Thermoplastic resin composition and article produced therefrom

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a polybutylene terephthalate; about 10 to about 40 parts by weight of a polycarbonate resin; about 50 to about 150 parts by weight of glass fibers; about 1 to about 15 parts by weight of glycidyl methacrylate-modified polyolefin; and about 0.1 to about 3 parts by weight of nigrosine, wherein the weight ratio of the glycidyl methacrylate-modified polyolefin and the nigrosine is about 1:0.05 to about 1:0.6. The thermoplastic resin composition is excellent in terms of metal adhesiveness, rigidity, injection moldability, and a balance among these properties.

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 having excellent metal bonding properties, rigidity, injection moldability, and a balance of these properties, and a molded article manufactured therefrom.

[0002]

[0003] As engineering plastics, polyester resins, blends of polyester resins, and polycarbonate resins each exhibit useful properties and are used in a variety of fields, including interior and exterior materials for electrical and electronic products. However, polyester resins have a rapid crystallization rate, which reduces their injection moldability under harsh conditions, such as thin-film molding.

[0004] To address this, numerous attempts have been made to improve mechanical properties, such as rigidity, by mixing additives like inorganic fillers into polyester resins. For example, polybutylene terephthalate (PBT) materials reinforced with inorganic fillers like glass fiber are used in applications such as mobile and automotive components. However, these materials also have problems, such as reduced metal bonding and injection moldability, when formed into thin films.

[0005] Therefore, there is a need to develop a thermoplastic resin composition with excellent metal bonding properties, rigidity, injection moldability, and a balance of these properties.

[0006] The background technology of the present invention is disclosed in Korean Patent No. 10-0709878, etc.

[0007]

[0008] The purpose of the present invention is to provide a thermoplastic resin composition having excellent metal bonding properties, rigidity, injection moldability, and a balance of these properties.

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

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

[0011]

[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of polybutylene terephthalate resin; about 10 to about 40 parts by weight of polycarbonate resin; about 50 to about 150 parts by weight of glass fiber; about 1 to about 15 parts by weight of glycidyl methacrylate-modified polyolefin; and about 0.1 to about 3 parts by weight of nigrosine; wherein the weight ratio of the glycidyl methacrylate-modified polyolefin and the nigrosine is about 1:0.05 to about 1:0.6.

[0013] 2. In the above 1 specific example, the polybutylene terephthalate resin may have an intrinsic viscosity [η] measured according to ASTM D2857 of about 0.5 to about 1.5 dl / g.

[0014] 3. In the above 1 or 2 specific examples, the polycarbonate resin may have a weight average molecular weight of about 10,000 to about 50,000 g / mol as measured by GPC (gel permeation chromatography).

[0015] 4. In the above specific examples 1 to 3, the glycidyl methacrylate-modified polyolefin may have a glycidyl methacrylate content of about 4 to about 15 wt%.

[0016] 5. In the above specific examples 1 to 4, the nigrosine may have a pH of 4 to 6.

[0017] 6. In the above 1 to 5 specific examples, the weight ratio of the glass fiber and the glycidyl methacrylate modified polyolefin may be about 1:0.01 to about 1:0.2.

[0018] 7. In the above 1 to 6 specific examples, the thermoplastic resin composition may have a metal bonding strength of about 35 to about 45 MPa, measured after bonding an aluminum-based metal specimen of 1.2 cm × 4 cm × 0.3 cm in size and a thermoplastic resin composition specimen of 1.2 cm × 4 cm × 0.3 cm in size through insert injection molding so that the 1.2 cm × 0.3 cm cross-sections of each specimen are attached to each other, according to ISO 19095.

[0019] 8. In the above 1 to 7 specific examples, the thermoplastic resin composition has a flexural modulus of about 80,000 to about 135,000 kgf / cm for a 6.4 mm thick specimen measured according to ASTM D790. 2 It could be.

[0020] 9. In the above 1 to 8 specific examples, when the thermoplastic resin composition is inserted into an aluminum metal specimen of 1.2 cm × 4 cm × 0.3 cm in size and a thermoplastic resin composition specimen of 1.2 cm × 4 cm × 0.3 cm in size and joined to each other through insert injection molding under the conditions of an injection temperature of 270°C and a mold temperature of 150°C, the injection pressure required is about 550 to about 660 kgf / cm 2 It could be.

[0021] 10. In the above 1 to 9 specific examples, the thermoplastic resin composition may have a crystallization temperature of about 165 to about 185°C, as measured from an exothermic peak that occurs when 5 to 10 mg of a sample is vacuum dried at 80°C for 4 hours, then heated from 30°C to 300°C at a rate of 10°C / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then cooled at a rate of 10°C / min after staying at 300°C for 1 minute.

[0022] 11. 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 10.

[0023] 12. Another aspect of the present invention relates to a composite material. The composite material is characterized by comprising: a plastic member formed from a thermoplastic resin composition according to any one of 1 to 10; and a metal member in contact with the plastic member.

[0024] 13. In the above 12 specific examples, the metal member may include one or more metals selected from aluminum, titanium, iron, and zinc.

[0025]

[0026] The present invention has the effect of providing a thermoplastic resin composition having excellent metal bonding properties, rigidity, injection moldability, and a balance of these properties, and a molded product (such as a plastic member of a composite material) formed therefrom.

[0027]

[0028] Hereinafter, the present invention will be described in detail as follows.

[0029] A thermoplastic resin composition according to the present invention comprises (A) polybutylene terephthalate resin; (B) polycarbonate resin; (C) glass fiber; (D) glycidyl methacrylate-modified polyolefin; and (E) nigrosine.

[0030] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0031]

[0032] (A) Polybutylene terephthalate resin

[0033] The polybutylene terephthalate (PBT) resin of the present invention can be applied together with a polycarbonate resin, glass fiber, a glycidyl methacrylate-modified polyolefin at a specific content ratio, nigrosine, etc., to improve the metal bonding property, rigidity, injection moldability, and physical property balance thereof of a thermoplastic resin composition, and a polybutylene terephthalate resin used in a typical thermoplastic resin composition can be used. For example, the polybutylene terephthalate resin can be obtained by polycondensation of terephthalic acid (TPA) or the like as a dicarboxylic acid component and 1,3-butanediol, 1,4-butanediol or the like as a diol component.

[0034] In a specific example, the polybutylene terephthalate resin of the present invention may have an intrinsic viscosity [η] measured according to ASTM D2857 of about 0.5 to about 1.5 dl / g, for example, about 0.7 to about 1.3 dl / g. Within this range, the mechanical properties, metal bonding properties, injection moldability, etc. of the thermoplastic resin composition may be excellent.

[0035]

[0036] (B) Polycarbonate resin

[0037] According to one specific example of the present invention, a polycarbonate resin can be applied together with polybutylene terephthalate resin, glass fiber, a glycidyl methacrylate-modified polyolefin at a specific content ratio, nigrosine, etc., to improve the metal bonding property, rigidity, injection moldability, and physical property balance thereof of a thermoplastic resin composition, and a polycarbonate resin used in a typical 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.

[0038] 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.

[0039] 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 0.05 to 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.

[0040] 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.

[0041] 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 50,000 g / mol, for example, about 15,000 to about 40,000 g / mol. Within this range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), etc.

[0042] In a specific example, the polycarbonate resin may be included in an amount of about 10 to about 40 parts by weight, for example, about 15 to about 35 parts by weight, based on about 100 parts by weight of the polybutylene terephthalate resin. If the content of the polycarbonate resin is less than about 10 parts by weight based on about 100 parts by weight of the polybutylene terephthalate resin, there is a concern that the metal bonding property, injection moldability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 40 parts by weight, there is a concern that the injection moldability, etc. of the thermoplastic resin composition may be reduced.

[0043]

[0044] (C) Glass fiber

[0045] According to one specific example of the present invention, glass fiber can be applied together with polybutylene terephthalate resin, polycarbonate resin, glycidyl methacrylate modified polyolefin at a specific content ratio, nigrosine, etc. to improve the metal bonding property, rigidity, injection moldability, and physical property balance of the thermoplastic resin composition, and glass fiber used in a typical thermoplastic resin composition can be used.

[0046] In specific embodiments, the glass fibers may be in the form of fibers and may have various cross-sections such as circular, oval, rectangular, etc. For example, the use of fibrous glass fibers having circular and / or rectangular cross-sections may be preferable in terms of mechanical properties.

[0047] In a specific example, the glass fibers having a circular cross-section may have a cross-sectional diameter of about 5 to about 20 μm as measured using a Scanning Electron Microscope (SEM) and a length before processing of about 2 to about 20 mm, and the glass fibers having a rectangular (flat) cross-section may have a cross-sectional aspect ratio (major axis of the cross-section / minor axis of the cross-section) as measured using a Scanning Electron Microscope (SEM) of about 1.5 to about 10, a minor axis of about 2 to about 10 μm, and a length before processing of about 2 to about 20 mm. In the above range, the rigidity, moldability, etc. of the thermoplastic resin composition may be improved.

[0048] In a specific example, the glass fiber may be treated with a conventional surface treatment agent. The surface treatment agent may include, but is not limited to, a silane compound, a urethane compound, an epoxy compound, or the like.

[0049] In a specific example, the glass fiber may be included in an amount of about 50 to about 150 parts by weight, for example, about 60 to about 140 parts by weight, relative to about 100 parts by weight of the polybutylene terephthalate resin. If the content of the glass fiber is less than about 50 parts by weight relative to about 100 parts by weight of the polybutylene terephthalate resin, there is a concern that the rigidity, injection moldability, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 150 parts by weight, there is a concern that the metal bonding property, injection moldability, etc. of the thermoplastic resin composition may be reduced.

[0050]

[0051] (D) Glycidyl methacrylate modified polyolefin

[0052] According to one specific example of the present invention, a glycidyl methacrylate-modified polyolefin can be applied together with a polybutylene terephthalate resin, a polycarbonate resin, glass fiber, nigrosine at a specific content ratio, etc., to maintain metal bonding properties of a thermoplastic resin composition and improve rigidity, injection moldability, and physical property balance thereof. A glycidyl methacrylate compound, which is a reactive functional group, can be used by polymerizing it into a polyolefin (olefin homopolymer, olefin copolymer, olefin-(meth)acrylate copolymer, etc.).

[0053] In a specific example, the glycidyl methacrylate-modified polyolefin may have a glycidyl methacrylate content of about 4 to about 15 wt%, for example, about 5 to about 13 wt%. Within this range, the thermoplastic resin composition (molded product) may have excellent metal bonding properties, mechanical properties, fluidity (molding properties), etc.

[0054] In specific examples, the glycidyl methacrylate modified polyolefin may include a glycidyl methacrylate-ethylene copolymer, a glycidyl methacrylate-methyl acrylate-ethylene copolymer, a combination thereof, and the like.

[0055] In a specific example, the glycidyl methacrylate-modified polyolefin may have a melt-flow index of about 2 to about 8 g / 10 min, for example, about 3 to about 7 g / 10 min, measured under conditions of 190°C and 2.16 kg load according to ASTM D1238. Within this range, the mechanical properties, injection moldability, and metal bonding properties of the thermoplastic resin composition (molded product) may be excellent.

[0056] In a specific example, the glycidyl methacrylate-modified polyolefin may be included in an amount of about 1 to about 15 parts by weight, for example, about 2 to about 13 parts by weight, based on about 100 parts by weight of the polybutylene terephthalate resin. If the content of the glycidyl methacrylate-modified polyolefin is less than about 1 part by weight based on about 100 parts by weight of the polybutylene terephthalate resin, there is a concern that the metal bonding property, injection moldability, etc. of the thermoplastic resin composition may be deteriorated, and if it exceeds about 15 parts by weight, there is a concern that the injection moldability, etc. of the thermoplastic resin composition may be deteriorated.

[0057] In a specific example, the weight ratio (C:D) of the glass fiber and the glycidyl methacrylate-modified polyolefin may be from about 1:0.01 to about 1:0.2, for example from about 1:0.02 to about 1:0.15. In this range, the metal bonding property, injection moldability, etc. of the thermoplastic resin composition may be more excellent.

[0058]

[0059] (E) Nigrosine

[0060] According to one specific example of the present invention, nigrosin is applied together with polybutylene terephthalate resin, polycarbonate resin, glass fiber, glycidyl methacrylate modified polyolefin at a specific content ratio, etc., to lower the crystallization temperature (Tc) of polybutylene terephthalate resin or polybutylene terephthalate / polycarbonate blend resin, thereby improving metal bonding property, rigidity, injection moldability, and physical property balance thereof of the thermoplastic resin composition. Nigrosin used in a typical thermoplastic resin composition can be used. For example, nigrosin prepared from a mixture containing nitrobenzene, aniline, and aniline hydrochloride can be used.

[0061] In a specific example, the nigrosine may have a pH of 4 to 6. In this range, the injection moldability of the thermoplastic resin composition may be excellent.

[0062] In a specific example, the nigrosine may be included in an amount of about 0.1 to about 3 parts by weight, for example, about 0.7 to about 2.4 parts by weight, relative to about 100 parts by weight of the polybutylene terephthalate resin. If the content of the nigrosine is less than about 0.1 parts by weight relative to about 100 parts by weight of the polybutylene terephthalate resin, there is a concern that the injection moldability, etc. of the thermoplastic resin composition may be deteriorated, and if it exceeds about 3 parts by weight, there is a concern that the metal bonding property, injection moldability, etc. of the thermoplastic resin composition may be deteriorated.

[0063] In a specific example, the weight ratio (D:E) of the glycidyl methacrylate-modified polyolefin and the nigrosine may be about 1:0.05 to about 1:0.6, for example, about 1:0.06 to about 1:0.5, specifically about 1:0.09 to about 1:0.4. When the weight ratio of the glycidyl methacrylate-modified polyolefin and the nigrosine is less than about 1:0.05, there is a concern that the injection moldability of the thermoplastic resin composition may deteriorate, and when it exceeds about 1:0.6, there is a concern that the metal bonding property of the thermoplastic resin composition may deteriorate.

[0064]

[0065] A thermoplastic resin composition according to one specific 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, flame retardants, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, 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 polybutylene terephthalate resin.

[0066]

[0067] 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 240 to about 300°C, for example, about 260 to about 290°C, using a conventional twin-screw extruder.

[0068] In a specific example, the thermoplastic resin composition may have a metal bonding strength of about 35 to about 45 MPa, for example, about 36 to about 44 MPa, measured after insert injection molding an aluminum-based metal specimen of 1.2 cm × 4 cm × 0.3 cm in size and a thermoplastic resin composition specimen of 1.2 cm × 4 cm × 0.3 cm in size so that the 1.2 cm × 0.3 cm cross-sections of each specimen are bonded to each other in accordance with ISO 19095.

[0069] In a specific example, the thermoplastic resin composition has a flexural modulus of about 80,000 to about 135,000 kgf / cm for a 6.4 mm thick specimen measured according to ASTM D790. 2 , for example, about 80,000 to about 130,000 kgf / cm 2 It could be.

[0070] In a specific example, the thermoplastic resin composition is formed by insert injection molding an aluminum metal specimen measuring 1.2 cm × 4 cm × 0.3 cm and a thermoplastic resin composition specimen measuring 1.2 cm × 4 cm × 0.3 cm under conditions of an injection temperature of 270°C and a mold temperature of 150°C, and the injection pressure required to bond the 1.2 cm × 0.3 cm cross-sections of each specimen to each other is about 550 to about 660 kgf / cm. 2 , for example, about 560 to about 655 kgf / cm 2 It could be.

[0071] In a specific example, the thermoplastic resin composition may have a crystallization temperature of about 165 to about 185°C, for example, about 170 to about 184°C, as measured from an exothermic peak that occurs when 5 to 10 mg of a sample is vacuum-dried at 80°C for 4 hours, then heated from 30°C to 300°C at a rate of 10°C / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then maintained at 300°C for 1 minute and then cooled at a rate of 10°C / min.

[0072]

[0073] 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. The molded article has excellent metal bonding properties, rigidity, injection moldability, and a balance of these physical properties, and is therefore useful as interior and exterior materials for electronic devices, automobile interior and exterior materials, and portable electronic communication devices.

[0074]

[0075] A composite according to the present invention may include a plastic member formed from the thermoplastic resin composition; and a metal member in contact with the plastic member.

[0076] In a specific example, the plastic member and the metal member may be in direct contact without the use of an adhesive. For example, the plastic member and the metal member may be manufactured in an integrated form through insert injection molding.

[0077] In a specific example, the metal member may include one or more metals selected from the group consisting of aluminum, titanium, iron, and zinc.

[0078]

[0079] 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.

[0080]

[0081] Example

[0082] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0083] (A) Polybutylene terephthalate resin

[0084] Polybutylene terephthalate resin (PBT, manufacturer: Shinkong Synthetic Fibers, product name: Shinite K006, intrinsic viscosity [η]: approximately 1.3 dl / g) was used.

[0085] (B) Polycarbonate resin

[0086] Bisphenol-A polycarbonate resin (PC, manufacturer: Lotte Chemical, weight average molecular weight: approximately 25,000 g / mol) was used.

[0087] (C) Glass fiber

[0088] Flat glass fiber (manufacturer: Nittobo, product name: CSG 3PA-832) was used.

[0089] (D) Glycidyl methacrylate modified polyolefin

[0090] Glycidyl methacrylate-ethylene copolymer (manufacturer: Sumitomo, product name: BF-E) was used.

[0091] (E) Nigrosine

[0092] Nigrosin (Manufacturer: Orient, Product name: SPIRIT BLACK SZ) was used.

[0093] (F) Carbon black

[0094] Carbon black (Manufacturer: LG Chemical, Product Name: HI-BLACK 50L) was used.

[0095]

[0096] Examples 1 to 9 and Comparative Examples 1 to 11

[0097] 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 80°C for more than 4 hours, and then injection-molded using a 6 oz injection molding machine (molding temperature: about 270°C, mold temperature: about 150°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.

[0098]

[0099] Method of measuring physical properties

[0100] (1) Metal bonding strength (unit: MPa): According to ISO 19095, the bonding strength was measured after bonding an aluminum-based metal specimen and a thermoplastic resin composition specimen through insert injection molding (injection temperature: approximately 270℃, mold temperature: approximately 150℃). Here, the metal specimen used was an aluminum-based metal specimen with Geo Nation's TRI surface treatment to facilitate bonding with the resin composition specimen. In addition, the metal and thermoplastic resin composition specimens used were 1.2 cm × 4 cm × 0.3 cm in size, and the bonding strength was measured by bonding the 1.2 cm × 0.3 cm cross-sections together.

[0101] (2) Flexural modulus (unit: kgf / cm) 2 ): According to ASTM D790, the flexural modulus of a 6.4 mm thick specimen was measured.

[0102] (3) Injection pressure (unit: kgf / cm) 2): Under the conditions of an injection temperature of approximately 270℃ and a mold temperature of approximately 150℃, an injection molding machine (manufacturer: JSW, model name: J140AD) was used to insert injection mold aluminum metal specimens measuring 1.2 cm × 4 cm × 0.3 cm and thermoplastic resin composition specimens measuring 1.2 cm × 4 cm × 0.3 cm to bond the 1.2 cm × 0.3 cm cross-sections of each specimen together, and the injection pressure required was measured. (Here, if the injection pressure is less than the claimed range, more cross-sections than 1.2 cm × 0.3 cm in size may be bonded or burrs may occur in the injection specimens, and if the injection pressure exceeds the claimed range, molding may not be possible or bonding may not occur.)

[0103] (4) Crystallization temperature (unit: ℃): 5 to 10 mg of the thermoplastic resin composition samples of the above examples and comparative examples were vacuum-dried at 80℃ for 4 hours, and then, using a differential scanning calorimeter (DSC, manufacturer: TA, device name: Q20), the temperature was increased from 30℃ to 300℃ at a rate of 10℃ / min in a nitrogen atmosphere, and after staying at 300℃ for 1 minute, the crystallization temperature was measured from the exothermic peak that appeared while cooling at a rate of 10℃ / min.

[0104]

[0105] Example 12345 (A) (parts by weight) 100 100 100 100 100 (B) (parts by weight) 1525.935 14.3 14.3 (C) (parts by weight) 101 101 101 60 140 (D) (parts by weight) 7.17.17.17.17.1 (E) (parts by weight) 1.21.21.21.21.2 (F) (parts by weight)----- (D): (E) (weight ratio) 1:0.17 1:0.17 1:0.17 1:0.17 1:0.17 1:0.17 Metal bonding strength 38 40 434 237 Flexural modulus 110,000 112,000 118,000 81,000 129,000 Injection pressure 58 0 62 0 65 0 56 0 65 5 Crystallization Temperature 184175171173176

[0106]

[0107] Example 6789 (A) (parts by weight) 100 100 100 100 (B) (parts by weight) 25.9 25.9 25.9 25.9 (C) (parts by weight) 101 101 101 101 (D) (parts by weight) 313 7.17 1 (E) (parts by weight) 1.2 1.2 0.7 2.4 (F) (parts by weight) ---- (D): (E) (weight ratio) 1:0.4 0 1:0.09 1:0.10 1:0.34 Metal bonding strength 364 143 37 Flexural modulus 121,000 100,100 107,000 115,000 Injection pressure 590 640 650 570 Crystallization temperature 183 172 177 170

[0108]

[0109] Comparative Example 123456 (A) (parts by weight) 100100100100100100 (B) (parts by weight) 54525.925.925.925.9 (C) (parts by weight) 10110140160101101 (D) (parts by weight) 7.17.17.17.10.520 (E) (parts by weight) 1.21.21.21.21.21.21.2 (F) (parts by weight)------ (D): (E) (weight ratio) 1:0.171:0.171:0.171:0.171:2.41:0.06 Metal Bonding strength 324543333144 Flexural modulus 105,000120,00078,000133,000124,00098,000 Injection pressure 560750510700570490 Crystallization temperature 189169172176186170

[0110]

[0111] Comparative Example 7891011(A) (parts by weight)100100100100100(B) (parts by weight)25.925.925.925.925.9(C) (parts by weight)101101101101101(D) (parts by weight)7.17.17.1101.5(E) (parts by weight)0.015-0.13(F) (parts by weight)--1.2--(D):(E) (weight ratio)1:0.0011:0.701:0.171:0.011:2Metal bonding strength4430424332Flexural modulus114,000112,000102,000113,000112,000Injection pressure690500680690550Crystallization Temperature 187168190187170

[0112]

[0113] From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in metal bonding properties (metal bonding force), rigidity (flexural modulus), injection molding properties (injection pressure, crystallization temperature), etc.

[0114] On the other hand, in the case of Comparative Example 1 where a small amount of polycarbonate resin was applied, it can be seen that metal bonding, injection moldability, etc. were deteriorated. In the case of Comparative Example 2 where an excessive amount of polycarbonate resin was applied, it can be seen that injection moldability, etc. were deteriorated. In the case of Comparative Example 3 where a small amount of glass fiber was applied, it can be seen that rigidity, injection moldability, etc. were deteriorated. In the case of Comparative Example 4 where an excessive amount of glass fiber was applied, it can be seen that metal bonding, injection moldability, etc. were deteriorated. In the case of Comparative Example 5 where a small amount of glycidyl methacrylate-modified polyolefin was applied, it can be seen that metal bonding, injection moldability, etc. were deteriorated. In the case of Comparative Example 6 where an excessive amount of glycidyl methacrylate-modified polyolefin was applied, it can be seen that injection moldability, etc. were deteriorated. In the case of Comparative Example 7, where a small amount of nigrosine was applied, it can be seen that injection moldability, etc. were deteriorated, and in the case of Comparative Example 8, where an excessive amount of nigrosine was applied, it can be seen that metal bonding, injection moldability, etc. were deteriorated, and in the case of Comparative Example 9, where carbon black (F) was applied instead of the nigrosine of the present invention, it can be seen that injection moldability, etc. were deteriorated. In addition, even if the contents of the glycidyl methacrylate-modified polyolefin and nigrosine are included in the scope of the present invention, in the case of Comparative Example 10, where the weight ratio (D:E) of the glycidyl methacrylate-modified polyolefin and nigrosine is less than the range of the present invention, it can be seen that injection moldability, etc. were deteriorated, and in the case of Comparative Example 11, where the weight ratio exceeds the range of the present invention, it can be seen that metal bonding, etc. were deteriorated.

[0115]

[0116] The present invention has been described with reference to exemplary 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 polybutylene terephthalate resin; About 10 to about 40 parts by weight of polycarbonate resin; About 50 to about 150 parts by weight of glass fiber; About 1 to about 15 parts by weight of glycidyl methacrylate modified polyolefin; and Containing about 0.1 to about 3 parts by weight of nigrosine; A thermoplastic resin composition characterized in that the weight ratio of the glycidyl methacrylate-modified polyolefin and the nigrosine is about 1:0.05 to about 1:0.

6.

2. A thermoplastic resin composition according to claim 1, wherein the polybutylene terephthalate resin has an intrinsic viscosity [η] of about 0.5 to about 1.5 dl / g as measured according to ASTM D2857.

3. A thermoplastic resin composition according to claim 1 or 2, wherein the polycarbonate resin has a weight average molecular weight of about 10,000 to about 50,000 g / mol as measured by GPC (gel permeation chromatography).

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the glycidyl methacrylate-modified polyolefin has a content of glycidyl methacrylate of about 4 to about 15 wt%.

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the nigrosine has a pH of 4 to 6.

6. A thermoplastic resin composition according to any one of claims 1 to 5, wherein the weight ratio of the glass fiber and the glycidyl methacrylate-modified polyolefin is about 1:0.01 to about 1:0.

2.

7. A thermoplastic resin composition according to any one of claims 1 to 6, characterized in that the thermoplastic resin composition has a metal bonding strength of about 35 to about 45 MPa, measured after bonding an aluminum-based metal specimen of 1.2 cm × 4 cm × 0.3 cm in size and a thermoplastic resin composition specimen of 1.2 cm × 4 cm × 0.3 cm in size so that the 1.2 cm × 0.3 cm cross-sections of each specimen are bonded together through insert injection molding in accordance with ISO 19095.

8. In any one of claims 1 to 7, the thermoplastic resin composition has a flexural modulus of about 80,000 to about 135,000 kgf / cm for a 6.4 mm thick specimen measured according to ASTM D790. 2 A thermoplastic resin composition characterized by:

9. In any one of claims 1 to 8, the thermoplastic resin composition is formed by insert injection molding an aluminum metal specimen measuring 1.2 cm × 4 cm × 0.3 cm and a thermoplastic resin composition specimen measuring 1.2 cm × 4 cm × 0.3 cm under conditions of an injection temperature of 270°C and a mold temperature of 150°C, and the injection pressure required to join the 1.2 cm × 0.3 cm cross-sections of each specimen to each other is about 550 to about 660 kgf / cm. 2 A thermoplastic resin composition characterized by:

10. A thermoplastic resin composition according to any one of claims 1 to 9, characterized in that the thermoplastic resin composition has a crystallization temperature of about 165 to about 185°C, measured from an exothermic peak that occurs when 5 to 10 mg of a sample is vacuum dried at 80°C for 4 hours, then heated from 30°C to 300°C at a rate of 10°C / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then cooled at a rate of 10°C / min after staying at 300°C for 1 minute.

11. A molded product characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 10.

12. A plastic member formed from a thermoplastic resin composition according to any one of claims 1 to 10; and A composite material characterized by including a metal member in contact with the plastic member.

13. A composite material according to claim 12, characterized in that the metal member comprises at least one metal selected from the group consisting of aluminum, titanium, iron, and zinc.