In the above 1 to 3 embodiments, the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin may comprise about 1 to about 3 weight% of a glycidyl (meth)acrylate-derived component, about 65 to about 75 weight% of a methyl methacrylate-derived component, about 15 to about 30 weight% of an aromatic vinyl monomer-derived component, and about 1 to about 10 weight% of a vinyl cyanide monomer-derived component.

[0016] 5. In the above 1 to 4 embodiments, the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin may have a weight-average molecular weight of about 50,000 to about 200,000 g / mol.

[0017] 6. In the above 1 to 5 embodiments, the weight ratio of the aromatic vinyl-vinyl cyanide copolymer resin and the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin may be about 1:0.2 to about 1:0.35.

[0018] 7. In the above 1 to 6 embodiments, the thermoplastic resin composition may not discolor when a 3.2 mm thick tensile specimen made according to ASTM D638 is immersed in a 10 wt% diluted detergent solution for 5 days.

[0019] 8. In the above 1 to 7 embodiments, the thermoplastic resin composition may have a light transmittance of about 84% or more of a 1 mm thick specimen measured according to ASTM D1003.

[0020] 9. In the above 1 to 8 embodiments, the thermoplastic resin composition may have a haze of about 5% or less of a 1 mm thick specimen measured according to ASTM D1003.

[0021] 10. In the above 1 to 9 embodiments, the thermoplastic resin composition may have an unnotched Izod impact strength of about 55 to about 70 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

[0022] 11. In the above embodiments 1 to 10, the thermoplastic resin composition has a tensile strength of about 400 to about 500 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 It could be.

[0023] 12. In the above embodiments 1 to 11, the thermoplastic resin composition has a flexural strength of about 550 to about 700 kgf / cm² of a 6.4 mm thick specimen measured at 2.8 mm / min in accordance with ASTM D790. 2 It may be, and according to ASTM D790, the flexural modulus of a 6.4 mm thick specimen measured under a condition of 2.8 mm / min is approximately 15,600 to approximately 17,500 kgf / cm 2 It could be.

[0024] 13. In the above 1 to 12 embodiments, the thermoplastic resin composition may have a Vicat softening temperature (VST) of about 86 to about 90°C, measured under a 5 kg load and a 50°C / hr heating condition in accordance with ISO 306.

[0025] 14. In the above 1 to 13 embodiments, the thermoplastic resin composition may have a melt-flow index (MI) of about 6 to about 14 g / 10 min, measured at 200°C and a 5 kgf load condition according to ASTM D1238.

[0026] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized by being formed from a thermoplastic resin composition according to any one of 1 to 14.

[0027]

[0028] The present invention has the effect of providing a thermoplastic resin composition having excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, moldability, and a balance of these physical properties, and a molded article formed therefrom.

[0029]

[0030] The present invention will be described in detail below.

[0031] The thermoplastic resin composition according to the present invention comprises (A) a thermoplastic polyurethane resin; (B) an aromatic vinyl-vinyl cyanide copolymer resin; and (C) a glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin.

[0032] In this specification, "a to b" indicating a numerical range is defined as "≥a and ≤b".

[0033]

[0034] (A) Thermoplastic polyurethane resin

[0035] A thermoplastic polyurethane resin (TPU) according to one embodiment of the present invention can be applied together with an aromatic vinyl-vinyl cyanide copolymer resin and a glycidyl (meth)acrylate modified aromatic vinyl copolymer resin, etc., to improve the chemical resistance, transparency, impact resistance, stiffness, thermal stability, moldability, and balance of physical properties of the thermoplastic resin composition, and a thermoplastic polyurethane resin having a Shore D hardness of about 60 to about 65 and a refractive index of about 1.562 to about 1.565 can be used.

[0036] In a specific example, the thermoplastic polyurethane resin may have a Shore D hardness of about 60 to about 65, for example, about 61 to about 64, measured by a Shore hardness tester according to ASTM D2240. If the Shore D hardness of the thermoplastic polyurethane resin is less than about 60, there is a risk that the chemical resistance, transparency, impact resistance, stiffness, thermal stability, etc. of the thermoplastic resin composition will be reduced, and if it exceeds about 65, there is a risk that the chemical resistance, transparency, impact resistance, stiffness, thermal stability, moldability, etc. of the thermoplastic resin composition will be reduced.

[0037] In a specific example, the thermoplastic polyurethane resin may have a refractive index of about 1.562 to about 1.565, for example, about 1.5625 to about 1.5643, of a 2.5 mm thick specimen measured at a temperature of 20°C using a refractive index meter (manufacturer: ATAGO, device name: Abbe refractometer DR-A1). If the refractive index of the thermoplastic polyurethane resin is less than about 1.562, there is a risk that the chemical resistance, transparency, impact resistance, stiffness, thermal stability, etc. of the thermoplastic resin composition will be reduced, and if it exceeds about 1.565, there is a risk that the chemical resistance, transparency, impact resistance, stiffness, thermal stability, moldability, etc. of the thermoplastic resin composition will be reduced.

[0038] In a specific example, the thermoplastic polyurethane resin may be a thermoplastic polyurethane resin prepared by reacting a polycarbonate diol, a polyisocyanate including diphenylmethane diisocyanate, and a chain extender including one or more of butanediol and hexanediol.

[0039] Here, polyol is a compound having two or more hydroxyl groups (-OH) in its molecule, and is a substance obtained by reacting propylene oxide or ethylene oxide with an initiator, such as a polyfunctional alcohol or aromatic amine having two or more hydroxyl groups (-OH) or amine groups (-NH2) in its molecule, under appropriate conditions.

[0040] In a specific example, the polycarbonate polyol may include, but is not limited to, aromatic polycarbonate diols, polyalkylene carbonate diols such as polyhexamethylene carbonate, and combinations thereof.

[0041] In a specific example, the polyisocyanate is a compound having two or more isocyanate groups (-NCO), which is lachrymic and highly reactive, and can form various bonds by reacting with a compound having active hydrogen.

[0042] In a specific example, the polyisocyanate may include, but is not limited to, diphenylmethane diisocyanate (MDI), aromatic diisocyanates excluding diphenylmethane diisocyanate (toluene diisocyanate, xylene diisocyanate, etc.), aliphatic diisocyanates (hexamethylene diisocyanate, isophorone diisocyanate, etc.), and combinations thereof.

[0043] In a specific example, the chain extender refers to a reactive monomer used to strengthen polymerization or intermolecular bonding, and is a difunctional substance such as a diol or diamine. In the present invention, the chain extender may include butanediol and / or hexanediol.

[0044] In a specific example, the thermoplastic polyurethane resin may comprise about 40 to about 80 weight% of the polycarbonate polyol, for example, about 45 to about 75 weight%, about 10 to about 30 weight% of the polyisocyanate, for example, about 10 to about 25 weight%, and about 1 to about 30 weight% of the chain extender, for example, about 10 to about 20 weight%. Within the above range, the chemical resistance, moldability, etc. of the thermoplastic resin composition may be excellent.

[0045] In a specific example, the thermoplastic polyurethane resin may have a weight-average molecular weight of about 100,000 to about 250,000 g / mol, for example, about 140,000 to about 220,000 g / mol, as measured by gel permeation chromatography (GPC). Within this range, the chemical resistance, impact resistance, etc. of the thermoplastic resin composition may be excellent.

[0046]

[0047] (B) Aromatic vinyl-vinyl cyanide copolymer resin

[0048] An aromatic vinyl-vinyl cyanide copolymer resin according to one embodiment of the present invention can be applied together with the thermoplastic polyurethane resin and the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin, etc., to improve the chemical resistance, transparency, impact resistance, stiffness, thermal stability, moldability, and balance of physical properties thereof of the thermoplastic resin composition, and an aromatic vinyl-vinyl cyanide copolymer resin used in conventional thermoplastic resin compositions may be used. For example, the aromatic vinyl-vinyl cyanide copolymer resin may be a polymer of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer.

[0049] In a specific example, the aromatic vinyl-vinyl cyanide copolymer resin can be obtained by mixing an aromatic vinyl monomer and a cyanocyclic vinyl monomer, etc., and then polymerizing the mixture, and the polymerization can be carried out by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization.

[0050] In a specific example, the aromatic vinyl monomer may be styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be applied individually or in a mixture of two or more. The content of the aromatic vinyl monomer may be about 60 to about 90 weight%, for example, about 65 to about 85 weight%, of the total 100 weight% of the aromatic vinyl-vinyl cyanide copolymer resin. Within this range, the impact resistance, moldability, appearance characteristics, etc. of the thermoplastic resin composition may be excellent.

[0051] In a specific example, examples of the vinyl cyanide monomers include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile. These may be used alone or in a mixture of two or more types. For example, acrylonitrile, methacrylonitrile, etc. may be used. The content of the vinyl cyanide monomer may be about 10 to about 40 weight%, for example, about 15 to about 35 weight%, of the total 100 weight% of the aromatic vinyl-vinyl cyanide copolymer resin. Within this range, the impact resistance, moldability, thermal stability, appearance characteristics, etc. of the thermoplastic resin composition may be excellent.

[0052] In a specific example, the aromatic vinyl-vinyl cyanide copolymer resin may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 50,000 to about 300,000 g / mol, for example, about 60,000 to about 250,000 g / mol. Within this range, the mechanical properties, moldability, etc. of the thermoplastic resin composition may be excellent.

[0053] In a specific example, the aromatic vinyl-vinyl cyanide copolymer resin may be included in an amount of about 105 to about 135 parts by weight, for example, about 110 to about 130 parts by weight, with respect to about 100 parts by weight of the thermoplastic polyurethane resin. If the content of the aromatic vinyl-vinyl cyanide copolymer resin is less than about 105 parts by weight with respect to about 100 parts by weight of the thermoplastic polyurethane resin, there is a risk that the transparency, impact resistance, moldability, etc. of the thermoplastic resin composition will be reduced, and if it exceeds about 135 parts by weight, there is a risk that the transparency, impact resistance, etc. of the thermoplastic resin composition will be reduced.

[0054]

[0055] (C) Glycidyl (meth)acrylate modified aromatic vinyl copolymer resin

[0056] A glycidyl (meth)acrylate modified aromatic vinyl copolymer resin according to one embodiment of the present invention can be applied together with the thermoplastic polyurethane resin and the aromatic vinyl-vinyl cyanide copolymer resin, etc., to improve the chemical resistance, transparency, impact resistance, stiffness, thermal stability, moldability, and balance of physical properties thereof of the thermoplastic resin composition. A glycidyl (meth)acrylate modified aromatic vinyl copolymer resin composed of a methyl methacrylate-derived component, an aromatic vinyl monomer-derived component, a vinyl cyanide monomer-derived component, and a glycidyl (meth)acrylate-derived component may be used.

[0057] In a specific example, the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin is a resin prepared such that unsaturated epoxy groups are present within the aromatic vinyl copolymer resin, and can be prepared by polymerizing a monomer mixture comprising glycidyl (meth)acrylate, methyl methacrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer. The polymerization can be carried out by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization.

[0058] In a specific example, the content of the glycidyl (meth)acrylate-derived component may be about 1 to about 3 weight%, for example, about 1.5 to about 2.5 weight%, of the total 100 weight% of the glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin. Within this range, the transparency, impact resistance, etc., of the thermoplastic resin composition may be excellent.

[0059] In a specific example, the content of the methyl methacrylate-derived component may be about 65 to about 75 weight%, for example, about 68 to about 72 weight%, of the total 100 weight% of the glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin. Within this range, the transparency of the thermoplastic resin composition may be excellent.

[0060] In a specific example, the aromatic vinyl monomer may be styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be applied individually or in a mixture of two or more. The content of the component derived from the aromatic vinyl monomer may be about 15 to about 30 weight%, for example, about 18 to about 26 weight%, of the total 100 weight% of the glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin. Within this range, the transparency and moldability of the thermoplastic resin composition may be excellent.

[0061] In a specific example, examples of the vinyl cyanide monomers include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile. These may be used alone or in a mixture of two or more types. For example, acrylonitrile, methacrylonitrile, etc. may be used. The content of the component derived from the vinyl cyanide monomer may be about 1 to about 10 weight%, for example, about 3 to about 7 weight%, of the total 100 weight% of the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin. Within this range, the transparency and chemical resistance of the thermoplastic resin composition may be excellent.

[0062] In a specific example, the glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 50,000 to about 200,000 g / mol, for example, about 60,000 to about 170,000 g / mol. Within this range, the chemical resistance, impact resistance, etc. of the thermoplastic resin composition may be excellent.

[0063] In a specific example, the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin may be included in an amount of about 20 to about 40 parts by weight, for example, about 27 to about 33 parts by weight, per about 100 parts by weight of the thermoplastic polyurethane resin. If the content of the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin is less than about 20 parts by weight per about 100 parts by weight of the thermoplastic polyurethane resin, there is a risk that the transparency, impact resistance, etc. of the thermoplastic resin composition will decrease, and if it exceeds about 40 parts by weight, there is a risk that the transparency, impact resistance, rigidity, moldability, etc. of the thermoplastic resin composition will decrease.

[0064] In a specific example, the weight ratio of the aromatic vinyl-vinyl cyanide copolymer resin and the glycidyl (meth)acrylate-modified aromatic vinyl copolymer resin may be about 1:0.2 to about 1:0.35, for example, about 1:0.22 to about 1:0.3. Within this range, the transparency, impact resistance, moldability, etc., of the thermoplastic resin composition may be superior.

[0065]

[0066] A thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of such additives include, but are not limited to, impact modifiers, fillers, flame retardants, anti-dripping agents, lubricants, nucleating agents, release agents, pigments, dyes, and mixtures thereof. When using such additives, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, per about 100 parts by weight of the thermoplastic polyurethane resin.

[0067]

[0068] A thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets, which are formed by mixing the above components and melt-extruding them using a conventional twin-screw extruder at about 180 to about 280°C, for example, about 200 to about 260°C.

[0069] In a specific example, the thermoplastic resin composition may not discolor when a 3.2 mm thick tensile specimen made according to ASTM D638 is immersed in a 10 wt% diluted detergent solution for 5 days.

[0070] In a specific example, the thermoplastic resin composition may have a light transmittance of about 84% or more, for example, about 85 to about 90%, of a 1 mm thick specimen measured according to ASTM D1003.

[0071] In a specific example, the thermoplastic resin composition may have a haze of about 5% or less, for example, about 2 to about 4.5%, of a 1 mm thick specimen measured according to ASTM D1003.

[0072] In a specific example, the thermoplastic resin composition may have an unnotched Izod impact strength of about 55 to about 70 kgf·cm / cm, for example, about 60 to about 67 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0073] In a specific example, the thermoplastic resin composition has a tensile strength of about 400 to about 500 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 , for example, about 450 to about 490 kgf / cm² 2 It could be.

[0074] In a specific example, the thermoplastic resin composition has a flexural strength of about 550 to about 700 kgf / cm² of a 6.4 mm thick specimen measured at 2.8 mm / min in accordance with ASTM D790. 2 , for example, about 590 to about 660 kgf / cm² 2 It could be.

[0075] In a specific example, the thermoplastic resin composition has a flexural modulus of about 15,600 to about 17,500 kgf / cm² of a 6.4 mm thick specimen measured at 2.8 mm / min according to ASTM D790. 2 , for example, about 16,000 to about 17,000 kgf / cm² 2 It could be.

[0076] In a specific example, the thermoplastic resin composition may have a Vicat softening temperature (VST) of about 86 to about 90°C, for example, about 87 to about 89°C, measured under a 5 kg load and a 50°C / hr heating condition in accordance with ISO 306.

[0077] In a specific example, the thermoplastic resin composition may have a melt-flow index (MI) of about 6 to about 14 g / 10 min, for example, about 8 to about 12 g / 10 min, measured according to ASTM D1238 at 200°C and a 5 kgf load.

[0078]

[0079] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be produced into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention belongs. The molded article has excellent chemical resistance, transparency, impact resistance, rigidity, thermal stability, moldability, and a balance of these physical properties, and is useful as an exterior material for small home appliances and a chemical-resistant interior material.

[0080]

[0081] The present invention is to be explained more specifically through the following examples, but these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0082]

[0083] Examples

[0084] The specifications of each component used in the examples and comparative examples below are as follows.

[0085] (A) Thermoplastic polyurethane resin

[0086] (A1) A thermoplastic polyurethane resin with a Shore D hardness of 61 and a refractive index of 1.5627 (Manufacturer: Songwon Industrial, Product name: P2160D) was used.

[0087] (A2) A thermoplastic polyurethane resin with a Shore A hardness of 86 and a refractive index of 1.5303 (Manufacturer: Songwon Industrial, Product name: P3285A) was used.

[0088] (A3) A thermoplastic polyurethane resin with a Shore A hardness of 87 and a refractive index of 1.5355 (Manufacturer: Songwon Industrial, Product name: P7185A) was used.

[0089] (A4) A thermoplastic polyurethane resin with a Shore A hardness of 96 and a refractive index of 1.5533 (Manufacturer: Songwon Industrial, Product name: P7195A) was used.

[0090] (A5) A thermoplastic polyurethane resin with a Shore D hardness of 68 and a refractive index of 1.5676 (Manufacturer: Songwon Industrial, Product name: P1168D) was used.

[0091] (A6) A thermoplastic polyurethane resin with a Shore D hardness of 72 and a refractive index of 1.57 (Manufacturer: Songwon Industrial, Product name: P1175D) was used.

[0092] (B) Aromatic vinyl-vinyl cyanide copolymer resin

[0093] A SAN resin (weight-average molecular weight: 150,000 g / mol) polymerized with 75 wt% styrene and 25 wt% acrylonitrile was used.

[0094] (C) Glycidyl (meth)acrylate modified aromatic vinyl copolymer resin

[0095] (C1) Glycidyl methacrylate-methyl methacrylate-styrene-acrylonitrile copolymer (GMA-MSAN, glycidyl methacrylate 2 wt%, methyl methacrylate 68 wt%, styrene 25 wt%, acrylonitrile 5 wt%, weight-average molecular weight: 154,500 g / mol) was used.

[0096] (C2) Glycidyl methacrylate-styrene-acrylonitrile copolymer (GMA-SAN, glycidyl methacrylate 2 wt%, styrene 71 wt%, acrylonitrile 29 wt%, weight-average molecular weight: 154,500 g / mol) was used.

[0097]

[0098] Examples 1 to 5 and Comparative Examples 1 to 10

[0099] Each of the above components was added in the amounts listed in Tables 1, 2, and 3 below, and pellets were prepared by extrusion at approximately 200°C. A twin-screw extruder with L / D=36 and a diameter of 45 mm was used for extrusion. The prepared pellets were dried at approximately 80°C for at least 4 hours, and then specimens were prepared by injection molding in a 10 Oz injection molding machine (molding temperature: approximately 230°C, mold temperature: approximately 60°C). The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1, 2, and 3 below.

[0100]

[0101] Methods for measuring physical properties

[0102] (1) Chemical resistance evaluation: A 3.2 mm thick tensile specimen prepared according to ASTM D638 standards was immersed in a diluted detergent solution (Manufacturer: Reckitt Benckiser, Product name: Dettol, Detergent content: 10 wt% diluted detergent containing 4.8 wt% chloroxylenol) for 5 days, and the discoloration of the specimen was checked visually. (×: No discoloration, ○: Discoloration occurred)

[0103] (2) Light transmittance and haze (unit: %): In accordance with ASTM D1003, the light transmittance (total light transmittance) and haze of a 1 mm thick specimen were measured using a Haze meter NDH 2000 from Nippon Denshoku.

[0104] (3) Unnotched Izod impact strength (unit: kgf·cm / cm): The unnotched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0105] (4) Tensile strength (unit: kgf / cm²) 2 In accordance with ASTM D638, the tensile strength of a 3.2 mm thick specimen was measured under conditions of 5 mm / min.

[0106] (5) Flexural strength (unit: kgf / cm²) 2According to ASTM D790, the flexural strength of a 6.4 mm thick specimen was measured under conditions of 2.8 mm / min.

[0107] (6) Flexural modulus (unit: kgf / cm²) 2 According to ASTM D790, the flexural modulus of a 6.4 mm thick specimen was measured under conditions of 2.8 mm / min.

[0108] (7) Vicat softening temperature (unit: ℃): According to ISO 306, the Vicat softening temperature (VST) was measured under conditions of a 5 kg load and a 50℃ / hr increase in temperature.

[0109] (8) Melt-flow Index (unit: g / 10 min): According to ASTM D1238, the Melt-flow Index (MI) was measured at 200℃ and a 5 kgf load.

[0110]

[0111] Example 1 2345 (A1) (parts by weight) 100 100 100 100 100 (A2) (parts by weight) ----- (A3) (parts by weight) ----- (A4) (parts by weight) ----- (A5) (parts by weight) ----- (A6) (parts by weight) ----- (B) (parts by weight) 110 120 130 120 120 (C1) (parts by weight) 30 30 30 27 33 (C2) (parts by weight) ----- Discoloration × × × × × Light transmittance 85 89 85 85 85 Haze 42.5 4 44 Unnotched Izod Impact Strength 60 60 60 60 Tensile Strength 4 60 47 0 49 0 48 0 450 Flexural Strength 600 610 650 630 590 Flexural Modulus 16,000 16,500 17,000 16,800 16,200 Vicat Softening Temperature 89 88 88 8789 Melt Flow Index 810 12 108

[0112]

[0113] Comparative Example 12345(A1) (parts by weight)-----(A2) (parts by weight)100----(A3) (parts by weight)-100---(A4) (parts by weight)--100--(A5) (parts by weight)---100-(A6) (parts by weight)----100(B) (parts by weight)120120120120120(C1) (parts by weight)3030303030(C2) (parts by weight)-----Discoloration ○○○○○Light transmittance 7070758382Haze 20201767Unnotched Izod Impact Strength 40 40 50 60 60 Tensile Strength 30 40 0 ​​46 0 46 0 470 Flexural Strength 50 55 0 60 0 60 0 610 Flexural Modulus 13,000 14,000 16,000 16,000 16,000 16,500 Vicat Softening Temperature 65 68 83 88 88 Melt Flow Index 20 15 10 88

[0114]

[0115] Comparative Example 678910(A1) (parts by weight) 100 100 100 100 100 (A2) (parts by weight) -----(A3) (parts by weight) -----(A4) (parts by weight) -----(A5) (parts by weight) -----(A6) (parts by weight) -----(B) (parts by weight) 100 140 120 120 120 (C1) (parts by weight) 30 30 17 43 -(C2) (parts by weight) ---- 30 Discoloration × × × × × Light transmittance 85 85 75 75 60 Haze 10 10 17 17 30 Unnotched Izod Impact Strength 50 40 40 50 20 Tensile Strength 46 0 50 0 48 0 45 0 500 Flexural Strength 60 0 65 0 63 0 59 0 650 Flexural Modulus 16,000 17,000 16,800 15,000 17,000 Vicat Softening Temperature 89 88 87 89 88 Melt Flow Index 51 51 15 5

[0116]

[0117] From the above results, it can be seen that the thermoplastic resin composition of the present invention exhibits excellent chemical resistance (discoloration), transparency (light transmittance, haze), impact resistance (unnotched Izod impact strength), stiffness (tensile strength, flexural strength, flexural modulus), thermal stability (Vicat softening temperature), moldability (melt flow index), and the balance of these physical properties.

[0118] On the other hand, in Comparative Example 1, which applies a thermoplastic polyurethane resin (A2) having a hardness range less than the range of the present invention and a refractive index less than the range of the present invention instead of the thermoplastic polyurethane resin of the present invention, it can be seen that chemical resistance, transparency, impact resistance, stiffness, thermal stability, etc. are reduced; in Comparative Example 2, which applies a thermoplastic polyurethane resin (A3) having a hardness range less than the range of the present invention and a refractive index less than the range of the present invention, it can be seen that chemical resistance, transparency, impact resistance, stiffness, thermal stability, etc. are reduced; in Comparative Example 3, which applies a thermoplastic polyurethane resin (A4) having a hardness range less than the range of the present invention and a refractive index less than the range of the present invention, it can be seen that chemical resistance, transparency, impact resistance, etc. are reduced; and in Comparative Example 4, which applies a thermoplastic polyurethane resin (A5) having a hardness range exceeding the range of the present invention and a refractive index exceeding the range of the present invention, chemical resistance, It can be seen that transparency, impact resistance, rigidity, thermal stability, etc. are reduced, and in the case of Comparative Example 5, which uses a thermoplastic polyurethane resin (A6) in which the hardness range exceeds the range of the present invention and the refractive index exceeds the range of the present invention, it can be seen that chemical resistance, transparency, etc. are reduced.

[0119] In addition, in Comparative Example 6, in which a small amount of aromatic vinyl-vinyl cyanide copolymer resin was applied, it can be seen that transparency, impact resistance, and moldability were reduced, and in Comparative Example 7, in which an excessive amount of aromatic vinyl-vinyl cyanide copolymer resin was applied, it can be seen that transparency and impact resistance were reduced. In Comparative Example 8, in which a small amount of glycidyl (meth)acrylate modified aromatic vinyl copolymer resin was applied, it can be seen that transparency, impact resistance, etc. were reduced; in Comparative Example 9, in which an excessive amount of glycidyl (meth)acrylate modified aromatic vinyl copolymer resin was applied, it can be seen that transparency, impact resistance, rigidity, moldability, etc. were reduced; and in Comparative Example 10, in which GMA-SAN (C2) was applied instead of the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin of the present invention, it can be seen that transparency, impact resistance, moldability, etc. were reduced.

[0120]

[0121] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. About 100 parts by weight of a thermoplastic polyurethane resin having a Shore D hardness of about 60 to about 65 and a refractive index of about 1.562 to about 1.565; About 105 to about 135 parts by weight of an aromatic vinyl-vinyl cyanide copolymer resin; and A thermoplastic resin composition characterized by comprising about 20 to about 40 parts by weight of a glycidyl (meth)acrylate modified aromatic vinyl copolymer resin composed of a methyl methacrylate-derived component, an aromatic vinyl monomer-derived component, a vinyl cyanide monomer-derived component, and a glycidyl (meth)acrylate-derived component.

2. A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic polyurethane resin has a weight-average molecular weight of about 100,000 to about 250,000 g / mol.

3. A thermoplastic resin composition according to claim 1 or 2, characterized in that the aromatic vinyl-vinyl cyanide copolymer resin has a weight-average molecular weight of about 50,000 to about 300,000 g / mol.

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin comprises about 1 to about 3 weight% of a glycidyl (meth)acrylate-derived component, about 65 to about 75 weight% of a methyl methacrylate-derived component, about 15 to about 30 weight% of an aromatic vinyl monomer-derived component, and about 1 to about 10 weight% of a vinyl cyanide monomer-derived component.

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin has a weight-average molecular weight of about 50,000 to about 200,000 g / mol.

6. A thermoplastic resin composition characterized in that, in any one of claims 1 to 5, the weight ratio of the aromatic vinyl-vinyl cyanide copolymer resin and the glycidyl (meth)acrylate modified aromatic vinyl copolymer resin is about 1:0.2 to about 1:0.

35.

7. A thermoplastic resin composition according to any one of claims 1 to 6, characterized in that no discoloration occurs when a 3.2 mm thick tensile specimen manufactured according to ASTM D638 is immersed in a diluted detergent solution with a concentration of 10 wt% for 5 days.

8. A thermoplastic resin composition according to any one of claims 1 to 7, characterized in that the thermoplastic resin composition has a light transmittance of about 84% or more of a 1 mm thick specimen measured according to ASTM D1003.

9. A thermoplastic resin composition according to any one of claims 1 to 8, characterized in that the haze of a 1 mm thick specimen measured according to ASTM D1003 is about 5% or less.

10. A thermoplastic resin composition according to any one of claims 1 to 9, characterized in that the unnotched Izod impact strength of a 1 / 8" thick specimen measured according to ASTM D256 is about 55 to about 70 kgf·cm / cm.

11. In any one of claims 1 to 10, the thermoplastic resin composition has a tensile strength of about 400 to about 500 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 A thermoplastic resin composition characterized by being 12. In any one of claims 1 to 11, the thermoplastic resin composition has a flexural strength of about 550 to about 700 kgf / cm² of a 6.4 mm thick specimen measured at 2.8 mm / min in accordance with ASTM D790. 2 And, in accordance with ASTM D790, the flexural modulus of a 6.4 mm thick specimen measured under a condition of 2.8 mm / min is approximately 15,600 to approximately 17,500 kgf / cm 2 A thermoplastic resin composition characterized by being 13. A thermoplastic resin composition according to any one of claims 1 to 12, wherein the thermoplastic resin composition has a Vicat softening temperature (VST) of about 86 to about 90°C as measured under a 5 kg load and a 50°C / hr heating condition in accordance with ISO 306.

14. A thermoplastic resin composition according to any one of claims 1 to 13, wherein the thermoplastic resin composition has a melt-flow index (MI) of about 6 to about 14 g / 10 min measured at 200°C and a 5 kgf load condition in accordance with ASTM D1238.

15. A molded article characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 14.