Thermoplastic resin composition, method for preparing the 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 present invention relates to: a thermoplastic resin composition comprising 32.5 wt% to 49 wt% of a polymer (a), 7 wt% to 20.5 wt% of a ceramic-forming binder (b), 6.5 wt% to 20.5 wt% of a ceramic-forming metal precursor (c), 13 wt% to 37 wt% of a ceramic-forming non-metal precursor (d), and 2 wt% to 8 wt% of a flame retardant (e); methods of making the same; comprising the same. According to the present invention, the present invention has the effects of providing a thermoplastic resin composition having excellent flame retardancy and electrical insulation properties, and having excellent flame retardancy during thermal runaway by forming ceramics and retarding flame propagation at a high temperature and in the case of flame generation, thereby being capable of securing property and life safety, and having excellent flame retardancy during thermal runaway. The method is environment-friendly; methods of making the same; and a molded article including the same.

Description

Technical Field

[0001] [Cross-references to related applications] This application claims priority to Korean Patent Application No. 10-2024-0053331 and Korean Patent Application No. 10-2024-0053332, filed on April 22, 2024, respectively, the disclosures of which are incorporated herein by reference.

[0002] This invention relates to a thermoplastic resin composition, a method for preparing the same, and molded articles comprising the same. More specifically, this invention relates to an environmentally friendly thermoplastic resin composition, a method for preparing the same, and molded articles comprising the same, said thermoplastic resin composition having excellent flame retardant and electrical insulating properties, and being able to ensure the safety of property and life by forming ceramics and delaying flame propagation in the event of an accidental ultra-high temperature flame and the resulting pressure. Background Technology

[0003] Thermoplastic resins have excellent impact resistance, abrasion resistance, cold resistance, chemical resistance and electrical insulation properties, and are widely used in various fields such as household products, electronic and electrical components, automotive parts, building materials and various industrial materials.

[0004] Recently, thermoplastic resins used in automotive parts, especially electric vehicle batteries, have required higher fire safety. Therefore, thermoplastic resins are required to have flame retardancy in the event of thermal runaway.

[0005] Thermal runaway is a major cause of electric vehicle battery fires. It refers to the phenomenon where the temperature rises uncontrollably and explodes when abnormal pressure is applied to a single battery cell. A fire can occur when the internal temperature of the battery rises above a certain level due to a short circuit caused by factors such as overvoltage or over-discharge. However, lithium-ion batteries are highly reactive with water, making it difficult to extinguish the flames with water. Furthermore, the risk of thermal runaway increases with the use of larger capacity batteries to improve driving range.

[0006] Typically, when preparing thermoplastic resins, flame retardancy and flame retardancy are imparted by combining halogen and antimony compounds. This method of imparting flame retardancy through the combination of halogen and antimony compounds ensures flame retardancy ratings of V-0 or 5V according to UL 94 testing. However, according to the above method, flame retardancy performance deteriorates significantly when flames above 1200°C and the resulting pressure are generated. Furthermore, hydrogen halide gases produced during processing or endocrine disruptors released during combustion may have fatal adverse effects on human health.

[0007] Furthermore, halogen-free flame retardants are called halogen-free flame retardants, and the most widely used halogen-free flame retardants are phosphorus-based flame retardants containing phosphorus. However, the flame retardancy of phosphorus-based flame retardants is significantly lower than that of halogen-based flame retardants. Therefore, by adding a large amount of flame retardant, a V-0 or 5V flame retardancy rating according to the UL 94 test can be obtained, but it lacks flame delay properties to prevent thermal runaway when faced with accidental ultra-high temperature flames above 1200°C and the resulting pressure.

[0008] In addition, thermoplastic resins used in electric vehicle battery components require electrical insulation properties because the components are exposed to electric current for a long time.

[0009] Therefore, there is a need to develop a thermoplastic resin composition that has excellent electrical insulation and flame retardancy, ensures safety from additional damage during thermal runaway due to its excellent flame delay properties, and meets the quality requirements of automotive parts, especially electric vehicle battery components.

[0010] [Related Technical Documents] [Patent Literature] Japanese Patent Application Publication No. Hei 2-187456 Summary of the Invention

[0011] Technical issues Therefore, the present invention was made in view of the above-mentioned problems. One object of the present invention is to provide an environmentally friendly thermoplastic resin composition that has excellent flame retardancy, electrical insulation properties and flame delay properties, thereby ensuring high safety of property and life by forming ceramics during thermal runaway.

[0012] Another object of the present invention is to provide a method for preparing the thermoplastic resin composition.

[0013] Another object of the present invention is to provide a molded article manufactured using the said thermoplastic resin composition.

[0014] The above and other objectives can be achieved by the invention described below.

[0015] Technical solution I) According to one aspect of the present invention, a thermoplastic resin composition is provided, comprising: 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d), and 2% to 8% by weight of a flame retardant (e).

[0016] II) According to I), the polymer (a) may include one or more selected from polyamide resins, poly(arylene ether) resins, polyalkylene terephthalate resins, polystyrene resins, polycarbonate resins and modified resins thereof.

[0017] III) According to I) or II), the ceramic forming binder (b) may include a metal phosphorus-based flame retardant.

[0018] IV) According to I) to III), the ceramic forming metal precursor (c) may include metal silicates, or may include less than 3% by weight of magnesium (excluding magnesium oxide) or magnesium oxide based on the total weight of the ceramic forming metal precursor.

[0019] V) According to I) to IV), the metal silicate may include one or more selected from aluminosilicates and calcium silicates.

[0020] VI) According to I) to V), the aluminosilicate may include one or more selected from kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene and sulphite.

[0021] VII) According to I) to VI), the calcium silicate may include wollastonite.

[0022] VIII) According to I) to VII), the ceramic forming nonmetallic precursor (d) may include glass fiber.

[0023] IX) According to I) to VIII), the flame retardant (e) may include one or more selected from melamine flame retardants, phosphazene flame retardants and phosphate ester flame retardants.

[0024] X) According to I) to IX), when a 1200°C flame of oxygen and propane gas is applied to a 150mm × 150mm × 3mm specimen and the flame retardancy time is measured until pores or dripping occurs, the flame retardancy time of the thermoplastic resin composition may be greater than 600 seconds, or when the Comparative Tracking Index (CTI) is measured using a 3mm thick specimen according to IEC 60112, the thermoplastic resin composition may be classified as Grade 1 or higher according to the Performance Class Category (PLC).

[0025] XII) According to another aspect of the present invention, a method for preparing a thermoplastic resin composition is provided, the method comprising: kneading and extruding 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d) and 2% to 8% by weight of a flame retardant (e), wherein the kneading and extrusion are performed using an extruder having nine or more kneading blocks.

[0026] XIII) According to another aspect of the present invention, a flame retardant composition is provided, comprising: a ceramic forming binder, a ceramic forming metal precursor, a ceramic forming non-metal precursor, and a flame retardant.

[0027] XIV) According to XIII), based on its total weight, the flame retardant composition may comprise: 11% to 34% by weight of ceramic-forming binder, 14.5% to 41% by weight of ceramic-forming metal precursor, 24% to 59% by weight of ceramic-forming non-metal precursor and 4% to 14% by weight of flame retardant.

[0028] XV) According to another aspect of the invention, a molded article is provided, comprising the thermoplastic resin composition according to I) to XI).

[0029] Beneficial effects According to the present invention, the advantages of the present invention are that it provides a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molded article comprising the thermoplastic resin composition, wherein the thermoplastic resin composition has flame retardancy of V-0 or higher as evaluated according to UL 94 testing, has excellent electrical insulation properties, and blocks flame propagation by forming ceramics when subjected to ultra-high temperature flames above 1200°C and the resulting pressure, thereby ensuring the safety of property and life even during thermal runaway (e.g., the thermoplastic resin composition has a flame resistance time of 600 seconds or more, or is classified as Level 1 or higher according to Performance Class Category (PLC) by measuring the Comparative Tracking Index (CTI). Furthermore, due to its environmental friendliness, the thermoplastic resin composition is suitable for automotive parts, particularly electric vehicle batteries. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of an extruder having nine or more kneading blocks according to the present invention.

[0031] Figure 2 This is a schematic diagram illustrating the measurement method for evaluating blowtorches and gravel according to UL 2596.

[0032] Figure 3These are photos of actual measurement scenarios for torch and gravel evaluation according to UL 2596.

[0033] Figure 4 The actual measurement scenario (left) of the UL 2596 torch and gravel evaluation of the thermoplastic resin composition according to Example 1 and the specimen after 600 seconds of flame application are shown (right).

[0034] Figure 5 The actual measurement scenario (left) and the evaluated specimen (right) of the thermoplastic resin composition according to Example 5 under UL 2596 blowtorch and gravel evaluation are shown.

[0035] Figure 6 The following are specimens after evaluation by torch and gravel according to Comparative Example 6 thermoplastic resin composition under UL 2596. The left image shows the front of the specimen and the right image shows the back of the specimen. Detailed Implementation

[0036] The thermoplastic resin compositions of the present invention, methods for preparing them, and molded articles comprising them will be described in detail below.

[0037] The inventors have demonstrated that when a thermoplastic resin composition is prepared by comprising a predetermined amount of a polymer, a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming non-metal precursor, and a flame retardant, the thermoplastic resin composition exhibits a flame retardancy rating of V-0 or higher as measured by UL 94 testing, and possesses excellent insulation properties. Furthermore, in the event of an ultra-high temperature flame exceeding 1200°C and the resulting pressure, the thermoplastic resin composition ensures the safety of property and life even in the event of thermal runaway by forming ceramics and delaying flame propagation. Based on these results, the inventors conducted further research to complete this invention.

[0038] The thermoplastic resin composition according to the present invention is specifically described below.

[0039] The thermoplastic resin composition of the present invention comprises: 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d), and 2% to 8% by weight of a flame retardant (e). In this configuration, excellent flame retardancy and insulation properties can be achieved. Furthermore, in the event of an accidental ultra-high temperature flame, by forming a ceramic and delaying flame propagation, the safety of property and life can be ensured, and environmental friendliness can be achieved.

[0040] The components of the thermoplastic resin composition of the present invention will be described in detail below.

[0041] In this invention, ceramics as defined in the technical or scientific field to which this invention pertains can be used without particular limitation. As a specific example, ceramics can refer to a sintering process in which metals and nonmetals or quasi-metals are combined through heat treatment to form crystals, and the formed crystals then aggregate to form a three-dimensional network structure. According to these definitions, in this invention, ceramic precursors corresponding to metals are defined as inorganic substances containing metallic elements, and ceramic precursors corresponding to nonmetals or quasi-metals are defined as substances containing more than 50% by weight of silicon dioxide.

[0042] (a) Polymer For example, the polymer may include one or more selected from polyamide resins, poly(aryl ether) resins, polyalkylene terephthalate resins, polystyrene resins, polycarbonate resins, and modified resins thereof, preferably one or more selected from polyamide resins, poly(aryl ether) resins, and polyalkylene terephthalate resins. In this case, mechanical properties such as impact strength, tensile strength, elongation, flexural strength, and surface hardness, as well as electrical insulation properties and flame retardancy, can be excellent. Furthermore, in the event of thermal runaway, the excellent flame delay properties can ensure the safety of property and life.

[0043] For example, based on the total weight of components (a) to (e), the content of polymer (a) can be from 32.5% to 49% by weight, preferably from 34% to 47% by weight, more preferably from 35% to 46% by weight or 36% to 45% by weight, even more preferably from 38% to 45% by weight, and even more preferably from 38% to 43% by weight. Within this range, mechanical properties, electrical insulation properties, and flame retardancy can be excellent. Furthermore, in the event of thermal runaway, the excellent flame delay properties ensure the safety of property and life.

[0044] In this invention, thermal runaway refers to an environmental state altered by a temperature change that further accelerates the temperature change. Specifically, thermal runaway can be described as a process in which a mechanical process is initiated by an increase in temperature, and the energy released by this process causes the temperature to rise further, accelerating the process.

[0045] In this invention, when the modification is carried out by a resin modification method commonly used in the technical field to which this invention pertains, there are no particular limitations on the modification. For example, the above-mentioned modification may refer to grafting by introducing at least one compound of α,β-unsaturated dicarboxylic acid and its anhydride into an unmodified resin. As another example, the above-mentioned modification may refer to introducing at least one compound of α,β-unsaturated dicarboxylic acid and its anhydride as a comonomer and copolymerizing it when manufacturing an unmodified resin.

[0046] polyamide resin For example, the polyamide resin may be a polyamide prepared by polycondensation of lactam or ω-amino acid, or by polycondensation of two or more types of lactam and ω-amino acid, or by polycondensation of diacid and diamine, but the present invention is not limited thereto.

[0047] Preferably, the polyamide resin may include one or more selected from: copolymers of diamines having 2 to 30 carbon atoms and dicarboxylic acids having 4 to 30 carbon atoms; lactam polymers; aminocarboxylic acid polymers; and copolymers of lactams and aminocarboxylic acids. In this case, the mechanical properties and appearance quality can be excellent.

[0048] Alternatively, the polyamide resin may be, for example, homopolymer, copolyimide, or a mixture thereof.

[0049] For example, the polyamide resin may be crystalline, semi-crystalline, or amorphous.

[0050] Polymers of diamines having 2 to 30 carbon atoms and dicarboxylic acids having 4 to 30 carbon atoms may preferably include one or more polymers selected from a polyamide, said polyamide being formed by reacting an aliphatic or aromatic diamine, such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecylmethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonylhexanediamine, m-xylenediamine, p-xylenediamine, 1,3-diaminodiamine, etc. Methylcyclohexane, 1,4-diaminomethylcyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexane)methane, bis(4-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperidine are obtained by polymerization with aliphatic or aromatic dicarboxylic acids, such as adipic acid, sebacic acid, azelaic acid, terephthalic acid, 2-chloroterephthalic acid, and 2-methylterephthalic acid.

[0051] Lactam polymers can preferably be obtained by ring-opening polymerization of lactam compounds such as caprolactam and laurolactam.

[0052] Aminocarboxylic acid polymers can preferably be obtained by polymerizing aminocarboxylic acids such as aminohexanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

[0053] The polyamide resin may preferably include one or more selected from the following: polyamide 6, polyamide 66, polyamide 46, polyamide 56, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6 / 66, polyamide 6 / 612, polyamide MXD6, polyamide 6 / MXD6, polyamide 66 / MXD6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 9T, polyamide 9I, polyamide 6 / 9T, polyamide 6 / 9I, polyamide 66 / 9T, polyamide 6 / 12 / 9T, polyamide 66 / 12 / 9T, polyamide 6 / 12 / 9I, and polyamide 66 / 12 / 6I, more preferably selected from one or more of polyamide 6, polyamide 56, and polyamide 66. In this case, economic efficiency or processing performance can be excellent. Furthermore, mechanical properties and heat resistance can be improved.

[0054] For example, the relative viscosity (RV) of the polyamide resin can be from 1.5 to 3.5, preferably from 1.7 to 3, and more preferably from 2.0 to 2.7. In this case, overheating due to friction between the extruder screw and the molten composition during extrusion molding can be prevented. Furthermore, since the tension applied to the molten composition is appropriate, the extrusion processing performance can be excellent.

[0055] In this invention, unless otherwise stated, the relative viscosity is measured at 20°C using a UFIT-UVS instrument using a solution prepared by dissolving 1 g of polyamide in 100 ml of sulfuric acid (96 wt%).

[0056] Poly(arylene ether) resin For example, a poly(arylene ether) resin can be a homopolymer or copolymer comprising units represented by chemical formula 1 or chemical formula 2 below.

[0057] [Chemical Formula 1] [Chemical Formula 2] In Formula 1 and Formula 2, R1, R2, R3, R4, R'1, R'2, R'3, and R'4 can be substituents of arylene (Ar) or phenylene, and can be hydrogen, chlorine, bromine, iodine, alkyl, allyl, phenyl, alkylbenzyl, chloroalkyl, bromoalkyl, cyanoalkyl, cyano, alkoxy, phenoxy, or nitro, Ar can be an arylene having 6 to 20 carbon atoms, and alkoxy can be an alkoxy having 1 to 4 carbon atoms.

[0058] Preferably, R1, R2, R3, R4, R'1, R'2, R'3, and R'4 can be substituents of arylene (Ar) or phenylene, and can be hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy, or nitro, and Ar can be an arylene having 6 to 20 carbon atoms.

[0059] There is no particular limitation on the average degree of polymerization of the poly(arylene ether) resin relative to the unit of chemical formula 1 or chemical formula 2, as long as the average degree of polymerization meets the definition of this invention.

[0060] For example, homopolymers of poly(aryl ether) resins may include one or more selected from the following: poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-dichloromethyl-1,4-phenylene) ether, poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, and poly(2,5-dimethyl-1,4-phenylene) ether. In this case, mechanical properties such as impact strength, tensile strength, and flexural strength, as well as processing properties, can be excellent, thereby improving appearance quality.

[0061] Additionally, the copolymer of poly(aryl ether) resin may include one or more selected from: copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresol, and copolymers of 2,3,6-trimethylphenol and o-cresol. In this case, mechanical properties such as impact strength and tensile strength, as well as processability, can be excellent, thereby improving appearance quality.

[0062] The poly(arylene ether) resin is preferably a polyphenylene ether resin.

[0063] For example, the intrinsic viscosity of the poly(aryl ether) resin can be from 25 dl / g to 55 dl / g, preferably from 30 dl / g to 50 dl / g, and more preferably from 32 dl / g to 45 dl / g. Within this range, the mechanical properties of the composition, such as impact strength and tensile strength, can be maintained at a high level, while ensuring suitable flowability for molding.

[0064] When measuring the intrinsic viscosity of poly(aryl ether) resins, unless otherwise specified, the sample to be tested shall be dissolved in chloroform at a concentration of 0.5 g / dl, and the intrinsic viscosity of the sample shall be measured using an Ubbelohde viscometer at 25°C.

[0065] Polyalkylene terephthalate resin For example, the polyalkylene terephthalate resin can be polybutylene terephthalate, polyethylene terephthalate, or mixtures thereof, preferably polybutylene terephthalate. In this case, the mechanical properties, flowability, and heat resistance can be excellent.

[0066] As the polybutylene terephthalate resin, conventional polybutylene terephthalate resins can be used without particular limitations. For example, polybutylene terephthalate resins obtained by direct esterification of 1,4-butanediol and terephthalic acid or dimethyl terephthalate, or by polycondensation via transesterification reaction, can be used.

[0067] Polybutylene terephthalate resins may contain repeating units represented by the following chemical formula 3.

[0068] [Chemical Formula 3] In chemical formula 3, n is the average degree of polymerization in the integer range of 50 to 200.

[0069] For example, the melting point of polybutylene terephthalate resin, measured by differential scanning calorimetry (DSC), can be between 200°C and 240°C, preferably between 210°C and 230°C, and more preferably between 220°C and 230°C. Within this range, mechanical properties can be maintained even at high temperatures.

[0070] According to ISO 1133, the melt flow rate of polybutylene terephthalate resin, measured at 250°C and 2.16 kgf, can be from 7 g / 10 min to 11 g / 10 min, preferably from 8 g / 10 min to 10 g / 10 min. Within this range, the processing properties can be excellent.

[0071] This invention may use methods commonly used in the technical field to prepare polyalkylene terephthalate resins, without particular limitation. When a commercially available product meets the definition of a polyalkylene terephthalate resin according to this invention, the product may be used in this invention.

[0072] The intrinsic viscosity of the polyalkylene terephthalate resin is preferably from 0.6 dl / g to 1.4 dl / g, more preferably from 0.8 dl / g to 1.4 dl / g, and even more preferably from 1.0 dl / g to 1.3 dl / g. Within this range, the melt index can be appropriate, thus resulting in excellent processability, molding performance, and molding stability.

[0073] Unless otherwise stated, the intrinsic viscosity of polyethylene terephthalate (PET) resins can be measured according to ASTM D2857. As a concrete example, the sample can be completely dissolved in dichloromethane, filtered, and the intrinsic viscosity of the filtrate can be measured using an Ubbelohde viscometer at 20°C.

[0074] polystyrene resin For example, the polystyrene resin can be general-purpose polystyrene, high-impact polystyrene resin, or mixtures thereof, preferably high-impact polyethylene resin. In this case, processing properties, dimensional stability, and tensile strength can be excellent.

[0075] For example, general-purpose polystyrene resin can be a polymer obtained by polymerizing styrene alone. In this case, the processing properties can be excellent.

[0076] For example, high-impact polystyrene resin can be rubber-reinforced polystyrene resin.

[0077] For example, the rubber may include one or more selected from butadiene rubber, isoprene rubber, copolymers of butadiene and styrene, and alkyl acrylate rubber, preferably butadiene rubber. In this case, the impact strength can be improved.

[0078] For example, based on 100% by weight of high-impact polystyrene resin, the rubber content can be from 3% by weight to 25% by weight, preferably from 6% by weight to 14% by weight, and more preferably from 8% by weight to 12% by weight. Within this range, the impact strength and flowability can be excellent.

[0079] For example, the volume average particle size of the rubber can be from 0.1 µm to 20 µm, preferably from 1.0 µm to 15 µm. Within this range, impact strength and flowability can be excellent.

[0080] In this invention, the volume average particle size can be measured as follows: 3g of high-impact polystyrene resin is dissolved in 100ml of methyl ethyl ketone using a Coulter counter LS230 device, and then the undissolved rubber particles are dispersed in the form of particles by laser scattering.

[0081] Rubber-reinforced polystyrene resins may include one or more selected from the following: high-impact styrene-butadiene (HIPS) copolymer, styrene-butadiene-styrene (SBS) copolymer, styrene-ethylene-butene-styrene (SEBS) copolymer, styrene-butadiene (SB) copolymer, styrene-isoprene (SI) copolymer, styrene-isoprene-styrene (SIS) copolymer, α-methylstyrene-butadiene copolymer, styrene-ethylene-propylene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-(ethylene-butene-styrene copolymer)-styrene copolymer.

[0082] For example, rubber-reinforced polystyrene resins can be prepared by bulk polymerization, suspension polymerization, emulsion polymerization, or combinations thereof of rubber and aromatic vinyl compounds. The polymerization can be thermal polymerization or can be carried out in the presence of a polymerization initiator.

[0083] For example, polymerization initiators that can be used for polymerization can be peroxide initiators, azo initiators, or mixtures thereof.

[0084] The peroxide initiator may include one or more selected from benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide and cumene hydroperoxide, and the azo initiator may preferably be azobisisobutyronitrile.

[0085] For example, according to ASTM D1238, the melt flow index of polystyrene resin measured at 200°C and 5 kg can be from 2 g / 10 min to 20 g / 10 min, preferably from 3 g / 10 min to 15 g / 10 min. Within this range, a good balance between processing performance and physical properties can be achieved.

[0086] polycarbonate resin For example, polycarbonate resin can be a resin obtained by polymerizing an aromatic diol compound and a carbonate precursor.

[0087] For example, aromatic diol compounds may include one or more selected from the following: 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, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5-hydroxyphenyl)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 α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, preferably bisphenol A.

[0088] For example, carbonate precursors may include one or more selected from: dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, xylene carbonate, bis(chlorophenyl) carbonate, m-cresol carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and dihalocarbamates. Triphosgene, phosgene, or mixtures thereof may be preferred in terms of manufacturing efficiency and physical properties.

[0089] As a specific example, polycarbonate formed by the polymerization of aromatic diol compounds and carbonate precursors contains repeating units represented by the following chemical formula 4.

[0090] [Chemical Formula 4] In chemical formula 4, R'5 to R'8 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkyl or halogen, Z' is an unsubstituted C 1-10 Alkylene or C 1-6 Alkyl or C 6-20 aryl-substituted C 1-10 Alkylene, unsubstituted C 3-15 Cycloalkylene or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2 or CO.

[0091] Preferably, in chemical formula 4, R'5 to R'8 are each independently hydrogen or C. 1-3 Alkyl group, Z' is an unsubstituted C 1-6Alkylene or C substituted with methyl or phenyl 1-6 Alkylene.

[0092] For example, the melt index (300°C, 1.2 kg) of polycarbonate can be from 3 g / 10 min to 20 g / 10 min, preferably from 5 g / 10 min to 17 g / 10 min, and more preferably from 7 g / 10 min to 15 g / 10 min. Within this range, mechanical properties and heat resistance can be excellent.

[0093] In this invention, the melt index is measured at 300°C and under a load of 1.2 kg, according to ASTM D1238.

[0094] There are no particular restrictions on the average degree of polymerization of the repeating units of chemical formula 4 of the polycarbonate resin, as long as the average degree of polymerization meets the definition of this invention.

[0095] (b) Ceramic forming binder In this invention, when an ultra-high temperature flame and the resulting pressure are generated, the ceramic-forming binder is thermally decomposed, producing a metal phosphate component. This metal phosphate component acts as a binder, binding together the ceramic-forming metallic precursor and the ceramic-forming non-metallic precursor reaching the Gob temperature, causing physical and chemical structural changes to form a ceramic. When the battery experiences thermal runaway, the formed ceramic slows flame propagation, ensuring the safety of property and life and achieving environmental friendliness.

[0096] In this invention, the Gob temperature refers to the temperature at which the ceramic forming nonmetallic precursor melts and transforms into a hot block called Gob, which can be formed into a desired shape.

[0097] In this invention, the ultra-high temperature flame and the resulting pressure refer to the pressure generated by the ultra-high temperature flame being transmitted to the sample along with the flame when a 1200°C flame formed of oxygen and propane gas is applied to the sample in a blowtorch and gravel evaluation based on UL 2596.

[0098] In this invention, the ceramic may preferably contain the components Al, Si, Ca, and P. In this case, the flame retardation performance can be excellent when the battery experiences thermal runaway.

[0099] For example, based on the total weight of components (a) to (e), the content of the ceramic forming binder (b) can be from 7% to 20.5% by weight, preferably from 8% to 19% by weight, more preferably from 9% to 18% by weight, even more preferably from 9% to 17% by weight, and even more preferably from 9% to 13% by weight. Within this range, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperatures and the resulting pressure occur, the ceramic forms and slows flame propagation. Therefore, even in the event of thermal runaway, safety from additional damage can be ensured, and environmental friendliness can be achieved.

[0100] For example, the ceramic forming binder (b) may include a metal phosphorus-based flame retardant, preferably an organophosphonic acid metal salt, more preferably a dialkylphosphonate represented by Formula 5 below, a diphosphonate represented by Formula 6 below, or a mixture thereof. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperatures and the resulting pressure occur, the ceramic forms and slows flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured, and environmental friendliness can be achieved.

[0101] [Chemical Formula 5] [Chemical Formula 6] In chemical formulas 5 and 6, R 5 R 6 R 7 and R 8 Each is independently either a straight chain or a branched chain C1-C 10 Alkyl, C3-C 12 cycloalkyl, C6-C 10 Aryl or H;R 9 Is it a straight chain or a branched chain C1-C? 10 Alkylene, C6-C 10 Aspartic, C6-C 20 Alkyl arylene or C6-C 20 Arylalkylene; M1 is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na or K; M2 is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na or K; m is an integer from 1 to 4; m' is an integer from 1 to 4; n is an integer from 1 to 4; x is an integer from 1 to 4.

[0102] In formulas 5 and 6, preferably, the cycloalkyl group can be cyclohexyl or cyclohexyldimethyl independently.

[0103] Preferably, R5 R 6 R 7 and R 8 Each of these can be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or phenyl, and each can be independent of the other.

[0104] R 9 The preferred materials are methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene.

[0105] Preferably, M1 and M2 can each be independently Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, or K. More preferably, M1 and M2 can each be independently Mg, Ca, Al, Ti, or Zn.

[0106] R 5 and R 6 and R 7 and R 8 They can combine with each other to form rings with adjacent phosphorus atoms. (By R) 5 and R 6 and R 7 and R 8 The rings formed by the atoms bonded together with each other and adjacent phosphorus atoms are heterocycles having phosphorus atoms as constituent atoms of the ring. For example, the number of atoms constituting such a ring can be 4 to 20, preferably 5 to 16. The heterocycle having phosphorus atoms can be a bicyclic ring or have substituents.

[0107] The dialkyl phosphinate represented by Formula 5 may preferably include one or more of the following: calcium dimethyl phosphinate, magnesium dimethyl phosphinate, aluminum dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, magnesium ethyl methyl phosphinate, aluminum ethyl methyl phosphinate, zinc ethyl methyl phosphinate, calcium diethyl phosphinate, magnesium diethyl phosphinate, aluminum diethyl phosphinate, zinc diethyl phosphinate, calcium methyl-n-propyl phosphinate, magnesium methyl-n-propyl phosphinate, aluminum methyl-n-propyl phosphinate, zinc methyl-n-propyl phosphinate, calcium methyl phenyl phosphinate, magnesium methyl phenyl phosphinate, aluminum methyl phenyl phosphinate, zinc methyl phenyl phosphinate, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate.

[0108] The secondary phosphonates represented by chemical formula 6 may preferably include one or more selected from the following: calcium methylene bis(methylphosphonic acid), magnesium methylene bis(methylphosphonic acid), aluminum methylene bis(methylphosphonic acid), zinc methylene bis(methylphosphonic acid), calcium 1,4-phenylene bis(methylphosphonic acid), magnesium 1,4-phenylene bis(methylphosphonic acid), aluminum 1,4-phenylene bis(methylphosphonic acid), and zinc 1,4-phenylene bis(methylphosphonic acid).

[0109] More preferably, the ceramic forming binder (b) may include one or more selected from calcium dimethyl phosphinate, aluminum dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, aluminum ethyl methyl phosphinate, zinc ethyl methyl phosphinate, calcium diethyl phosphinate, aluminum diethyl phosphinate, and zinc diethyl phosphinate, and even more preferably aluminum diethyl phosphinate. In this case, high flame retardancy can be achieved with a small amount of flame retardant while maintaining mechanical properties. Furthermore, even in the event of thermal runaway, the excellent flame delay properties ensure the safety of property and life, and environmental friendliness can be achieved.

[0110] As a specific example, when aluminum diethylphosphonate is used as a ceramic forming binder (b), the organic components volatilize into phosphoric acid gas under ultra-high temperature flame, and the remaining components change from an amorphous structure to a crystalline structure, and the structure of AlPO3 changes to the structure of AlPO4, thereby combining the ceramic forming metal and the ceramic forming non-metal together.

[0111] For example, the average particle size of the ceramic forming binder (b) can be from 0.1 µm to 100 µm, preferably from 0.1 µm to 80 µm, and more preferably from 1 µm to 60 µm. Within this range, flame retardancy and mechanical properties can be excellent.

[0112] In this invention, the average particle size of the ceramic forming binder refers to the number-average particle size obtained from the frequency distribution of particle size and number measured using a laser diffraction particle size analyzer, using a dispersion of the binder dispersed in a medium such as acetone as a measurement sample.

[0113] The phosphorus content of the ceramic forming binder (b) is preferably from 20% to 35% by weight, more preferably from 22% to 30% by weight. Within this range, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperatures and the resulting pressure are generated, the ceramic forms and slows down flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0114] In this invention, phosphorus content refers to the weight (weight %) of phosphorus obtained by converting the molecular weight of phosphorus contained in the molecular structure of phosphorus-based flame retardants.

[0115] (c) Ceramic forming metal precursors In this invention, when an ultra-high temperature flame and the resulting pressure are generated, the metal phosphate component produced by the thermal decomposition of the ceramic forming binder causes the ceramic forming metal precursor to combine with the Gob-state ceramic forming non-metal precursor, thereby inducing physical and chemical structural changes to form a ceramic. The formed ceramic slows down the flame. Therefore, even when the battery experiences thermal runaway, the safety of property and life can be ensured.

[0116] For example, based on the total weight of components (a) to (e), the content of the ceramic-forming metal precursor (c) can be from 6.5% to 20.5% by weight, preferably from 8% to 19% by weight or from 8% to 18% by weight, more preferably from 9% to 18% by weight, even more preferably from 10% to 17% by weight, and even more preferably from 13% to 17% by weight. Within this range, flame retardancy and electrical insulation properties can be excellent. Furthermore, when ultra-high temperature flames and the resulting pressure occur, the ceramic-forming binder is used to form a ceramic by bonding with the ceramic-forming non-metallic precursor, thereby delaying flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0117] For example, the ceramic-forming metal precursor (c) may include metal silicates, or may include less than 3% by weight of magnesium (excluding magnesium oxide) or magnesium oxide. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, the ceramic-forming binder is used to form a ceramic by bonding with the ceramic-forming non-metallic precursor, thereby slowing flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0118] For example, metal silicates may include one or more selected from aluminosilicates and calcium silicates, preferably aluminosilicates. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, ceramics are formed by bonding with ceramic-forming non-metallic precursors using ceramic-forming binders, thereby slowing flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0119] For example, aluminosilicates may include one or more selected from kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and selenite, preferably kaolin, mica, or mixtures thereof, and more preferably kaolin. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, ceramics are formed by bonding with ceramic-forming non-metallic precursors using ceramic-forming binders, thereby slowing flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0120] For example, calcium silicates can include wollastonite. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, ceramics are formed by bonding with ceramic-forming nonmetallic precursors using ceramic-forming binders, thereby slowing flame propagation. Therefore, even in the event of thermal runaway, the safety of property and life can be ensured.

[0121] For example, the ceramic forming metal precursor (c) can be a magnesium-free silicate. In this case, excellent flame retardancy and electrical insulation properties can be achieved without being affected by magnesium. Furthermore, when ultra-high temperature flames and the resulting pressure occur, the flame propagation is slowed by forming a ceramic through bonding with the ceramic forming non-metal precursor. Therefore, safety can be ensured even in the event of thermal runaway.

[0122] For example, based on the total weight of the ceramic-forming metal precursor, the "magnesium-free silicate" may contain less than 3% by weight, preferably less than 2% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight, even more preferably less than 1% by weight, and even more preferably more than 0.01% by weight and less than 1% by weight of magnesium (excluding magnesium oxide) or magnesium oxide. Within this range, flame retardancy and electrical insulation properties can be excellent. Furthermore, when an ultra-high temperature flame and the resulting pressure occur, ceramics are formed by bonding with the ceramic-forming non-metal precursor using a ceramic-forming binder, thereby delaying flame propagation. Therefore, safety can be ensured even in the event of thermal runaway. Furthermore, when the magnesium or magnesium oxide content in the metal silicate exceeds the aforementioned range, ceramics cannot be properly formed when an ultra-high temperature flame and the resulting pressure occur. Moreover, even if ceramics are formed, they will immediately rupture without having the effect of delaying flame propagation.

[0123] A ceramic-forming metal precursor (c) is defined as a material that forms a ceramic by bonding it with a Gob-state ceramic-forming nonmetallic precursor using a ceramic-forming binder under ultra-high temperature flame and the resulting pressure. Therefore, according to the definition of the invention, talc that does not form a ceramic does not correspond to the ceramic-forming metal precursor.

[0124] For example, the average particle size of the ceramic-forming metal precursor (c) can be from 0.1 µm to 170 µm, preferably from 0.1 µm to 150 µm, more preferably from 0.1 µm to 100 µm, and even more preferably from 0.1 µm to 60 µm. Within this range, compatibility with ceramic-forming nonmetal precursors can be improved, thereby resulting in excellent mechanical properties, electrical insulation properties, flame retardancy, and flame delay properties.

[0125] In this invention, the average particle size of the ceramic-forming metal precursor can be measured using methods commonly used in the technical field to which this invention pertains, such as electron microscopy. As a specific example, the average particle size can be measured using X-ray diffraction.

[0126] (d) Ceramic-formed nonmetallic precursors In this invention, when an ultra-high temperature flame and the resulting pressure are generated, the ceramic-forming nonmetallic precursor transforms into a Gob state. The Gob-state ceramic-forming nonmetallic precursor then combines with the ceramic-forming metallic precursor using a metal phosphate component generated from the thermal decomposition of the ceramic-forming binder, causing changes in its physical and chemical structure to form a ceramic. Therefore, the formation of pores or dripping due to the flame is prevented. Thus, in the event of thermal runaway, safety is ensured due to its excellent flame-retarding properties.

[0127] For example, based on the total weight of components (a) to (e), the content of the ceramic-forming nonmetallic precursor (d) can be from 13% to 37% by weight, preferably from 18% to 34% by weight, more preferably from 19% to 32% by weight, even more preferably from 20% to 30% by weight, and even more preferably from 25% to 32% by weight. Within this range, excellent mechanical properties, flame retardancy, and appearance characteristics can be achieved. Furthermore, safety can be ensured by forming ceramics and delaying flame propagation in the event of ultra-high temperature flames and the resulting pressure.

[0128] For example, the ceramic-forming nonmetallic precursor (d) may include glass fiber, preferably E-glass fiber. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, the ceramic-forming binder is used to form a ceramic by bonding with the ceramic-forming nonmetallic precursor, thereby slowing flame propagation. Therefore, safety can be ensured even in the event of thermal runaway.

[0129] For example, glass fibers may include chopped glass fibers. In this case, compatibility with polymers can be excellent.

[0130] In this invention, chopped glass fibers commonly used in the technical field to which this invention pertains can be used without any particular limitation.

[0131] In this invention, E-glass fiber is a type of glass fiber with excellent electrical properties, and commonly used E-glass fibers in the technical field to which this invention pertains can be used without particular limitation. The E-glass fiber comprises SiO2, Al2O3, CaO, and B2O3 as its upper components.

[0132] For example, the average particle size of the ceramic-formed nonmetallic precursor (d) can be from 3 µm to 25 µm, preferably from 5 µm to 20 µm, and more preferably from 7 µm to 15 µm. Within this range, the mechanical strength of the polymer can be improved, and the appearance properties of the final product can be excellent.

[0133] For example, the average length of the ceramic-formed nonmetallic precursor (d) can be 1 to 10 mm, preferably 2 to 7 mm, and more preferably 2 to 5 mm. Within this range, the mechanical strength of the polymer can be improved, and the appearance properties of the final product can be excellent.

[0134] For example, the aspect ratio (L / D) of the ceramic-formed nonmetallic precursor (d), i.e., the ratio of average length (L) to average particle size (D), can be from 200 to 550, preferably from 220 to 450, more preferably from 250 to 350, and even more preferably from 270 to 320. Within this range, the surface appearance can be excellent due to its excellent compatibility with polymers.

[0135] In this invention, the average particle size, average length, and aspect ratio of the ceramic-formed nonmetallic precursor are measured by microscopic analysis. The corresponding values ​​for 30 samples are then calculated, and their average value is determined.

[0136] For example, the ceramic-forming nonmetal precursor (d) can be surface-treated with a silane compound or a urethane compound. Preferably, the ceramic-forming nonmetal precursor (d) can be surface-treated with one or more surface-treatment agents selected from aminosilane compounds, epoxysilane compounds, and urethane compounds, more preferably with an aminosilane compound. In this case, by combining with the polymer, dispersibility and surface wettability can be improved. As a result, the mechanical properties of the resin composition, including tensile strength, can be improved.

[0137] For example, based on a total of 100% by weight of surface-treated ceramic-forming nonmetallic precursor (ceramic-forming nonmetallic precursor + surface treatment agent), the content of the surface treatment agent can be from 0.1% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight, more preferably from 0.1% by weight to 3% by weight, even more preferably from 0.1% by weight to 0.8% by weight, and even more preferably from 0.2% by weight to 0.5% by weight. Within this range, the mechanical properties, physical properties, and appearance of the final product can be excellent.

[0138] As an aminosilane compound, aminosilanes commonly used as coating agents for glass fibers can be used without particular limitation. For example, an aminosilane compound may include one or more selected from the following: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, γ-acetoacetylpropyltrimethoxysilane, acetoacetylpropyltriethoxysilane, γ-cyanoacetyltrimethoxysilane, γ-cyanoacetyltriethoxysilane, and acetoxyacetyltrimethoxysilane. In this case, mechanical properties and heat resistance can be excellent, and the surface properties of injection-molded products can be excellent.

[0139] As the epoxy silane compound, epoxy silanes commonly used as coating agents for glass fibers can be used without particular limitation. For example, the epoxy silane compound may include one or more selected from: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In this case, the mechanical properties and heat resistance can be excellent, and the surface properties of the injection-molded product can be excellent.

[0140] Glass fibers can be appropriately selected and used within the range commonly used in the art, provided that the glass fibers meet the definition of this invention, and there are no particular restrictions on cross-sectional shapes such as cylindrical or elliptical.

[0141] For example, based on the total weight of components (a) to (e), the total amount of ceramic-forming metal precursor (c) and ceramic-forming non-metal precursor (d) can be from 30% to 52% by weight, preferably from 32% to 50% by weight, more preferably from 34% to 48% by weight, and even more preferably from 38% to 43% by weight or from 40% to 46% by weight. Within this range, flame retardancy and electrical insulation properties can be excellent. Furthermore, ceramics can be formed when ultra-high temperature flames and the resulting pressure occur.

[0142] (e) Flame retardants In this invention, the flame retardant imparts high flame retardancy (V-0 or higher) and excellent electrical insulation properties to the thermoplastic resin composition according to UL 94 testing. Furthermore, the flame retardant undergoes thermal decomposition when subjected to ultra-high temperature flames and the resulting pressure. During thermal decomposition, virtually no toxic gases are produced, and no endocrine disruptors are released; therefore, the flame retardant has no harmful effects on humans or the environment.

[0143] For example, based on the total weight of components (a) to (e), the content of flame retardant (e) can be from 2% to 8% by weight, preferably from 2.5% to 7% by weight, more preferably from 3% to 6.5% by weight, even more preferably from 3% to 6% by weight, and even more preferably from 4% to 6% by weight. Within this range, high flame retardancy of V-0 or higher according to UL 94 testing can be provided, and excellent mechanical and electrical insulation properties can be achieved.

[0144] For example, flame retardant (e) may include one or more selected from melamine flame retardants, phosphazene flame retardants, and phosphate flame retardants, preferably melamine flame retardants. In this case, it can provide high flame retardancy of V-0 or higher according to UL 94 testing, excellent mechanical and electrical insulation properties, and does not produce gases or endocrine disruptors harmful to humans or the environment.

[0145] For example, melamine flame retardants may include one or more selected from melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine borate, and melamine sulfate, preferably melamine polyphosphate. In this case, high flame retardancy of V-0 or higher according to UL 94 testing can be provided, and excellent mechanical and electrical insulation properties can be achieved.

[0146] For example, phosphazene flame retardants can be organic compounds having -P=N- bonds in their molecules. Preferably, phosphazene flame retardants can include one or more selected from cyclic phosphazene compounds, chain phosphazene compounds, and cross-linked phosphazene compounds, more preferably cyclic phosphazene compounds. In this case, flame retardancy and mechanical properties can be excellent.

[0147] Cyclic phosphazene compounds are preferably compounds represented by the following chemical formula 7.

[0148] [Chemical Formula 7] In chemical formula 7, m is an integer from 3 to 25, and R 13 and R 14 Same or different, and indicates aryl or alkylaryl.

[0149] In chemical formula 7, m is preferably an integer between 3 and 5.

[0150] More preferably, the cyclic phosphazene compound represented by Formula 7 can be a cyclic phenoxyphosphazene, wherein R 13 and R 14 It is phenyl. More preferably, the cyclic phosphazene compound represented by Formula 7 may include one or more selected from phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaphenoxycyclopentaphosphazene.

[0151] The chain-like phosphazene compound is preferably a compound represented by the following chemical formula 8.

[0152] [Chemical Formula 8] In chemical formula 8, n is an integer between 3 and 10,000, and X represents -N=P(OR 15 )3 group or -N=P(O)OR 15 Group Y represents -P(OR) 16 )4 group or -P(O)(OR 16 )2 group. R 15 and R 16 Same or different, and indicates aryl or alkylaryl.

[0153] In chemical formula 8, n is preferably an integer from 3 to 100, more preferably an integer from 3 to 25.

[0154] The chain-like phosphazene compound represented by chemical formula 8 can preferably be R. 15 and R 16 It is a chain-like phenoxyphosphazene of phenyl.

[0155] For example, crosslinked phosphazene compounds are obtained by crosslinking one or more phosphazene flame retardants selected from cyclic and chain phosphazene compounds with a crosslinking group represented by the following chemical formula 9.

[0156] [Chemical Formula 9] In chemical formula 9, (A) I It is -C(CH3)2-, -SO2-, -S-, or -O-, where I is an integer of 0 or 1. Indicates a key.

[0157] The cross-linked phosphazene compound can preferably be: using a cross-linking agent represented by chemical formula 9, wherein R in chemical formula 7... 13 and R 14 Crosslinked phenoxyphosphazene compounds obtained by crosslinking cyclic phenoxyphosphazene compounds of phenyl groups; using a crosslinking agent represented by chemical formula 9, by causing R in chemical formula 8 therein... 15 and R16 A cross-linked phenoxyphosphazene compound obtained by cross-linking a phenyl chain phenoxyphosphazene compound; or a mixture thereof, more preferably a cross-linked phenoxyphosphazene compound obtained by cross-linking a cyclic phenoxyphosphazene compound using a cross-linking agent represented by Formula 9.

[0158] For example, phosphate flame retardants may include one or more selected from the following: trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), tri(xylyl) phosphate (TXP), resorcinol bis(xylyl) phosphate (RDP), phenyl resorcinol phosphate, bisphenol diphenyl phosphate (BDP), tolyl diphenyl phosphate, xylyl diphenyl phosphate, phenyl di(isopropylphenyl) phosphate, triisophenyl phosphate, diphenyl phosphate, resorcinol diphosphate, resorcinol bis(2,6-bis(xylyl) phosphate), and aromatic polyphosphates.

[0159] For example, thermoplastic resin compositions may contain lubricants, antioxidants, or mixtures thereof.

[0160] For example, based on the total weight of components (a) to (e), the lubricant content can be from 0.01% to 5% by weight, preferably from 0.1% to 3% by weight, more preferably from 0.2% to 1% by weight, and even more preferably from 0.2% to 0.5% by weight. Within this range, the mechanical properties can be excellent, and the molding and processing performance can be improved.

[0161] For example, the lubricant may include one or more selected from ester lubricants, fatty acid amide lubricants, olefin lubricants, and lignite wax lubricants, preferably ester lubricants, fatty acid amide lubricants, or mixtures thereof. In this case, the mechanical properties can be excellent, and the molding and processing performance can be improved.

[0162] For example, ester lubricants may include one or more selected from fatty acid esters of alcohols, hydrogenated oils, butyl stearate, glyceryl monostearate, pentaerythritol tetrastearate, stearoyl stearate, ester waxes, and alkyl phosphates. In this case, mechanical properties can be excellent, and molding and processing properties can be improved.

[0163] For example, fatty acid amide lubricants may include one or more selected from stearamide, docosamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bisoleamide. In this case, the mechanical properties can be excellent, and the molding and processing performance can be improved.

[0164] For example, olefin lubricants can be polyethylene wax, polypropylene wax, or mixtures thereof. In this case, mechanical properties can be excellent, and molding and processing properties can be improved.

[0165] For example, lignite wax lubricants can be lignite wax, lignite ester wax, or mixtures thereof. For instance, lignite ester waxes can include one or more selected from: waxes obtained by esterifying lignite wax with ethylene glycol and lignite esters, waxes esterified with glycerol and lignite esters, calcium lignite containing lignite esters, and lignite acid-based ester mixtures. In this case, mechanical properties can be excellent, and molding and processing properties can be improved.

[0166] For example, based on the total weight of components (a) to (e), the antioxidant content can be from 0.01% by weight to 5% by weight, preferably from 0.1% by weight to 3% by weight, more preferably from 0.2% by weight to 1% by weight, and even more preferably from 0.2% by weight to 0.5% by weight. Within this range, oxidation due to heat can be prevented during extrusion, and excellent mechanical properties and heat resistance can be achieved.

[0167] For example, the antioxidant may include one or more selected from phosphorus-based antioxidants, hindered phenolic antioxidants, and phenolic antioxidants. In this case, oxidation due to heat can be prevented during extrusion, and excellent mechanical properties and heat resistance can be achieved.

[0168] For example, phosphorus-based antioxidants may include one or more selected from the following: bis(dialkylphenyl)pentaerythritol diphosphite, phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentadene phosphite, tetra(tridecyl)-1,1, 3-Tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tetrazyl)-4,4'-butylidene bis(3-methyl-6-tert-butylphenol) diphosphite, tris(mono- and di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, phenyl(4,4'-isopropylidene diphenol) pentaerythritol Alcohol diphosphite, distearyl pentaerythritol diphosphite, tris[4,4'-isopropylidene bis(2-tert-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidene bis(2-tert-butylphenol) bis(nonylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2-[{2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]-dioxophosphorus heterocyclic hepten-6] [-[2-[{2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxophosphoric heterocyclic hepten-6-yl}oxy]ethyl]ethylamine and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxophosphoric heterocyclic heptenene, more preferably tris(2,4-di-tert-butylphenyl) phosphite (IF168). In this case, oxidation due to heat can be prevented during extrusion, and excellent mechanical properties and heat resistance can be achieved.

[0169] For example, hindered phenolic antioxidants may include one or more selected from pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, preferably pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. In this case, oxidation due to heat can be prevented during extrusion, and excellent mechanical properties and heat resistance can be achieved.

[0170] For example, phenolic antioxidants may include one or more selected from the following: 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 1,6-hexanediol bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] Isocyanurate, tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2,2-bis[4-(2-3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate stearyl ester, more preferably octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IR1076). In this case, oxidation caused by heat can be prevented during the extrusion process, and excellent mechanical properties and heat resistance can be achieved.

[0171] The thermoplastic resin composition may further include one or more additives selected from plasticizers, heat stabilizers, anti-drip agents, light stabilizers, pigments, dyes, inorganic additives (excluding glass fibers) and carbon fibers.

[0172] For example, based on a total of 100 parts by weight of components (a) to (e), the content of the additive can be from 0.01 parts by weight to 5 parts by weight, preferably from 0.01 parts by weight to 3 parts by weight, and more preferably from 0.05 parts by weight to 1 part by weight. Within this range, the desired performance can be effectively achieved without degrading the inherent properties of the thermoplastic resin composition of the present invention.

[0173] Thermoplastic resin composition According to the UL 94 test (vertical burning test), the flame retardancy of the thermoplastic resin composition, measured using an injection-molded specimen with dimensions of 127mm × 12.7mm × 1.5mm, can reach a rating of V-0 or higher. In this case, the balance between physical properties and flame retardancy can be excellent.

[0174] When evaluated according to UL 2596 for blowtorch and gravel tests, a 1200°C flame consisting of oxygen and propane gas is applied to a 150mm × 150mm × 3mm specimen, and the flame resistance time until pores or dripping is measured, the flame resistance time of the thermoplastic resin composition can be over 600 seconds. Within this range, the balance of physical properties is excellent. Furthermore, safety is ensured by forming a ceramic layer and delaying flame propagation in the event of ultra-high temperature flames and the resulting pressure.

[0175] When the Comparative Tracking Index (CTI) is measured using a 3 mm thick sample according to IEC 60112, the thermoplastic resin composition can be classified as Grade 1 or higher, preferably Grade 0 or higher, based on the Performance Class Category (PLC). Within this range, excellent balance of physical properties and electrical insulation properties can be achieved.

[0176] Method for preparing thermoplastic resin compositions The method for preparing a thermoplastic resin composition according to the present invention comprises: kneading and extruding 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d), and 2% to 8% by weight of a flame retardant (e). In this process, an extruder with nine or more kneading blocks is used for kneading and extrusion. Under these conditions, excellent flame retardancy and insulation properties can be achieved. Furthermore, in the event of an accidental ultra-high temperature flame and the resulting pressure, safety can be ensured and environmental friendliness can be achieved by forming ceramics and delaying flame propagation.

[0177] For example, kneading and extrusion can be carried out at a barrel temperature of 200°C to 350°C, preferably 220°C to 330°C, and more preferably 220°C to 310°C. In this case, the production rate per unit time can be increased, melt kneading can be fully carried out, and thermal decomposition of the polymer can be prevented.

[0178] For example, kneading and extrusion can be performed at screw speeds of 100 rpm to 500 rpm, preferably 150 rpm to 400 rpm, and more preferably 150 rpm to 300 rpm. Within this range, the production rate per unit time can be increased, and the process efficiency can be excellent.

[0179] Thermoplastic resin compositions obtained by kneading and extrusion can be provided in granular form.

[0180] Flame retardant composition The flame retardant composition of the present invention comprises a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming non-metal precursor, and a flame retardant. In this configuration, excellent flame retardancy and insulation properties can be achieved. Furthermore, by forming ceramics and delaying flame propagation in the event of an accidental ultra-high temperature flame and the resulting pressure, the safety of property and life can be ensured even in the event of thermal runaway. Moreover, environmental friendliness is achieved because no toxic gases or endocrine disruptors are produced during thermal decomposition.

[0181] In flame retardant compositions, when ultra-high temperature flames exceeding 1200°C and the resulting pressure are generated, the ceramic-forming binder undergoes thermal decomposition, producing a metal phosphate component. This metal phosphate component combines the ceramic-forming metallic precursor and the ceramic-forming non-metallic precursor reaching the Gob temperature, causing physical and chemical structural changes to form a ceramic. When thermal runaway occurs in the battery, the formed ceramic slows flame propagation, ensuring the safety of property and life.

[0182] For example, based on its total weight, the flame retardant composition may comprise 11% to 34% by weight of a ceramic-forming binder, 14.5% to 41% by weight of a ceramic-forming metal precursor, 24% to 59% by weight of a ceramic-forming nonmetal precursor, and 4% to 14% by weight of a flame retardant, preferably 13% to 32% by weight of a ceramic-forming binder, 16% to 35% by weight of a ceramic-forming metal precursor, 30% to 57% by weight of a ceramic-forming nonmetal precursor, and 4.5% to 12% by weight of a flame retardant. The composition includes, more preferably, 15.5% to 31% by weight of a ceramic-forming binder, 17.5% to 28% by weight of a ceramic-forming metal precursor, 35% to 55% by weight of a ceramic-forming non-metal precursor, and 5% to 9.5% by weight of a flame retardant; even more preferably, 15.5% to 25% by weight of a ceramic-forming binder, 20% to 27% by weight of a ceramic-forming metal precursor, 43% to 53% by weight of a ceramic-forming non-metal precursor, and 7% to 9% by weight of a flame retardant. Within this range, excellent flame retardancy and insulation properties can be achieved. Furthermore, by forming a ceramic and delaying flame propagation in the event of an accidental ultra-high temperature flame and the resulting pressure, the safety of property and life can be ensured even in the event of thermal runaway. Moreover, since no toxic gases or endocrine disruptors are produced during thermal decomposition, environmental friendliness is achieved.

[0183] The contents of the flame retardant composition include those of the thermoplastic resin composition described above, which are omitted here to avoid repetition.

[0184] Molded products The molded articles of this invention comprise the thermoplastic resin composition of this invention. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, ceramics form and slow flame propagation. Therefore, even in the event of thermal runaway, safety can be ensured and environmental friendliness can be achieved.

[0185] For example, the molded article can be an electrical / electronic component or an automotive part, specifically an electric vehicle electrical component or battery component. In this case, excellent flame retardancy and electrical insulation properties can be achieved. Furthermore, when ultra-high temperature flames and the resulting pressure occur, the ceramic forms and slows flame propagation. Therefore, even in the event of thermal runaway, safety can be ensured and environmental friendliness can be achieved.

[0186] For example, electric vehicle battery components can be plastic covers, module housings, or busbars for electric vehicle batteries.

[0187] The method for manufacturing molded articles according to the present invention comprises: a step of producing granules of a thermoplastic resin composition by kneading and extruding 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d), and 2% to 8% by weight of a flame retardant (e); and a step of injection molding the granules to manufacture molded articles. In this case, kneading and extrusion are performed using an extruder having nine or more kneading blocks. Under these conditions, excellent flame retardancy and insulation properties can be achieved. Furthermore, in the event of an accidental ultra-high temperature flame and the resulting pressure, safety can be ensured even in the event of thermal runaway by forming ceramics and delaying flame propagation, and environmental friendliness can be achieved.

[0188] Injection is not particularly limited by the methods and conditions commonly used in the technical field to which this invention pertains, and can be appropriately selected and applied as needed.

[0189] In describing the thermoplastic resin compositions, molded articles and methods thereof of the present invention, unless otherwise stated, other conditions (e.g., the construction and specifications of extruders and injection molding machines, extrusion and injection molding conditions, additives, etc.) may be appropriately selected and implemented as needed when the conditions are within the range commonly used in the art, without particular limitation.

[0190] The invention will be described with reference to the following figures.

[0191] under Figure 1 This is a schematic diagram of an extruder having nine or more kneading blocks for preparing the thermoplastic resin composition of the present invention.

[0192] There are no particular restrictions on the type of extruder; any extruder commonly used in the field can be appropriately selected and used. For example, a single-screw extruder equipped with one screw or a multi-screw extruder equipped with multiple screws can be used. Considering the uniform kneading of the material, ease of processing, and economic benefits, a twin-screw extruder equipped with two screws is preferred.

[0193] An extruder includes a feeder for feeding material into a barrel, a screw for conveying and kneading the feed, and a die for extruding the kneaded material. In this case, the screw consists of multiple screw elements for various functions.

[0194] One or more feeders can be configured. Optionally, two or more feeders can be configured. For example, a main inlet and optional auxiliary inlets can be configured. Optionally, more than two auxiliary inlets can be configured.

[0195] As a specific example, polymers, ceramic-forming binders, flame retardants, and additives including lubricants and antioxidants can be injected into the main inlet, ceramic-forming metal precursors can be injected into auxiliary inlet 1, and ceramic-forming non-metal precursors can be injected into auxiliary inlet 2. In this case, the components can be uniformly mixed, thus achieving excellent balance of physical properties, electrical insulation properties, and flame retardancy. Furthermore, excellent flame delay performance during thermal runaway under ultra-high temperature flames and pressure can be achieved.

[0196] As another example, polymers and additives can be injected into the main inlet, ceramic-forming binders and flame retardants can be injected into auxiliary inlet 1, and ceramic-forming metal precursors and ceramic-forming non-metal precursors can be injected into auxiliary inlet 2. In this case, the components can be uniformly mixed, thus achieving excellent balance of physical properties, electrical insulation properties, and flame retardancy. Furthermore, excellent flame delay performance during thermal runaway can be achieved when ultra-high temperature flames and the resulting pressure occur.

[0197] As another example, the polymer can be injected into the main inlet, while a portion of the ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming non-metal precursor, flame retardant, and additives can be injected into auxiliary inlet 1, with the remainder injected into auxiliary inlet 2. In this case, the components can be uniformly mixed, resulting in excellent physical property balance, electrical insulation properties, and flame retardancy. Furthermore, excellent flame delay performance can be achieved under ultra-high temperature flames and the resulting pressure.

[0198] The kneading block of the present invention corresponds to a screw element. Specifically, each kneading block consists of multiple disks, preferably 3 to 7 disks, 5 to 7 disks, 3 to 5 disks, or 4 to 5 disks, and has a polygonal or elliptical cross-section. The kneading blocks are arranged continuously in the material conveying direction. Furthermore, in the kneading block, the phase angle (representing the travel angle between disks) of the disks is preferably 45°. o Up to 90 o .

[0199] Additionally, kneading blocks include: forward kneading blocks capable of conveying, dispensing, and mixing materials; neutral kneading blocks capable of dispensing and mixing materials without conveying; and reverse kneading blocks capable of conveying materials in the opposite direction to the conveying direction.

[0200] For example, the thermoplastic resin composition according to the invention can be prepared by a method comprising the steps of kneading and extruding using an extruder having 9 or more, preferably 10 or more, more preferably 12 or more, 9 to 18 as a preferred example, 10 to 18 as a more preferred example, and 12 to 16 as an even more preferred example. In this case, the kneading blocks can be effectively arranged in the order of forward kneading blocks, neutral kneading blocks, and reverse kneading blocks relative to the resin flow direction. Depending on the combination method, continuous or individual block combinations can be used. In this case, the dispersibility of ceramic-forming metal precursors and ceramic-forming non-metal precursors and the compatibility of the composition can be further improved, thereby providing a high-quality thermoplastic resin composition.

[0201] Nine or more kneading blocks can be arranged continuously or discontinuously between the screws. As a specific example, three to six kneading blocks can be continuously arranged between the main inlet and auxiliary inlet 1, three to eight kneading blocks can be continuously arranged between auxiliary inlet 1 and auxiliary inlet 2, and two to five kneading blocks can be arranged between auxiliary inlet 2 and the outlet (not shown). This configuration allows for control of localized heating during the melt kneading process, preventing thermal deformation of the raw material. Furthermore, it prevents excessive cutting of the glass fiber, thereby preventing deterioration of mechanical properties, electrical insulation properties, flame retardancy, and flame delay properties during thermal runaway.

[0202] The invention will now be described in more detail with reference to the preferred embodiments described below. However, these embodiments are provided for illustrative purposes only and should not be construed as limiting the scope and concept of the invention. Furthermore, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the concept and scope of the invention, and such changes and modifications are also within the scope of the appended claims.

[0203] [Example] The materials used in the following embodiments and comparative examples are as follows.

[0204] *(a) Polymer - (a-1) PA6: Polyamide 6 resin (relative viscosity: 2.2) - (a-2) PA66: Polyamide 66 resin (relative viscosity: 2.4) - (a-3) PA56: Polyamide 56 resin (relative viscosity: 2.5) - (a-4) PPE: Poly(2,6-dimethyl-1,4-phenylene) ether (intrinsic viscosity: 35~42 dl / g) *(b) Ceramic forming adhesive - (b-1) ADP: Aluminum diethylphosphinate (Clariant Co., OP1230) *(c)Ceramic forming metal precursors -(c-1) Kaolin: Aluminum Silicate -(c-2) Mica: Aluminosilicate - (c-3) Wollastonite: calcium silicate *(c') Non-ceramic forming metal precursors -(c'-1)talc:magnesium silicate *(d) Ceramic forming nonmetallic precursors - (d-1) Glass fiber: Short-cut glass fibers with an average particle size of 10µm to 13µm and an average length of 34mm to 4mm, treated with aminosilane. *(e) Flame retardants -(e-1)MPP: Melamine polyphosphate -(e-2)RDX: Resorcinol bis(2,6-bis(di(xyl)phosphate) *(f) Additives: - Lubricant: EP184 (Hanyang Hwa Seong Co.) and Sunlube EBS DA-01 (Seon Gu Co.): 0.25% by weight - Antioxidant: A mixture of AO-412S, IR1010, IR1098 and IR68: 0.25% by weight Examples 1 to 10 and Comparative Examples 1 to 9 The polymer, ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming nonmetal precursor, flame retardant, and additives were added to a twin-screw extruder (SM Co., T40) with more than nine mixing blocks in the amounts shown in Tables 1 and 2 below. The mixture was melt-kneaded and extruded at temperatures ranging from 230°C to 310°C and speeds from 150 rpm to 300 rpm to obtain granules. Evaluation specimens were fabricated using an injection molding machine (80 tons, Engel Co.). The fabricated specimens were left at room temperature for more than 48 hours, and their physical properties were measured. The results are shown in Tables 1 and 2 below.

[0205] At this point, the twin-screw extruder has two or more inlets. The polymer, ceramic-forming binder, flame retardant, and additives are injected into the main inlet, the ceramic-forming metal precursor is injected into auxiliary inlet 1, and the ceramic-forming non-metal precursor is injected into auxiliary inlet 2.

[0206] [Experimental Example] The performance of the samples manufactured in Examples 1 to 10 and Comparative Examples 1 to 9 was measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0207] Measurement methods *Flame retardancy: Flame retardancy was measured using an injection-molded sample measuring 127mm × 12.7mm × 1.5mm, according to the UL 94 V test (vertical burning test).

[0208] *Comparative Tracking Index (CTI): Calculate the short-circuit voltage when 50 drops of electrolyte solution are dropped onto a 3 mm thick sample, according to IEC 60112. Based on the CTI, the Performance Class Category (PLC) is shown in Table 3 below.

[0209] [Table 3] *Flame resistance time (seconds): e.g., Figure 2 and Figure 3 As shown, the torch and grit evaluation based on UL 2596 involves applying a 1200°C flame of oxygen and propane gas to a 150mm × 150mm × 3mm specimen and measuring the time until holes or dripping occur.

[0210] [Table 1] [Table 2] - Due to the inability to extrude, the physical properties cannot be measured. As shown in Tables 1 and 2, the thermoplastic resin compositions of the present invention (Examples 1 to 10) exhibit excellent flame retardancy and insulation properties compared to Comparative Examples 1 to 9. Furthermore, when subjected to an ultra-high temperature flame of 1200°C and the resulting pressure, ceramics form, flame propagation is slowed, and the flame resistance time is over 600 seconds. Moreover, no pores are formed. Therefore, even in the event of thermal runaway of the battery, the safety of property and life can be ensured. Furthermore, since no toxic gases or endocrine disruptors are produced, there are no harmful effects on human health or the environment.

[0211] Specifically, in Comparative Examples 1 and 5, which contained a small amount of ADP(b-1) as a ceramic forming binder and an excess of MPP(e-1) as a flame retardant, the flame retardancy was reduced and the flame retardancy time was very poor. In Comparative Example 2, which contained a small amount of MPP(e-1), the flame retardancy was reduced.

[0212] Furthermore, in Comparative Example 3, which contained a small amount of glass fiber (d-1) as a ceramic-forming nonmetal precursor and an excessive amount of kaolin (c-1) as a ceramic-forming metal precursor, the flame retardancy was reduced and the flame retardancy time was very poor.

[0213] Furthermore, in Comparative Example 4, which contains a small amount of kaolin (c-1) as a precursor for ceramic forming metal, and in Comparative Example 6, which contains talc (c'-1) as a precursor for ceramic forming non-metal, the flame retardancy is reduced and the flame retardancy time is very poor.

[0214] Furthermore, in Comparative Example 7, which contained a small amount of kaolin (c-1), the flame retardancy was very poor. In Comparative Example 8, which contained an excessive amount of glass fiber (d-1), and in Comparative Example 9, which contained an excessive amount of ADP (b-1), extrusion was difficult.

[0215] As shown below Figure 4 and Figure 5 As shown, when the samples made using the thermoplastic resin compositions of Examples 1 and 5 according to the present invention were subjected to a flame of 1200°C formed by oxygen and propane gas and the resulting pressure as evaluated by a blowtorch and gravel according to UL 2596, ceramics were formed, and no pores were formed even after 600 seconds or more, indicating a significant increase in flame retardancy.

[0216] On the other hand, as follows Figure 6 As shown, when the sample made using the thermoplastic resin composition according to Comparative Example 6 was subjected to a flame of 1200°C formed by oxygen and propane gas and the resulting pressure as evaluated by a blowtorch and gravel according to UL 2596, no ceramic was formed, and pores were formed within 70 seconds.

[0217] In summary, the thermoplastic resin composition according to the present invention, comprising a predetermined amount of polymer, ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming non-metal precursor, and flame retardant, exhibits excellent flame retardancy and electrical insulation properties. Furthermore, by forming ceramics and delaying flame propagation in the event of ultra-high temperature flames and the resulting pressure, safety is ensured even in the event of thermal runaway. In addition, environmental friendliness is achieved.

Claims

1. A thermoplastic resin composition comprising: 32.5% to 49% by weight of a polymer (a), 7% to 20.5% by weight of a ceramic-forming binder (b), 6.5% to 20.5% by weight of a ceramic-forming metal precursor (c), 13% to 37% by weight of a ceramic-forming non-metal precursor (d), and 2% to 8% by weight of a flame retardant (e).

2. The thermoplastic resin composition according to claim 1, wherein, The polymer (a) includes one or more selected from polyamide resins, poly(arylene ether) resins, polyalkylene terephthalate resins, polystyrene resins, polycarbonate resins, and modified polymers thereof.

3. The thermoplastic resin composition according to claim 1, wherein, The ceramic forming binder (b) includes a metal phosphorus-based flame retardant.

4. The thermoplastic resin composition according to claim 1, wherein, The ceramic forming metal precursor (c) comprises a metal silicate, or comprises less than 3% by weight of magnesium or magnesium oxide without magnesium oxide, based on the total weight of the ceramic forming metal precursor.

5. The thermoplastic resin composition according to claim 4, wherein, The metal silicate includes one or more selected from aluminosilicates and calcium silicates.

6. The thermoplastic resin composition according to claim 5, wherein, The aluminosilicate includes one or more selected from kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite.

7. The thermoplastic resin composition according to claim 5, wherein, The calcium silicate includes wollastonite.

8. The thermoplastic resin composition according to claim 1, wherein, The ceramic forming nonmetallic precursor (d) includes glass fibers.

9. The thermoplastic resin composition according to claim 1, wherein, The flame retardant (e) includes one or more selected from melamine flame retardants, phosphazene flame retardants, and phosphate ester flame retardants.

10. The thermoplastic resin composition according to claim 1, wherein, When a 1200°C flame of oxygen and propane gas is applied to a 150mm × 150mm × 3mm specimen and the flame time is measured until pores or dripping occurs, according to the torch and gravel evaluation of UL 2596, the flame time of the thermoplastic resin composition is greater than 600 seconds; or when the Comparative Tracking Index (CTI) is measured using a 3mm thick specimen according to IEC 60112, the thermoplastic resin composition is classified as Grade 1 or higher according to the Performance Class Category (PLC).

11. The thermoplastic resin composition according to claim 1, wherein, The thermoplastic resin composition contains a lubricant, an antioxidant, or a mixture thereof.

12. A method for preparing a thermoplastic resin composition, comprising: The polymer (a) of 32.5% to 49% by weight, the ceramic-forming binder (b) of 7% to 20.5% by weight, the ceramic-forming metal precursor (c) of 6.5% to 20.5% by weight, the ceramic-forming non-metal precursor (d) of 13% to 37% by weight, and the flame retardant (e) of 2% to 8% by weight are kneaded and extruded, wherein the kneading and extrusion are performed using an extruder having nine or more kneading blocks.

13. A flame retardant composition comprising: a ceramic forming binder, a ceramic forming metal precursor, a ceramic forming nonmetal precursor, and a flame retardant.

14. The flame retardant composition according to claim 13, wherein, Based on the total weight of the flame retardant composition, the flame retardant composition comprises: 11% to 34% by weight of the ceramic-forming binder, 14.5% to 41% by weight of the ceramic-forming metal precursor, 24% to 59% by weight of the ceramic-forming non-metal precursor, and 4% to 14% by weight of the flame retardant.

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

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