Thermoplastic resin composition, method for preparing same, and molded article

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article comprising the same. More specifically, the thermoplastic resin composition according to the present invention is prepared using a modified material, such that a heat distortion temperature and impact strength in a trade-off relationship can be improved, thereby satisfying heat resistance required for improving radar performance and impact strength required for diversified applications of radomes, and improving the durability of radomes, such as radomes, radomes, radomes, radomes, radomes, radomes, radomes, radomes, radomes, radomes, radomes, etc. And the antenna housing can be used in a wider range of electrical assemblies including the antenna housing.

Description

Technical Field

[0001] [Cross - Reference to Related Applications]

[0002] This application claims priority based on Korean Patent Application No. 10 - 2023 - 0132213, filed with the Korean Intellectual Property Office on October 05, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present invention relates to a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molded article including the thermoplastic resin composition, and more particularly, to a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molded article including the thermoplastic resin composition that can be used for a wider range of electrical components including radomes by improving the heat distortion temperature and impact strength, which are in a trade - off relationship. Background Art

[0004] Polyester resins are used in various components, including automotive interior materials, due to their low unit price, mechanical properties, thermal characteristics, and excellent molding properties.

[0005] In particular, polybutylene terephthalate (PBT) is used as a laser transmission material due to its low crystallinity. Here, polycarbonate (PC), an amorphous resin, is mixed and used as a material for improving laser transmission.

[0006] However, when a polyester resin with low crystallinity is mixed with an amorphous resin, there is a problem of a decrease in heat distortion temperature and impact strength.

[0007] Therefore, there is a need to develop a material that can be used for a wider range of electrical components including radomes by improving heat resistance and impact strength.

[0008] [Related Technical Literature]

[0009] [Patent Literature]

[0010] Korean Patent Application Publication No. 2020 - 0066480 (published on June 10, 2020) Summary of the Invention

[0011] Technical Problem

[0012] Accordingly, in view of the above problems, the present invention has been made, and an object of the present invention is to provide a thermoplastic resin composition that has excellent economic efficiency and can be used for a wider range of radomes and other electrical components by improving heat resistance and impact strength in response to market demands for improving radar performance and diversifying radome applications.

[0013] Another object of the present invention is to provide a method for preparing the thermoplastic resin composition.

[0014] Yet another object of the present invention is to provide a molded article made using the thermoplastic resin composition.

[0015] The above and other objects can be achieved by the present invention described below.

[0016] Technical Solution

[0017] According to one aspect of the present invention, the above and other objects can be achieved by providing a thermoplastic resin composition comprising: polybutylene terephthalate (PBT), polycarbonate (PC), and silicone copolymerized polycarbonate (Si-PC), and glass fiber, wherein the weight ratio of the polybutylene terephthalate (PBT) to the polycarbonate (PC) and the silicone copolymerized polycarbonate (Si-PC) is in the range of 4:6 to 6:4 (PBT: PC + Si-PC), and the weight ratio of the polycarbonate (PC) to the silicone copolymerized polycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC: Si-PC).

[0018] The amount of the polybutylene terephthalate (PBT) used is a, the amount of the glass fiber used is b, and the amount of the polycarbonate (PC) used is c, satisfying a > b > c.

[0019] The amount of the polybutylene terephthalate (PBT) used is a', the amount of the glass fiber used is b', and the amount of the silicone copolymerized polycarbonate (Si-PC) used is d, satisfying a' > b' > d.

[0020] II) In I), relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymerized polycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the polybutylene terephthalate (PBT) can be included in an amount of 31.3% to 37% by weight.

[0021] III) In I) or II), relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymerized polycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the glass fiber can be included in an amount of 10% to 40% by weight.

[0022] IV) In I) to III), the siloxane-based copolycarbonate (Si-PC) may be included in an amount of 22% by weight or less based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition.

[0023] V) According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: 31.3% to 37% by weight of the polybutylene terephthalate (PBT), 24% by weight or less of the polycarbonate (PC), 24% by weight or less of the siloxane-based copolycarbonate (Si-PC), and 10% to 40% by weight of the glass fiber, based on a total of 100% by weight of the polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

[0024] VI) In V), the polybutylene terephthalate (PBT) may have a weight-average molecular weight of 10,000 g / min to 80,000 g / min.

[0025] VII) In V) to VI), the polybutylene terephthalate (PBT) and polycarbonate (PC) may be included in a weight ratio (PBT:PC) of 1:0.3 to 1:1.1.

[0026] VIII) In V) to VII), the polycarbonate (PC) may be included in an amount of 13% to 21% by weight based on a total of 100% by weight of the polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

[0027] IX) In V) to VIII), the siloxane-based copolycarbonate (Si-PC) may be included in an amount of 13% to 21% by weight based on a total of 100% by weight of the polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

[0028] X) In V) to IX), the polycarbonate (PC) may have a melt index of 0.1 g / 10 min to 30 g / 10 min measured at 300 °C under a load of 1.2 kg according to ASTM D1238.

[0029] XI) In V) to X), the polycarbonate (PC) may have a molding shrinkage rate of 0.005 in / in to 0.007 in / in as measured according to ASTM D955.

[0030] XII) In V) to XI), the glass fiber may be a chopped strand having an average diameter of 7 μm to 15 μm and an average length of 3 mm to 9 mm.

[0031] XIII) In V) to XII), the additive may include one or more selected from a nucleating agent, an activator, talc, an antioxidant, and a colorant.

[0032] XIV) In V) to XIII), the thermoplastic resin composition may be a material for electrical components.

[0033] XV) In V) to XIV), the thermoplastic resin composition may have a laser transmittance (%) of more than 67.5% measured using an ETM-31 device (980 nm) manufactured by EVlaser Co.

[0034] XVI) In V) to XV), the thermoplastic resin composition may have a heat distortion temperature of more than 167.6 °C measured according to ISO 75 using a specimen with a thickness of 4 mm under a load of 0.45 MPa (flat).

[0035] XVII) In V) to XVI), the thermoplastic resin composition may have a room temperature cantilever beam impact strength (23 °C, notched) of more than 9.5 kJ / m 2 as measured according to ISO 180 using a specimen with a thickness of 4 mm.

[0036] XVIII) In V) to XVII), the thermoplastic resin composition may have a low temperature cantilever beam impact strength (-30 °C, notched) of more than 8.4 kJ / m 2 as measured according to ISO 180 using a specimen with a thickness of 4 mm.

[0037] According to another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising: feeding polybutylene terephthalate (PBT), polycarbonate (PC), and silicone copolymerized polycarbonate (Si-PC), glass fiber, and an additive into an extruder, and performing melt kneading and extrusion, wherein the weight ratio of the polybutylene terephthalate (PBT) to the polycarbonate (PC) and the silicone copolymerized polycarbonate (Si-PC) is in the range of 4:6 to 6:4 (PBT:PC + Si-PC), and the weight ratio of the polycarbonate (PC) to the silicone copolymerized polycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC).

[0038] The usage amount of the polybutylene terephthalate (PBT) is a, the usage amount of the glass fiber is b, and the usage amount of the polycarbonate (PC) is c, satisfying a > b > c.

[0039] The usage amount of the polybutylene terephthalate (PBT) is a′, the usage amount of the glass fiber is b′, and the usage amount of the silicone copolymerized polycarbonate (Si-PC) is d, satisfying a′ > b′ > d.

[0040] According to still another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising: feeding 31.3 wt% to 37 wt% of the polybutylene terephthalate (PBT), 24 wt% or less of the polycarbonate (PC), 24 wt% or less of the silicone copolymerized polycarbonate (Si-PC), and 10 wt% to 40 wt% of the glass fiber into an extruder with respect to a total of 100 wt% of the polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymerized polycarbonate (Si-PC), glass fiber, and an additive, and performing melt kneading and extrusion.

[0041] XXI) According to another aspect of the present invention, there is provided a molded article comprising the above thermoplastic resin composition.

[0042] XXII) In XXI), the molded article may be an electrical component.

[0043] XXIII) In XXI) or XXII, the electrical component may be a connector, a sensor component, a component for a parking brake system, etc.

[0044] XXIV) In XXI) or XXIII, the sensor component may be a radome, an advanced driver assistance system (ADAS), etc.

[0045] Beneficial effects

[0046] A thermoplastic resin composition according to the present invention can improve the heat distortion temperature and impact strength, which are in a trade-off relationship, in response to the market demands for improved radar performance and diversified radome applications, and thus can provide a thermoplastic resin that can be used in a wider range of electrical components including radomes.

[0047] Therefore, the thermoplastic resin composition according to the present invention can be applied to various electrical material fields including connectors, sensors, and parking brake systems that particularly require their physical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 A photograph of a specimen manufactured by injection molding a material according to an embodiment of the present invention is shown, and the photograph shows the laser transmittance measured at one position and another position of the specimen.

[0049] Figure 2 A cross-section of an extruder used in a method for manufacturing a molded article according to an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0050] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0051] The terms and words used in this specification and the appended claims should not be construed as limited to common meanings or dictionary meanings, but should be construed as having meanings and concepts matching the technical concept of the present invention in order to describe the present invention in the best way.

[0052] In this specification, a polymer containing a certain compound means a polymer prepared by polymerizing the compound, and the units in the polymer are from the compound.

[0053] Unless otherwise specified, all numbers, values, and / or expressions representing amounts of components, reaction conditions, polymer components, and formulations used in this specification should be understood to be defined by the term "about". This is because these numbers are inherently approximate, reflecting the various uncertainties in the measurements made in obtaining these values. In addition, when a numerical range is disclosed in the present invention, unless otherwise specified, such a range is continuous and includes all values from the minimum value to the maximum value of the range. In addition, when such a range refers to an integer, unless otherwise specified, all integers from the minimum value to the maximum value are included.

[0054] In the present invention, when a range is specified for a variable, it should be understood that the variable includes all values within the range including the endpoints of the range. For example, the range of "5 to 10" includes the values of 5, 6, 7, 8, 9, and 10, any sub-ranges such as 6 to 10, 7 to 10, 6 to 9, and 7 to 9, and any value among the integers that conform to the ranges such as 5.5 to 8.5 and 6.5 to 9. In addition, the range of 10% to 30% includes values such as 10%, 11%, 12%, and 13%, all integers up to 30%, and any value among all rational numbers within the ranges such as 10.5%, 15.5%, 25.5%.

[0055] The present inventors have confirmed that when polycarbonate (PC) is mixed with siloxane-based copolycarbonate (Si-PC), etc., the heat distortion temperature and impact strength of the molded article are improved, so that the heat resistance important for radar performance and the impact strength important for diversifying the uses of the radome are greatly improved. Devoted to further research, the present invention has been completed.

[0056] The thermoplastic resin composition according to an embodiment of the present invention contains, for example, polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), and glass fiber.

[0057] According to an embodiment of the present invention, the content ratio of polybutylene terephthalate (PBT) to polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) can be within a weight ratio range of, for example, 4:6 to 6:4 (PBT:PC + Si-PC).

[0058] Within this weight ratio range (PBT:PC + Si-PC), a physical property balance among laser transmittance, heat distortion temperature, and impact strength can be provided. The weight ratio (PBT:PC + Si-PC) can preferably be 4.5:5.5 to 6:4, more preferably 4.5∶5.5 to 5.5:6.5.

[0059] Hereinafter, the components constituting the thermoplastic resin composition will be described in detail.

[0060] Polybutylene terephthalate (PBT)

[0061] The polybutylene terephthalate (PBT) according to an embodiment of the present invention imparts molding properties and chemical resistance to the thermoplastic resin composition containing it.

[0062] The polybutylene terephthalate (PBT) prevents the penetration of chemicals introduced from the outside and improves the fluidity of the thermoplastic resin composition containing it during injection molding, thereby improving the appearance quality.

[0063] When polybutylene terephthalate (PBT) has an intrinsic viscosity (I.V.) of 0.6 to 1.4 or 0.7 to 1.2, the heat distortion temperature and impact strength, which are in an inverse relationship, can be appropriately increased.

[0064] Unless otherwise specified, when measuring the intrinsic viscosity, a sample solution with a concentration of 0.05 g / ml is prepared by completely dissolving the sample in dichloromethane as the solvent, and then filtered using a filter to obtain a filtrate. Then, using the obtained filtrate, the intrinsic viscosity is measured at 20 °C using an Ubbelohde viscometer.

[0065] Polybutylene terephthalate (PBT) can have, for example, a weight-average molecular weight (Mw) of 10,000 g / min to 80,000 g / min, as a specific example 20,000 g / min to 100,000 g / min, and as a preferred example 30,000 g / min to 90,000 g / min. As a more preferred example, the weight-average molecular weight (Mw) can be 40,000 g / min to 80,000 g / min, or 50,000 g / min to 70,000 g / min.

[0066] In the present disclosure, the weight-average molecular weight (Mw) can be measured by end-group analysis or gel permeation chromatography (GPC).

[0067] When using GPC, as a specific example of using tetrahydrofuran as the eluent, the weight-average molecular weight as the relative value of a standard polystyrene (PS) sample is measured by gel permeation chromatography (GPC, waters breeze).

[0068] Polybutylene terephthalate (PBT) can be prepared using methods known in the art without particular limitation, or commercially available products can be used.

[0069] Relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymer polycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, polybutylene terephthalate (PBT) can be included in an amount of, for example, 31.3% by weight to 37% by weight, as a specific example 32% by weight to 36% by weight, and preferably 33% by weight to 36% by weight. In this case, the physical property balance between the heat distortion temperature and the impact strength can be satisfied.

[0070] Polycarbonate (PC)

[0071] The melt index of polycarbonate (PC) measured at 300 °C under a load of 1.2 kg according to ASTM D1238 can be, for example, from 0.1 g / min to 30 g / min, preferably from 1 g / 10 min to 25 g / 10 min, more preferably from 10 g / 10 min to 22 g / 10 min. Within this range, the thermal properties such as molding properties and processing properties, as well as the workability of the final thermoplastic resin composition can be improved.

[0072] When the melt index is greater than 30 g / 10 min, it may cause quality non-uniformity and molding defects.

[0073] Polycarbonate (PC) can be, for example, a solid polymer of a melt polymer of an aromatic dicarboxylic acid or its derivative, an aliphatic diol, and a polyalkylene oxide.

[0074] The aromatic dicarboxylic acid or its derivative and the aliphatic diol can form the hard part of the above polycarbonate (PC), and the polyalkylene oxide can form the soft part of the above polycarbonate (PC).

[0075] The aromatic dicarboxylic acid can be one or more selected from, for example, terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (2,6-NDCA), 1,5-naphthalenedicarboxylic acid (1,5-NDCA), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA), dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC), and dimethyl 1,4-cyclohexanedicarboxylate (DMCD), preferably dimethyl terephthalate (DMT).

[0076] Based on 100% by weight of the total amount of all components (aromatic dicarboxylic acid or its derivative, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC), the aromatic dicarboxylic acid or its derivative can be contained, for example, in an amount of 25% to 60% by weight, preferably 29% to 55% by weight, more preferably 34% to 45% by weight. Within this range, an excellent reaction equilibrium can be provided.

[0077] The aliphatic diol can be a diol having a number average molecular weight (Mn) of, for example, 300 g / min or less. As specific examples, the aliphatic diol can be one or more selected from ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, preferably 1,4-butanediol.

[0078] In the present disclosure, the number average molecular weight (Mn) can be measured by end group analysis or gel permeation chromatography (GPC).

[0079] As a specific example of measuring the number-average molecular weight using GPC, the relative value of a standard polystyrene (PS) sample can be measured by gel permeation chromatography (GPC, water breeze) using tetrahydrofuran as an eluent.

[0080] Relative to 100% by weight of the total amount of all components (aromatic dicarboxylic acids or their derivatives, aliphatic diols, and polyalkylene oxides) constituting the polycarbonate (PC), the aliphatic diol can be included in an amount of, for example, 10% to 40% by weight, preferably 15% to 40% by weight, more preferably 20% to 30% by weight. Within this range, an excellent reaction equilibrium can be provided.

[0081] The polyalkylene oxide can include an aliphatic component having a number-average molecular weight (Mn) of, for example, 600 g / min to 3,000 g / min, 1,000 g / min to 2,500 g / min, 1,500 g / min to 2,200 g / min, or 2,000 g / min to 3,000 g / min, thereby constituting the soft part.

[0082] The polyalkylene oxide can be, for example, one or more selected from polyethylene glycol, polypropylene glycol, poly(tetramethylene ether) glycol (PTMEG), poly(oxyhexamethylene) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide adduct polymers of polypropylene glycol, and copolymers of ethylene oxide and tetrahydrofuran, preferably poly(tetramethylene ether) glycol (PTMEG).

[0083] The polyalkylene oxide having a number-average molecular weight (Mn) of 600 g / min to 3,000 g / min can be, for example, poly(tetramethylene ether) glycol.

[0084] As another example, the polyalkylene oxide having a number-average molecular weight (Mn) of 2,000 g / min to 3,000 g / min can be polypropylene glycol capped at its ends with ethylene oxide.

[0085] Relative to 100% by weight of the total amount of all components (aromatic dicarboxylic acids or their derivatives, aliphatic diols, and polyalkylene oxides) constituting the polycarbonate (PC), the polyalkylene oxide can be included in an amount of, for example, 15% to 60% by weight, preferably 15% to 55% by weight, more preferably 15% to 45% by weight. Within this range, an excellent reaction equilibrium can be provided.

[0086] The polycarbonate (PC) can include additives as needed, and can, for example, increase the melt viscosity and melt strength of the elastomer by using a branching agent.

[0087] The branching agent can be, for example, one or more selected from glycerol, pentaerythritol, trimellitic acid or its anhydride, trimethylolpropane, and neopentyl glycol, preferably trimellitic anhydride.

[0088] Relative to 100 parts by weight of the total amount of all components (aromatic dicarboxylic acid or its derivative, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC), the branching agent can be included in an amount of, for example, 0.05 parts by weight to 0.1 parts by weight, preferably 0.05 parts by weight to 0.09 parts by weight, more preferably 0.06 parts by weight to 0.09 parts by weight. Within this range, it is easy to control the intrinsic viscosity during melt polymerization by increasing the melt viscosity.

[0089] The polycarbonate (PC) can be a solid polymer for the melt (condensation) polymer of the above components.

[0090] As a specific example, the polycarbonate (PC) can be prepared as follows: at 140 °C to 215 °C in the presence of a titanium butoxide (TBT) catalyst, the transesterification reaction of the above aromatic dicarboxylic acid, aliphatic diol, and polyalkylene oxide is carried out for about 120 minutes to produce bis(4-hydroxy)butyl terephthalate (BHBT) oligomer, then a TBT catalyst is added, and the melt (condensation) polymerization reaction is carried out at 215 °C to 245 °C for about 120 minutes while gradually reducing the pressure from 760 Torr to 0.3 Torr.

[0091] The melt (condensation) polymerization reaction can be carried out, for example, until the melt (condensation) polymer has a melt flow index (MFI) of 20 g / 10 min to 25 g / 10 min measured at 230 °C under a load of 2.16 kg according to ASTM D1238.

[0092] After the completion of the melt (condensation) polymerization reaction, the reactor interior can be discharged under nitrogen pressure while strand pelletizing to produce pellets.

[0093] The pellets can be solid-state polymerized, for example, in a solid-state polymerization reactor or a rotary vacuum dryer, at 140 °C to 200 °C under high-vacuum inert gas conditions for about 10 hours to 24 hours.

[0094] The solid-state polymerization can be carried out, for example, until the solid polymer has a melt flow index (MFI) of 30 g / 10 min or less measured at 230 °C under a load of 2.16 kg according to ASTM D-1238, preferably 0.1 g / 10 min to 30 g / 10 min (230 °C, 2.16 kg), more preferably 1 g / 10 min to 30 g / 10 min (300 °C, 1.2 kg), in order to produce a high-viscosity polymer.

[0095] The hardness of polycarbonate (PC) can be expressed as Shore hardness - D measured according to ISO 868, and the hardness can be determined based on the content of polyalkylene oxide.

[0096] Based on a total of 100% by weight of polycarbonate (PC), the polyalkylene oxide can be used in an amount of 10% to 50% by weight, preferably 15% to 50% by weight, more preferably 15% to 45% by weight, such that the Shore hardness - D of the polycarbonate (PC) is 35 to 60, preferably 40 to 55. Within this range, the polycarbonate (PC) has low hardness, resulting in good flexibility, and excellent heat resistance and compatibility of the resin.

[0097] Relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone - containing copolycarbonate (Si - PC), glass fiber, and additives) constituting the thermoplastic resin composition, the content of polycarbonate (PC) can be, for example, 24% by weight or less, as a specific example 4% to 24% by weight, preferably 5% to 22% by weight. When the polycarbonate (PC) is included in an amount greater than this range, the heat distortion temperature of the molded article manufactured using the thermoplastic resin composition containing the polycarbonate (PC) may be reduced, while when the polycarbonate (PC) is included in an amount less than this range, the laser transmittance of the molded article manufactured using the thermoplastic resin composition containing the polycarbonate (PC) may be reduced.

[0098] Siloxane copolymerized polycarbonate (Si-PC)

[0099] The silicone - containing copolycarbonate (Si - PC) according to one embodiment of the present invention refers to a copolymer that simultaneously contains polycarbonate - type repeating units in which a polysiloxane structure is not introduced into its main chain and polycarbonate - type repeating units in which a polysiloxane structure is introduced into its main chain.

[0100] The copolycarbonate simultaneously contains a first repeating unit represented by the following formula 1 that does not have a siloxane bond, and a second repeating unit having one or more siloxane bonds and containing repeating units represented by the following formula 2 and formula 3 respectively.

[0101] Here, the molar ratio of the aromatic polycarbonate - type first repeating unit to the aromatic polycarbonate - type second repeating unit having one or more siloxane bonds is preferably 1:0.004 - 0.006, and the weight ratio is preferably 1:0.04 - 0.07.

[0102] Specifically, the repeating unit represented by the following formula 1 is formed by reacting an aromatic diol compound with a carbonate precursor:

[0103] [Formula 1]

[0104]

[0105] In formula 1, preferably, each of R1 to R4 is independently hydrogen, methyl, chlorine or bromine.

[0106] Preferably, Z is an unsubstituted or phenyl-substituted straight-chain or branched C1-10 alkylene group, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl or diphenylmethylene.

[0107] Preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO2 or CO.

[0108] The repeating unit represented by formula 1 can be derived from one or more aromatic diol compounds selected from bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and a,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

[0109] "Derived from an aromatic diol compound" means that the hydroxyl groups of the aromatic diol compound react with a carbonate precursor to form the repeating unit represented by formula 1. For example, when bisphenol A as an aromatic diol compound polymerizes with triphosgene as a carbonate precursor, the first repeating unit represented by formula 1 is represented by the following formula 1-1:

[0110] [Formula 1-1]

[0111]

[0112] As the carbonate precursor, one or more selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, dimethylxylene carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, bisphosgene, bromophosgene and dihaloformate can be used. Preferably, triphosgene or phosgene can be used.

[0113] Specifically, the unit represented by Formula 2 below can be expressed as follows:

[0114] [Formula 2]

[0115]

[0116] In Formula 2, X 1 are each independently a C1-10 alkylene group, and the four Rs 5 are each independently hydrogen; a C1-10 alkoxy group which is unsubstituted or substituted by an oxiranyl group, or a C1-15 alkyl group substituted by a C6-20 aryl group; a halogen; a C1-10 alkoxy group; an aryl group; a C1-10 haloalkyl group; or a C6-20 aryl group, and n is an integer from 1 to 200.

[0117] In Formula 2, preferably, X 1 are each independently a C2-10 alkylene group, more preferably a C2-4 alkylene group, and most preferably a propane-1,3-diyl group.

[0118] Preferably, the four Rs 5 are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, an aryl group, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

[0119] Preferably, the four Rs 5 are each independently a C1-10 alkyl group, more preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and most preferably a methyl group.

[0120] Preferably, n is an integer from 10 to 50.

[0121] More preferably, n is an integer that is 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 31 or more, or 32 or more, and 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, 37 or less, or 35 or less.

[0122] In addition, the repeating unit represented by Formula 3 can be expressed as follows:

[0123] [Formula 3]

[0124]

[0125] In Formula 3, each of the two X2s is independently a C1-10 alkylene group, each of the two Y1s is independently hydrogen, a C1-6 alkyl group, a halogen, a hydroxyl group, a C1-6 alkoxy group, or a C6-20 aryl group, each of the four R6s is independently hydrogen; a C1-10 alkoxy group that is unsubstituted or substituted with an oxiranyl group, or a C1-15 alkyl group substituted with a C6-20 aryl group; a halogen; a C1-10 alkoxy group; an aryl group; a C1-10 haloalkyl group; or a C6-20 aryl group, and m is an integer from 1 to 200.

[0126] In addition, in Formula 3, preferably each of the two X2s is independently a C2-10 alkylene group, more preferably a C2-6 alkylene group, and most preferably an isobutylene group.

[0127] Preferably, Y1 is hydrogen.

[0128] In addition, preferably, each of the two R6s is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, aryl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

[0129] In addition, preferably, each of the two R6s is independently a C1-10 alkyl group, more preferably a C1-6 alkyl group, still more preferably a C1-3 alkyl group, and most preferably a methyl group.

[0130] In addition, preferably, m is an integer from 40 to 100. More preferably, m is an integer greater than or equal to 40, greater than or equal to 45, greater than or equal to 50, greater than or equal to 55, greater than or equal to 56, greater than or equal to 57, or greater than or equal to 58, and less than or equal to 100, less than or equal to 80, less than or equal to 75, less than or equal to 70, less than or equal to 65, less than or equal to 64, less than or equal to 63, or less than or equal to 62.

[0131] The repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are respectively derived from a siloxane compound represented by the following Formula 2-1 and a siloxane compound represented by the following Formula 3-1:

[0132] [Formula 2-1]

[0133]

[0134] In Formula 2-1, X 1 、R 5 and n are as defined above.

[0135] [Formula 3-1]

[0136]

[0137] In Formula 3-1, X2, Y1, R6, and m are as defined above.

[0138] "From the siloxane compound" means that the hydroxyl group of each siloxane compound reacts with the carbonate precursor to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3, respectively.

[0139] The carbonate precursor that can be used to form the repeating units of Formula 2 and Formula 3 is the same as that described in the carbonate precursor that can be used to form the repeating unit of Formula 1 above.

[0140] The methods for preparing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 are, for example, the same as Reaction Scheme 1 and Reaction Scheme 2 below, respectively:

[0141] [Reaction Scheme 1]

[0142]

[0143] In Reaction Scheme 1, X 1 ′ is a C2-10 alkenyl group, and X 1 , R 5 and n are as defined above.

[0144] [Reaction Scheme 2]

[0145]

[0146] In Reaction Scheme 2, X2 is a C2-10 alkenyl group, and X2, Y1, R6 and m are as defined above.

[0147] The reactions of Reaction Scheme 1 and Reaction Scheme 2 are preferably carried out in the presence of a metal catalyst. As the metal catalyst, a Pt catalyst is preferred, and as the Pt catalyst, one or more selected from Ashby catalyst, Karstedt catalyst, Lamoreaux catalyst, Speier catalyst, PtCl 2 (COD), bis(phenylcyano)platinum dichloride and H 2 PtBr 6 can be used.

[0148] Based on 100 parts by weight of the compound represented by Formula 7 or Formula 9, the metal catalyst can be used in an amount of 0.001 part by weight or more, 0.005 part by weight or more, or 0.01 part by weight or more, and 1 part by weight or less, 0.1 part by weight or less, or 0.05 part by weight or less.

[0149] The reaction temperature is preferably 80 °C to 100 °C.

[0150] The reaction time is preferably 1 hour to 5 hours.

[0151] The compound represented by Formula 7 or Formula 9 can be prepared by reacting an organodisiloxane with an organocyclosiloxane in the presence of an acid catalyst, and n and m can be controlled by controlling the contents of the reactants. The reaction temperature is preferably 50 °C to 70 °C. Additionally, the reaction time is preferably 1 hour to 6 hours.

[0152] As the organodisiloxane, one or more selected from tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane can be used.

[0153] Furthermore, the organocyclosiloxane can be, for example, an organocyclotetrasiloxane, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.

[0154] Based on 100 parts by weight of the organocyclosiloxane, the organodisiloxane can be used in an amount of 0.1 part by weight or more, or 2 parts by weight or more, and 10 parts by weight or less, or 8 parts by weight or less.

[0155] The acid catalyst can be one or more selected from H 2 SO 4 、HClO 4 、AlCl 3 、SbCl 5 、SnCl 4 、and acidic clay.

[0156] Furthermore, based on 100 parts by weight of the organocyclosiloxane, the acid catalyst can be used in an amount of 0.1 part by weight or more, 0.5 part by weight or more, or 1 part by weight or more, and 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less.

[0157] Specifically, the low-temperature impact strength and the yellowness index (YI) of the siloxane-based copolycarbonate (Si-PC) can be simultaneously improved by controlling the contents of the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3.

[0158] The weight ratio between the repeating units can be 1:99 to 99:1. The weight ratio is preferably 3:97 to 97:3, 5:95 to 95:5, 10:90 to 90:10, or 15:85 to 85:15, more preferably 20:80 to 80:20. The weight ratio between the repeating units corresponds to the weight ratio between the siloxane compounds, such as the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1.

[0159] Preferably, the repeating unit represented by Formula 2 is represented by the following Formula 2-2:

[0160] [Formula 2-2]

[0161]

[0162] In Formula 2-2, R 5 and n are as defined above.

[0163] Preferably, R 5 is methyl.

[0164] Preferably, the repeating unit represented by Formula 3 is represented by the following Formula 3-2:

[0165] [Formula 3-2]

[0166]

[0167] In Formula 3-2, R6 and m are as defined above.

[0168] Preferably, R6 is methyl.

[0169] Preferably, the weight ratio of the repeating unit represented by Formula 1 to the total weight of the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 (Formula 1:(Formula 2 + Formula 3)) is 1:0.001 to 1:0.2, more preferably 1:0.01 to 1:0.1. The weight ratio between the repeating units corresponds to the weight ratio of the aromatic diol compound used to form the repeating unit of Formula 1 to the siloxane compound used to form the repeating units of Formulas 2 and 3.

[0170] The siloxane-based copolycarbonate (Si-PC) has a weight-average molecular weight of 1,000 g / min to 100,000 g / min, more preferably 15,000 g / min to 35,000 g / min. More preferably, the weight-average molecular weight (g / min) is 23,000 or more, 24,000 or more, or 25,000 or more. In addition, the weight-average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less.

[0171] The siloxane-based copolycarbonate (Si-PC) can be prepared, for example, by polymerizing an aromatic diol compound and siloxane compounds represented by Formulas 2-1 and 3-1 and a carbonate precursor.

[0172] At the time of polymerization, relative to a total of 100% by weight of the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds, the siloxane compound can be used in an amount of 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 1.5% by weight or more, 2.0% by weight or more, 2.5% by weight or more, 2.5% by weight or more, or 3.0% by weight or more, and 20% by weight or less, 10% by weight or less, 7% by weight or less, 5% by weight or less, or 4% by weight or less.

[0173] Based on a total of 100% by weight of the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds, the aromatic diol compound can be used in an amount of 40% by weight or more, 50% by weight or more, or 55% by weight or more, and 80% by weight or less, 70% by weight or less, or 65% by weight or less.

[0174] Based on a total of 100% by weight of the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds, the carbonate precursor can be used in an amount of 10% by weight or more, 20% by weight or more, or 30%, and 60% by weight or less, 50% by weight or less, or 40% by weight or less.

[0175] The polymerization method can be, for example, an interfacial polymerization method. In this case, the polymerization reaction can be carried out at a low temperature under normal pressure, and the molecular weight can be easily controlled.

[0176] The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent.

[0177] In addition, the interfacial polymerization can include, for example, the step of adding a coupling agent after prepolymerization and then polymerizing again. In this case, a high molecular weight copolycarbonate can be obtained.

[0178] There is no particular limitation on the materials used in the interfacial polymerization as long as they can be used for the polymerization of polycarbonate, and their amounts can also be controlled as needed.

[0179] As the acid coupling agent, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, or amine compounds such as pyridine can be used.

[0180] There is no particular limitation on the organic solvent as long as it is a commonly used solvent in the polymerization of polycarbonate. For example, halogenated hydrocarbons such as dichloromethane or chlorobenzene can be used.

[0181] In the interfacial polymerization, reaction promoters such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, quaternary ammonium compounds, or quaternary phosphonium compounds can be additionally used to promote the reaction.

[0182] The reaction temperature of the interfacial polymerization is preferably 0°C to 40°C, and the reaction time is preferably 10 minutes to 5 hours.

[0183] In addition, during the interfacial polymerization reaction, it is preferable to maintain the pH at 9 or above or 11 or above.

[0184] In addition, when carrying out the interfacial polymerization, a molecular weight regulator can be further included. The molecular weight regulator can be added before, during, or after the start of the polymerization.

[0185] As a molecular weight regulator, a monoalkylphenol can be used, and the monoalkylphenol is selected from, for example, one or more of p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol, preferably p-tert-butylphenol. In this case, the effect of the molecular weight regulator is greatly improved.

[0186] Based on 100 parts by weight of the aromatic diol compound, the molecular weight regulator can be included, for example, in an amount of 0.01 part by weight or more, 0.1 part by weight or more, or 1 part by weight or more, and 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less. Within this range, a desired molecular weight can be obtained.

[0187] There is no particular limitation on the siloxane-based copolycarbonate (Si-PC), and it can be produced and used by methods known in the art, or commercially available materials can be used.

[0188] Relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the siloxane-based copolycarbonate (Si-PC) can be included, for example, in an amount of 22% by weight or less, specifically 10% to 21% by weight, preferably 13% to 21% by weight. In this case, the physical property balance between the heat distortion temperature and the impact strength can be satisfied.

[0189] Glass fiber

[0190] In the present disclosure, the glass fiber can be an unsized glass fiber or a sized glass fiber having an adhesive. The adhesive can be selected from silane coupling agents, polyurethane adhesives, epoxy adhesives, and / or aminosilane copolymers.

[0191] In the present disclosure, the preferred silane coupling agent is at least one selected from epoxy-functionalized silanes, urethane-functionalized silanes, and semicarbazide-functionalized silanes, more preferably at least one selected from epoxycyclohexyl-functionalized silanes, glycidyl ether-oxy-functionalized silanes, isocyanate-functionalized silanes, and semicarbazide-functionalized silanes, and most preferably at least one selected from 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyl ether-oxypropylmethyldimethoxysilane, 3-glycidyl ether-oxypropyltrimethoxysilane, 3-glycidyl ether-oxypropylmethyldiethoxysilane, 3-glycidyl ether-oxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltributoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrialkoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0192] The preferred polyurethane adhesive is a polyurethane adhesive, such as a one-component polyurethane adhesive or a two-component polyurethane adhesive.

[0193] In the present disclosure, the glass fiber is preferably a chopped glass fiber or a milled glass fiber. The glass fiber can have various cross-sections, such as circular or non-circular.

[0194] The average length of the glass fiber is preferably 3 mm to 9 mm or 3 mm to 6 mm, and the average diameter of the cross-section of the glass fiber is preferably 7 μm to 15 μm or 7 μm to 14 μm. Within this range, the reinforcing effect can be maximized while not adversely affecting the heat distortion temperature.

[0195] The average length and the average diameter can be the average values measured 10 times by conventional methods.

[0196] There is no particular limitation on the glass fiber, and it can be manufactured and used by methods known in the art, or commercially available materials can be used.

[0197] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the glass fiber can be included, for example, in an amount of 10% to 40% by weight, as a specific example 15% to 30% by weight, preferably 25% to 33% by weight. In this case, the physical property balance between the heat distortion temperature and the impact strength can be satisfied.

[0198] For example, E-glass fiber can be used.

[0199] As a specific example, NEG T187H grade manufactured by Nippon Electric Glass Co., Ltd. can be used.

[0200] Thermoplastic resin composition

[0201] The thermoplastic resin composition according to an embodiment of the present invention may contain appropriate additives to improve its fluidity and the like.

[0202] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone-based polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the additives can be included, for example, in an amount of 0.01% to 10% by weight, as a preferred example 0.1% to 8% by weight, as a more preferred example 0.1% to 5% by weight, as an even more preferred example 0.1% to 5% by weight, as a most preferred example 0.1% to 1% by weight. When the additives are included in an amount less than this range, the molecular chains of the polymer in the molded article manufactured using the thermoplastic resin composition containing the additives may break, resulting in performance deterioration and discoloration. When the additives are included in an amount greater than this range, the rigidity and heat resistance of the molded article manufactured using the thermoplastic resin composition containing the additives may deteriorate.

[0203] The additives can include, for example, one or more selected from nucleating agents, activators, talc, antioxidants, and colorants.

[0204] The nucleating agent can be of a known type as long as it does not adversely affect the thermoplastic resin composition of the present invention. For example, sodium ionomer compounds in commercially available materials can be used.

[0205] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the nucleating agent can be included in an amount of, for example, 0.01% to 5% by weight, preferably 0.1% to 3% by weight, more preferably 0.1% to 2% by weight, even more preferably 0.1% to 1% by weight, and most preferably 0.1% to 0.5% by weight. When the content of the nucleating agent is too high and exceeds this range, the laser transmittance of the molded article manufactured using the thermoplastic resin composition containing the nucleating agent may be reduced.

[0206] There is no particular limitation on the activator as long as it can ensure the ejection ease and fluidity of the injection molding screw for manufacturing a molded article from the thermoplastic resin composition containing the activator, but polyethylene wax is preferably included.

[0207] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition, the activator can be included in an amount of, for example, 0.01% to 5% by weight, preferably 0.1% to 3% by weight, more preferably 0.1% to 2% by weight, even more preferably 0.1% to 1% by weight, and most preferably 0.1% to 0.5% by weight. When the content of the activator is too high and exceeds this range, appearance problems such as stains may occur on the surface of the molded article manufactured using the thermoplastic resin composition containing the activator, thereby reducing the appearance quality.

[0208] The activator can be of various known types as long as it does not adversely affect the thermoplastic resin composition of the present invention.

[0209] Talc is a plate-like inorganic particle that chemically belongs to the magnesium silicate group, and products commonly used as strength enhancers for thermoplastic materials are preferably used.

[0210] Talc may have an average particle size of 4.0 ± 0.5 μm or 4.0 ± 0.3 μm. Within this range, the strength can be sufficiently enhanced without adversely affecting the heat distortion temperature of the thermoplastic resin.

[0211] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition, talc can be added in an amount of, for example, 0.01% to 5% by weight, preferably 0.1% to 3% by weight, more preferably 0.1% to 2% by weight, even more preferably 0.1% to 1% by weight, and most preferably 0.1% to 0.5% by weight. When the content of talc is too high and exceeds this range, the laser transmittance of molded articles made from the thermoplastic resin composition containing the talc may be reduced. When the content of talc is too low, the improvement in strength may be insufficient.

[0212] The talc can be of various known types as long as it does not adversely affect the thermoplastic resin composition of the present invention.

[0213] There is no particular limitation on the antioxidant as long as it can prevent the high-temperature degradation of molded articles made from the thermoplastic resin composition containing the antioxidant. However, for example, it can include a primary antioxidant, a secondary antioxidant, or both of them. In this case, oxidation due to heat can be prevented during the extrusion process, and the present invention can exhibit excellent mechanical properties.

[0214] The primary antioxidant and the secondary antioxidant can be included in a weight ratio of 1:0.5 to 1.5, 1:0.5 to 1.2, or 1:0.5 to 1 (primary antioxidant: secondary antioxidant). In this case, a balance between processability and physical properties can be provided.

[0215] The primary antioxidant can preferably be a phenolic antioxidant and can include, for example, a hindered phenol stabilizer having a crystallization temperature (Tm) of 110°C to 130°C. As specific examples, the primary antioxidant can include tetra[ethylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or a combination thereof.

[0216] In the present disclosure, the crystallization temperature (Tm) refers to the temperature at which the irregular material structure changes to a regular arrangement due to the attraction of molecules / atoms to be crystallized, and can be measured using differential scanning calorimetry (DSC). As a specific example of measuring the crystallization temperature, the measurement container can be filled with about 0.5 mg to 10 mg of the sample, the nitrogen flow rate can be set to 20 ml / min, and the temperature can be increased from 0 °C to 150 °C at a heating rate of 20 °C to create the same thermal history of the sample to be measured. After maintaining this state for 2 minutes, while cooling from 150 °C to -100 °C at a rate of 10 °C, the peak of the cooling curve of the heat flow measured by DSC, that is, the exothermic peak temperature during cooling, can be measured as the crystallization temperature. Here, "peak" refers to the vertex or apex of the cooling curve or heating curve described below, for example, excluding the inflection point where the sign of the slope of the tangent changes based on the point where the slope of the tangent is 0.

[0217] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition, the primary antioxidant can be included in an amount of, for example, 0.01% to 5% by weight, as a preferred example 0.01% to 3% by weight, as a more preferred example 0.01% to 2% by weight, as an even more preferred example 0.01% to 1% by weight, as a most preferred example 0.05% to 0.5% by weight. When the content of the primary antioxidant is too high, appearance problems such as stains may occur on the surface of the molded article manufactured using the thermoplastic resin composition containing the primary antioxidant, resulting in possible deterioration of the appearance quality.

[0218] The secondary antioxidant can preferably be a phosphorus-based antioxidant and can include, for example, phosphite antioxidants. As a specific example, the secondary antioxidant can include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0219] Based on 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition, the secondary antioxidant can be included in an amount of, for example, 0.01% to 5% by weight, as a preferred example 0.01% to 3% by weight, as a more preferred example 0.01% to 2% by weight, as an even more preferred example 0.01% to 1% by weight, as a most preferred example 0.1% to 0.5% by weight. When the content of the secondary antioxidant is too high, appearance problems such as stains may occur on the surface of the molded article manufactured using the thermoplastic resin composition containing the secondary antioxidant, resulting in possible deterioration of the appearance quality.

[0220] The primary antioxidant and the secondary antioxidant can be of various known types, as long as they do not adversely affect the thermoplastic resin composition of the present invention.

[0221] The colorant according to the present invention can be a colorant containing a dye or a pigment.

[0222] The dye can be a blue-violet series dye, a red-orange series dye, etc.

[0223] The blue-violet series dye can be anthraquinone.

[0224] The red-orange series dye can be perinone.

[0225] The pigment can be, for example, an inorganic pigment.

[0226] The inorganic pigment can be, for example, one or more selected from metal compounds such as Ti, Pb, Fe, and Cr, and the metal compound can preferably be a metal oxide or a metal hydroxide.

[0227] Relative to 100% by weight of the total amount of all components (polybutylene terephthalate (PBT), polycarbonate (PC), silicone polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, the colorant can be contained in an amount of, for example, 0.01% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.1% to 3% by weight, and even more preferably 0.2% to 3% by weight. When the content of the colorant is too high, the crack resistance quality of the molded article manufactured using the thermoplastic resin composition containing the activator may deteriorate.

[0228] The thermoplastic resin composition according to an embodiment of the present invention contains polybutylene terephthalate (PBT) and polycarbonate homopolymer (PC) in a weight ratio of 1:0.3 to 1:1.1 (PBT:PC) or in a weight ratio of 1:0.4 to 1:1.0 (PBT:PC). In this case, the heat distortion temperature and the impact strength can be improved, thereby satisfying the performance balance and providing product reliability suitable for electrical components.

[0229] In a thermoplastic resin composition according to an embodiment of the present invention, the content ratio of polybutylene terephthalate (PBT) to polycarbonate homopolymer (PC) and siloxane-based polycarbonate copolymer (Si-PC) is in the range of 4:6 to 6:4 by weight (PBT:PC+Si-PC) or in the range of 4.5:5.5 to 5.5:4.5 by weight (PBT:PC+Si-PC). In this case, the heat distortion temperature and impact strength can be improved, thereby achieving a performance balance and providing product reliability suitable for electrical components.

[0230] In a thermoplastic resin composition according to an embodiment of the present invention, the content ratio of polycarbonate homopolymer (PC) to siloxane-based polycarbonate copolymer (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 by weight (PC:Si-PC) or 3.8:6.2 to 6.2:3.8 by weight (PC:Si-PC). In this case, the heat distortion temperature and impact strength can be improved, thereby achieving a performance balance and providing product reliability suitable for electrical components.

[0231] When the usage amount of polybutylene terephthalate (PBT) is a, the usage amount of glass fiber is b, and the usage amount of polycarbonate homopolymer (PC) is c, a thermoplastic resin composition according to an embodiment of the present invention satisfies a > b > c. In this case, the heat distortion temperature and impact strength can be improved, thereby achieving a performance balance and providing product reliability suitable for electrical components.

[0232] When the usage amount of polybutylene terephthalate (PBT) is a′, the usage amount of glass fiber is b′, and the usage amount of siloxane-based polycarbonate copolymer (Si-PC) is d, a thermoplastic resin composition according to an embodiment of the present invention satisfies a′ > b′ > d. In this case, the heat distortion temperature and impact strength can be improved, thereby achieving a performance balance and providing product reliability suitable for electrical components.

[0233] Relative to 100% by weight of the total amount of the base resin containing polybutylene terephthalate (PBT), polycarbonate homopolymer (PC), and siloxane-based polycarbonate copolymer (Si-PC); glass fiber; and additives, a thermoplastic resin composition according to an embodiment of the present invention contains 34.58% to 37% by weight of polybutylene terephthalate (PBT), 24% by weight or less of polycarbonate homopolymer (PC), and 24% by weight or less of siloxane-based polycarbonate copolymer (Si-PC). In this case, the heat distortion temperature and impact strength can be improved, thereby achieving a performance balance and providing product reliability suitable for electrical components.

[0234] The thermoplastic resin composition can be used in injection molded articles.

[0235] The thermoplastic resin composition can be used in electrical components.

[0236] The electrical components can be used in connectors, sensor components, or components for a parking brake system, etc.

[0237] The sensor component can be a radome, an advanced driver assistance system (ADAS), etc.

[0238] Method for preparing a thermoplastic resin composition

[0239] Hereinafter, a method for preparing the thermoplastic resin composition of the present invention will be described. In the description of the method for preparing the thermoplastic resin composition of the present invention, all the contents including the above-mentioned thermoplastic resin composition are included.

[0240] The method for preparing the thermoplastic resin composition of the present invention may include, for example, feeding a base resin containing polybutylene terephthalate (PBT), a polycarbonate homopolymer (PC), and a silicone polycarbonate copolymer (Si-PC); glass fiber; and an additive into an extruder, and melt-kneading and extruding them.

[0241] The content ratio of polybutylene terephthalate (PBT) to the polycarbonate homopolymer (PC) and the silicone polycarbonate copolymer (Si-PC) is in the range of a weight ratio of 4:6 to 6:4 (PBT:PC + Si-PC).

[0242] The content ratio of the polycarbonate homopolymer (PC) to the silicone polycarbonate copolymer (Si-PC) may satisfy a weight ratio of 3.5:6.5 to 6.5:3.5 (PC:Si-PC).

[0243] When the usage amount of polybutylene terephthalate (PBT) is a, the usage amount of glass fiber is b, and the usage amount of the polycarbonate homopolymer (PC) is c, it can satisfy a > b > c.

[0244] When the usage amount of polybutylene terephthalate (PBT) is a′, the usage amount of glass fiber is b′, and the usage amount of the silicone polycarbonate copolymer (Si-PC) is d, it can satisfy a′ > b′ > d.

[0245] In 100% by weight of the total amount of the base resin comprising polybutylene terephthalate (PBT), polycarbonate homopolymer (PC), and siloxane-based polycarbonate copolymer (Si-PC); glass fiber; and additives, polybutylene terephthalate (PBT) can be included in an amount of 34.58% to 37% by weight, polycarbonate homopolymer (PC) can be included in an amount of 24% by weight or less, siloxane-based polycarbonate copolymer (Si-PC) can be included in an amount of 24% by weight or less, and glass fiber can be included in an amount of 25% to 33% by weight.

[0246] In melt kneading, for example, the above other additives can be included.

[0247] One or more selected from a single-screw extruder, a twin-screw extruder, and a Banbury mixer can be used, and preferably a twin-screw extruder is used for melt kneading and extrusion. The composition can be uniformly mixed using an extruder to obtain, for example, a pellet-type thermoplastic resin composition. In this case, deterioration of mechanical properties and thermal characteristics can be prevented, and excellent plating adhesion and appearance quality can be provided.

[0248] The step of manufacturing pellets using an extrusion kneader can be carried out under conditions such as an extrusion temperature of 230°C to 300°C, a flow ratio (F / R) of 50 kg / hr to 90 kg / hr, and a screw rotation speed of 200 rpm to 490 rpm, preferably under conditions of an extrusion temperature of 230°C to 260°C, an F / R of 50 kg / hr to 90 kg / hr, and a screw rotation speed of 250 rpm to 350 rpm.

[0249] After extruding the thermoplastic resin composition, injection molding can be carried out at an injection molding temperature of 240°C to 280°C, specifically 250°C to 270°C, a mold temperature of 40°C to 80°C, specifically 50°C to 70°C, and an injection molding rate of 10 mm / sec to 80 mm / sec, specifically 20 mm / sec to 60 mm / sec.

[0250] Below Figure 2 The cross-section of an extruder in a method for manufacturing a molded article according to an embodiment of the present invention is shown.

[0251] The extruder may include, for example, more than 6 kneading blocks, preferably more than 7 kneading blocks, more preferably more than 8 kneading blocks, as a preferred example 8 to 15 kneading blocks, and as a more preferred example 9 to 12 kneading blocks. Here, it may be effective to use the kneading blocks in the order of forward, orthogonal, and reverse in turn with respect to the resin flow direction, and continuous or separated block combinations may be used according to the mixing method. In this case, the dispersibility of the components, the compatibility of the composition, etc. can be further improved, so that a kneaded product of higher quality can be provided.

[0252] There is no particular limitation on the type of the extruder, and when considering uniform mixing and dispersion, easy processing, and economic efficiency, a twin-screw extruder having two screws may be preferably used.

[0253] The extruder includes a feeder for supplying raw materials into the barrel, a screw for transporting and mixing the materials supplied into the barrel, and a die head for extruding the kneaded materials, and the screw is composed of a plurality of screw elements to provide various functions.

[0254] One or more raw material feeders may be provided, and optionally, two or more feeders may be provided as needed. For example, a main inlet and an optional auxiliary inlet may be provided. Two or more auxiliary inlets may be provided as needed.

[0255] For example, all components except glass fiber may be fed into the main inlet, and halogenated glass fiber may be fed into auxiliary inlet 1.

[0256] Referring to the following Figure 1 , as a specific example, the extruder 100 may include first to third inlets 11, 12, and 13, and first to third kneading blocks 21, 22, and 23, and the materials introduced along the first direction (DR1) may be kneaded therein and discharged therefrom.

[0257] Specifically, the materials injected into the first inlet 11 may be kneaded during the movement to the first kneading block 21, so that the first kneaded materials can be formed in the first kneading block 21. The materials injected into the second inlet 12 may be mixed with the first kneaded materials and may be kneaded during the movement to the second kneading block 22, so that the second kneaded materials can be formed in the second kneading block 22. In addition, the materials injected into the third inlet 13 may be mixed with the second kneaded materials and may be kneaded during the movement to the third kneading block 23, so that the final product can be formed in the third kneading block 23.

[0258] In addition, molded articles including the thermoplastic resin composition of the present invention will be described. When describing the molded articles including the thermoplastic resin composition of the present invention, all the contents including the above thermoplastic resin composition are included.

[0259] Molded article

[0260] The thermoplastic resin composition of the present invention can be effectively applied to molded articles that require heat distortion temperature and impact strength through the synergistic effect among components.

[0261] The method for manufacturing a molded article can be a method commonly used in the art. For example, a melt-kneaded mixture or pellet of the thermoplastic resin composition according to the present invention, or a sheet (plate) formed therefrom, can be used as a raw material for extrusion molding, casting, press molding, pressure molding, thermo-bending molding, compression molding, calendering molding, rotational molding, injection molding, injection compression molding, etc.

[0262] The thermoplastic resin composition of the present invention can be prepared in the form of pellets through the following steps: for example, under the conditions of 250 rpm and a flow rate of 50 kg / h, polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymer polycarbonate (Si-PC), glass fiber, and additives are fed into the main inlet of a twin-screw extruder ( L / D: 42, SM Platek equipment) set at 230°C, and the components are melt-kneaded and extruded.

[0263] As another example, the thermoplastic resin composition of the present invention can be prepared in the form of pellets through the following steps: under the condition of 375 rpm, polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolymer polycarbonate (Si-PC), and additives are introduced into the main inlet of a twin-screw extruder ( L / D: 42, SM Platek equipment) set at 260°C, glass fiber is introduced into the auxiliary inlet at a flow rate of 75 kg / h, and the components are melt-kneaded and extruded.

[0264] The molded article can be manufactured by introducing the pellets into an injection molding machine.

[0265] In order to indirectly check the physical properties of the manufactured molded article, the pellets can be injection-molded using an injection molding machine (ENGEL CO., 80 tons) at an injection temperature of 260°C, a mold temperature of 60°C, and an injection rate of 30 mm / second to obtain ISO standard specimens.

[0266] The manufactured specimens can have a melt flow index (260°C, 2.16 kgf) measured according to ISO 1133, for example, above 5 g / 10 min, and as a specific example, 10 g / 10 min to 20 g / 10 min.

[0267] The laser transmittance (%) of a molded article comprising the thermoplastic resin composition of the present invention, measured using an ETM-31 device (980 nm) manufactured by EVlaser, may be 67.5% or more, specifically 67.5% to 80%, preferably 67.5% to 75%.

[0268] To obtain the laser transmittance, as shown below Figure 1 A rectangular specimen measuring 60 mm (width) × 60 mm (height) × 1.5 mm (thickness) is manufactured by injection molding the resin molded article and the material, and a laser with a wavelength of 980 nm and an output of 10 mW is irradiated onto each of the gate region (A) and the non-gate region (B) of the specimen using an ETM-31 (EV Laser Co., Ltd.), and then the return intensity value is measured. The laser transmittance is calculated according to the following mathematical equation 1.

[0269] Here, the laser transmittance is measured 5 times for each region. In Tables 1 and 2 below, the laser transmittance of the gate portion is the average value of the measured values of the laser transmittance of the gate portion, and the maximum transmittance is the average value of the measured values of the laser transmittance at positions other than the gate portion.

[0270] [Mathematical Equation 1]

[0271] Laser transmittance (%) = 100 × Po / Pi

[0272] In Mathematical Equation 1, Po is the laser output (output) passing through the specimen, and Pi is the laser output (input) before passing through the specimen.

[0273] Here, the laser output before passing through the specimen may be, for example, 10 mW.

[0274] A molded article comprising the thermoplastic resin composition of the present invention may have a heat distortion temperature of 167.6 °C or more, specifically 167.6 °C to 185.4 °C, measured on a 4 mm thick specimen according to ISO 75 under a load of 0.45 MPa (flat).

[0275] A molded article comprising the thermoplastic resin composition of the present invention may have, for example, 9.5 kJ / m 2 or more, specifically 9.75 kJ / m 2 to 11.52 kJ / m 2 of the room temperature cantilever beam impact strength (23 °C, notched).

[0276] A molded article comprising the thermoplastic resin composition of the present invention may have, for example, 8.4 kJ / m 2As a specific example above, 8.55 kJ / m 2 to 9.8 kJ / m 2 of the low-temperature cantilever impact strength (-30 °C, notched).

[0277] The molded article comprising the thermoplastic resin composition of the present invention may refer to a molded article made of or including the thermoplastic resin composition.

[0278] The molded article may particularly be an electrical component, but is not limited to a specific type.

[0279] That is, in the thermoplastic resin composition according to an embodiment of the present invention, polybutylene terephthalate (PBT) is mixed with polycarbonate (PC) and silicone-based copolycarbonate (Si-PC) at a predetermined mixing ratio. In this case, the molded article made of the thermoplastic resin composition can satisfy the physical property balance between the heat distortion temperature and the impact strength, and can further improve the heat resistance required for improving the radar performance and the impact strength required for the diverse applications of the radome, so that it can be used for a wider range of electrical components including the radome.

[0280] In the description of the thermoplastic resin composition of the present invention, the method for preparing the thermoplastic resin composition, and the molded article including the thermoplastic resin composition, it should be noted that other conditions or equipment not specifically described in this specification can be appropriately selected within the range that can be generally implemented in the art, without particular limitation. In addition, unless otherwise defined, % refers to % by weight.

[0281] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in this specification.

[0282] [Examples]

[0283] Examples 1 to 3 and Comparative Examples 1 to 8

[0284] The raw materials used in the examples and comparative examples are as follows:

[0285] (A) Polybutylene terephthalate (PBT): Intrinsic viscosity (IV) 0.83, product name: TH6082A

[0286] (B) Polycarbonate

[0287] B-1) Polycarbonate (PC): It has a melt index of 22 g / 10 min measured at 300 °C under a load of 1.2 kg according to ASTM D1238, and a molding shrinkage rate of 0.005 in / in to 0.007 in / in measured according to ASTM D955. The product name is LUPOY PC1300, manufactured by LG Chemical Co.

[0288] B-2) Siloxane copolymer polycarbonate (Si-PC): The product name is LUPOY PC8000-05, manufactured by LG Chemical Co.

[0289] (C) Glass fiber: It has an average length of 7 μm to 15 μm, T-187H manufactured by NEG Co.

[0290] (D) Additives

[0291] D-1) Nucleating agent: P250 (sodium ionomer series), manufactured by Bruggemann Co.

[0292] D-2) Talc: KC-3000 (average particle size: 4.0 ± 0.5 μm), manufactured by Koch Co.

[0293] D-3) Primary antioxidant: IR 1010

[0294] D-4) Secondary antioxidant: PEP 36

[0295] Mix the raw materials of the thermoplastic resin composition summarized in Table 1 and Table 2, then make the thermoplastic resin composition with a uniform dispersion into pellet form by extrusion, then heat the pellets, inject them into a mold, and then cool to produce specimens through an injection process.

[0296] Specifically, each component summarized in Table 1 and Table 2 below is mixed with a mixer, and then fed into the main inlet of a twin-screw extruder ( L / D: 42, SM Platek equipment) set at 250 °C at a feeding rate of 50 kg / h and 250 rpm, and then extruded to manufacture pellets formed from the thermoplastic resin composition. Here, the glass fiber is fed into the auxiliary inlet of the extruder, and the extruder is equipped with 9 mixing blocks.

[0297] Dry the pellets in a convection oven at 120 °C for more than 4 hours, and then perform injection molding using an injection molding machine (ENGEL Co., 80 tons) at an injection molding temperature of 250 °C, a mold temperature of 60 °C, and an injection molding rate of 30 mm / second to manufacture specimens.

[0298] [Table 1]

[0299] Classification Example 1 Example 2 Example 3 A 34.6 34.6 34.6 B-1 20.8 17.3 13.8 B-2 13.8 17.3 20.8 C 30 30 30 D-1 - - - D-2 - - - D-3 0.4 0.4 0.4 D-4 0.4 0.4 0.4

[0300] (Each raw material used in Table 1 is added in units of % by weight based on a total of 100% by weight of A to D-4.)

[0301] [Table 2]

[0302] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 A 41.5 27.7 34.55 34.55 34.6 34.6 34.6 29.2 B-1 27.7 41.5 344.55 34.55 34.6 - 29.6 - B-2 - - - - - 34.6 5 40 C 30 30 30 30 30 30 30 30 D-1 - - 0.1 - - - - - D-2 - - - 0.1 - - - - D-3 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 D-4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

[0303] (Each raw material used in Table 2 is added in units of % by weight based on a total of 100% by weight of A-1 to D-4.)

[0304] Experimental Example 1: Performance evaluation of molded article specimens

[0305] Evaluate the properties of the molded product specimens manufactured according to each of Examples 1 to 3 and Comparative Examples 1 to 8. The evaluation criteria are as follows.

[0306] - Laser transmittance (%):

[0307] To obtain the laser transmittance, as shown below Figure 1 A rectangular specimen measuring 60 mm (width) × 60 mm (height) × 1.5 mm (thickness) is manufactured by injection molding the resin and the material. Then, a laser with a wavelength of 980 nm and an output of 10 mW is irradiated onto each of the gate region (A) and the non-gate region (B) of the specimen using an ETM-31 (EV Laser Co., Ltd.), and the return intensity value is measured. The laser transmittance is calculated according to the following mathematical equation 1.

[0308] Here, the laser transmittance is measured 5 times for each region. In Tables 3 and 4 below, the laser transmittance of the gate portion is the average value of the measured values of the laser transmittance of the gate portion, and the maximum transmittance is the average value of the measured values of the laser transmittance at positions other than the gate portion.

[0309] [Mathematical Equation 1]

[0310] Laser transmittance (%) = 100 × Po / Pi

[0311] In Mathematical Equation 1, Po is the laser output (output) passing through the specimen, and Pi is the laser output (input) before passing through the specimen.

[0312] - Heat distortion temperature (HDT): Measured according to ISO 75 using a specimen with a thickness of 4 mm under a load of 0.45 MPa (flat).

[0313] - Room temperature impact strength (IZOD): Measured according to ISO 180 using specimens with a thickness of 4 mm (notch, 23 °C).

[0314] - Low temperature impact strength (IZOD): Measured according to ISO 180 using specimens with a thickness of 4 mm (notch, -30 °C).

[0315] The results measured according to the evaluation criteria are shown in Tables 3 and 4 below:

[0316] [Table 3]

[0317] Classification Example 1 Example 2 Example 3 Laser transmittance (%) 67.5 67.6 68.2 Heat distortion temperature (°C) 167.6 181.1 185.4 <![CDATA[Room temperature impact strength (kJ / m 2 )]]> 9.73 10.96 11.52 <![CDATA[Low temperature impact strength (kJ / m 2 )]]> 8.55 8.91 9.6

[0318] [Table 4]

[0319]

[0320] Referring to Tables 3 and 4, it is confirmed that since the thermoplastic resin compositions according to Examples 1 to 3 of the present invention contain polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) in a predetermined mixing ratio, the physical property balance between the heat distortion temperature and the impact strength is improved, such that the heat resistance required for improving radar performance and the impact strength required for diverse applications of the radome are satisfied, thereby providing product reliability. On the other hand, it is confirmed that Comparative Examples 1 to 5 that do not contain siloxane-based copolycarbonate (Si-PC) show reduced laser transmittance, room temperature impact strength and low temperature impact strength compared to Example 1, and thus cannot provide the heat resistance required for improving radar performance and the impact strength required for diverse applications of the radome.

[0321] Meanwhile, it is confirmed that Comparative Example 5, which does not contain siloxane-based copolycarbonate (Si-PC), but contains polybutylene terephthalate (PBT) and polycarbonate (PC) mixed in an appropriate range and does not contain a nucleating agent and talc, shows improved laser transmittance and room temperature / low temperature impact strength compared to Comparative Examples 1 to 4, but shows a significantly reduced heat distortion temperature.

[0322] In addition, it is confirmed that Comparative Example 6, which contains siloxane-based copolycarbonate (Si-PC) but does not contain polycarbonate (PC), shows reduced laser transmittance compared to Example 1.

[0323] In addition, it is confirmed that Comparative Example 7, which contains a small amount of siloxane-based copolycarbonate (Si-PC) outside the appropriate range, shows a reduced heat distortion temperature compared to Example 2.

[0324] In addition, it was confirmed that Comparative Example 8 containing a large amount of siloxane copolycarbonate (Si-PC) exceeding the appropriate range showed a reduced laser transmittance and a reduced heat distortion temperature compared to Example 1.

[0325] That is, since the thermoplastic resin composition according to an embodiment of the present invention contains polybutylene terephthalate (PBT), polycarbonate (PC), siloxane polycarbonate (Si-PC), and glass fiber, the molded article manufactured using the thermoplastic resin composition satisfies the physical property balance between heat distortion temperature and impact strength, the heat resistance required for radar performance improvement, and the impact strength required for various applications of radomes, and thus is suitable for electrical components and the like.

[0326] [Description of Reference Numerals]

[0327] 100: Extruder 11: First Inlet 12: Second Inlet

[0328] 13: Third Inlet 21: First Kneading Block 22: Second Kneading Block

[0329] 23: Third Kneading Block DR1: First Direction

Claims

1. A thermoplastic resin composition comprising: polybutylene terephthalate (PBT), polycarbonate (PC), siloxane copolycarbonate (Si-PC), and glass fiber, in, The weight ratio of the polybutylene terephthalate (PBT) to the polycarbonate (PC) and the siloxane copolycarbonate (Si-PC) is in the range of 4:6 to 6:4 (PBT:PC+Si-PC), The weight ratio of the polycarbonate (PC) to the siloxane copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC), The amount of polybutylene terephthalate (PBT) used is a, the amount of glass fiber used is b, and the amount of polycarbonate (PC) used is c, satisfying a>b>c. The usage amount of the polybutylene terephthalate (PBT) is a′, the usage amount of the glass fiber is b′, and the usage amount of the siloxane copolycarbonate (Si-PC) is d, satisfying a′>b′>d.

2. A thermoplastic resin composition comprising: polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane copolycarbonate (Si-PC), glass fiber, and additives, relative to a total of 100 wt %; 31.3 wt % to 37 wt % of said polybutylene terephthalate (PBT), 24% by weight or less of the polycarbonate (PC), 24 wt% or less of the siloxane copolycarbonate (Si-PC), and 10 to 40 wt% of said glass fibers.

3. The thermoplastic resin composition according to claim 1 or 2, wherein The polybutylene terephthalate (PBT) has a weight average molecular weight of about 10,000 to about 80,000 g / min.

4. The thermoplastic resin composition according to claim 1 or 2, wherein The polybutylene terephthalate (PBT) and polycarbonate (PC) are included in a weight ratio (PBT:PC) of 1:0.3 to 1:1.

1.

5. The thermoplastic resin composition according to claim 1, wherein 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber and additives in total, wherein the polycarbonate (PC) is contained in an amount of 13 wt% to 21 wt%.

6. The thermoplastic resin composition according to claim 1, wherein A total of 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber and additives, wherein the siloxane-based copolycarbonate (Si-PC) is contained in an amount of 13 wt% to 21 wt%.

7. The thermoplastic resin composition according to claim 1, wherein The polycarbonate (PC) has a melt index of 0.1 to 30 g / 10 min measured at 300° C. under a load of 1.2 kg according to ASTM D1238, and a mold shrinkage of 0.005 to 0.007 in / in measured according to ASTM D955.

8. The thermoplastic resin composition according to claim 1, wherein The glass fibers are chopped strands having an average diameter of 7 to 15 μm and an average length of 3 to 9 mm.

9. The thermoplastic resin composition according to claim 1, wherein The additives include one or more selected from the group consisting of a nucleating agent, an activator, talc, an antioxidant and a colorant.

10. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition is a material for electric components.

11. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition has a heat deformation temperature of 167.6° C. or higher measured under a load of 0.45 MPa (laid flat) using a specimen having a thickness of 4 mm according to ISO 75, and a heat deflection temperature of 9.5 kJ / m 2 measured using a specimen having a thickness of 4 mm according to ISO 180. 2 Room temperature Izod impact strength (23°C, notched) and 8.4 kJ / m measured according to ISO 180 using a 4 mm thick specimen 2 Low temperature Izod impact strength (-30°C, notched) or above.

12. A method for preparing a thermoplastic resin composition, the method comprising: Polybutylene terephthalate (PBT), polycarbonate (PC), silicone copolycarbonate (Si-PC), glass fiber, and additives are fed into an extruder, melt-kneaded, and extruded. The weight ratio of the polybutylene terephthalate (PBT) to the polycarbonate (PC) and the siloxane copolycarbonate (Si-PC) is in the range of 4:6 to 6:4 (PBT:PC+Si-PC). The weight ratio of the polycarbonate (PC) to the siloxane copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC), The amount of polybutylene terephthalate (PBT) used is a, the amount of glass fiber used is b, and the amount of polycarbonate (PC) used is c, satisfying a>b>c. The usage amount of the polybutylene terephthalate (PBT) is a′, the usage amount of the glass fiber is b′, and the usage amount of the siloxane copolycarbonate (Si-PC) is d, satisfying a′>b′>d.

13. A method for preparing a thermoplastic resin composition, the method comprising: Relative to 100 wt % of the total of polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC), glass fiber, and additives, 31.3 wt % to 37 wt % of the polybutylene terephthalate (PBT), 24 wt % or less of the polycarbonate (PC), 24 wt % or less of the siloxane-based copolycarbonate (Si-PC), and 10 wt % to 40 wt % of the glass fiber are fed into an extruder, and melt-kneaded and extruded.

14. A molded article comprising the thermoplastic resin composition according to one of claims 1 to 11.

15. The molded article according to claim 14, wherein The molded article is an electrical component.

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