Thermoplastic resin composition and molded article produced therefrom

Abstract

The thermoplastic resin composition according to the present invention comprises: about 100 parts by weight of a polycarbonate resin; about 20-80 parts by weight of a glass fiber; about 1-15 parts by weight of a recycled polyamide resin derived from marine debris; about 1-10 parts by weight of an epoxy modified olefin-based polymer; about 0.1-1 part by weight of a hindered phenol-based compound; about 0.1-1 part by weight of a phosphite-based compound; and about 0.005-0.1 parts by weight of an organic acid. The thermoplastic resin composition is superior in terms of environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, balance of these properties, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition exhibiting excellent environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, and a balance of these properties, and to a molded article manufactured therefrom.

[0002]

[0003] Polycarbonate resin is an engineering plastic. It boasts excellent impact resistance, heat resistance, weather resistance, and electrical properties, as well as transparency, making it useful for housing electrical and electronic products and interior and exterior materials for other office equipment. Furthermore, it has the ability to enhance various physical properties through the application of various fillers.

[0004] However, fillers such as glass fiber, talc, mica, and wollastonite applied to improve the dimensional stability and rigidity of polycarbonate resin may have differences in physical properties depending on the type, and there is a concern that the appearance characteristics may be deteriorated due to filler protrusion, etc., and when a certain amount is added, the physical properties may actually be deteriorated.

[0005] Furthermore, with the recent passage of marine plastic reduction legislation, particularly in the US and Europe, global companies are increasingly demanding eco-friendly materials. Consequently, products using high levels of recycled raw materials are being developed. For example, there are attempts to blend recycled polyamide resin with polycarbonate resin to improve its environmental friendliness and heat resistance. However, mixing polyamide resin with polycarbonate resin raises concerns about deterioration of its physical properties due to decomposition of the polycarbonate resin.

[0006] Therefore, there is a need to develop a thermoplastic resin composition that has excellent environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, and a balance of these properties without these problems.

[0007] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2019-0071154, etc.

[0008]

[0009] The purpose of the present invention is to provide a thermoplastic resin composition having excellent environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, and a balance of these physical properties.

[0010] Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012]

[0013] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is characterized by comprising: about 100 parts by weight of a polycarbonate resin; about 20 to about 80 parts by weight of glass fiber; about 1 to about 15 parts by weight of a recycled polyamide resin derived from marine waste; about 1 to about 10 parts by weight of an epoxy-modified olefin polymer; about 0.1 to about 1 part by weight of a hindered phenol compound; about 0.1 to about 1 part by weight of a phosphite compound; and about 0.005 to about 0.1 part by weight of an organic acid.

[0014] 2. In the above 1 specific example, the regenerated polyamide resin may have a crystallization temperature (Tc) of about 180 to about 190°C and a melting enthalpy (ΔH) of about 60 to about 70 J / g, measured using a differential scanning calorimeter (DSC) under conditions of a heating rate of 20°C / min and a cooling rate of -10°C / min for 10 to 15 mg of a sample.

[0015] 3. In the above 1 or 2 specific examples, the regenerated polyamide resin may have a content of at least one of titanium (Ti), calcium (Ca), potassium (K), and sodium (Na) of about 10 ppm or more.

[0016] 4. In the above 1 to 3 specific examples, the epoxy-modified olefin polymer may include at least one of a glycidyl (meth)acrylate-modified ethylene-methyl acrylate copolymer, a glycidyl (meth)acrylate-modified polyethylene, and a glycidyl (meth)acrylate-modified ethylene-butyl acrylate copolymer.

[0017] 5. In the above 1 to 4 specific examples, the hindered phenol compound may include at least one of alkyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis(methylene-3-dodecylthiopropionate)methane, 2,6-di-tert-butyl-4-methylphenol, and 2,2'-methylene bis(4-methyl-6-tert-butylphenol).

[0018] 6. In the above 1 to 5 specific examples, the phosphite compound may include at least one of triphenylphosphite, tri(2,4-di-tert-butylphenyl)phosphite, tri(4-methoxyphenyl)phosphite, and bis(2,6-di-tert-butyl-4-methyl-phenyl)pentaerythritol diphosphite.

[0019] 7. In the above 1 to 6 specific examples, the organic acid may include at least one of citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid.

[0020] 8. In the above 1 to 7 specific examples, the weight ratio of the glass fiber and the regenerated polyamide resin may be about 1.5:1 to about 10:1.

[0021] 9. In the above 1 to 8 specific examples, the weight ratio of the regenerated polyamide resin and the epoxy modified olefin polymer may be about 1:0.3 to about 1:1.2.

[0022] 10. In the above 1 to 9 specific examples, the content of the regenerated polyamide resin may be about 2.5 wt% or more among 100 wt% of the total thermoplastic resin composition.

[0023] 11. In the above 1 to 10 specific examples, the thermoplastic resin composition may have a notched Izod impact strength of about 10 to about 30 kgf·cm / cm for a 1 / 8" thick specimen measured according to ASTM D256.

[0024] 12. In the above 1 to 11 specific examples, the thermoplastic resin composition has a tensile strength of about 1,150 to about 2,000 kgf / cm of a 4 mm thick specimen measured under conditions of 5 mm / min according to ISO 527. 2 It could be.

[0025] 13. In the above 1 to 12 specific examples, the thermoplastic resin composition may have a heat distortion temperature (HDT) of about 135 to about 150°C of a 6.4 mm thick specimen measured under conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

[0026] 14. In the above 1 to 13 specific examples, the thermoplastic resin composition is injection-molded 100 times continuously at a temperature of 250 to 320°C using a 150MT hydraulic injection molding machine, a spiral mold (a spiral-shaped mold having a thickness of 1 mm and a width of 1 cm), a pressure of 120 MPa, and a speed of 50 mm / s while maintaining the same cushion amount, and the number of times at which the spiral length of the injection specimen becomes constant may be about 30 or less.

[0027] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a thermoplastic resin composition according to any one of 1 to 14.

[0028]

[0029] The present invention has the effect of providing a thermoplastic resin composition having excellent environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, and a balance of these physical properties, and a molded article formed therefrom.

[0030]

[0031] Hereinafter, the present invention will be described in detail as follows.

[0032] A thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) glass fiber; (C) a regenerated polyamide resin; (D) an epoxy-modified olefin polymer; (E) a hindered phenol compound; (F) a phosphite compound; and (G) an organic acid.

[0033] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0034]

[0035] (A) Polycarbonate resin

[0036] As a polycarbonate resin according to one specific example of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition can be used. For example, an aromatic polycarbonate resin produced by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic diester can be used.

[0037] In specific examples, the diphenols may include, but are not limited to, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, and specifically, 2,2-bis(4-hydroxyphenyl)propane, also called bisphenol-A, can be used.

[0038] In a specific example, the polycarbonate resin may be one having a branched chain, and for example, a branched polycarbonate resin may be used that is prepared by adding about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound, specifically, a compound having a trivalent or higher phenol group, to the total diphenols used in the polymerization.

[0039] In specific examples, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a difunctional carboxylic acid.

[0040] In a specific example, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g / mol, for example, about 15,000 to about 80,000 g / mol. Within this range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), etc.

[0041] In a specific example, the polycarbonate resin may have a melt flow index (MI) of about 5 to about 80 g / 10 min, measured under conditions of 300°C and a load of 1.2 kg, according to ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.

[0042]

[0043] (B) Glass fiber

[0044] According to one specific example of the present invention, glass fibers can be applied to polycarbonate resins together with regenerated polyamide resins, epoxy-modified olefin polymers, hindered phenol compounds, phosphite compounds, organic acids, etc., thereby improving the eco-friendliness, impact resistance, rigidity, heat resistance, long-term heat stability, and balance of these physical properties of a thermoplastic resin composition. Glass fibers used in conventional thermoplastic resin compositions can be used.

[0045] In specific embodiments, the glass fibers may include circular cross-sectional glass fibers, flat-shaped glass fibers, combinations thereof, and the like.

[0046] In a specific example, the circular cross-section glass fiber may be a glass fiber having an average diameter of a circular cross-section measured using an optical microscope of about 5 to about 15 μm, for example, about 6 to about 14 μm. Within this range, the thermoplastic resin composition may have excellent rigidity, impact resistance, etc.

[0047] In a specific example, the flat glass fiber may have an aspect ratio of a cross-section measured by an optical microscope of about 1.5 to about 4, for example, about 2 to about 4, and a short diameter of about 6 to about 10 μm, for example, about 6 to about 9 μm. In this range, the thermoplastic resin composition may have excellent rigidity, impact resistance, etc.

[0048] In a specific example, the glass fibers may have an average length of about 1 to about 5 mm before extrusion, and an average length of about 100 to about 700 μm, for example, about 110 to about 690 μm, after extrusion (processing). Within this range, the thermoplastic resin composition may have excellent impact resistance, rigidity, appearance properties, etc.

[0049] In a specific example, the glass fiber may be surface-treated with an epoxy sizing agent to increase bonding strength with the constituent components. The epoxy sizing agent may include, but is not limited to, epoxy resin, modified epoxy resin, hydrogenated modified epoxy resin, and combinations thereof.

[0050] In a specific example, the glass fiber may be included in an amount of about 20 to about 80 parts by weight, for example, about 25 to about 75 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the glass fiber is less than about 20 parts by weight relative to about 100 parts by weight of the polycarbonate resin, there is a concern that the rigidity, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 80 parts by weight, there is a concern that the impact resistance, long-term thermal stability, etc. of the thermoplastic resin composition may be reduced.

[0051]

[0052] (C) Regenerated polyamide resin

[0053] According to one specific example of the present invention, a regenerated polyamide resin is applied to a polycarbonate resin together with glass fiber, an epoxy-modified olefin polymer, a hindered phenol compound, a phosphite compound, an organic acid, etc., to impart properties to a thermoplastic resin composition and improve impact resistance, rigidity, heat resistance, long-term heat stability, and the balance of these physical properties, and a regenerated polyamide resin derived from marine waste (waste fishing nets, etc.) can be used.

[0054] In specific examples, the recycled polyamide resin may be commercially available, and may include, but is not limited to, polyamide 6 derived from marine inflow waste, polyamide 6.6 derived from marine inflow waste, and combinations thereof.

[0055] In a specific example, the regenerated polyamide resin may have a crystallization temperature (Tc) of about 180 to about 190°C and a melting enthalpy (ΔH) of about 60 to about 70 J / g, measured using a differential scanning calorimeter (DSC) under conditions of a heating rate of 20°C / min and a cooling rate of -10°C / min, of 10 to 15 mg of the sample. Here, the regenerated polyamide resin has a higher crystallization temperature than the virgin polyamide resin.

[0056] In a specific example, the regenerated polyamide resin may have a content of at least one of titanium (Ti), calcium (Ca), potassium (K), and sodium (Na) of about 10 ppm or more, for example, about 10 to about 100 ppm. In the case of a typical virgin polyamide resin, titanium (Ti), calcium (Ca), potassium (K), and / or sodium (Na) is not detected.

[0057] In a specific example, the regenerated polyamide resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g / mol, for example, about 20,000 to about 40,000 g / mol.

[0058] In a specific example, the recycled polyamide resin may be included in an amount of about 1 to about 15 parts by weight, for example, about 5 to about 15 parts by weight, and specifically about 7 to about 13 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the recycled polyamide resin is less than about 1 part by weight relative to about 100 parts by weight of the polycarbonate resin, it is difficult to impart the desired environmental friendliness to the thermoplastic resin composition, and if it exceeds about 20 parts by weight, there is a concern that the impact resistance, rigidity, heat resistance, long-term heat stability, etc. of the thermoplastic resin composition may be reduced.

[0059] In a specific example, the weight ratio of the glass fiber and the regenerated polyamide resin may be from about 1.5:1 to about 10:1, for example from about 1.8:1 to about 9.5:1. Within this range, the thermoplastic resin composition may have better rigidity, heat resistance, etc.

[0060]

[0061] (D) Epoxy modified olefin polymer

[0062] An epoxy-modified olefin polymer according to one specific example of the present invention can be applied to a polycarbonate resin together with glass fiber, a regenerated polyamide resin, a hindered phenol compound, a phosphite compound, an organic acid, etc., to improve the eco-friendliness, impact resistance, rigidity, heat resistance, long-term heat stability, and the balance of these physical properties of a thermoplastic resin composition. An epoxy compound, which is a reactive functional group, can be used by polymerizing an olefin polymer (alkylene-alkyl(meth)acrylate copolymer, olefin homopolymer, olefin copolymer, etc.).

[0063] In specific examples, the epoxy compound may include glycidyl (meth)acrylate, allyl glycidyl ether, 2-methylallyl glycidyl ether, mixtures thereof, and the like.

[0064] In a specific example, the olefin polymer may be an alkylene-alkyl(meth)acrylate copolymer, a homopolymer of an alkylene monomer, and / or a copolymer of an alkylene monomer, and the alkylene monomer may be an alkylene having 2 to 10 carbon atoms, for example, ethylene, propylene, isopropylene, butylene, isobutylene, octene, etc.

[0065] In specific examples, the epoxy-modified olefin polymer may include a glycidyl (meth)acrylate-modified ethylene-methyl acrylate copolymer, a glycidyl (meth)acrylate-modified polyethylene, a glycidyl (meth)acrylate-modified ethylene-butyl acrylate copolymer, a combination thereof, and the like.

[0066] In a specific example, the epoxy-modified olefin polymer may have a melt-flow index of about 1 to about 50 g / 10 min, for example, about 2 to about 25 g / 10 min, measured under conditions of 250°C and a 10 kg load according to ASTM D1238. Within this range, the impact resistance, etc. of the thermoplastic resin composition may be excellent.

[0067] In a specific example, the epoxy-modified olefin-based polymer may be included in an amount of about 1 to about 10 parts by weight, for example, about 3 to about 8 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the epoxy-modified olefin-based polymer is less than about 1 part by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the impact resistance, rigidity, long-term heat stability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 10 parts by weight, there is a concern that the heat resistance, long-term heat stability, etc. of the thermoplastic resin composition may be reduced.

[0068] In a specific example, the weight ratio of the regenerated polyamide resin and the epoxy-modified olefin polymer may be from about 1:0.3 to about 1:1.2, for example from about 1:0.4 to about 1:1.1. In this range, the impact resistance, long-term thermal stability, etc. of the thermoplastic resin composition may be better.

[0069]

[0070] (E) hindered phenolic compounds

[0071] According to one specific example of the present invention, a hindered phenol-based compound can be applied to a polycarbonate resin together with glass fiber, a regenerated polyamide resin, an epoxy-modified olefin-based polymer, a phosphite-based compound, an organic acid, etc., thereby improving the eco-friendliness, impact resistance, rigidity, heat resistance, long-term heat stability, and the balance of these physical properties of a thermoplastic resin composition. A hindered phenol-based stabilizer used in a typical thermoplastic resin composition can be used.

[0072] In specific examples, the hindered phenol compound may include alkyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis(methylene-3-dodecylthiopropionate)methane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylene bis(4-methyl-6-tert-butylphenol), combinations thereof, and the like.

[0073] In a specific example, the hindered phenol-based compound may be included in an amount of about 0.1 to about 1 part by weight, for example, about 0.2 to about 0.9 part by weight, specifically about 0.3 to about 0.8 part by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the hindered phenol-based compound is less than about 0.1 part by weight relative to about 100 parts by weight of the polycarbonate resin, there is a concern that the rigidity, long-term thermal stability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 1 part by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

[0074]

[0075] (F) Phosphite compounds

[0076] A phosphite-based compound according to one specific example of the present invention can be applied to a polycarbonate resin together with glass fiber, a regenerated polyamide resin, an epoxy-modified olefin-based polymer, a hindered phenol-based compound, an organic acid, etc., thereby improving the eco-friendliness, impact resistance, rigidity, heat resistance, long-term heat stability, and the balance of these physical properties of a thermoplastic resin composition. A phosphite-based heat stabilizer used in a typical thermoplastic resin composition can be used.

[0077] In specific examples, the phosphite compound may include triphenylphosphite, tri(2,4-di-tert-butylphenyl)phosphite, tri(4-methoxyphenyl)phosphite, bis(2,6-di-tert-butyl-4-methyl-phenyl)pentaerythritol diphosphite, combinations thereof, and the like.

[0078] In a specific example, the phosphite-based compound may be included in an amount of about 0.1 to about 1 part by weight, for example, about 0.2 to about 0.9 part by weight, specifically about 0.3 to about 0.8 part by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the phosphite-based compound is less than about 0.1 part by weight relative to about 100 parts by weight of the polycarbonate resin, there is a concern that the rigidity, long-term thermal stability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 1 part by weight, there is a concern that the impact resistance, etc. of the thermoplastic resin composition may be reduced.

[0079]

[0080] (G) Organic acid

[0081] According to one specific example of the present invention, an organic acid can be applied to a polycarbonate resin together with glass fiber, a regenerated polyamide resin, an epoxy-modified olefin polymer, a hindered phenol compound, a phosphite compound, etc., thereby improving the eco-friendliness, impact resistance, rigidity, heat resistance, long-term heat stability, and the balance of these physical properties of a thermoplastic resin composition. An organic acid used in a typical thermoplastic resin composition can be used.

[0082] In specific examples, the organic acid may include citric acid, lactic acid, malic acid, tartaric acid, glycolic acid, combinations thereof, and the like.

[0083] In a specific example, the organic acid may be included in an amount of about 0.005 to about 0.1 part by weight, for example, about 0.01 to about 0.08 part by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the organic acid is less than about 0.005 part by weight based on about 100 parts by weight of the polycarbonate resin, there is a concern that the long-term thermal stability of the thermoplastic resin composition may deteriorate, and if it exceeds about 0.1 part by weight, there is a concern that the impact resistance of the thermoplastic resin composition may deteriorate.

[0084] In a specific example, the weight ratio of the regenerated polyamide resin and the organic acid may be from about 1:0.0005 to about 1:0.01, for example from about 1:0.001 to about 1:0.008. Within this range, the processability, impact resistance, etc. of the thermoplastic resin composition may be further improved.

[0085]

[0086] A thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additives include, but are not limited to, antioxidants, flame retardants, anti-drip agents, release agents, nucleating agents, antistatic agents, dyes, pigments, and mixtures thereof. When the additives are used, 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, based on about 100 parts by weight of the polycarbonate resin.

[0087]

[0088] A thermoplastic resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 230 to about 310°C, for example, about 240 to about 290°C, using a conventional twin-screw extruder.

[0089] In a specific example, the content of the regenerated polyamide resin may be about 2.5 wt% or more based on 100 wt% of the total thermoplastic resin composition. Within this range, desirable environmental friendliness can be imparted to the thermoplastic resin composition.

[0090] In a specific example, the thermoplastic resin composition may have a notched Izod impact strength of about 10 to about 30 kgf·cm / cm, for example, about 11 to about 20 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0091] In a specific example, the thermoplastic resin composition has a tensile strength of about 1,150 to about 2,000 kgf / cm when measured under conditions of 5 mm / min according to ASTM D638. 2 , for example, about 1,200 to about 1,900 kgf / cm 2 It could be.

[0092] In a specific example, the thermoplastic resin composition may have a heat deflection temperature (HDT) of 130 to 150°C, for example, about 135 to about 145°C, of ​​a 6.4 mm thick specimen measured under conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

[0093] In a specific example, the thermoplastic resin composition is injection-molded 100 times continuously at a temperature of 250 to 320°C using a 150MT hydraulic injection molding machine, a spiral mold (a spiral-shaped mold having a thickness of 1 mm and a width of 1 cm), a pressure of 120 MPa, and a speed of 50 mm / s while maintaining the same cushion amount, and the number of times at which the spiral length of the injection specimen becomes constant may be about 30 times or less, for example, about 10 to about 20 times.

[0094]

[0095] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured 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 pertains.

[0096] In a specific example, the molded product is excellent in environmental friendliness, impact resistance, rigidity, heat resistance, long-term thermal stability, and balance of these properties, and is therefore useful as an exterior / interior material for electronic products.

[0097]

[0098] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0099]

[0100] Example

[0101] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0102] (A) Polycarbonate resin

[0103] Bisphenol-A polycarbonate resin (manufacturer: Lotte Chemical, weight average molecular weight: approximately 25,000 g / mol) was used.

[0104] (B) Glass fiber

[0105] Glass fiber (Manufacturer: KCC, Product name: CS321-EC10-3) was used.

[0106] (C) Regenerated polyamide resin

[0107] Polyamide derived from waste net (manufacturer: YONGHONG, crystallization temperature (Tc): approximately 190°C) was used.

[0108] (D) Olefin polymer

[0109] (D1) As an epoxy-modified olefin polymer, a glycidyl methacrylate-modified ethylene-methyl acrylate copolymer (EMA-GMA, manufacturer: TOSHIBA, product name: XF42-C2999) was used.

[0110] (D2) Ethylene-methyl acrylate copolymer (EMA, manufacturer: DOW, product name: ELVALOY 1330AC) was used.

[0111] (E) hindered phenolic compounds

[0112] Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Manufacturer: CIBA GEIGY, Product name: IRGANOX 1076) was used.

[0113] (F) Phosphite compounds

[0114] Bis(2,6-di-tert-butyl-4-methyl-phenyl)pentaerythritol diphosphite (Manufacturer: ASAHI DENKA, Product name: ADK STAB PEP-36) was used.

[0115] (G) Organic acid

[0116] Citric acid (manufacturer: Samjeon Chemical) was used.

[0117]

[0118] Examples 1 to 13 and Comparative Examples 1 to 12

[0119] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at about 260°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 44 and a diameter of 45 mm. The manufactured pellets were dried at about 100°C for about 4 hours or more, and then injection-molded using a 6 oz injection molding machine (molding temperature: about 290°C, mold temperature: about 60°C) to produce specimens. The physical properties of the manufactured specimens were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0120]

[0121] Method of measuring physical properties

[0122] (1) Notched Izod impact strength (unit: kgf·cm / cm): The notched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0123] (2) Tensile strength (unit: kgf / cm) 2 ): According to ASTM D638, the tensile strength of a 3.2 mm thick specimen was measured under the condition of 5 mm / min.

[0124] (3) Heat deflection temperature (unit: ℃): According to ASTM D648, the heat deflection temperature (HDT) of a 6.4 mm thick specimen was measured under the conditions of 1.82 MPa and a heating rate of 120℃ / hr.

[0125] (4) Long-term thermal stability evaluation: The temperature of a 150MT hydraulic injection molding machine was set to 250 to 320℃, and a spiral mold (a spiral-shaped mold with a thickness of 1 mm and a width of 1 cm) was used. When injection molding was performed continuously 100 times at a pressure of 120 MPa and a speed of 50 mm / s while maintaining the same cushion amount, the number of times (unit: times) at which the spiral length of the injection specimen became constant was measured. Here, it was determined that the long-term thermal stability was excellent when the number of times was 30 or less.

[0126]

[0127] Example 1234567 (A) (parts by weight) 100 100 100 100 100 100 100 (B) (parts by weight) 25 50 75 25 25 25 25 (C) (parts by weight) 8.38 38 37 138 38 3 (D1) (parts by weight) 6.76 76 76 76 74 8 (D2) (parts by weight) ------- (E) (parts by weight) 0.70 70 70 30 80 70 7 (F) (parts by weight) 0.70 70 70 80 80 70 7 (G) (parts by weight) 0.01 0.05 0.03 0.03 0.03 0.03 0.03 0.03 Notched Izod impact strength (kgf·cm / cm)15151115111511Tensile strength (MPa)1,2001,5002,0001,2001,2001,2001,200Heat deflection temperature (℃)138138141138138138138Long-term thermal stability evaluation (times)15152015152020

[0128]

[0129] Example 8910111213(A) (parts by weight)100100100100100100(B) (parts by weight)252525252525(C) (parts by weight)8.38.38.38.38.38.38.3(D1) (parts by weight)6.76.76.76.76.76.7(D2) (parts by weight)------(E) (parts by weight)0.30.80.70.70.70.7(F) (parts by weight)0.70.70.30.80.70.7(G) (parts by weight)0.050.050.050.050.010.07Notched Izod impact strength (kgf·cm / cm)121212121515Tensile strength (MPa)1,2001,2001,2001,2001,2001,200 Heat distortion temperature (℃)138138138138139139 Long-term thermal stability evaluation (times)151515151515

[0130]

[0131] Comparative Example 123456 (A) (parts by weight) 100 100 100 100 100 100 (B) (parts by weight) 158 525 25 25 25 (C) (parts by weight) 8.38 320 8.38 38.3 (D1) (parts by weight) 6.7 6.7 6.7 6.7 0.5 15- (D2) (parts by weight) ----- 6.7 (E) (parts by weight) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 (F) (parts by weight) 0.7 0.7 0.7 0.7 0.7 0.7 (G) (parts by weight) 0.05 0.05 0.05 0.05 0.05 0.05 Notched Izod Impact Strength (kgf cm / cm) 105 44 108 Tensile Strength (MPa)1,1002,0001,0001,0001,2001,200Heat distortion temperature (℃)137141129135129138Long-term thermal stability evaluation (times)305080604060

[0132]

[0133] Comparative Example 789101112(A) (parts by weight)100100100100100100(B) (parts by weight)252525252525(C) (parts by weight)8.38.38.38.38.38.38.3(D1) (parts by weight)6.76.76.76.76.76.7(D2) (parts by weight)------(E) (parts by weight)0.0120.70.70.70.7(F) (parts by weight)0.70.70.0120.70.7(G) (parts by weight)0.050.050.050.050.0010.2Notched Izod impact strength (kgf·cm / cm)108108154Tensile strength (MPa)1,0001,2001,0001,2001,2001,200 Heat distortion temperature (℃)137137137137138138 Long-term thermal stability evaluation (times)502050204520

[0134]

[0135] From the above results, it can be seen that the thermoplastic resin composition of the present invention is environmentally friendly with a content of recycled material (regenerated polyamide resin) of 2.8 wt% or more, and has excellent impact resistance (notched Izod impact strength), rigidity (tensile strength), heat resistance (heat distortion temperature), long-term thermal stability, and a balance of these physical properties.

[0136] On the other hand, in the case of Comparative Example 1, where a small amount of glass fiber was applied, it can be seen that the rigidity, etc. were reduced, and in the case of Comparative Example 2, where an excessive amount of glass fiber was applied, it can be seen that the impact resistance, long-term heat stability, etc. were reduced, and in the case of Comparative Example 3, where an excessive amount of recycled polyamide resin was applied, it can be seen that the impact resistance, rigidity, heat resistance, long-term heat stability, etc. were reduced. In the case of Comparative Example 4, where a small amount of epoxy-modified olefin-based polymer was applied, it can be seen that the impact resistance, rigidity, long-term heat stability, etc. were reduced, and in the case of Comparative Example 5, where an excessive amount of epoxy-modified olefin-based polymer was applied, it can be seen that the heat resistance, long-term heat stability, etc. were reduced, and in the case of Comparative Example 6, where an ethylene-methyl acrylate copolymer (D2) was applied instead of the epoxy-modified olefin-based polymer of the present invention, it can be seen that the impact resistance, long-term heat stability, etc. were reduced. In the case of Comparative Example 7, where a small amount of a hindered phenol-based compound was applied, it can be seen that rigidity, long-term thermal stability, etc. were reduced. In the case of Comparative Example 9, where an excessive amount of a hindered phenol-based compound was applied, it can be seen that impact resistance, etc. were reduced. In the case of Comparative Example 9, where a small amount of a phosphite-based compound was applied, it can be seen that rigidity, long-term thermal stability, etc. were reduced. In the case of Comparative Example 10, where an excessive amount of a phosphite-based compound was applied, it can be seen that impact resistance, etc. were reduced. In addition, in the case of Comparative Example 11, where a small amount of an organic acid was applied, it can be seen that long-term thermal stability, etc. were reduced. In the case of Comparative Example 12, where an excessive amount of an organic acid was applied, it can be seen that impact resistance, etc. were reduced.

[0137]

[0138] The present invention has been described above, focusing on specific embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of polycarbonate resin; About 20 to about 80 parts by weight of glass fiber; About 1 to about 15 parts by weight of recycled polyamide resin derived from marine waste; About 1 to about 10 parts by weight of an epoxy modified olefin polymer; About 0.1 to about 1 part by weight of a hindered phenolic compound; About 0.1 to about 1 part by weight of a phosphite compound; and A thermoplastic resin composition characterized by comprising about 0.005 to about 0.1 parts by weight of an organic acid.

2. In the first paragraph, the regenerated polyamide resin is a thermoplastic resin composition characterized in that the crystallization temperature (Tc) of a 10 to 15 mg sample, measured using a differential scanning calorimeter (DSC) under conditions of a heating rate of 20°C / min and a cooling rate of -10°C / min, is about 180 to about 190°C, and the melting enthalpy (ΔH) is about 60 to about 70 J / g.

3. A thermoplastic resin composition according to claim 1 or 2, characterized in that the content of at least one of titanium (Ti), calcium (Ca), potassium (K), and sodium (Na) is about 10 ppm or more.

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the epoxy-modified olefin polymer comprises at least one of a glycidyl (meth)acrylate-modified ethylene-methyl acrylate copolymer, a glycidyl (meth)acrylate-modified polyethylene, and a glycidyl (meth)acrylate-modified ethylene-butyl acrylate copolymer.

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the hindered phenol compound comprises at least one of alkyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis(methylene-3-dodecylthiopropionate)methane, 2,6-di-tert-butyl-4-methylphenol, and 2,2'-methylene bis(4-methyl-6-tert-butylphenol).

6. A thermoplastic resin composition according to any one of claims 1 to 5, wherein the phosphite compound comprises at least one of triphenylphosphite, tri(2,4-di-tert-butylphenyl)phosphite, tri(4-methoxyphenyl)phosphite, and bis(2,6-di-tert-butyl-4-methyl-phenyl)pentaerythritol diphosphite.

7. A thermoplastic resin composition according to any one of claims 1 to 6, characterized in that the organic acid comprises at least one of citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid.

8. A thermoplastic resin composition according to any one of claims 1 to 7, characterized in that the weight ratio of the glass fiber and the regenerated polyamide resin is about 1.5:1 to about 10:

1.

9. A thermoplastic resin composition according to any one of claims 1 to 8, characterized in that the weight ratio of the regenerated polyamide resin and the epoxy-modified olefin polymer is about 1:0.3 to about 1:1.

2.

10. A thermoplastic resin composition according to any one of claims 1 to 9, characterized in that the content of the regenerated polyamide resin is about 2.5 wt% or more of 100 wt% of the total thermoplastic resin composition.

11. A thermoplastic resin composition according to any one of claims 1 to 10, characterized in that the thermoplastic resin composition has a notched Izod impact strength of about 10 to about 30 kgf·cm / cm for a 1 / 8" thick specimen measured according to ASTM D256.

12. In any one of claims 1 to 11, the thermoplastic resin composition has a tensile strength of about 1,150 to about 2,000 kgf / cm of a 4 mm thick specimen measured under conditions of 5 mm / min according to ISO 527. 2 A thermoplastic resin composition characterized by:

13. A thermoplastic resin composition according to any one of claims 1 to 12, characterized in that the thermoplastic resin composition has a heat distortion temperature (HDT) of about 135 to about 150°C of a 6.4 mm thick specimen measured under conditions of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

14. A thermoplastic resin composition according to any one of claims 1 to 13, wherein the thermoplastic resin composition is injection-molded 100 times continuously while setting the temperature of a 150MT hydraulic injection molding machine to 250 to 320°C and maintaining the same cushion amount at a pressure of 120 MPa and a speed of 50 mm / s, characterized in that the number of times the spiral length of the injection specimen becomes constant is about 30 or less.

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