Thermoplastic resin compositions and molded articles made therefrom

Abstract

The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of polyester resin; about 5 to 30 parts by weight of polycarbonate resin; about 50 to 150 parts by weight of flat glass fiber; about 2 to 10 parts by weight of epoxy-modified olefin copolymer; and about 2 to 10 parts by weight of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, wherein the weight ratio of the epoxy-modified olefin copolymer to the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer is about 1:0.5 to 1:2. The thermoplastic resin composition exhibits excellent metal adhesion, impact resistance, rigidity, and a balance of thermal stability and physical properties.

Description

Technical Field

[0001] This invention relates to thermoplastic resin compositions and molding articles thereof. More specifically, this invention relates to thermoplastic resin compositions exhibiting good properties in terms of metal adhesion, impact resistance, rigidity, retention of thermal stability, and a balance therein, and molding articles thereof. Background Technology

[0002] As engineered plastics, polyester resins, as well as blends of polyester and polycarbonate resins, exhibit useful properties and are used in a variety of fields, including internal and external materials for electrical / electronic products. However, polyester resins suffer from problems such as low crystallization rate, low mechanical strength, and low impact strength.

[0003] Therefore, various attempts have been made to improve the mechanical properties (including impact resistance and rigidity) of polyester resins by adding additives (such as inorganic fillers). For example, polybutylene terephthalate (PBT) resin reinforced with inorganic fillers (such as glass fiber) is used in automotive components or mobile phone housings. However, these materials offer limited improvements in impact resistance, rigidity, and thermal stability, and lead to deterioration in properties such as metal adhesion.

[0004] Therefore, thermoplastic resin compositions with good properties in terms of metal adhesion, impact resistance, rigidity, maintaining thermal stability, and the balance between them are needed.

[0005] The background technology of this invention is disclosed in Korean Patent Registration No. 10-0709878, etc. Summary of the Invention

[0006] Technical issues

[0007] One aspect of the present invention is to provide a thermoplastic resin composition that exhibits good properties in terms of metal adhesion, impact resistance, rigidity, thermal stability, and a balance therebetween.

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

[0009] The above and other aspects of the present invention can be realized by means of the 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 polyester resin; about 5 parts by weight to about 30 parts by weight of a polycarbonate resin; about 50 parts by weight to about 150 parts by weight of a flat glass fiber; about 2 parts by weight to about 10 parts by weight of an epoxy-modified olefin copolymer; and about 2 parts by weight to about 10 parts by weight of a maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, wherein the epoxy-modified olefin copolymer and the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer are present in a weight ratio of about 1:0.5 to about 1:2.

[0012] 2. In embodiment 1, the polyester resin may include at least one of polybutylene terephthalate, polyethylene terephthalate, and dimethyl cyclohexane terephthalate.

[0013] 3. In embodiment 1 or 2, the flat glass fiber may have a rectangular cross-section with curved corners, the aspect ratio (length of the long side / length of the short side in the cross-section) is about 1.5 to about 10, and the length of the short side in the cross-section is about 2 μm to about 10 μm.

[0014] 4. In embodiments 1 to 3, the epoxy-modified olefin copolymer may include at least one of (meth)glycidyl acrylate modified ethylene-butyl acrylate copolymer, (meth)glycidyl acrylate modified ethylene-methyl acrylate copolymer, and (meth)glycidyl acrylate modified ethylene-ethyl acrylate copolymer.

[0015] 5. In embodiments 1 to 4, when measured against an aluminum sample according to ISO 19095, the thermoplastic resin composition may have a metal bonding strength of about 30 MPa to about 50 MPa.

[0016] 6. In embodiments 1 to 5, the thermoplastic resin composition may have a dart drop height of about 65 cm to about 100 cm, at which a 500 g dart is dropped onto a 2 mm thick sample according to the DuPont drop test method, and cracks are generated on the sample; and when measured on a 1 / 8” thick sample according to ASTM D256, the thermoplastic resin composition may have a notched cantilever beam impact strength of about 10 kgf·cm / cm to about 25 kgf·cm / cm.

[0017] 7. In embodiments 1 to 6, when measured at 2.8 mm / min on a 1 / 4" thick sample according to ASTM D790, the thermoplastic resin composition can have approximately 90,000 kgf / cm². 2 Approximately 140,000 kgf / cm 2 Flexural modulus.

[0018] 8. In embodiments 1 to 7, the thermoplastic resin composition may have a dart drop height of about 40 cm to about 70 cm. After placing a 2 mm thick injection-molded sample inside the cylinder of an injection molding machine at 280°C for 2 minutes, a 500 g dart is dropped onto the sample at this dart drop height according to the DuPont drop test method, resulting in cracks in the sample.

[0019] 9. Another aspect of the present invention relates to a molded article. The molded article may be formed from a thermoplastic resin composition according to any one of embodiments 1 to 8.

[0020] 10. Another aspect of the present invention relates to composite materials. The composite material includes a plastic component produced from the molding article according to embodiment 9; and a metal component adjacent to the plastic component.

[0021] 11. In embodiment 10, the metal component may include at least one of aluminum, titanium, iron and zinc.

[0022] 12. In embodiment 10 or 11, the metal component may include aluminum, and when measured against the metal component according to ISO 19095, the plastic component may have a metal bond strength of about 30 MPa to about 50 MPa; the plastic component may have a dart drop height of about 65 cm to about 100 cm, at which a 500 g dart is dropped onto a 2 mm thick plastic component according to the DuPont drop test method, causing cracks to form on the sample; when measured against ASTM D256 on a 1 / 8" thick sample, the plastic component may have a notched cantilever beam impact strength of about 10 kgf·cm / cm to about 25 kgf·cm / cm; when measured against ASTM D790 on a 1 / 4" thick sample at 2.8 mm / min, the metal component may have a strength of about 90,000 kgf / cm. 2 Approximately 140,000 kgf / cm 2 The flexural modulus; and the plastic component may have a dart drop height of about 40 cm to about 70 cm. After placing a 2 mm thick injection-molded sample (plastic component) inside the cylinder of an injection molding machine at 280°C for 2 minutes, a 500 g dart is dropped onto the sample at this dart drop height according to the DuPont drop test method, and cracks are generated on the sample.

[0023] Beneficial effects

[0024] The present invention provides thermoplastic resin compositions with good properties in terms of metal adhesion, impact resistance, rigidity, thermal stability and the balance between them, and molded articles formed therefrom. Detailed Implementation

[0025] The embodiments of the present invention will be described in detail below.

[0026] The thermoplastic resin composition according to the present invention comprises: (A) polyester resin; (B) polycarbonate resin; (C) flat glass fiber; (D) epoxy-modified olefin copolymer; and (E) maleic anhydride-modified ethylene-propylene-diene monomer terpolymer.

[0027] As used in this article, in order to indicate a specific numerical range, the expression "a to b" means "≥a and ≤b".

[0028] (A) Polyester resin

[0029] According to the present invention, the polyester resin may be selected from any polyester resin used in typical thermoplastic resin compositions. For example, the polyester resin may be obtained by polycondensation of a dicarboxylic acid component and a diol component, wherein the dicarboxylic acid component may include: aromatic dicarboxylic acids, such as terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; and aromatic dicarboxylic acid esters, such as dimethyl terephthalate (DMT), dimethyl isophthalate, 1,2-naphthalenedicarboxylic acid, etc. Dimethyl dicarboxylate, 1,5-naphthalenedicarboxylate, 1,7-naphthalenedicarboxylate, 1,8-naphthalenedicarboxylate, 2,3-naphthalenedicarboxylate, 2,6-naphthalenedicarboxylate, and 2,7-naphthalenedicarboxylate, etc., and the diol component may include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and cycloenediol.

[0030] In some embodiments, the polyester resin may include at least one selected from polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene terephthalate (PTT), and polycyclohexanedimethyl terephthalate (PCT). Preferably, the polyester resin includes at least one selected from polybutylene terephthalate, polyethylene terephthalate, and polycyclohexanedimethyl terephthalate.

[0031] In some embodiments, the polyester resin may have an intrinsic viscosity [η] of about 0.5 dl / g to about 1.5 dl / g, for example, about 0.7 dl / g to about 1.4 dl / g, when measured according to ASTM D2857. Within this range, the thermoplastic resin composition may exhibit good mechanical properties, etc.

[0032] (B) Polycarbonate resin

[0033] According to the present invention, polycarbonate resins are used to improve the impact resistance and appearance characteristics of thermoplastic resin compositions, and may include any polycarbonate resin used in typical thermoplastic resin compositions. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting biphenol (an aromatic diol compound) with a precursor (such as phosgene, haloformate, or carbonate diester).

[0034] In some embodiments, biphenol may include, for example, 4,4'-diol, 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, and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, but is not limited thereto. For example, biphenol can be 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, specifically 2,2-bis(4-hydroxyphenyl)propane, which is also known as bisphenol A.

[0035] In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a polycarbonate resin prepared by adding a trifunctional or higher-functional polyfunctional compound, specifically a trivalent or higher-valent phenolic compound, in an amount of about 0.05 mol% to about 2 mol% based on the total moles of biphenyl used in the polymerization.

[0036] In some embodiments, the polycarbonate resin may be a homopolymer polycarbonate resin, a copolymer polycarbonate resin, or a blend thereof. Alternatively, the polycarbonate resin may be partially or completely replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor (e.g., a difunctional carboxylic acid).

[0037] In some embodiments, the polycarbonate resin may have a weight-average molecular weight (Mw) of about 20,000 g / mol to about 50,000 g / mol, for example, about 25,000 g / mol to about 40,000 g / mol, when measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition may have good flowability (processing properties).

[0038] In some embodiments, the amount of polycarbonate resin present relative to about 100 parts by weight of polyester resin may be from about 5 parts by weight to about 30 parts by weight, for example, from about 10 parts by weight to about 15 parts by weight. If the content of polycarbonate resin is less than about 5 parts by weight relative to about 100 parts by weight of polyester resin, the resin composition may suffer from deterioration in metal adhesion, impact resistance, and thermal stability, etc., and if the content of polycarbonate resin exceeds about 30 parts by weight, the resin composition may suffer from deterioration in metal adhesion, impact resistance, and thermal stability, etc.

[0039] (C) Flat glass fiber

[0040] According to the present invention, flat glass fibers, together with epoxy-modified olefin copolymers and maleic anhydride-modified ethylene-propylene-diene monomer terpolymers, are used to improve the rigidity, impact resistance and metal adhesion of thermoplastic resin compositions comprising polyester resins and polycarbonate resins.

[0041] In some embodiments, the flat glass fibers may have a rectangular cross-section, a rectangular cross-section with curved corners, or an elliptical cross-section, and may have a cross-sectional aspect ratio (long side length / short side length in the cross-section) of about 1.5 to about 10, a short side length of about 2 μm to about 10 μm, and a pre-processed length of about 2 mm to about 20 mm. Within this range, the thermoplastic resin composition may have good properties in terms of rigidity and processability.

[0042] In some embodiments, the flat glass fibers can be surface-treated with typical surface treatment agents. Surface treatment agents may include, but are not limited to, silane compounds, urethane compounds, and epoxy compounds.

[0043] In some embodiments, the amount of flat glass fibers present relative to about 100 parts by weight of polyester resin may be from about 50 parts by weight to about 150 parts by weight, for example, from about 70 parts by weight to about 100 parts by weight. If the content of flat glass fibers is less than about 50 parts by weight relative to about 100 parts by weight of polyester resin, the resin composition may suffer from deterioration in rigidity and elasticity (warping), etc., and if the content of flat glass fibers exceeds about 150 parts by weight, the resin composition may suffer from deterioration in metal adhesion, impact resistance, thermal stability, and appearance characteristics, etc.

[0044] (D) Epoxy-modified olefin copolymers

[0045] According to the present invention, an epoxy-modified olefin copolymer, together with flat glass fibers and a maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, is used to improve the metal adhesion, impact resistance, rigidity, and thermal stability of thermoplastic resin compositions comprising polyester resins and polycarbonate resins, and can be a reactive olefin copolymer prepared by adding an epoxy compound as a reactive functional group to the modified olefin copolymer for use as an olefin copolymer.

[0046] In some embodiments, the epoxy compound may include glycidyl (meth)acrylate, allyl glycidyl ether, 2-methyl-allyl glycidyl ether, and mixtures thereof.

[0047] In some embodiments, epoxy-modified olefin copolymers can be prepared by copolymerizing an epoxy compound with an olefin copolymer, which is obtained by copolymerizing an alkylene monomer and a (meth)acrylate alkyl ester monomer. The alkylene monomer can be C2 to C3. 10 Alkylenes, such as ethylene, propylene, isopropylene, butene, isobutylene, octene, and combinations thereof. Alkyl (meth)acrylate monomers may be C1 to C8 alkyl (meth)acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and combinations thereof.

[0048] In some embodiments, the epoxy-modified olefin copolymer may include glycidyl acrylate-modified ethylene-methyl acrylate copolymer, glycidyl acrylate-modified ethylene-ethyl acrylate copolymer, glycidyl acrylate-modified ethylene-butyl acrylate copolymer, and combinations thereof.

[0049] In some embodiments, when measured at 190°C under a load of 2.16 kg according to ASTM D1238, the epoxy-modified olefin copolymer may have a melt flow index of about 1 g / 10 min to about 50 g / 10 min, for example, about 2 g / 10 min to about 25 g / 10. Within this range, the thermoplastic resin composition may exhibit good impact resistance.

[0050] In some embodiments, the amount of epoxy-modified olefin copolymer present relative to about 100 parts by weight of polyester resin may be from about 2 parts by weight to about 10 parts by weight, for example, from about 3 parts by weight to about 6 parts by weight. If the content of epoxy-modified olefin copolymer is less than about 2 parts by weight relative to about 100 parts by weight of polyester resin, the thermoplastic resin composition may suffer from deterioration in metal adhesion and rigidity, etc., and if the content of epoxy-modified olefin copolymer exceeds about 10 parts by weight, the thermoplastic resin composition may suffer from deterioration in metal adhesion and the like.

[0051] In some embodiments, the flat glass fiber (C) and the epoxy-modified olefin copolymer (D) may be present in a weight ratio (C:D) of about 1:0.02 to about 1:0.1, for example, about 1:0.03 to about 1:0.08. Within this range, the thermoplastic resin composition may exhibit further improved properties in terms of metal adhesion and retention of thermal stability.

[0052] (E) Maleic anhydride modified ethylene-propylene-diene monomer terpolymer

[0053] According to the present invention, maleic anhydride-modified ethylene-propylene-diene monomer terpolymers, together with flat glass fibers and epoxy-modified olefin copolymers, are used to improve the metal adhesion, impact resistance, rigidity, and thermal stability of thermoplastic resin compositions comprising polyester resins and polycarbonate resins, and can be obtained by graft polymerization of maleic anhydride (MAH) with ethylene-propylene-diene monomer terpolymer (EPDM) rubber. For example, maleic anhydride-grafted ethylene-propylene-diene monomer terpolymers can be prepared by reactive extrusion using a twin-screw extruder, wherein a peroxide is added to the ethylene-propylene-diene monomer terpolymer to break ethylene bonds and generate free radicals, thereby allowing maleic anhydride to be introduced into the ethylene bonds.

[0054] In some embodiments, when measured at 230°C under a 2.16 kg load according to ASTM D1238, the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer may have a melt flow index of about 1 g / 10 min to about 10 g / 10 min, for example, about 2 g / 10 min to about 5 g / 10 min.

[0055] In some embodiments, the amount of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer present relative to about 100 parts by weight of polyester resin may be from about 2 parts by weight to about 10 parts by weight, for example, from about 3 parts by weight to about 8 parts by weight. If the content of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer is less than about 2 parts by weight relative to about 100 parts by weight of polyester resin, the resin composition may suffer from deterioration in impact resistance and thermal stability, etc., and if the content of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer exceeds about 10 parts by weight, the resin composition may suffer from deterioration in metal adhesion, etc.

[0056] In some embodiments, the epoxy-modified olefin copolymer (D) and the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer (E) may be present in a weight ratio (D:E) of about 1:0.5 to about 1:2, for example, about 1:0.5 to about 1:1.8. If the weight ratio (D:E) is less than about 1:0.5, the resin composition may suffer from deterioration in metal adhesion, impact resistance, and thermal stability, etc., and if the weight ratio (D:E) exceeds about 1:2, the resin composition may suffer from deterioration in metal adhesion, etc.

[0057] In some embodiments, the thermoplastic resin composition may further include additives used in typical thermoplastic resin compositions. Examples of additives may include, but are not limited to, impact modifiers, flame retardants, antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. The amount of additive present relative to about 100 parts by weight of polyester resin may be from about 0.001 parts by weight to about 40 parts by weight, for example, from about 0.1 parts by weight to about 10 parts by weight.

[0058] In some embodiments, the thermoplastic resin composition can be prepared into spheres by mixing the aforementioned components and then melt-extruding it using a typical twin-screw extruder at about 240°C to about 300°C, for example, at about 250°C to about 290°C.

[0059] In some embodiments, when measured against an aluminum sample according to ISO 19095, the thermoplastic resin composition may have a metal bond strength of about 30 MPa to about 50 MPa, for example, about 35 MPa to about 40 MPa.

[0060] In some embodiments, the thermoplastic resin composition may have a dart drop height of about 65 cm to about 100 cm, for example, about 70 cm to about 99 cm, at which a 500 g dart is dropped onto a 2 mm thick sample according to the DuPont drop test method, causing cracks to form on the sample.

[0061] In some embodiments, when measured on a 1 / 8" thick sample according to ASTM D256, the thermoplastic resin composition may have a notched cantilever beam impact strength of about 10 kgf·cm / cm to about 25 kgf·cm / cm, for example, about 12 kgf·cm / cm to about 20 kgf·cm / cm.

[0062] In some embodiments, when measured at 2.8 mm / min on a 1 / 4" thick sample according to ASTM D790, the thermoplastic resin composition can have approximately 90,000 kgf / cm². 2 Approximately 140,000 kgf / cm 2 For example, approximately 95,000 kgf / cm³ 2 Approximately 135,000 kgf / cm 2 Flexural modulus.

[0063] In some embodiments, the thermoplastic resin composition may have a drop height of about 40 cm to about 70 cm, for example, about 40 cm to about 60 cm, at which point a dart height of about 40 cm to about 60 cm is dropped onto the sample after a 2 mm thick injection-molded sample has been placed inside the cylinder of an injection molding machine at 280°C for 2 minutes, and a 500 g dart is dropped onto the sample at this drop height in accordance with the DuPont drop test method, resulting in cracks in the sample.

[0064] The molded articles according to the invention are produced from the thermoplastic resin compositions described above. The thermoplastic resin compositions can be prepared in the form of small spheres. The prepared spheres can be produced into various molded articles (molded products) by various molding methods (e.g., injection molding, extrusion molding, vacuum molding, and casting). These molding methods are well known to those skilled in the art. The molded articles exhibit good properties in terms of metal adhesion, impact resistance, rigidity, maintenance of thermal stability, and the balance between these properties, and are therefore advantageously suited for use as internal / external materials in electrical / electronic products and internal / external materials in automobiles, etc.

[0065] The compositional materials according to the invention may include plastic components produced by molding; and metal components adjacent to the plastic components.

[0066] In some embodiments, the plastic component can be directly adjacent to the metal component without an adhesive inserted between them. For example, the plastic component can be formed to be directly adjacent to the metal component by molding the plastic component onto the metal component (which is surface-treated by an electrochemical method) using injection molding or the like.

[0067] In some embodiments, the metal component may include at least one of aluminum, titanium, iron, and zinc.

[0068] In some embodiments, the metal component comprises aluminum, and when measured against the metal component according to ISO 19095, the plastic component may have a metal bond strength of about 30 MPa to about 50 MPa, for example, about 35 MPa to about 40 MPa; the plastic component may have a dart drop height of about 65 cm to about 100 cm, for example, about 70 cm to about 99 cm, at which a 500 g dart is dropped onto a 2 mm thick plastic component according to the DuPont drop test method, causing cracks to form on the sample; when measured against ASTM D256 on a 1 / 8" thick sample, the plastic component may have a notched cantilever beam impact strength of about 10 kgf·cm / cm to about 25 kgf·cm / cm, for example, about 12 kgf·cm / cm to about 20 kgf·cm / cm; when measured against ASTM D790 on a 1 / 4" thick sample at 2.8 mm / min, the plastic component may have about 90,000 kgf / cm 2 Approximately 140,000 kgf / cm 2 For example, approximately 95,000 kgf / cm³ 2 Approximately 135,000 kgf / cm 2 The flexural modulus; and the plastic component may have a drop height of about 40 cm to about 70 cm, for example, about 40 cm to about 60 cm, at which point a dart is dropped on the sample at this drop height, according to the DuPont drop test method, after the 2 mm thick injection-molded sample is placed inside the cylinder of the injection molding machine at 280°C for 2 minutes, cracks are generated on the sample.

[0069] Inventive Method

[0070] The invention will now be described in more detail with reference to some embodiments. It should be understood that these embodiments are provided for illustrative purposes only and are in no way intended to limit the invention.

[0071] Example

[0072] Details of the components used in the examples and comparative examples are as follows.

[0073] (A) Polyester resin

[0074] Polybutylene terephthalate (PBT) resin with an intrinsic viscosity [η] of about 1.3 dl / g (manufacturer: Shinkong Co., Ltd., product name: Shinite K006) was used.

[0075] (B) Polycarbonate resin

[0076] Bisphenol A polycarbonate resin with a weight-average molecular weight of approximately 25,000 g / mol (manufacturer: Rakuten Chemical Co., Ltd.) was used.

[0077] (C) Flat glass fiber

[0078] Flat glass fiber with a short side length of about 7 μm, a cross-sectional aspect ratio of about 4, and a pre-processed length of about 3 mm (manufacturer: Nittobo Co., Ltd., product: CSG 3PA-820).

[0079] (D) Olefin copolymers

[0080] Ethylene-methyl acrylate copolymer modified with glycidyl methacrylate (manufacturer: Sumitomo Chemical Co., Ltd., product: Igetabond BF-7M).

[0081] (E) Maleic anhydride modified ethylene-propylene-diene monomer terpolymer

[0082] (E1) Using maleic anhydride modified ethylene-propylene-diene monomer terpolymer (manufacturer: ExxonMobilCo.,Ltd., product name: Exxelor VA 1803).

[0083] (E2) Use maleic anhydride modified ethylene-butene copolymer (manufacturer: Mitsui Chemicals Co., Ltd., product name: Tafmer MH7020).

[0084] Examples 1 to 9 and Comparative Examples 1 to 11

[0085] The above components were mixed in the amounts listed in Tables 1 to 4 and extruded at 260°C to prepare a thermoplastic resin composition in the form of microspheres. Extrusion was performed using a twin-screw extruder (L / D = 44, Φ: 45 mm), and the prepared microspheres were dried at 100°C for 4 hours or longer, and then injection molded in a 6-ounce injection molding machine (molding temperature: 270°C, mold temperature: 120°C) to prepare samples. The properties of the prepared samples were evaluated using the methods described below, and the results are shown in Tables 1 to 4.

[0086] Characteristic Measurement

[0087] (1) Metal-to-metal bond strength (unit: MPa): A sample was prepared by bonding an aluminum sample to a thermoplastic resin composition sample by embedding the resin composition into a mold, wherein the metal sample was placed inside the mold, and the bond strength was measured according to ISO 19095. Here, the metal sample was subjected to TRI surface treatment (Geo Nation Co., Ltd.) to promote adhesion to the sample. The metal sample and the thermoplastic resin composition sample had dimensions of 1.2 cm × 4 cm × 0.3 cm, and the bond strength was measured with the two samples bonded to each other through a bonding area with a cross-section of 1.2 cm × 0.3 cm.

[0088] (2) Thin sheet impact strength (unit: cm): The drop height of the dart is measured. At this drop height, when a 500g dart is dropped onto a 2mm thick plastic component according to the DuPont drop test method, cracks are generated on the sample.

[0089] (3) Notched cantilever beam impact resistance (unit: kgf·cm / cm): The notched cantilever beam impact strength was measured on a 1 / 8" thick sample according to ASTM D256.

[0090] (4) Retained sheet impact strength (unit: cm): After placing a small ball of thermoplastic resin composition inside the cylinder of an injection molding machine at 280°C for 2 min, a 2 mm thick sample was prepared from the small ball, and the retained thermal stability was evaluated by measuring the drop height of the dart. At this drop height, a 500 g dart was used according to the DuPont drop method, and cracks were generated on the sample.

[0091] (5) Elastic modulus (unit: kgf / cm) 2 ): The elastic modulus was measured on a 1 / 4" thick sample at a speed of 2.8 mm / min according to ASTM D790.

[0092] Table 1

[0093]

[0094] Table 2

[0095]

[0096]

[0097] Table 3

[0098]

[0099] Table 4

[0100]

[0101]

[0102] The results show that the thermoplastic resin composition according to the present invention has good properties in terms of metal adhesion, impact resistance, rigidity, thermal stability, and the balance between them.

[0103] Conversely, it can be seen that the resin composition of Comparative Example 1, which includes insufficient polycarbonate resin, suffers from deterioration in metal adhesion and impact resistance (sheet impact strength); the resin composition of Comparative Example 2, which includes excessive polycarbonate resin, suffers from deterioration in metal adhesion, impact resistance (sheet impact strength), and thermal stability; the resin composition of Comparative Example 3, which includes insufficient flat glass fiber, suffers from deterioration in rigidity; and the resin composition of Comparative Example 4, which includes excessive flat glass fiber, suffers from deterioration in metal adhesion, impact resistance (sheet impact strength, notched cantilever beam impact strength), and thermal stability. As can be seen, the resin composition of Comparative Example 5, which includes an insufficient amount of epoxy-modified olefin copolymer, suffers from deterioration in metal adhesion and rigidity; the resin composition of Comparative Example 6, which includes an excessive amount of epoxy-modified olefin copolymer, suffers from deterioration in metal adhesion; the resin composition of Comparative Example 7, which includes an insufficient amount of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, suffers from deterioration in impact resistance (sheet impact strength) and thermal stability; the resin composition of Comparative Example 8, which includes an excessive amount of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, suffers from deterioration in metal adhesion; and the resin composition of Comparative Example 9, which includes maleic anhydride-modified ethylene-butene copolymer (E2) instead of the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer according to the present invention, suffers from deterioration in metal adhesion, impact resistance (sheet impact strength), and thermal stability.

[0104] Furthermore, it can be seen that even the epoxy-modified olefin copolymer and the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, the thermoplastic resin composition (Comparative Example 10) with a weight ratio (D:E) of less than about 1:0.5 (weight ratio of 1:0.4) suffers from deterioration in metal adhesion, impact resistance (sheet impact strength), and thermal stability; and the thermoplastic resin composition (Comparative Example 11) with a weight ratio (D:E) greater than about 1:2 (weight ratio of 1:2.5) suffers from deterioration in metal adhesion, etc.

[0105] Although the invention has been described with reference to some exemplary embodiments, those skilled in the art will understand that these embodiments are given by way of illustration only, and various modifications, variations, and changes can be made without departing from the spirit and scope of the invention. Therefore, the embodiments should not be construed as limiting the technical spirit of the invention, but rather as illustrative of it. The scope of the invention should be interpreted according to the appended claims to cover all modifications or variations derived from the appended claims and their equivalents.

Claims

1. A thermoplastic resin composition comprising: 100 parts by weight of polyester resin; 5 to 30 parts by weight of bisphenol A polycarbonate resin; 50 to 150 parts by weight of flat glass fiber; 2 to 10 parts by weight of epoxy-modified olefin copolymers; and 2 to 10 parts by weight of maleic anhydride-modified ethylene-propylene-diene monomer terpolymer, The epoxy-modified olefin copolymer and the maleic anhydride-modified ethylene-propylene-diene monomer terpolymer are present in a weight ratio of 1:0.5 to 1:

2. The polyester resin includes at least one of polybutylene terephthalate, polyethylene terephthalate, and dimethyl cyclohexane terephthalate. The epoxy-modified olefin copolymers include at least one of glycidyl acrylate-modified ethylene-methyl acrylate copolymers, glycidyl acrylate-modified ethylene-ethyl acrylate copolymers, and glycidyl acrylate-modified ethylene-butyl acrylate copolymers.

2. The thermoplastic resin composition according to claim 1, wherein the flat glass fiber has a rectangular cross-section with curved corners, the aspect ratio of the cross-section is 1.5 to 10, and the length of the short side of the cross-section is 2 μm to 10 μm.

3. The thermoplastic resin composition according to claim 1 or 2, wherein, When measured against aluminum samples according to ISO 19095, the thermoplastic resin composition has a metal bond strength of 30 MPa to 50 MPa.

4. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition has a dart drop height of 65 cm to 100 cm, at which a 500 g dart is dropped onto a 2 mm thick sample according to the DuPont drop test method, and cracks are generated on the sample; and when measured on a 1 / 8" thick sample according to ASTM D256, the thermoplastic resin composition has a notched cantilever beam impact strength of 10 kgf·cm / cm to 25 kgf·cm / cm.

5. The thermoplastic resin composition according to claim 1 or 2, wherein, When measured at 2.8 mm / min on a 1 / 4" thick sample according to ASTM D790, the thermoplastic resin composition has a strength of 90,000 kgf / cm². 2 Up to 140,000 kgf / cm 2 Flexural modulus.

6. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition has a dart drop height of 40 cm to 70 cm, and after placing a 2 mm thick injection-molded sample inside the cylinder of an injection molding machine at 280°C for 2 minutes, a 500 g dart is dropped onto the sample at the dart drop height according to the DuPont drop test method, resulting in cracks in the sample.

7. A molded article formed from a thermoplastic resin composition according to any one of claims 1 to 6.

8. A composite material, comprising: Plastic components produced from the molding article according to claim 7; and Metal components adjacent to the plastic component.

9. The composite material according to claim 8, wherein the metal component comprises at least one selected from aluminum, titanium, iron, and zinc.

10. The composite material according to claim 8 or 9, wherein the metal component comprises aluminum, and the plastic component has a metal bond strength of 30 MPa to 50 MPa when measured for the metal component according to ISO 19095; the plastic component has a dart drop height of 65 cm to 100 cm, at which point a 500 g dart is dropped onto a 2 mm thick plastic component according to the DuPont drop test method, causing cracks to form on the 2 mm thick plastic component; the plastic component has a notched cantilever beam impact strength of 10 kgf·cm / cm to 25 kgf·cm / cm when measured on a 1 / 8" thick sample according to ASTM D256; and the plastic component has a notched cantilever beam impact strength of 90,000 kgf / cm when measured on a 1 / 4" thick sample at 2.8 mm / min according to ASTM D790. 2 Up to 140,000 kgf / cm 2 The flexural modulus; and the plastic component has a dart drop height of 40cm to 70cm. After placing a 2mm thick injection-molded sample inside the cylinder of an injection molding machine at 280°C for 2 minutes, a 500g dart is dropped onto the sample at the dart drop height according to the DuPont drop test method, resulting in cracks in the sample.

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