Thermoplastic resin composition, method for producing same, and molded article including same

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing same, and a molded article including same. The thermoplastic resin composition according to the present invention improves thermal deformation temperature and impact strength, which are in a trade-off relationship, by changing a material to be used, thereby satisfying heat generation durability required by the improvement of radar performance and the impact strength required by the diversification of applications for radomes and having the effect of being usable for military field components including more various radomes.

Description

Thermoplastic resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0132213, filed October 5, 2023, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition capable of being used in a wider variety of electrical components, including radomes, by improving heat distortion temperature and impact strength, which are in a trade-off relationship, a method for producing the same, and a molded article comprising the same.

[0004] Polyester resins are used in various parts, including automotive interior materials, due to their low cost, mechanical properties, thermal properties, and excellent moldability.

[0005] In particular, polybutylene terephthalate (PBT) is used as a laser-transmitting material due to its low crystallinity, and at this time, polycarbonate (PC), an amorphous resin, is mixed and used as a material to improve laser transmittance.

[0006] However, when an amorphous resin is mixed with a polyester resin with a low crystallinity, a problem occurs in which the heat distortion temperature and impact strength are reduced.

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

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] Korean Patent Publication No. 2020-0066480 (published on June 10, 2020)

[0011] In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition that is economically efficient and can be used in a wider variety of electrical components, including radomes, by improving heat resistance and impact strength in accordance with the market's demand for improved radar performance and diversification of radome applications.

[0012] In addition, an object of the present invention is to provide a method for producing the thermoplastic resin composition.

[0013] In addition, the present invention aims to provide a molded product using the thermoplastic resin composition.

[0014] The above and other objects of the present invention can all be achieved by the present invention described below.

[0015] In order to achieve the above object, the present invention comprises: I) polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC); and glass fiber; wherein the weight ratio of the polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) to the polybutylene terephthalate (PBT) is within the range of 4:6 to 6:4 (PBT:PC+Si-PC), and the weight ratio of the polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC).

[0016] If 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, then a>b>c is satisfied.

[0017] A thermoplastic resin composition is provided, characterized in that a'>b'>d is satisfied, where the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based copolycarbonate (Si-PC) used is d.

[0018] II) In the above I), the polybutylene terephthalate (PBT) may be included in an amount of 31.3 to 37 wt% of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition.

[0019] III) In the above I) or II), the glass fiber may be included in an amount of 10 to 40 wt% of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition.

[0020] IV) In the above I) to III), the siloxane-based copolycarbonate (Si-PC) may be included in an amount of 22 wt% or less among 100 wt% 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.

[0021]

[0022] In addition, the present invention provides a thermoplastic resin composition characterized in that, among a total of 100 wt% of V) polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives, the composition comprises 31.3 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 to 40 wt% of the glass fiber.

[0023] VI) In the above V), the polybutylene terephthalate (PBT) may have a weight average molecular weight of 10,000 to 80,000 g / min.

[0024] VII) In the above 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.

[0025] VIII) In the above V) to VII), the polycarbonate (PC) may be included in an amount of 13 to 21 wt% among a total of 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

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

[0027] X) In the above V) to IX), the polycarbonate (PC) may have a melting index of 0.1 to 30 g / 10 min, measured at 300°C and 1.2 kg according to ASTM D1238.

[0028] XI) In the above V) to X), the polycarbonate (PC) may have a mold shrinkage of 0.005 to 0.007 in / in as measured according to ASTM D955.

[0029] XII) In the above V) to XI), the glass fiber may be a chopped strand having an average diameter of 7 to 15 μm and an average length of 3 to 9 mm.

[0030] XIII) In the above V) to XII), the additive may include at least one selected from a nucleating agent, an activator, talc, an antioxidant, and a colorant.

[0031] XIV) In the above V) to XIII), the thermoplastic resin composition may be a material used for a battlefield component.

[0032] XV) In the above V) to XIV), the thermoplastic resin composition may have a laser transmittance (%) of 67.5% or more as measured using EVlaser's ETM-31 equipment (980 nm).

[0033] XVI) In the above V) to XV), the thermoplastic resin composition may have a heat distortion temperature of 167.6°C or higher measured under a load of 0.45 MPa (flatwise) on a 4 mm thick specimen according to ISO 75.

[0034] XVII) In the above V) to XVI), the thermoplastic resin composition may have a room temperature Izod impact strength (23°C, Notched) of 9.5 kJ / m2 or more measured on a 4 mm thick specimen according to ISO 180.

[0035] XVIII) In the above I) to XVII), the thermoplastic resin composition may have a low-temperature Izod impact strength (-30°C, Notched) of 8.4 kJ / m2 or more measured on a 4 mm thick specimen according to ISO 180.

[0036]

[0037] In addition, the present invention includes a step of melt-mixing and extruding XIX) polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives; by feeding them into an extruder, wherein the weight ratio of the polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) to the polybutylene terephthalate (PBT) is within the range of 4:6 to 6:4 (PBT:PC+Si-PC), and the weight ratio of the polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC).

[0038] If 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, then a>b>c is satisfied.

[0039] A method for producing a thermoplastic resin composition is provided, characterized in that a'>b'>d is satisfied, where the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based copolycarbonate (Si-PC) used is d.

[0040]

[0041] In addition, the present invention provides a method for producing a thermoplastic resin composition, characterized in that it comprises the step of introducing into an extruder, melt kneading, and extruding the composition, wherein the composition comprises 31.3 to 37 wt% of polybutylene terephthalate (PBT), 24 wt% or less of polycarbonate (PC), 24 wt% or less of siloxane-based copolycarbonate (Si-PC), and 10 to 40 wt% of glass fiber, among a total of 100 wt% of XX) polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives.

[0042]

[0043] In addition, the present invention provides a molded article characterized by including the thermoplastic resin composition described above XXI).

[0044] XXII) In the above XXI), the molded product may be a component for electric vehicles.

[0045] XXIII) In the above XXI) or XXII), the electrical component may be a connector, a sensor component, or a component for a parking brake system.

[0046] XXIV) In the above XXI) or XXIII), the sensor component may be a radome, an advanced driver assistance system (ADAS), etc.

[0047]

[0048] The thermoplastic resin composition according to the present invention has the effect of providing a thermoplastic resin usable in a wider variety of electrical components, including radomes, by improving heat distortion temperature and impact strength, which are in a trade-off relationship, in response to the market's demand for improved radar performance and diversification of radome applications.

[0049] 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, which particularly require its physical properties.

[0050] FIG. 1 is a photograph of a specimen in which a material according to one embodiment of the present invention was injection-molded and laser transmittance was measured at one location and another location.

[0051] FIG. 2 is a cross-sectional view of an extruder used in a method for manufacturing a molded product according to one embodiment of the present invention.

[0052]

[0053] To help understand the present invention, the present invention will be described in more detail below.

[0054]

[0055] Terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, but should be construed as meanings and concepts that conform to the technical spirit of the present invention, taking into account that the inventor can appropriately define the concept of the term in order to explain the invention in the best way.

[0056] In this document, unless otherwise defined, the meaning of “comprising” may be defined as “comprising manufactured by polymerization,” “comprising polymerized,” or “comprising as a derived unit.”

[0057] Unless otherwise specified, all numbers, values, and / or expressions expressing quantities of ingredients, reaction conditions, polymer compositions, and blends used in this disclosure are approximations that inherently reflect, among other things, the various uncertainties of measurement that arise in obtaining such values, and therefore should be understood as being modified in all instances by the term "about." Furthermore, whenever a numerical range is disclosed herein, such range is continuous and includes every value from the minimum value to the maximum value in that range, unless otherwise indicated. Furthermore, whenever such a range refers to an integer, every integer from the minimum value to the maximum value, inclusive, is included, unless otherwise indicated.

[0058] In this disclosure, when a range is described for a variable, the variable will be understood to include all values ​​within the described range including the described endpoints of the range. For example, a range of "5 to 10" will be understood to include not only the values ​​5, 6, 7, 8, 9, and 10, but also any subranges of 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., and any value between the integers reasonable within the range of the described range, such as 5.5 to 8.5, and 6.5 to 9, etc. Similarly, a range of 10 to 30% will be understood to include not only the values ​​10%, 11%, 12%, 13%, etc., and all integers up to and including 30%, but also any value between the rational numbers within the range of the described range, such as 10.5%, 15.5%, 25.5%, etc.

[0059] The inventors of the present invention confirmed that when polycarbonate (PC) is mixed with siloxane copolycarbonate (Si-PC), the heat distortion temperature and impact strength of the molded product are improved, and the heat resistance, which is important for radar performance, and the impact strength, which is important for diversifying the use of radomes, are greatly improved, and further devoted themselves to research to complete the present invention.

[0060]

[0061] A thermoplastic resin composition according to one embodiment of the present invention includes, for example, polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); and glass fiber.

[0062] According to one embodiment of the present invention, the content ratio of the polybutylene terephthalate (PBT) and polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) may be, for example, within a weight ratio range of 4:6 to 6:4 (PBT:PC+Si-PC).

[0063] Within the above weight ratio (PBT:PC+Si-PC), a balance of properties between laser transmittance, heat distortion temperature, and impact strength can be provided, and preferably, the weight ratio (PBT:PC+Si-PC) can be 4.5:5.5 to 6:4, and more preferably, the weight ratio (PBT:PC+Si-PC) can be 4.5:5.5 to 5.5:6.5.

[0064]

[0065] Below, the components that make up the thermoplastic resin composition will be examined in detail.

[0066]

[0067] polybutylene terephthalate (PBT)

[0068] Polybutylene terephthalate (PBT) according to one embodiment of the present invention imparts moldability and chemical resistance to a thermoplastic resin composition containing the same.

[0069] The above polybutylene terephthalate (PBT) prevents the penetration of chemicals flowing in from the outside, while also improving the flowability of a thermoplastic resin composition containing it during injection molding, thereby improving the appearance quality.

[0070] The above polybutylene terephthalate (PBT) is suitable for improving the heat distortion temperature and impact strength, which are in a trade-off relationship, with an intrinsic viscosity (IV) of 0.6 to 1.4 or 0.7 to 1.2.

[0071] Unless otherwise specified, the above intrinsic viscosity is a value measured at 20°C using an Ubbelohde viscometer after completely dissolving the sample to be measured in a methylene chloride solvent at a concentration of 0.05 g / ml and filtering the filtrate using a filter.

[0072] The polybutylene terephthalate (PBT) may have a weight average molecular weight (Mw) of, for example, 10,000 to 80,000 g / min, specifically 20,000 to 100,000 g / min, and preferably 30,000 to 90,000 g / min. More preferably, it may be 40,000 to 80,000 g / min, or 50,000 to 70,000 g / min.

[0073] In this description, the weight average molecular weight (Mw) can be measured by terminal group analysis or gel permeation chromatography (GPC).

[0074] The weight average molecular weight measurement using the above GPC can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, water breeze) using tetrahydrofuran as an eluent, as a specific example.

[0075] The above polybutylene terephthalate (PBT) is not particularly limited and may be manufactured and used through a method known in the art, or a commercially available material may be used.

[0076] The polybutylene terephthalate (PBT) may be included in an amount of, for example, 31.3 to 37 wt%, specifically 32 to 36 wt%, and preferably 33 to 36 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition. In this case, the physical property balance between the heat distortion temperature and the impact strength can be satisfied.

[0077]

[0078] polycarbonate (PC)

[0079] The polycarbonate (PC) may have a melting index of, for example, 0.1 to 30 g / min, preferably 1 to 25 g / 10min, and more preferably 10 to 22 g / 10min, measured at 300°C and 1.2 kg according to ASTM D1238, and within this range, there is an effect of improving thermal properties and workability, such as moldability and processability, of the final thermoplastic resin composition.

[0080] If the above melting index exceeds 30 g / 10 min, it may cause quality unevenness and molding defects.

[0081] The above polycarbonate (PC) may be, for example, a solid polymer of a melt polymer of an aromatic dicarboxylic acid or a derivative thereof, an aliphatic diol, and a polyalkylene oxide.

[0082] The above aromatic dicarboxylic acid or its derivative and the above aliphatic diol can constitute a hard fraction of the above polycarbonate (PC), and the above polyalkylene oxide can constitute a soft fraction of the above polycarbonate (PC).

[0083] The above aromatic dicarboxylic acids include, for example, terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalene dicarboxylic acid (2,6-NDCA), 1,5-naphthalene dicarboxylic acid (1,5-NDCA), 1,4-cyclohexane dicarboxylic acid (1,4-CHDA), dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene dicarboxylate (2,6-NDC), and dimethyl 1,4-cyclohexane dicarboxylate. It may be at least one selected from the group consisting of 1,4-cyclohexanedicarboxylate (DMCD), and preferably dimethyl terephthalate (DMT).

[0084] The aromatic dicarboxylic acid or its derivative may be included in an amount of, for example, 25 to 60 wt%, preferably 29 to 55 wt%, and more preferably 34 to 45 wt% of the total amount of all components (aromatic dicarboxylic acid or its derivative, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC) of 100 wt%, and within this range, excellent reaction balance is achieved.

[0085] The above aliphatic diol may be, for example, a diol having a number average molecular weight (Mn) of 300 g / min or less, and as a specific example, may be at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, and preferably, may be 1,4-butanediol.

[0086] In this description, the number average molecular weight (Mn) can be measured by end group analysis or gel permeation chromatography (GPC).

[0087] The number average molecular weight measurement using the above GPC can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, water breeze) using tetrahydrofuran as an eluent, as a specific example.

[0088] The aliphatic diol may be, for example, 10 to 40 wt%, preferably 15 to 40 wt%, and more preferably 20 to 30 wt%, of the total 100 wt% of all components (aromatic dicarboxylic acid or derivative thereof, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC), and within this range, excellent reaction balance is achieved.

[0089] The above polyalkylene oxide may comprise a soft fraction including an aliphatic component having a number average molecular weight (Mn) of, for example, 600 to 3,000 g / min, 1,000 to 2,500 g / min, 1,500 to 2,200 g / min or 2,000 to 3,000 g / min.

[0090] The above polyalkylene oxide may be, for example, at least one selected from the group consisting of polyoxyethylene glycol, polypropylene glycol, poly(tetramethylene ether) glycol (PTMEG), polyoxyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene oxide glycol, and a copolymer of ethylene oxide and tetrahydrofuran, and preferably poly(tetramethylene ether) glycol (PTMEG).

[0091] For example, the polyalkylene oxide having a number average molecular weight (Mn) of 600 to 3,000 g / min may be poly(tetramethylene ether) glycol.

[0092] As another example, the polyalkylene oxide having a number average molecular weight (Mn) of 2,000 to 3,000 g / min may be polypropylene glycol terminally capped with ethylene oxide.

[0093] The polyalkylene oxide may be included in an amount of, for example, 15 to 60 wt%, preferably 15 to 55 wt%, and more preferably 15 to 45 wt% of the total amount of all components (aromatic dicarboxylic acid or derivative thereof, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC) of 100 wt%, and within this range, excellent reaction balance is achieved.

[0094] The above polycarbonate (PC) may contain additives as needed, for example, a branching agent may be used to increase the melt viscosity and melt strength of the elastomer.

[0095] The branching agent may be, for example, at least one selected from the group consisting of glycerol, pentaerythritol, trimellitic acid or anhydride thereof, trimethylol propane, and neopentyl glycol, and preferably trimellitic acid anhydride.

[0096] The branching agent may be included, for example, in an amount of 0.05 to 0.1 parts by weight, preferably 0.05 to 0.09 parts by weight, and more preferably 0.06 to 0.09 parts by weight, per 100 parts by weight of the total amount of all components (aromatic dicarboxylic acid or derivative thereof, aliphatic diol, and polyalkylene oxide) constituting the polycarbonate (PC), and within this range, the melt viscosity is increased, making it easy to control the intrinsic viscosity during melt polymerization.

[0097] The above polycarbonate (PC) may be a solid polymer of a melt (condensation) polymer of the above-mentioned components.

[0098] As a specific example, the polycarbonate (PC) can be manufactured by performing an ester exchange reaction of the above-mentioned aromatic dicarboxylic acid, aliphatic diol, and polyalkylene oxide in the presence of a titanium butoxide (TBT) catalyst at 140 to 215°C for about 120 minutes to produce a bis(4-hydroxy)butyl terephthalate (BHBT) oligomer, then adding a TBT catalyst and performing a melt (condensation) polymerization reaction at 215 to 245°C for about 120 minutes while stepwise reducing the pressure from 760 torr to 0.3 torr.

[0099] The above melt (condensation) polymerization reaction can be performed, for example, until the melt (condensation) polymer has a flow index (MFI) measured at 230°C and a load of 2.16 kg according to ASTM D1238, within the range of 20 to 25 g / 10 min.

[0100] After the above melt (condensation) polymerization reaction is completed, the strands can be pelletized while discharging the inside of the reactor under nitrogen pressure to produce pellets.

[0101] The above pellets can be solid-state polymerized under high vacuum inert gas flow conditions at 140 to 200° C. for about 10 to 24 hours, for example, in a solid-state polymerization reactor or a rotary vacuum dryer.

[0102] The above solid-state polymerization can be performed, for example, until the solid-state polymer has a flow index (MFI) of 30 g / 10 min or less, preferably 0.1 to 30 g / 10 min (230 ℃, 2.16 kg), and more preferably 1 to 30 g / 10 min (300 ℃, 1.2 kg), as measured at 230 ℃ and a load of 2.16 kg according to ASTM D-1238, to produce a high-viscosity polymer.

[0103] The hardness of the above polycarbonate (PC) can be expressed as shore hardness-D measured according to ISO 868, and the hardness can be determined according to the content of polyalkylene oxide.

[0104] The polyalkylene oxide may be used in an amount of 10 to 50 wt%, preferably 15 to 50 wt%, and more preferably 15 to 45 wt%, based on 100 wt% of the total polycarbonate (PC), so that the shore hardness-D of the polycarbonate (PC) is 35 to 60, and preferably 40 to 55. Within the above range, the hardness of the polycarbonate (PC) is low, so that flexibility is good, and the heat resistance and compatibility of the resin are excellent.

[0105]

[0106] The content of the polycarbonate (PC) may be, for example, 24 wt% or less, specifically 4 to 24 wt%, and preferably 5 to 22 wt%, based on 100 wt% 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. If the content exceeds the above-described range, there is a disadvantage in that the heat distortion temperature of a molded article manufactured using a thermoplastic resin composition containing the same decreases, and if the content is less than the above-described range, there is a disadvantage in that the laser transmittance of a molded article manufactured using a thermoplastic resin composition containing the same decreases.

[0107]

[0108] Siloxane-based copolycarbonate (Si-PC)

[0109] According to one embodiment of the present invention, siloxane-based copolycarbonate (Si-PC) means a copolymer of polybutylene terephthalate (PBT) and polycarbonate-based repeating units having no polysiloxane structure introduced into the main chain and polycarbonate-based repeating units having a polysiloxane structure introduced into the main chain.

[0110] The above copolycarbonate simultaneously includes a first repeating unit having no siloxane bond represented by the following chemical formula 1, and a second repeating unit having at least one siloxane bond, each of which includes repeating units represented by the following chemical formulas 2 and 3.

[0111] At this time, the molar ratio of the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is preferably 1:0.004-0.006, and the weight ratio is preferably 1:0.04-0.07.

[0112] Specifically, the repeating unit represented by the following chemical formula 1 is formed by the reaction of an aromatic diol compound and a carbonate precursor.

[0113] [Chemical Formula 1]

[0114]

[0115] In the above chemical formula 1, preferably, R1 to R4 are each independently hydrogen, methyl, chloro, or bromo.

[0116] Preferably, Z is a straight or branched C1-10 alkylene which is unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene.

[0117] Preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO2, or CO.

[0118] The repeating unit represented by the above chemical formula 1 is 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, It may be derived from at least one aromatic diol compound selected from the group consisting of 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.

[0119] The meaning of the above 'derived from an aromatic diol compound' means that a hydroxyl group of an aromatic diol compound and a carbonate precursor react to form a repeating unit represented by the above chemical formula 1. For example, when bisphenol A, which is an aromatic diol compound, and triphosgene, which is a carbonate precursor, are polymerized, the first repeating unit represented by the above chemical formula 1 is represented by the following chemical formula 1-1.

[0120] [Chemical Formula 1-1]

[0121]

[0122] As the above carbonate precursor, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformates may be used. Preferably, triphosgene or phosgene may be used.

[0123]

[0124] Specifically, the unit represented by the following chemical formula 2 can be expressed as follows.

[0125] [Chemical Formula 2]

[0126]

[0127] In the above chemical formula 2, each X1 is independently C1-10 alkylene, four R5s are independently hydrogen; C1-15 alkyl which is unsubstituted or substituted with oxiranyl, C1-10 alkoxy substituted with oxiranyl, or C6-20 aryl; halogen; C1-10 alkoxy; allyl; C1-10 haloalkyl; or C6-20 aryl, and n is an integer from 1 to 200.

[0128] In the above chemical formula 2, preferably, X1 is each independently C2-10 alkylene, more preferably C2-4 alkylene, and most preferably propane-1,3-diyl.

[0129] Preferably, R5 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

[0130] Preferably, R5 is independently four C1-10 alkyl, more preferably C1-6 alkyl, more preferably C1-3 alkyl, and most preferably methyl.

[0131] Preferably, n is an integer from 10 to 50.

[0132] More preferably, n is an integer of 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.

[0133]

[0134] Additionally, the repeating unit represented by chemical formula 3 can be expressed as follows.

[0135] [Chemical Formula 3]

[0136]

[0137] In the above chemical formula 3, two X2s are each independently C1-10 alkylene, two Y1s are each independently hydrogen, C1-6 alkyl, halogen, hydroxy, C1-6 alkoxy or C6-20 aryl, four R6s are each independently hydrogen; C1-15 alkyl which is unsubstituted or substituted with oxiranyl, C1-10 alkoxy substituted with oxiranyl, or C6-20 aryl; halogen; C1-10 alkoxy; allyl; C1-10 haloalkyl; or C6-20 aryl, and m is an integer from 1 to 200.

[0138] In addition, in the above chemical formula 3, preferably, two X2s are each independently C2-10 alkylene, more preferably C2-6 alkylene, and most preferably isobutylene.

[0139] Preferably, Y1 is hydrogen.

[0140] Also preferably, R6 is two independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

[0141] Also preferably, R6 is independently C1-10 alkyl, more preferably C1-6 alkyl, more preferably C1-3 alkyl, and most preferably methyl.

[0142] Also preferably, m is an integer from 40 to 100. More preferably, m is an integer of 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, and 100 or less, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or 62 or less.

[0143]

[0144] The repeating unit represented by the above chemical formula 2 and the repeating unit represented by the above chemical formula 3 are derived from a siloxane compound represented by the following chemical formula 2-1 and a siloxane compound represented by the following chemical formula 3-1, respectively.

[0145] [Chemical Formula 2-1]

[0146]

[0147] In the above chemical formula 2-1, the definitions of X1, R5 and n are as defined above.

[0148] [Chemical Formula 3-1]

[0149]

[0150] In the above chemical formula 3-1, the definitions of X2, Y1, R6 and m are as defined above.

[0151] The meaning of the above 'derived from a siloxane compound' means that the hydroxyl group of each of the above siloxane compounds and the carbonate precursor react to form a repeating unit represented by each of the above chemical formulas 2 and 3.

[0152] The carbonate precursor that can be used to form the repeating unit of the above chemical formulas 2 and 3 is the same as that described in the carbonate precursor that can be used to form the repeating unit of the above chemical formula 1.

[0153] The methods for producing the siloxane compound represented by the above chemical formula 2-1 and the siloxane compound represented by the above chemical formula 3-1 are as follows, for example, in the following reaction formulas 1 and 2, respectively.

[0154] [Reaction Formula 1]

[0155]

[0156]

[0157] In the above reaction scheme 1, X1' is C2-10 alkenyl, and the definitions of X1, R5, and n are as defined above.

[0158] [Reaction Formula 2]

[0159]

[0160]

[0161] In the above reaction scheme 2, X2' is C2-10 alkenyl, and the definitions of X2, Y1, R6, and m are as defined above.

[0162] The reactions of the above reaction schemes 1 and 2 are preferably carried out under a metal catalyst. As the metal catalyst, it is preferable to use a Pt catalyst, and as the Pt catalyst, at least one selected from the group consisting of Ashby catalyst, Karstedt catalyst, Lamoreaux catalyst, Speier catalyst, PtCl2(COD), PtCl2(benzonitrile)2, and H2PtBr6 can be used.

[0163] The metal catalyst may 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, based on 100 parts by weight of the compound represented by the chemical formula 7 or 9.

[0164] The above reaction temperature is preferably 80 to 100°C.

[0165] The above reaction time is preferably 1 to 5 hours.

[0166] The compound represented by the above chemical formula 7 or 9 can be prepared by reacting organodisiloxane and organocyclosiloxane in the presence of an acid catalyst, and n and m can be controlled by adjusting the content of the reactant. The reaction temperature is preferably 50 to 70°C. In addition, the reaction time is preferably 1 to 6 hours.

[0167] As the above organodisiloxane, at least one selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane can be used.

[0168] In addition, the above organocyclosiloxane may be, for example, organocyclotetrasiloxane, and examples thereof include octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.

[0169] The above organodisiloxane can be used in an amount of 0.1 parts 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, based on 100 parts by weight of the above organocyclosiloxane.

[0170] As the above acid catalyst, one or more selected from the group consisting of H2SO4, HClO4, AlCl3, SbCl5, SnCl4, and acid clay can be used.

[0171] In addition, the acid catalyst may be used in an amount of 0.1 parts by weight or more, 0.5 parts 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, based on 100 parts by weight of organocyclosiloxane.

[0172] In particular, by controlling the content of the repeating unit represented by the above chemical formula 2 and the repeating unit represented by the above chemical formula 3, the low-temperature impact strength and YI (Yellow Index) of siloxane-based copolycarbonate (Si-PC) can be improved simultaneously.

[0173] The weight ratio between the above repeating units may be 1:99 to 99:1. Preferably, it is 3:97 to 97:3, 5:95 to 95:5, 10:90 to 90:10, or 15:85 to 85:15, and more preferably, it is 20:80 to 80:20. The weight ratio of the above repeating units corresponds to the weight ratio of the siloxane compound, for example, the siloxane compound represented by the above chemical formula 2-1, and the siloxane compound represented by the above chemical formula 3-1.

[0174] Preferably, the repeating unit represented by the above chemical formula 2 is represented by the following chemical formula 2-2:

[0175] [Chemical Formula 2-2]

[0176]

[0177] In the above chemical formula 2-2, R5 and n are as defined above.

[0178] Preferably, R5 is methyl.

[0179] Also preferably, the repeating unit represented by the above chemical formula 3 is represented by the following chemical formula 3-2:

[0180] [Chemical Formula 3-2]

[0181]

[0182] In the above chemical formula 3-2, R6 and m are as defined above.

[0183] Preferably, R6 is methyl.

[0184] Preferably, the weight ratio of the total weight of the repeating unit represented by the above chemical formula 1, the repeating unit represented by the above chemical formula 2, and the repeating unit represented by the above chemical formula 3 (Chemical formula 1: (Chemical formula 2 + Chemical formula 3)) is 1:0.001 to 1:0.2, more preferably 1:0.01 to 1:0.1. The weight ratio of the repeating unit corresponds to the weight ratio of the aromatic diol compound used to form the repeating unit of the above chemical formula 1 and the siloxane compound used to form the repeating units of the above chemical formulas 2 and 3.

[0185] The above siloxane-based copolycarbonate (Si-PC) has a weight average molecular weight of 1,000 to 100,000 g / min, more preferably 15,000 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.

[0186] The above siloxane-based copolycarbonate (Si-PC) can be produced, for example, by polymerizing the aromatic diol compound, the siloxane compound represented by the chemical formulas 2-1 and 3-1, and the carbonate precursor.

[0187] During the polymerization, the siloxane compound may be used in an amount of 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 2.5 wt% or more, or 3.0 wt% or more, and 20 wt% or less, 10 wt% or less, 7 wt% or less, 5 wt% or less, or 4 wt% or less, based on 100 wt% of the total of the aromatic diol compound, the carbonate precursor, and the at least one siloxane compound.

[0188] The above aromatic diol compound may be used in an amount of 40 wt% or more, 50 wt% or more, or 55 wt% or more, and 80 wt% or less, 70 wt% or less, or 65 wt% or less, based on 100 wt% of the total of the aromatic diol compound, the carbonate precursor, and the one or more siloxane compounds.

[0189] The above carbonate precursor may be used in an amount of 10 wt% or more, 20 wt% or more, or 30 wt%, and 60 wt% or less, 50 wt% or less, or 40 wt% or less, based on 100 wt% of the total of the aromatic diol compound, the carbonate precursor, and the one or more siloxane compounds.

[0190] As the above polymerization method, for example, an interfacial polymerization method can be used, in which case a polymerization reaction is possible at normal pressure and low temperature, and there is an effect that it is easy to control the molecular weight.

[0191] It is preferable that the above interfacial polymerization be performed in the presence of an acid binder and an organic solvent.

[0192] In addition, the above interfacial polymerization may include, for example, a step of adding a coupling agent after pre-polymerization and then polymerizing again, in which case a high molecular weight copolycarbonate can be obtained.

[0193] The materials used in the above interfacial polymerization are not particularly limited as long as they are materials that can be used in the polymerization of polycarbonate, and the amount used can be adjusted as needed.

[0194] As the acid binding agent, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine can be used.

[0195] The organic solvent is not particularly limited as long as it is a solvent commonly used in the polymerization of polycarbonate, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

[0196] The above interfacial polymerization may additionally use a reaction accelerator such as a tertiary amine compound, such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound to promote the reaction.

[0197] The reaction temperature of the above interfacial polymerization is preferably 0 to 40°C, and the reaction time is preferably 10 minutes to 5 hours.

[0198] Additionally, during the interfacial polymerization reaction, it is desirable to maintain the pH at 9 or higher or 11 or higher.

[0199] In addition, the above interfacial polymerization can be performed by further including a molecular weight regulator. The molecular weight regulator can be added before, at, or after the initiation of polymerization.

[0200] Mono-alkylphenol can be used as the above molecular weight modifier, and the mono-alkylphenol is, for example, at least one selected from the group consisting of p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol, and is preferably p-tert-butylphenol, in which case the molecular weight modifier effect is large.

[0201] The above molecular weight regulator is included in an amount of, for example, 0.01 parts by weight or more, 0.1 parts 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, based on 100 parts by weight of the aromatic diol compound, and a desired molecular weight can be obtained within this range.

[0202]

[0203] Siloxane-based copolycarbonate (Si-PC) is not particularly limited and can be manufactured and used through a method known in the art, or a commercially available material can be used.

[0204] The above siloxane-based copolycarbonate (Si-PC) may be included in an amount of, for example, 22 wt% or less, specifically 10 to 21 wt%, and preferably 13 to 21 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, and in this case, the physical property balance between the heat distortion temperature and the impact strength may be satisfied.

[0205]

[0206] fiberglass

[0207] In the present invention, the glass fiber may be an unsized glass fiber or a sized glass fiber with an adhesive. The adhesive is selected from the group consisting of a silane coupling agent, a urethane adhesive, an epoxide adhesive, and / or an amino-silane copolymer.

[0208] In the present invention, a preferred silane coupling agent is at least one selected from the group consisting of epoxy-functional silanes, urethane-functional silanes and amino-ureide-functional silanes, more preferably at least one selected from the group consisting of epoxycyclohexyl-functional silanes, glycidoxy-functional silanes, isocyanate-functional silanes and amino-ureide-functional silanes, and most preferably 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, At least one selected from N-2-(aminoethyl)-3-aminopropyltri butoxysilane, 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-isocyanatepropyltriethoxysilane It is one.

[0209] Preferred urethane adhesives are polyurethane adhesives, such as one-component polyurethane adhesives or two-component polyurethane adhesives.

[0210] In the present invention, the glass fibers are preferably chopped or milled glass fibers. The glass fibers may have various cross-sections, such as circular or non-circular.

[0211] The average length of the glass fibers is preferably in the range of 3 to 9 mm, or 3 to 6 mm, and the average cross-sectional diameter of the glass fibers is preferably in the range of 7 to 15 μm, or 7 to 14 μm. Within the above range, the reinforcing effect is maximized without adversely affecting the heat distortion temperature.

[0212] The above average length and average diameter may be the average values ​​measured 10 times using a conventional method.

[0213] Glass fiber is not particularly limited and can be manufactured and used through a method known in the art, or a commercially available material can be used.

[0214] The glass fiber may be included in an amount of, for example, 10 to 40 wt%, specifically 15 to 30 wt%, and preferably 25 to 33 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition, and in this case, the physical property balance between heat distortion temperature and impact strength may be satisfied.

[0215] For example, E-glass fibers can be used.

[0216] As a specific example, NEG T187H grade from Nippon Electric Glass Co., Ltd. can be used.

[0217]

[0218] thermoplastic resin composition

[0219] A thermoplastic resin composition according to one embodiment of the present invention may include appropriate additives to improve its flowability, etc.

[0220] The additive may be, for example, present in an amount of 0.01 to 10 wt%, preferably 0.1 to 8 wt%, more preferably 0.1 to 5 wt%, even more preferably 0.1 to 5 wt%, and most preferably 0.1 to 1 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition. If it is less than the above-mentioned range, there is a disadvantage in that the properties of a molded article manufactured using a thermoplastic resin composition containing the additive are deteriorated and discolored due to scission of molecular chains of polymers, and if it exceeds the above-mentioned range, there is a disadvantage in that the rigidity and heat resistance of a molded article manufactured using a thermoplastic resin composition containing the additive are deteriorated.

[0221] The above additive may include, for example, one or more selected from a nucleating agent, an activator, talc, an antioxidant, and a colorant.

[0222] The above-mentioned nucleating agent may be of a known type as long as it does not adversely affect the thermoplastic resin composition of the present invention, and among commercially available materials, a sodium ionomer series compound may be used as an example.

[0223] For example, the nucleating agent may be included in an amount of 0.01 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, even more preferably 0.1 to 1 wt%, and most preferably 0.1 to 0.5 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the nucleating agent is too large beyond the above range, there is a disadvantage in that the laser transmittance of a molded article manufactured using the thermoplastic resin composition containing it is lowered.

[0224] The above-mentioned active agent is not particularly limited as long as it can ensure the ease of extraction and flowability of an injection screw used to manufacture a molded product from a thermoplastic resin composition containing the active agent, but preferably, it may include a polyethylene wax.

[0225] The above-mentioned active agent may be, for example, present in an amount of 0.01 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, even more preferably 0.1 to 1 wt%, and most preferably 0.1 to 0.5 wt%, based on 100 wt% of the total components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the active agent is too high beyond the above range, there is a disadvantage in that appearance problems such as stains occur on the surface of a molded product manufactured using the thermoplastic resin composition containing the same, thereby lowering the appearance quality.

[0226] The above-mentioned active agent may be of various known types as long as it does not adversely affect the thermoplastic resin composition of the present invention.

[0227] The above talc is a mineral chemically classified as a magnesium silicate salt in the form of plate-shaped inorganic particles, and it is preferable to use a product that is generally used as a strength reinforcing agent for thermoplastic materials.

[0228] The above talc may have an average particle size of 4.0±0.5 um or 4.0±0.3 um, and within this range, it can sufficiently reinforce strength without adversely affecting the heat distortion temperature of the thermoplastic resin.

[0229] The amount of the talc added may be, for example, 0.01 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, even more preferably 0.1 to 1 wt%, and most preferably 0.1 to 0.5 wt%, based on 100 wt% of the total components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the talc is too large outside the above range, there is a disadvantage in that the laser transmittance of a molded article manufactured using the thermoplastic resin composition containing the same is lowered, and if the amount used is too small, the strength improvement may be insufficient.

[0230] The above talc may be of various known types as long as it does not adversely affect the thermoplastic resin composition of the present invention.

[0231] The above antioxidant is not particularly limited as long as it can prevent high-temperature degeneration of a molded product manufactured using a thermoplastic resin composition containing the antioxidant, but for example, it may include a primary antioxidant, a secondary antioxidant, or both, and in this case, oxidation due to heat is prevented during the extrusion process, and the mechanical properties of the present invention are excellent.

[0232] The above primary antioxidant and secondary antioxidant may be included in a weight ratio of 1:0.5 to 1.5 (primary antioxidant:secondary antioxidant), 1:0.5 to 1.2, or 1:0.5 to 1, respectively. In this case, there is an effect of providing a balance of processability and physical properties.

[0233] The above primary antioxidant may preferably be a phenolic antioxidant, and may include, for example, a hindered phenolic stabilizer having a crystallization temperature (Tm) of 110 to 130° C., and specific examples thereof include tetrakis[ethylene-3-(3,5-di-t-butyl-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, or a combination thereof.

[0234] In this paper, the crystallization temperature (Tm) refers to the temperature at which crystallization occurs, where the irregular material structure changes into a regular arrangement due to the attractive force between molecules / atoms, and can be measured using differential scanning calorimetry (DSC). For example, to measure a specific crystallization temperature, fill a measuring vessel with about 0.5 mg to 10 mg of a sample, set the nitrogen gas flow rate to 20 ml / min, and increase the temperature from 0 ℃ to 150 ℃ at a heating rate of 20 ℃ to make the thermal history of the measurement sample the same, then maintain it in that state for 2 minutes, and then cool it from 150 ℃ to -100 ℃ at a rate of 10 ℃. The peak of the cooling curve of the heat flow measured using DSC, i.e., the exothermic peak temperature during cooling, can be measured as the crystallization temperature. Here, “peak” means the vertex or apex of the cooling curve or the heating curve described below, and excludes, for example, an inflection point where the sign of the slope of the tangent line changes based on a point where the slope of the tangent line is 0.

[0235] The above primary antioxidant may be, for example, present in an amount of 0.01 to 5 wt%, preferably 0.01 to 3 wt%, more preferably 0.01 to 2 wt%, even more preferably 0.01 to 1 wt%, and most preferably 0.05 to 0.5 wt%, based on 100 wt% of the total components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the primary antioxidant is too high, there is a disadvantage in that appearance problems such as stains occur on the surface of a molded product manufactured using the thermoplastic resin composition containing the same, thereby lowering the appearance quality.

[0236] The above secondary antioxidant may preferably be a phosphorus-based antioxidant, and may include, for example, a phosphite-based antioxidant, and specific examples thereof may include tris-(2,4-di-tert-butylphenyl) phosphite, di-(2,4-di-t-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0237] The secondary antioxidant may be present in an amount of, for example, 0.01 to 5 wt%, preferably 0.01 to 3 wt%, more preferably 0.01 to 2 wt%, even more preferably 0.01 to 1 wt%, and most preferably 0.1 to 0.5 wt%, based on 100 wt% of the total components (polybutylene terephthalate (PBT), polycarbonate (PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the secondary antioxidant is too high, there is a disadvantage in that appearance problems such as stains occur on the surface of a molded product manufactured using the thermoplastic resin composition containing the same, thereby lowering the appearance quality.

[0238] As the above primary and secondary antioxidants, various known types can be used as long as they do not adversely affect the thermoplastic resin composition of the present invention.

[0239] The colorant according to the present invention may be a coloring agent including a dye or pigment.

[0240] The above dye may be a blue violet series dye or a red orange series dye.

[0241] The above blue violet series dye may be anthraquinone.

[0242] The above red-orange dye may be perinone.

[0243] The above pigment may be, for example, an inorganic pigment.

[0244] The above-mentioned inorganic pigment may be at least one selected from the group consisting of metal compounds such as Ti, Pb, Fe, and Cr, for example, and the metal compound may preferably be a metal oxide or metal hydroxide.

[0245] The above-mentioned colorant may be included, for example, in an amount of 0.01 to 5 wt%, preferably 0.01 to 3 wt%, more preferably 0.1 to 3 wt%, and even more preferably 0.2 to 3 wt%, of the total amount of 100 wt% of all components (polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based polycarbonate copolymer (Si-PC), glass fiber, and additives) constituting the thermoplastic resin composition. If the content of the colorant is too large, there is a disadvantage in that the crack resistance quality of a molded article manufactured using the thermoplastic resin composition including the colorant is deteriorated.

[0246]

[0247] A thermoplastic resin composition according to one embodiment of the present invention is characterized in that it contains polybutylene terephthalate (PBT) and polycarbonate homopolymer (PC) in a weight ratio of 1:0.3 to 1:1.1 (PBT:PC), or a weight ratio of 1:0.4 to 1:1.0 (PBT:PC), and in this case, the heat distortion temperature and impact strength are improved, thereby satisfying the physical property balance and providing product reliability suitable for electrical components.

[0248] According to one embodiment of the present invention, a thermoplastic resin composition is characterized in that the content ratio of the polybutylene terephthalate (PBT) and polycarbonate homopolymer (PC) and the siloxane-based polycarbonate copolymer (Si-PC) is within a range of a weight ratio of 4:6 to 6:4 (PBT:PC+Si-PC) or a weight ratio of 4.5:5.5 to 5.5:4.5 (PBT:PC+Si-PC), and in this case, the heat distortion temperature and impact strength are improved to satisfy the physical property balance and provide product reliability suitable for an electric component.

[0249] According to one embodiment of the present invention, a thermoplastic resin composition is characterized in that the content ratio of the polycarbonate homopolymer (PC) and the siloxane-based polycarbonate copolymer (Si-PC) satisfies a weight ratio (PC:Si-PC) of 3.5:6.5 to 6.5:3.5, or a weight ratio (PC:Si-PC) of 3.8:6.2 to 6.2:3.8, and in this case, the heat distortion temperature and impact strength are improved to satisfy the physical property balance and provide product reliability suitable for an electric component.

[0250] A thermoplastic resin composition according to one embodiment of the present invention is characterized in that it satisfies a>b>c, where the amount of polybutylene terephthalate (PBT) used is a, the amount of glass fiber used is b, and the amount of polycarbonate homopolymer (PC) used is c. In this case, the heat distortion temperature and impact strength are improved to satisfy the physical property balance and provide product reliability suitable for an electrical component.

[0251] A thermoplastic resin composition according to one embodiment of the present invention is characterized in that it satisfies a'>b'>d, where the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based polycarbonate copolymer (Si-PC) used is d. In this case, the heat distortion temperature and impact strength are improved, thereby satisfying the physical property balance and providing product reliability suitable for electrical components.

[0252]

[0253] According to one embodiment of the present invention, a thermoplastic resin composition comprises a base resin composed of polybutylene terephthalate (PBT), a polycarbonate homopolymer (PC), and a siloxane-based polycarbonate copolymer (Si-PC); glass fiber; and an additive; wherein, among a total of 100 wt% of the composition, the polybutylene terephthalate (PBT) is contained in an amount of 34.58 to 37 wt%, the polycarbonate homopolymer (PC) is contained in an amount of 24 wt% or less, the siloxane-based polycarbonate copolymer (Si-PC) is contained in an amount of 24 wt% or less, and the glass fiber is contained in an amount of 10 to 40 wt%. In this case, the heat distortion temperature and impact strength can be improved to satisfy a balance of physical properties and provide product reliability suitable for an electrical component.

[0254]

[0255] The above thermoplastic resin composition can be used in an injection molded product.

[0256] The above thermoplastic resin composition can be used in electrical components.

[0257] The above-mentioned electrical components may be connectors, sensor components, or components for a parking brake system.

[0258] The above sensor components may be radomes, advanced driver assistance systems (ADAS), etc.

[0259]

[0260] Method for producing a thermoplastic resin composition

[0261] Hereinafter, a method for manufacturing a thermoplastic resin composition of the present invention will be described. When describing the method for manufacturing a thermoplastic resin composition of the present invention, all of the contents of the thermoplastic resin composition described above are included.

[0262] The method for manufacturing the thermoplastic resin composition of the present invention may include, for example, a step of introducing a base resin composed of polybutylene terephthalate (PBT), polycarbonate homopolymer (PC), and siloxane-based polycarbonate copolymer (Si-PC); glass fiber; and additives into an extruder, melt-mixing, and extruding.

[0263] The content ratio of the above polybutylene terephthalate (PBT) and polycarbonate homopolymer (PC) and siloxane-based polycarbonate copolymer (Si-PC) may be within the range of a weight ratio of 4:6 to 6:4 (PBT:PC+Si-PC).

[0264] The content ratio of the above polycarbonate homopolymer (PC) and siloxane-based polycarbonate copolymer (Si-PC) can satisfy a weight ratio (PC:Si-PC) of 3.5:6.5 to 6.5:3.5.

[0265] If the amount of polybutylene terephthalate (PBT) used is a, the amount of glass fiber used is b, and the amount of polycarbonate homopolymer (PC) used is c, then a>b>c can be satisfied.

[0266] If the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based polycarbonate copolymer (Si-PC) used is d, then a'>b'>d can be satisfied.

[0267] A base resin comprising polybutylene terephthalate (PBT), polycarbonate homopolymer (PC), and siloxane-based polycarbonate copolymer (Si-PC); glass fiber; and an additive; of a total of 100 wt%, the polybutylene terephthalate (PBT) may be included in an amount of 34.58 to 37 wt%, the polycarbonate homopolymer (PC) may be included in an amount of 24 wt% or less, the siloxane-based polycarbonate copolymer (Si-PC) may be included in an amount of 24 wt% or less, and the glass fiber may be included in an amount of 25 to 33 wt%.

[0268] The above melt mixing step may include, for example, other additives as described above.

[0269] The above melt mixing and extruding step can be performed using, for example, at least one selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer, preferably a twin-screw extruder, and by using the same to uniformly mix the composition and then extrude it, a thermoplastic resin composition in the form of, for example, pellets can be obtained. In this case, deterioration of mechanical properties and thermal characteristics is prevented, and there is an effect of excellent plating adhesion and appearance quality.

[0270] The step of manufacturing pellets using the above extrusion mixer can be performed, for example, at an extrusion temperature of 230 to 300°C, a flow ratio (F / R) of 50 to 90 kg / hr, and a screw rotation speed of 200 to 490 rpm, and preferably, at an extrusion temperature of 230 to 260°C, a F / R of 50 to 90 kg / hr, and a screw rotation speed of 250 to 350 rpm.

[0271] The method may include a step of extruding the thermoplastic resin composition and then injecting the composition at an injection temperature of 240 to 280°C, specifically 250 to 270°C, a mold temperature of 40 to 80°C, specifically 50 to 70°C, and an injection speed of 10 to 80 mm / sec, specifically 20 to 60 mm / sec.

[0272] The following drawing 2 is a cross-sectional view of an extruder used in a method for manufacturing a molded product according to one embodiment of the present invention.

[0273] The above extruder may have, for example, 6 or more, preferably 7 or more, more preferably 8 or more, preferably 8 to 15, and more preferably 9 to 12 kneading blocks. At this time, it may be effective to use the kneading blocks in combination in the order of forward, orthogonal, and reverse with respect to the resin flow direction, and a continuous or separated block combination may be used depending on the mixing method. In this case, the dispersibility of the components, the compatibility of the composition, etc. are further improved, thereby providing a kneaded product of higher quality.

[0274] The type of the above extruder is not particularly limited, and considering uniform mixing and dispersion, ease of processing, and economy, it may be preferable to use a twin-screw extruder with two screws.

[0275] The extruder is composed of a feeder for supplying materials into a barrel, a screw for transporting and mixing the materials supplied into the barrel, and a die for extruding the mixed materials, and the screw is composed of a plurality of screw elements to provide various functions.

[0276] The above raw material feeder may be one or more, and optionally, two or more may be provided as needed. For example, a main feeder and optionally, an auxiliary feeder may be provided, and two or more auxiliary feeders may be provided as needed.

[0277] For example, all components except glass fiber can be injected into the main inlet, and halogenated glass fiber can be injected into the auxiliary inlet 1.

[0278] As a specific example, referring to the following Figure 1, the extruder (100) may include first to third inlets (11, 12, 13) and first to third mixing blocks (21, 22, 23), and the material input along the first direction (DR1) may be mixed and discharged.

[0279] Specifically, the materials injected into the first inlet (11) can be mixed during the process of being moved to the first mixing block (21), so that a first mixed material can be formed in the first mixing block (21). The materials injected into the second inlet (12) can be mixed with the first mixed material and mixed during the process of being moved to the second mixing block (22), so that a second mixed material can be formed in the second mixing block (22). In addition, the materials injected into the third inlet (13) can be mixed with the second mixed material and mixed during the process of being moved to the third mixing block (23), so that a final product can be formed in the third mixing block (23).

[0280]

[0281] Furthermore, a molded article comprising the thermoplastic resin composition of the present invention will be described. When describing a molded article comprising the thermoplastic resin composition of the present invention, all of the contents of the thermoplastic resin composition described above are included.

[0282]

[0283] molded products

[0284] The thermoplastic resin composition of the present invention can be usefully applied to molded products requiring heat distortion temperature and impact strength through synergy between components.

[0285] The above-mentioned molded product can be manufactured using a method commonly used in the art. For example, a molten mixture, pellets, or a sheet (plate) molded therefrom of the thermoplastic resin composition according to the present invention can be used as a raw material for molding such as extrusion molding, casting, press molding, pressure molding, thermal bending molding, compression molding, calendar molding, rotational molding, injection molding, or injection compression molding.

[0286] The thermoplastic resin composition of the present invention can be manufactured into pellets by, for example, using a twin-screw extruder (φ40, L / D: 42, SM Platek equipment) set to 230°C at 250 rpm, feeding polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives into the main inlet at a feeding rate of 50 kg / h, and melt-kneading and extruding.

[0287] As another example, the thermoplastic resin composition of the present invention can be manufactured into pellets by using a twin-screw extruder (φ40, L / D: 42, SM Platek equipment) set to 260°C at 375 rpm, by feeding polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), and additives into the main inlet, and feeding glass fibers into the auxiliary inlet at a feeding rate of 75 kg / h, and melt-kneading and extruding.

[0288] The above pellets can be fed into an injection molding machine to manufacture a molded product.

[0289] In order to indirectly confirm the physical properties of the manufactured molded product, the pellets can be injected using an injection molding machine (ENGEL, 80 tons) at an injection temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to manufacture a specimen meeting ISO standards.

[0290] The manufactured specimen may have a flow index (260°C, 2.16 kgf) measured according to ISO 1133 of, for example, 5 g / 10 min or more, and specifically, 10 to 20 g / 10 min.

[0291] A molded article including the thermoplastic resin composition of the present invention may have a laser transmittance (%) of 67.5% or more, specifically 67.5% to 80%, and preferably 67.5% to 75%, as measured using EVlaser's ETM-31 equipment (980 nm).

[0292] The above laser transmittance was calculated by injection molding a resin molded product and a material as shown in Fig. 1 to manufacture a square specimen measuring 60 mm (width) X 60 mm (height) X 1.5 mm (thickness), and using ETM-31 (EV Laser Co., Ltd.), a laser was shot at the specimen at a laser irradiation wavelength of 980 nm and an output of 10 mW at the gate area (A) and a non-gate area (B), and the returned intensity value was measured, and calculated by the following mathematical formula 1.

[0293] In addition, at this time, the laser transmittance was measured 5 times for each part, and in Tables 1 and 2 below, the laser transmittance of the gate part is the average value of the laser transmittance measurement values ​​of the gate part, and the maximum transmittance is the average value of the laser transmittance measurement values ​​of locations excluding the gate part.

[0294] [Mathematical Formula 1]

[0295] Laser transmittance (%) = 100 × Po / Pi

[0296] In the above mathematical expression 1, Po is the laser output passing through the specimen, and Pi is the laser output before passing through the specimen.

[0297] Here, the laser power before passing the sample can be, for example, 10 mW.

[0298]

[0299] A molded article including the thermoplastic resin composition of the present invention may have a heat distortion temperature of 167.6°C or higher, specifically, 167.6 to 185.4°C, measured under a load of 0.45 MPa (flatwise) on a 4 mm thick specimen according to ISO 75.

[0300] A molded article including the thermoplastic resin composition of the present invention may have a room temperature Izod impact strength (23°C, Notched) measured according to ISO 180 of, for example, 9.5 kJ / m2 or more, and specifically, 9.75 to 11.52 kJ / m2.

[0301] A molded article including the thermoplastic resin composition of the present invention may have a low-temperature Izod impact strength (-30°C, Notched) measured according to ISO 180 of, for example, 8.4 kJ / m2 or more, and specifically, 8.55 to 9.8 kJ / m2.

[0302] A molded article including the thermoplastic resin composition of the present invention may mean a molded article manufactured from a thermoplastic resin composition or manufactured including a thermoplastic resin composition.

[0303]

[0304] The above molded product may be specifically a component for a battlefield, but is not limited to a specific type.

[0305] That is, a thermoplastic resin composition according to one embodiment of the present invention is characterized by including polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC) in a predetermined mixing ratio, and in this case, a molded article manufactured from the thermoplastic resin composition satisfies a property balance between heat distortion temperature and impact strength, and has the advantage of being usable in a wider variety of electrical components, including radomes, by further improving the heat resistance required for improved radar performance and the impact strength required for diversified application of radomes.

[0306] In describing the thermoplastic resin composition, its manufacturing method, and molded article of the present invention, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. In addition, % means weight % unless otherwise defined.

[0307]

[0308] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0309]

[0310] [Example]

[0311] Examples 1 to 3 and Comparative Examples 1 to 8

[0312] The raw materials used in the examples and comparative examples are as follows.

[0313] (A) Polybutylene terephthalate (PBT): Intrinsic viscosity (IV) 0.83, product name TH6082A

[0314] (B) Polycarbonate

[0315] B-1) Polycarbonate (PC): Melt index of 22 g / 10 min measured at 300°C, 1.2 kg according to ASTM D1238, mold shrinkage of 0.005 to 0.007 in / in measured according to ASTM D955, LG Chemical, product name LUPOY PC1300

[0316] B-2) Siloxane-based copolycarbonate (Si-PC): LG Chemical, product name LUPOY PC8000-05

[0317] (C) Glass fiber: NEG T-187H with an average length of 7 to 15 um

[0318] (D) Additives

[0319] D-1) Nucleator: Bruggemann P250 (sodium ionomer series)

[0320] D-2) Talc: Koch KC-3000 (average particle size 4.0±0.5um)

[0321] D-3) Primary antioxidant: IR 1010

[0322] D-4) Secondary antioxidant: PEP 36

[0323]

[0324] The raw materials of the thermoplastic resin composition described in Tables 1 and 2 below were mixed, and then a thermoplastic resin composition having a uniform dispersion was manufactured in the form of pellets through extrusion. Then, a specimen was manufactured through an injection process in which the pellets were heated, injected into a mold, and then cooled.

[0325] Specifically, each component shown in Tables 1 and 2 below was mixed with a mixer, and then fed into a twin-screw extruder (φ40, L / D: 42, SM Platek equipment) set to 250°C at 250 rpm at a feed rate of 50 kg / h through the main inlet, and extrusion was performed to manufacture pellets of a thermoplastic resin composition. At this time, glass fiber was fed into the auxiliary inlet, and nine mixing blocks of the extruder were used.

[0326] The above pellets were dried in a convection oven at 120°C for more than 4 hours, and then injection molded using an injection molding machine (ENGEL, 80 tons) at an injection temperature of 250°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to produce a specimen.

[0327] Classification Example 1 Example 2 Example 3 A34.634.634.6B-120.817.313.8B-213.817.320.8C303030D-1---D-2---D-30.40.40.4D-40.40.40.4

[0328] (The raw materials used in Table 1 above are each added in weight % units based on 100 weight % of the total of A to D-4.)

[0329] Classification Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Comparison Example 7 Comparison Example 8 A4 1.527.734.5534.5534.634.634.629.2 B-127.741.5344.5534.5534.6-29.6-B-2-----34.6540 C303030303030303030D-1--0.1-----D-2---0.1----D-30.40.40.40.40.40.40.40.40.4D-40.40.40.40.40.40.40.40.40.4

[0330] (The raw materials used in Table 2 above are each added in weight % units based on 100 weight % of the total of A-1 to D-4.)

[0331] Test Example 1: Evaluation of physical properties of molded product specimens

[0332] The physical properties of the molded product specimens manufactured in Examples 1 to 3 and Comparative Examples 1 to 8 were evaluated. The evaluation criteria are as follows.

[0333] -Laser Transmittance (%):

[0334] As shown in the following Figure 1, a square specimen measuring 60 mm (width) X 60 mm (length) X 1.5 mm (thickness) was manufactured by injection molding a resin molded product and a material, and a laser was shot at the specimen at a laser irradiation wavelength of 980 nm and an output of 10 mW using ETM-31 (EV Laser Co.) for the gate area (A) and a non-gate area (B), and the returned intensity value was measured and calculated using the following mathematical formula 1.

[0335] In addition, at this time, the laser transmittance was measured 5 times for each part, and in Tables 3 and 4 below, the laser transmittance of the gate part is the average value of the laser transmittance measurement values ​​of the gate part, and the maximum transmittance is the average value of the laser transmittance measurement values ​​of locations excluding the gate part.

[0336] [Mathematical Formula 1]

[0337] Laser transmittance (%) = 100 × Po / Pi

[0338] In the above mathematical expression 1, Po is the laser output passing through the specimen, and Pi is the laser output before passing through the specimen.

[0339] - Heat deflection temperature (HDT): Measured under a load of 0.45 MPa (flatwise) on a 4 mm thick specimen according to ISO 75.

[0340] - Room temperature impact strength (IZOD): Measured on 4 mm thick specimens according to ISO 180 (Notched, 23 ℃)

[0341] -Low-temperature impact strength (IZOD): Measured on 4 mm thick specimens according to ISO 180 (Notched, -30 ℃)

[0342] The results measured using the above evaluation criteria are shown in Tables 3 and 4 below.

[0343] Classification Example 1 Example 2 Example 3 Laser transmittance (%) 67.5 67.6 68.2 Heat distortion temperature (℃) 167.6 181.1 185.4 Room temperature impact strength (kJ / m 2 )9.7310.9611.52Low-temperature impact strength (kJ / m) 2 )8.558.919.6

[0344] ClassificationComparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Laser Transmittance (%)47.570.246.332.367.462.967.963.5Heat Deflection Temperature (℃)197.6128.2190.2195.8167.5185.2168.2155.3Room Temperature Impact Strength (kJ / m 2 )8.89.18.138.429.2412.19.212.9Low-temperature impact strength (kJ / m) 2 )7.818.37.547.568.139.718.2110.2

[0345] Referring to Tables 3 and 4 above, it can be confirmed that the thermoplastic resin compositions of Examples 1 to 3 according to the present invention contain polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) in a predetermined mixing ratio in polybutylene terephthalate (PBT), thereby improving the physical property balance between heat distortion temperature and impact strength, thereby satisfying the heat resistance required for improved radar performance and the impact strength required for diversified applications of radomes, and providing product reliability. On the other hand, it was confirmed that Comparative Examples 1 to 5, which do not contain siloxane-based copolycarbonate (Si-PC), showed lower laser transmittance, room temperature impact strength, and low temperature impact strength compared to Example 1, and thus could not provide the heat resistance required for improved radar performance and the impact strength required for diversified applications of radomes.

[0346] Meanwhile, Comparative Example 5, which does not use a nucleating agent or talc while mixing polybutylene terephthalate (PBT) and polycarbonate (PC) in an appropriate range even without including siloxane-based copolycarbonate (Si-PC), was confirmed to have improved laser transmittance and impact strength at room temperature / low temperature compared to Comparative Examples 1 to 4, but it was confirmed that the heat distortion temperature was significantly reduced.

[0347] In addition, Comparative Example 6, which did not include polycarbonate (PC) even though it included siloxane-based copolycarbonate (Si-PC), showed a decrease in laser transmittance compared to Example 1.

[0348] In addition, Comparative Example 7, which included siloxane-based copolycarbonate (Si-PC) but used a small amount outside the appropriate range, confirmed that the heat distortion temperature was reduced compared to Example 2.

[0349] In addition, Comparative Example 8, which used an excessive amount of siloxane-based copolycarbonate (Si-PC) beyond the appropriate range, showed a decrease in laser transmittance and heat distortion temperature compared to Example 1.

[0350]

[0351] That is, the thermoplastic resin composition according to one embodiment of the present invention includes organic fibers, etc., in polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based polycarbonate (Si-PC), thereby satisfying the physical property balance between the heat distortion temperature and impact strength of the manufactured molded product, and satisfying the heat resistance required for improvement in radar performance and the impact strength required for diversification of the application of radomes, making it suitable for use in electrical components, etc.

[0352] [Explanation of symbols]

[0353] 100: Extruder 11: First inlet 12: Second inlet

[0354] 13: Third inlet 21: First mixing block 22: Second mixing block

[0355] 23: Third Mixing Block DR1: First Direction

Claims

1. Including polybutylene terephthalate (PBT), polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC); and glass fiber; The weight ratio of polycarbonate (PC) and siloxane copolycarbonate (Si-PC) to the above polybutylene terephthalate (PBT) is within the range of 4:6 to 6:4 (PBT:PC+Si-PC). The weight ratio of the above polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC), If 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, then a>b>c is satisfied. A thermoplastic resin composition characterized in that it satisfies a'>b'>d, where the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based copolycarbonate (Si-PC) used is d.

2. Among the total 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives; Containing 31.3 to 37 wt% of the above polybutylene terephthalate (PBT), Contains 24 wt% or less of the above polycarbonate (PC), Contains 24 wt% or less of the above siloxane-based copolycarbonate (Si-PC), A thermoplastic resin composition characterized in that it contains 10 to 40 wt% of the above glass fiber.

3. In paragraph 1 or 2, The above polybutylene terephthalate (PBT) is a thermoplastic resin composition characterized in that the weight average molecular weight is 10,000 to 80,000 g / min.

4. In paragraph 1 or 2, A thermoplastic resin composition characterized in that the above polybutylene terephthalate (PBT) and polycarbonate (PC) are included in a weight ratio (PBT:PC) of 1:0.3 to 1:1.

1.

5. In paragraph 1, A thermoplastic resin composition characterized in that the polycarbonate (PC) comprises 13 to 21 wt% of a total of 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

6. In paragraph 1, A thermoplastic resin composition characterized in that the above siloxane-based copolycarbonate (Si-PC) comprises 13 to 21 wt% of the total 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), siloxane-based copolycarbonate (Si-PC), glass fiber, and additives.

7. In paragraph 1, The above polycarbonate (PC) is a thermoplastic resin composition characterized in that the melt index measured at 300°C and 1.2 kg according to ASTM D1238 is 0.1 to 30 g / 10 min, and the mold shrinkage measured according to ASTM D955 is 0.005 to 0.007 in / in.

8. In paragraph 1, A thermoplastic resin composition characterized in that the above glass fibers are chopped strands having an average diameter of 7 to 15 μm and an average length of 3 to 9 mm.

9. In paragraph 1, A thermoplastic resin composition characterized in that the additive comprises at least one selected from a nucleating agent, an activator, talc, an antioxidant, and a colorant.

10. In paragraph 1, A thermoplastic resin composition characterized in that the above thermoplastic resin composition is a material used in electrical components.

11. In paragraph 1, The thermoplastic resin composition has a heat distortion temperature of 167.6°C or higher when measured under a load of 0.45 MPa (flatwise) on a 4 mm thick specimen according to ISO 75. A thermoplastic resin composition characterized in that the room temperature Izod impact strength (23 ℃, Notched) measured on a 4 mm thick specimen according to ISO 180 is 9.5 kJ / m2 or more, and the low temperature Izod impact strength (-30 ℃, Notched) measured on a 4 mm thick specimen according to ISO 180 is 8.4 kJ / m2 or more.

12. A step of introducing polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives into an extruder, and melt-mixing and extruding them. The weight ratio of polycarbonate (PC) and siloxane copolycarbonate (Si-PC) to the above polybutylene terephthalate (PBT) is within the range of 4:6 to 6:4 (PBT:PC+Si-PC). The weight ratio of the above polycarbonate (PC) and siloxane-based copolycarbonate (Si-PC) satisfies 3.5:6.5 to 6.5:3.5 (PC:Si-PC), If 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, then a>b>c is satisfied. A method for producing a thermoplastic resin composition characterized in that a'>b'>d is satisfied, where the amount of polybutylene terephthalate (PBT) used is a', the amount of glass fiber used is b', and the amount of siloxane-based copolycarbonate (Si-PC) used is d.

13. Among the total 100 wt% of polybutylene terephthalate (PBT), polycarbonate (PC), and siloxane-based copolycarbonate (Si-PC); glass fiber; and additives; Containing 31.3 to 37 wt% of the above polybutylene terephthalate (PBT), Contains 24 wt% or less of the above polycarbonate (PC), Contains 24 wt% or less of the above siloxane-based copolycarbonate (Si-PC), A method for producing a thermoplastic resin composition, characterized by comprising the step of introducing the glass fiber into an extruder, melt mixing, and extruding the composition, wherein the glass fiber is included in an amount of 10 to 40 wt%.

14. A molded product characterized by comprising a thermoplastic resin composition according to any one of claims 1 to 11.

15. In paragraph 14, A molded product characterized in that the above molded product is a component for a battlefield.

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