Environmentally friendly transparent thermoplastic resin composition and molded article formed therefrom

Abstract

The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin comprising about 15 wt% to 35 wt% of a rubber-modified vinyl-based graft copolymer obtained by grafting an alkyl (meth) acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide monomer onto a rubbery polymer, and about 65 wt% to 85 wt% of an aromatic vinyl-based copolymer resin obtained by polymerizing an alkyl (meth) acrylate, an aromatic vinyl-based monomer, and a vinyl cyanide monomer; and about 1-13 parts by weight of a poly (meth) acrylic acid alkyl ester resin, in which the (meth) acrylic acid alkyl ester in the aromatic vinyl-based copolymer resin includes about 30 wt% or more of a regenerated material based on total 100 wt% thereof, the haze of a sample having a thickness of 1 mm measured according to ASTM D1003 is about 3.5% or less, and the light transmittance is about 85% or more. The thermoplastic resin composition has excellent environmental friendliness, transparency, impact resistance and rigidity, a balance of physical properties thereof, and the like.

Description

Technical Field

[0001] The present invention relates to an environmentally friendly transparent thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having good properties in terms of environmental friendliness, transparency, impact resistance, rigidity, and the balance of properties therebetween, and a molded article formed therefrom. Background Art

[0002] Tempered glass products for use as external materials for electrical and electronic products have weak impact strength, high specific gravity (which makes it difficult to achieve weight reduction of products), high manufacturing costs due to difficult processing and handling, and concerns about breakage. To overcome these drawbacks, transparent resins are applied in place of tempered glass products. In addition, in response to environmental issues such as carbon emission reduction, it is necessary to develop recycled plastics using recycled materials.

[0003] However, when recycled materials recovered from waste plastics are used as raw materials for thermoplastic resins, there are problems such as deterioration of transparency, mechanical properties, etc.

[0004] Therefore, it is necessary to develop a thermoplastic resin composition having good properties in terms of environmental friendliness, transparency, impact resistance, rigidity, and the balance of properties therebetween.

[0005] The background art of the present invention is disclosed in Korean Patent Laid-Open Publication No. 10-2012-0072159, etc. Summary of the Invention

[0006]

Technical Problem

[0007] An object of the present invention is to provide a thermoplastic resin composition having good properties in terms of environmental friendliness, transparency, impact resistance, rigidity, and the balance of properties therebetween.

[0008] Another object of the present invention is to provide a molded article formed from a recycled thermoplastic resin composition.

[0009] The above and other objects of the present invention can be achieved by the embodiments of the present invention described below.

[0010]

Technical Solution

[0011] 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 rubber-modified aromatic vinyl copolymer resin, the rubber-modified aromatic vinyl copolymer resin comprising about 15 wt% to about 35 wt% of a rubber-modified vinyl graft copolymer prepared by graft polymerizing an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer onto a rubber polymer, and about 65 wt% to about 85 wt% of an aromatic vinyl copolymer resin prepared by polymerizing an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer; and about 1 part by weight to about 13 parts by weight of a poly((meth)acrylate) resin, wherein the alkyl (meth)acrylate of the aromatic vinyl copolymer resin comprises about 30% or more of recycled material based on 100 wt% of the alkyl (meth)acrylate, and wherein the thermoplastic resin composition has a haze of about 3.5% or less and a light transmittance of about 85% or more measured on a 1 mm thick sample in accordance with ASTM D1003.

[0012] 2. In Embodiment 1, the rubber-modified vinyl graft copolymer may comprise about 10 wt% to about 70 wt% of a rubber polymer and about 30 wt% to about 90 wt% of a monomer mixture comprising an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer.

[0013] 3. In Embodiment 1 or Embodiment 2, the monomer mixture may comprise about 55 wt% to about 85 wt% of an alkyl (meth)acrylate, about 10 wt% to about 40 wt% of an aromatic vinyl monomer, and about 1 wt% to about 30 wt% of a vinyl cyanide monomer.

[0014] 4. In Embodiments 1 to 3, the aromatic vinyl copolymer resin may be a copolymer of a monomer mixture comprising about 55 wt% to about 85 wt% of an alkyl (meth)acrylate, about 10 wt% to about 40 wt% of an aromatic vinyl monomer, and about 1 wt% to about 30 wt% of a vinyl cyanide monomer.

[0015] 5. In Embodiments 1 to 4, the aromatic vinyl copolymer resin may have a weight average molecular weight of about 50,000 g / mol to about 200,000 g / mol.

[0016] 6. In Embodiments 1 to 5, the poly((meth)acrylate) resin may comprise at least one of poly((meth)acrylate methyl), poly((meth)acrylate ethyl), poly((meth)acrylate propyl), and a copolymer of (meth)acrylate methyl and a C2 to C 10 alkyl (meth)acrylate.

[0017] 7. In Embodiments 1 to 6, the poly((meth)acrylic acid alkyl ester) resin may have a weight average molecular weight of from about 50,000 g / mol to about 130,000 g / mol.

[0018] 8. In Embodiments 1 to 7, the thermoplastic resin composition may have a notched Izod impact strength of from about 9 kgf·cm / cm to about 30 kgf·cm / cm measured on a 1 / 8" thick sample in accordance with ASTM D256.

[0019] 9. In Embodiments 1 to 8, the thermoplastic resin composition may have a tensile strength of from about 370 kgf / cm 2 to about 500 kgf / cm 2 measured on a 3.2 mm thick sample at 5 mm / min in accordance with ASTM D638.

[0020] 10. In Embodiments 1 to 9, the thermoplastic resin composition may have a flexural strength of from about 550 kgf / cm 2 to about 700 kgf / cm 2 measured on a 6.4 mm thick sample at 2.8 mm / min in accordance with ASTM D790.

[0021] 11. In Embodiments 1 to 10, the thermoplastic resin composition may have a flexural modulus of from about 15,000 kgf / cm 2 to about 25,000 kgf / cm 2 measured on a 6.4 mm thick sample at 2.8 mm / min in accordance with ASTM D790.

[0022] 12. Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition according to any one of Embodiments 1 to 11.

[0023]

Beneficial Effects

[0024] The present invention provides a thermoplastic resin composition having good properties in terms of environmental friendliness, transparency, impact resistance, rigidity, and the balance of properties therebetween, and a molded article produced therefrom. Detailed Embodiments

[0025] Hereinafter, embodiments of the present invention will be described in detail.

[0026] The thermoplastic resin composition according to the present invention comprises: (A) a rubber-modified aromatic vinyl copolymer resin; and (B) a poly((meth)acrylic acid alkyl ester) resin.

[0027] When representing a specific numerical range as used herein, "a to b" is defined as "≥a and ≤b".

[0028] (A) Rubber-modified aromatic vinyl copolymer resin

[0029] The rubber-modified aromatic vinyl copolymer resin according to the present invention comprises (A1) a rubber-modified vinyl graft copolymer and (A2) an aromatic vinyl copolymer resin.

[0030] (A1) Rubber-modified vinyl graft copolymer

[0031] The rubber-modified vinyl graft copolymer according to an embodiment of the present invention is used to improve the transparency, impact resistance, fluidity, etc. of a thermoplastic resin composition, and can be prepared by graft-polymerizing an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer onto a rubber polymer. For example, the rubber-modified vinyl graft copolymer can be prepared by graft-polymerizing a monomer mixture comprising an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer onto a rubber polymer, wherein the monomer mixture may further comprise monomers for imparting processability and heat resistance as needed. Here, the polymerization can be carried out by any suitable polymerization method known in the art (such as bulk polymerization, emulsion polymerization, suspension polymerization, etc.).

[0032] In some embodiments, the rubber polymer may include, for example, a diene rubber (such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), etc.), a saturated rubber obtained by hydrogenating a diene rubber, an isoprene rubber, an acrylic rubber (such as poly(butyl acrylate), etc.), an ethylene-propylene-diene terpolymer (EPDM), etc. These can be used alone or as a mixture thereof. For example, the rubber polymer may include a diene rubber, specifically, butadiene rubber.

[0033] In some embodiments, the rubber polymer (rubber particles) may have an average particle diameter of about 0.1 μm to about 0.5 μm, for example, about 0.2 μm to about 0.4 μm. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, etc. without deteriorating transparency. Here, the average (z-average) particle diameter of the rubber polymer (rubber particles) can be measured by a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a sieve to remove condensates generated during the polymerization of the rubber polymer, and then a mixed solution of 0.5 g of the latex and 30 ml of distilled water is placed in a 1000 ml flask, and then the flask is filled with distilled water to prepare a sample. Then, 10 ml of the sample is transferred to a quartz cell, and then the average particle diameter of the rubber polymer is measured using a light scattering particle analyzer (Nano ZS, Malvern Limited).

[0034] In some embodiments, based on 100 wt% of the rubber-modified vinyl graft copolymer, the rubber polymer may be present in an amount of about 10 wt% to about 70 wt%, such as about 15 wt% to about 65 wt%, and based on 100 wt% of the rubber-modified vinyl graft copolymer, the monomer mixture (including (meth)acrylate, aromatic vinyl monomer, and vinyl cyanide monomer) may be present in an amount of about 30 wt% to about 90 wt%, such as about 35 wt% to about 85 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, rigidity, transparency, etc.

[0035] In some embodiments, the (meth)acrylate may be graft copolymerized onto the rubber polymer or copolymerized with an aromatic vinyl monomer, etc., and may include C1 to C10 alkyl (meth)acrylates, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc., specifically methyl (meth)acrylate, etc. Based on 100 wt% of the monomer mixture, the (meth)acrylate may be present in an amount of about 55 wt% to about 85 wt%, such as about 60 wt% to about 80 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, rigidity, etc.

[0036] In some embodiments, the aromatic vinyl monomer may be graft copolymerized with the rubber polymer and may include, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be used alone or as a mixture thereof. Based on 100 wt% of the monomer mixture, the aromatic vinyl monomer may be present in an amount of about 10 wt% to about 40 wt%, such as about 15 wt% to about 35 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, rigidity, transparency, etc.

[0037] In some embodiments, the vinyl cyanide monomer may be copolymerized with the aromatic vinyl monomer and may include, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc., but is not limited thereto. These may be used alone or as a mixture thereof. For example, acrylonitrile, methacrylonitrile, etc. may be used. Based on 100 wt% of the monomer mixture, the vinyl cyanide monomer may be present in an amount of about 1 wt% to about 30 wt%, such as about 5 wt% to about 25 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, rigidity, transparency, etc.

[0038] In some embodiments, monomers for imparting processability and heat resistance may include, for example, (meth)acrylic acid, maleic anhydride, N-substituted maleimide, etc. Based on 100 wt% of the monomer mixture, the monomers for imparting processability and heat resistance may be present in an amount of 15 wt% or less, for example, about 0.1 wt% to about 10 wt%. Within this range, the monomers for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deteriorating other properties.

[0039] In some embodiments, the rubber-modified vinyl graft copolymer may include a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS), etc. Here, g-MABS may be composed of polybutadiene (PBD) as a rubber polymer (core) and a methyl methacrylate-acrylonitrile-styrene copolymer shell grafted onto the core, where the shell includes an inner shell composed of an acrylonitrile-styrene resin and an outer shell composed of poly(methyl methacrylate), but is not limited thereto.

[0040] In some embodiments, based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the rubber-modified vinyl graft copolymer may be present in an amount of about 15 wt% to about 35 wt%, for example, about 20 wt% to about 30 wt%. If the content of the rubber-modified vinyl graft copolymer is less than about 15 wt% based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the thermoplastic resin composition may suffer from deterioration in impact resistance, etc., and if the content of the rubber-modified vinyl graft copolymer exceeds about 35 wt%, the thermoplastic resin composition may suffer from deterioration in rigidity, transparency, etc.

[0041] (A2) Aromatic vinyl copolymer resin

[0042] The aromatic vinyl copolymer resin according to an embodiment of the present invention is used to improve the environmental friendliness, transparency, impact resistance, rigidity, etc. of the thermoplastic resin composition, and may be a copolymer of a monomer mixture including an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer. Based on 100 wt% of the alkyl (meth)acrylate, the alkyl (meth)acrylate includes about 30 wt% of recycled materials (recycled alkyl (meth)acrylate). For example, the aromatic vinyl copolymer resin can be prepared by typical polymerization of the monomer mixture. Additionally, the monomer mixture may further include monomers for imparting processability and heat resistance as needed.

[0043] In some embodiments, the alkyl (meth)acrylate may be graft copolymerized onto the rubber polymer or copolymerized with an aromatic vinyl monomer, etc., and may include C1 to C 10Alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc., specifically methyl (meth)acrylate, etc. Based on 100 wt% of the monomer mixture, the alkyl (meth)acrylate may be present in an amount of about 55 wt% to about 85 wt%, for example about 60 wt% to about 80 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, fluidity, etc.

[0044] In some embodiments, based on 100 wt% of the alkyl (meth)acrylate, the recycled material (recycled alkyl (meth)acrylate) may be present in an amount of about 30 wt% or more, for example about 35 wt% or more. If the content of the recycled material in the alkyl (meth)acrylate is less than about 30 wt%, the thermoplastic resin composition does not meet the market's demand for environmental friendliness.

[0045] In some embodiments, the aromatic vinyl monomer may be graft copolymerized with the rubber polymer and may include, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be used alone or as a mixture thereof. Based on 100 wt% of the monomer mixture, the aromatic vinyl monomer may be present in an amount of about 10 wt% to about 40 wt%, for example about 15 wt% to about 35 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, fluidity, etc.

[0046] In some embodiments, the vinyl cyanide monomer may be copolymerized with the aromatic vinyl monomer and may include, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc., but is not limited thereto. These may be used alone or as a mixture thereof. For example, acrylonitrile, methacrylonitrile, etc. may be used. Based on 100 wt% of the monomer mixture, the vinyl cyanide monomer may be present in an amount of about 1 wt% to about 30 wt%, for example about 5 wt% to about 25 wt%. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, fluidity, etc.

[0047] In some embodiments, monomers for imparting processability and heat resistance may include, for example, (meth)acrylic acid, maleic anhydride, N-substituted maleimide, etc., but are not limited thereto. Based on 100 wt% of the monomer mixture, the monomers for imparting processability and heat resistance may be present in an amount of 15 wt% or less, for example, about 0.1 wt% to about 10 wt%. Within this range, the monomers for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without degrading other properties.

[0048] In some embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight of about 50,000 g / mol to about 200,000 g / mol, for example, about 100,000 g / mol to about 180,000 g / mol, measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, processability, etc.

[0049] In some embodiments, based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the aromatic vinyl copolymer resin may be present in an amount of about 65 wt% to about 85 wt%, for example, about 70 wt% to about 80 wt%. If the content of the aromatic vinyl copolymer resin is less than about 65 wt% based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the thermoplastic resin composition may suffer from deterioration in rigidity, transparency, fluidity, etc., and if the content of the aromatic vinyl copolymer resin exceeds about 85 wt%, the thermoplastic resin composition may suffer from deterioration in impact resistance, etc.

[0050] In some embodiments, the rubber-modified aromatic vinyl copolymer resin may include a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin), which is in the form of a mixture of a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and a methyl methacrylate-styrene-acrylonitrile copolymer resin (MSAN), but is not limited thereto. Here, the MABS resin has a structure in which g-MABS is dispersed in MSAN.

[0051] (B) Poly((meth)acrylic acid alkyl ester) resin

[0052] The poly((meth)acrylic acid alkyl ester) resin according to an embodiment of the present invention is used to improve the transparency, impact resistance, rigidity, etc. of the thermoplastic resin composition together with the rubber-modified aromatic vinyl copolymer resin, and may be a poly((meth)acrylic acid alkyl ester) resin used in a typical transparent thermoplastic resin composition.

[0053] In some embodiments, the poly((meth)acrylic acid alkyl ester) resin may be a polymer prepared from monomers including at least one type of C1 to C 10 alkyl (meth)acrylate by a polymerization method known to those skilled in the art, such as poly((meth)acrylic acid methyl ester), poly((meth)acrylic acid ethyl ester), poly((meth)acrylic acid propyl ester), a copolymer of (meth)acrylic acid methyl ester and C2 to C 10 alkyl (meth)acrylate, etc., specifically poly(methyl methacrylate) (PMMA).

[0054] In some embodiments, the poly((meth)acrylic acid alkyl ester) resin may have a weight-average molecular weight of about 50,000 g / mol to about 130,000 g / mol, such as about 60,000 g / mol to about 120,000 g / mol, measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, rigidity, etc.

[0055] In some embodiments, the poly((meth)acrylic acid alkyl ester) resin may have a glass transition temperature of about 90 °C to about 110 °C, such as about 95 °C to about 110 °C. Within this range, the thermoplastic resin composition can exhibit good properties in terms of heat resistance, compatibility, transparency, etc.

[0056] In some embodiments, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the poly((meth)acrylic acid alkyl ester) resin may be present in an amount of about 1 part by weight to about 13 parts by weight, such as about 2 parts by weight to about 10 parts by weight, specifically about 3 parts by weight to about 7 parts by weight. If the content of the poly((meth)acrylic acid alkyl ester) resin is less than about 1 part by weight relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the thermoplastic resin composition may suffer from deterioration in transparency, etc., and if the content of the poly((meth)acrylic acid alkyl ester) resin exceeds about 13 parts by weight, the thermoplastic resin composition may suffer from deterioration in transparency, impact resistance, etc.

[0057] The thermoplastic resin composition according to an embodiment of the present invention may further include additives, such as flame retardants, fillers, antioxidants, lubricants, mold release agents, nucleating agents, stabilizers, colorants, and combinations thereof, within a range that does not impair the effects of the present invention. Relative to 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the additives may be present in an amount of about 10 parts by weight or less, such as about 0.01 part by weight to about 10 parts by weight.

[0058] The thermoplastic resin composition according to one embodiment of the present invention can be prepared in the form of pellets by mixing the above components and then melt-extruding the mixture using a typical twin-screw extruder at about 200°C to about 280°C, for example, about 210°C to about 250°C.

[0059] In some embodiments, the thermoplastic resin composition can have a haze of about 3.5% or less, for example, about 1% to about 3%, and a light transmittance of about 85% or more, for example, about 88% to about 95%, measured on a 1 mm thick sample according to ASTM D1003.

[0060] In some embodiments, the thermoplastic resin composition can have a notched Izod impact strength of about 9 kgf·cm / cm to about 30 kgf·cm / cm, for example, about 10 kgf·cm / cm to about 25 kgf·cm / cm, measured on a 1 / 8" thick sample according to ASTM D256.

[0061] In some embodiments, the thermoplastic resin composition can have a tensile strength of about 370 kgf / cm 2 to about 500 kgf / cm 2 for example, about 380 kgf / cm 2 to about 500 kgf / cm 2 measured on a 3.2 mm thick sample at 5 mm / min according to ASTM D638.

[0062] In some embodiments, the thermoplastic resin composition can have a flexural strength of about 550 kgf / cm 2 to about 700 kgf / cm 2 for example, about 570 kgf / cm 2 to about 700 kgf / cm 2 measured on a 6.4 mm thick sample at 2.8 mm / min according to ASTM D790.

[0063] In some embodiments, the thermoplastic resin composition can have a flexural modulus of about 15,000 kgf / cm 2 to about 25,000 kgf / cm 2 for example, about 18,000 kgf / cm 2 to about 25,000 kgf / cm 2 measured on a 6.4 mm thick sample at 2.8 mm / min according to ASTM D790.

[0064] The molded article according to the present invention is formed from the thermoplastic resin composition as described above. The thermoplastic resin composition can be prepared in the form of pellets and can be produced into various molded articles (products) by various molding methods such as injection molding, extrusion molding, vacuum molding, casting, etc. These molding methods are well-known to those of ordinary skill in the art. The molded article has good characteristics in terms of environmental friendliness, transparency, impact resistance, rigidity, balance therebetween, etc., and can thus be advantageously used as internal / external materials for electrical / electronic products, such as the outer casings of household appliances, etc.

[0065]

Mode of Invention

[0066] Next, the present invention will be described in more detail with reference to some embodiments. It should be understood that these embodiments are provided for illustration only and should not be construed as limiting the present invention in any way.

[0067] Examples

[0068] Details of the components used in the examples and comparative examples are as follows.

[0069] (A) Rubber-modified aromatic vinyl copolymer resin

[0070] (A1) Rubber-modified vinyl graft copolymer

[0071] A core-shell graft copolymer (g-MABS) prepared by graft copolymerizing 40 wt% of styrene, acrylonitrile, and methyl methacrylate (styrene / acrylonitrile / methyl methacrylate: 20 wt% / 10 wt% / 70 wt%) onto 60 wt% of butadiene rubber particles having an average particle size of 0.28 μm was used.

[0072] (A2) Aromatic vinyl copolymer resin

[0073] (A2-1) A resin (weight average molecular weight: about 140,000 g / mol) prepared by polymerization of 73 wt% of recycled methyl methacrylate (recycled material, manufacturer: Veolia Environment S.A., product name: methyl methacrylate), 18 wt% of styrene, and 9 wt% of acrylonitrile was used.

[0074] (A2-2) A resin (weight average molecular weight: about 140,000 g / mol) prepared by polymerization of 73 wt% of methyl methacrylate (non-recycled, manufacturer: Mitsubishi Chemical Corporation, product name: methyl methacrylate), 18 wt% of styrene, and 9 wt% of acrylonitrile was used.

[0075] (B) Poly((meth)acrylic acid alkyl ester) resin

[0076] (B1) Using poly(methyl methacrylate) resin (non-recycled PMMA, manufacturer: Asahi Kasei Corporation, product name: DELPET TM 720V, weight-average molecular weight: about 80,000 g / mol).

[0077] (B2) Using recycled poly(methyl methacrylate) resin (recycled PMMA, manufacturer: OSTECH Co., Ltd., product name: PMMA-02CP, weight-average molecular weight: about 80,000 g / mol).

[0078] Examples 1 to 6 and Comparative Examples 1 to 6

[0079] Mix the foregoing components in the amounts listed in Table 1, and then melt-extrude using a twin-screw extruder (L / D: 35, diameter: 45 mm) at about 230 °C and about 250 rpm to prepare a thermoplastic resin composition in the form of pellets. Dry the prepared pellets at about 80 °C for about 4 hours or longer, and then perform injection molding using an injection molding machine (molding temperature: about 230 °C, mold temperature: about 60 °C) to prepare samples. Evaluate the following properties of the prepared samples, and the results are shown in Table 1.

[0080] Characteristic evaluation

[0081] (1) Haze and light transmittance (unit: %): Measure the haze and light transmittance (total light transmittance) on a 1-mm-thick sample using a haze meter NDH 2000 (Nippon Denshoku Co., Ltd.) in accordance with ASTM D1003.

[0082] (2) Notched Izod impact strength (unit: kgf·cm / cm): Measure the notched Izod impact strength on a 1 / 8"-thick sample in accordance with ASTM D256.

[0083] (3) Tensile strength (unit: kgf / cm 2 ): Measure the tensile strength on a 3.2-mm-thick sample at 5 mm / min in accordance with ASTM D638.

[0084] (4) Flexural strength (unit: kgf / cm 2 ): Measure the flexural strength on a 6.4-mm-thick sample at 2.8 mm / min in accordance with ASTM D790.

[0085] (5) Flexural modulus (unit: kgf / cm 2 ): Measure the flexural modulus on a 6.4-mm-thick sample at 2.8 mm / min in accordance with ASTM D790.

[0086] Table 1

[0087]

[0088]

[0089] *Parts by weight: parts by weight relative to 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin (A)

[0090] Table 2

[0091]

[0092] *Parts by weight: parts by weight relative to 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin (A)

[0093] As can be seen from the above results, the thermoplastic resin composition according to the present invention is prepared using an aromatic vinyl copolymer resin containing about 30 wt% of recycled (meth)acrylic acid alkyl ester based on 100 wt% of the total (meth)acrylic acid alkyl ester, thereby ensuring good properties in terms of environmental friendliness, transparency (haze, light transmittance), impact resistance (notched Izod impact strength), rigidity (tensile strength, flexural strength, flexural modulus), and the balance of properties therebetween.

[0094] Conversely, it can be seen that the thermoplastic resin composition (Comparative Example 1) prepared using an insufficient amount of the rubber-modified vinyl graft copolymer (A1) and an excessive amount of the aromatic vinyl copolymer resin (A2) shows deterioration in impact resistance and the like; the thermoplastic resin composition (Comparative Example 2) prepared using an excessive amount of the rubber-modified vinyl graft copolymer (A1) and an insufficient amount of the aromatic vinyl copolymer resin (A2) shows deterioration in rigidity and the like; and the thermoplastic resin composition of Comparative Example 3 prepared using only non-recycled MSAN (A2-2) as the aromatic vinyl copolymer resin (A2) shows deterioration in environmental friendliness due to the absence of recycled materials. In addition, it can be seen that the thermoplastic resin composition of Comparative Example 4 prepared using an insufficient amount of the poly((meth)acrylic acid alkyl ester) resin (B) shows deterioration in transparency and the like; the thermoplastic resin composition of Comparative Example 5 prepared using an excessive amount of the poly((meth)acrylic acid alkyl ester) resin (B) shows deterioration in transparency, impact resistance, and the like; and the thermoplastic resin composition of Comparative Example 6 prepared using recycled PMMA (A2) prepared by polymerization of recycled (meth)acrylic acid alkyl ester instead of the poly((meth)acrylic acid alkyl ester) resin shows deterioration in transparency and the like.

[0095] Although some embodiments have been described herein, those skilled in the art will understand that various modifications, changes, and variations can be made without departing from the spirit and scope of the present invention. Therefore, it should be understood that these embodiments are provided for illustrative purposes only and are not to be construed in any way as limiting the present invention. The scope of the present invention is to be defined by the appended claims rather than by the foregoing description, and the claims and their equivalents are intended to cover such modifications and the like that fall within the scope of the present invention.

Claims

1. A thermoplastic resin composition, comprising: About 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin, which comprises about 15 wt% to about 35 wt% of a rubber-modified vinyl graft copolymer prepared by graft-polymerizing an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer onto a rubber polymer, and about 65 wt% to about 85 wt% of an aromatic vinyl copolymer resin prepared by polymerizing an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer; and About 1 part by weight to about 13 parts by weight of a poly((meth)acrylate) resin, wherein the alkyl (meth)acrylate of the aromatic vinyl copolymer resin comprises about 30% or more of recycled materials based on 100 wt% of the alkyl (meth)acrylate, and wherein the thermoplastic resin composition has a haze of about 3.5% or less and a light transmittance of about 85% or more measured on a 1 mm thick sample in accordance with ASTM D1003.

2. The thermoplastic resin composition according to claim 1, wherein the rubber-modified vinyl graft copolymer comprises about 10 wt% to about 70 wt% of the rubber polymer and about 30 wt% to about 90 wt% of a monomer mixture comprising the alkyl (meth)acrylate, the aromatic vinyl monomer, and the vinyl cyanide monomer.

3. The thermoplastic resin composition according to claim 2, wherein the monomer mixture comprises about 55 wt% to about 85 wt% of the alkyl (meth)acrylate, about 10 wt% to about 40 wt% of the aromatic vinyl monomer, and about 1 wt% to about 30 wt% of the vinyl cyanide monomer.

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the aromatic vinyl copolymer resin is a copolymer of a monomer mixture comprising about 55 wt% to about 85 wt% of the alkyl (meth)acrylate, about 10 wt% to about 40 wt% of the aromatic vinyl monomer, and about 1 wt% to about 30 wt% of the vinyl cyanide monomer.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the aromatic vinyl copolymer resin has a weight average molecular weight of about 50,000 g / mol to about 200,000 g / mol.

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the poly((meth)acrylic acid alkyl ester) resin comprises at least one of poly((meth)acrylic acid methyl ester), poly((meth)acrylic acid ethyl ester), poly((meth)acrylic acid propyl ester), and a copolymer of (meth)acrylic acid methyl ester and C2 to C 10 alkyl (meth)acrylate.

7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the poly((meth)acrylate) resin has a weight average molecular weight of about 50,000 g / mol to about 130,000 g / mol.

8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the thermoplastic resin composition has a notched Izod impact strength of about 9 kgf·cm / cm to about 30 kgf·cm / cm measured on a 1 / 8" thick sample in accordance with ASTM D256.

9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition has a tensile strength of about 370 kgf / cm 2 to about 500 kgf / cm 2 measured at 5 mm / min in accordance with ASTM D638 on a 3.2 mm thick sample.

10. The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic resin composition has a flexural strength of about 550 kgf / cm 2 to about 700 kgf / cm 2 measured in accordance with ASTM D790 at 2.8 mm / min on a 6.4 mm thick sample.

11. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the thermoplastic resin composition has a flexural modulus of about 15,000 kgf / cm 2 to about 25,000 kgf / cm 2 measured in accordance with ASTM D790 at 2.8 mm / min on a 6.4 mm thick sample.

12. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 11.

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