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

Abstract

This description relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, and more particularly to a thermoplastic resin composition characterized by comprising (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant, a method for producing the same, and a molded article containing the same. According to the present invention, a thermoplastic resin composition, a method for producing the same, and a molded article containing the same are provided, which are excellent in flame retardancy and electrical insulation, and also have excellent flame delay characteristics during thermal runaway by forming ceramics at ultra-high temperatures and when flames are generated, thereby delaying flame propagation, thus ensuring safety for property and human life, and are environmentally friendly.

Description

[Technical Field]

[0001] [Cross-reference with related applications] This application is an application claiming priority rights based on Korean Patent Application No. 10-2024-0053331 dated April 22, 2024 and Korean Patent Application No. 10-2024-0053332 dated April 22, 2024, and all content disclosed in the documents of said Korean Patent Applications is incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, and more particularly to a thermoplastic resin composition, a method for producing the same, and a molded article containing the same, which are excellent in flame retardancy and electrical insulation, and which ensure safety to property and human life by forming a ceramic when unexpected ultra-high temperature flames and the pressure caused thereby are generated, thereby delaying the propagation of flames, and are also environmentally friendly. [Background technology]

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

[0004] In recent years, thermoplastic resins used in automotive parts, particularly in electric vehicle batteries, require even higher levels of fire safety. Therefore, they are required to have not only flame retardancy but also flame delay properties in the event of thermal runaway.

[0005] Thermal runaway, the main cause of electric vehicle battery fires, is a phenomenon where, when battery cells are subjected to unsuitable stress, their temperature rises uncontrollably, potentially leading to explosion. When the internal temperature of the battery rises above a certain level due to short circuits such as overvoltage or over-discharge, flames are generated. However, lithium-ion batteries are highly reactive with water, making it difficult to extinguish a fire with water alone. Furthermore, the risk of thermal runaway is increasing as the use of high-capacity batteries to improve driving range increases.

[0006] Conventionally, flame retardancy and flame retardancy have been imparted to thermoplastic resins by applying both halogenated and antimony compounds. While this method of applying both halogenated and antimony compounds to impart flame retardancy can ensure flame retardancy of V-0 or 5V according to the UL94 test, the flame retardancy is significantly insufficient when flames exceed 1200°C and the pressure generated therefrom. Furthermore, the hydrogen halogen gas generated during processing and the endocrine disruptors released during combustion are highly likely to have fatal adverse effects on the human body.

[0007] Furthermore, flame retardants that do not contain halogens are called non-halogen flame retardants, and the most widely used non-halogen flame retardants are phosphorus-based flame retardants that contain phosphorus. However, phosphorus-based flame retardants have significantly inferior flame retardancy compared to halogen-containing flame retardants. Although a large amount of flame retardant can be added to achieve V-0 or 5V flame retardancy according to the UL94 test, the flame delay characteristics are insufficient to prevent thermal runaway in the event of unexpected flames above 1200°C and the resulting pressure.

[0008] Furthermore, thermoplastic resins used in electric vehicle battery components and other applications require electrical insulation properties because they are exposed to electricity for extended periods.

[0009] Therefore, there is a need to develop a thermoplastic resin composition that has excellent electrical insulation and flame retardancy, excellent flame retardation characteristics during thermal runaway, ensures safety against further damage, and can meet the quality requirements for automotive parts, especially battery parts of electric vehicles.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0011] In order to solve the problems of the prior art as described above, this description aims to provide a thermoplastic resin composition that is excellent in flame retardancy and electrical insulation, forms ceramics during thermal runaway, has excellent flame retardation characteristics, ensures high safety for property and human life, and is environmentally friendly.

[0012] Also, this description aims to provide a method for manufacturing the above thermoplastic resin composition.

[0013] Also, this description aims to provide a molded product manufactured from the above thermoplastic resin composition.

[0014] The above object and other objects of this description can all be achieved by this description described below.

Means for Solving the Problems

[0015] To achieve the above objectives, I) the present invention provides a thermoplastic resin composition characterized by comprising (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant.

[0016] II) In I) above, the polymer (a) may include one or more selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified resins thereof.

[0017] III) In I) or II) above, the (b) ceramic forming binder may include a metallic phosphorus flame retardant.

[0018] IV) In I) to III) above, the (c) ceramic-forming metal precursor may contain a metal silicate, or the content of magnesium (provided that magnesium oxide is not included) or magnesium oxide may be 3% by weight or less relative to the total weight of the ceramic-forming metal precursor.

[0019] V) In I) to IV) above, the metal silicate may include one or more selected from the group consisting of aluminum silicate and calcium silicate.

[0020] VI) In I) to V) above, the aluminum silicate may contain one or more selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite.

[0021] VII) In I) to VI) above, the calcium silicate may contain wollastonite.

[0022] VIII) In I) to VII) above, the (d) ceramic-forming nonmetallic precursor may include glass fibers.

[0023] IX) In I) to VIII) above, the (e) flame retardant may include one or more selected from the group consisting of melamine-based flame retardants, phosphazene-based flame retardants, and phosphate-based flame retardants.

[0024] X) In the above I) to IX), the thermoplastic resin composition may have a flame endurance time of 600 seconds or more, measured by applying a 1200°C flame formed with oxygen and propane gas to a 150 mm × 150 mm × 3 mm test piece in accordance with the Torch and Grit evaluation of UL 2596, and measuring the time until a hole or drip occurs, or it may have a performance level category (PLC) of 1 or higher, measured by measuring the comparative tracking index (CTI) on a 3 mm thick test piece in accordance with IEC 60112.

[0025] Furthermore, XII) The present invention provides a method for producing a thermoplastic resin composition comprising the steps of kneading and extruding (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant, wherein the kneading and extrusion are carried out using an extruder having 9 or more kneading blocks.

[0026] Furthermore, XIII) The present invention provides a flame retardant composition characterized by comprising a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming nonmetal precursor, and a flame retardant.

[0027] XIV) In the above XIII), the flame retardant composition may contain, based on its total weight, 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.

[0028] Furthermore, XV) The present invention provides a molded article characterized by containing the thermoplastic resin composition described in I) to X). [Effects of the Invention]

[0029] According to the present invention, the thermoplastic resin composition, its manufacturing method, and molded articles containing the same are available, which have the effect of providing high-quality applications to automotive parts, especially electrical components such as batteries for electric vehicles, as well as a thermoplastic resin composition that can be manufactured therein, has a flame retardancy of V-0 or higher according to the UL94 test, has excellent electrical insulation properties, and has a fire resistance time of 600 seconds or more by forming a ceramic to block the propagation of flames when ultra-high temperature flames of 1200°C or higher and the pressure generated thereby are generated, or a comparative tracking index (CTI) that is classified as PLC (Performance Level Category) of 1 or higher, ensures safety to property and human life even in the event of thermal runaway, and is environmentally friendly. [Brief explanation of the drawing]

[0030] [Figure 1] This is a schematic diagram of an extruder equipped with nine or more kneading blocks according to the present invention. [Figure 2] This diagram schematically illustrates the measurement method using the Torch and Grit evaluation standard of UL 2596. [Figure 3] This is a photograph showing an actual measurement scene using the Torch and Grit evaluation standard of UL 2596. [Figure 4]The left photo shows the actual measurement process of the thermoplastic resin composition according to Example 1 using the UL 2596 Torch and Grit evaluation method, and the right photo shows the test specimen after a flame has been applied for 600 seconds. [Figure 5] These are photographs showing the actual measurement process (left photo) and the test specimen after evaluation (right photo) of the thermoplastic resin composition according to Example 5 using the UL 2596 Torch and Grit method. [Figure 6] This image shows a test specimen of the thermoplastic resin composition according to Comparative Example 6 after UL 2596 torch and grit evaluation. The left side shows the front of the test specimen, and the right side shows the back of the test specimen. [Modes for carrying out the invention]

[0031] The thermoplastic resin composition, its manufacturing method, and molded articles containing the same will be described in detail below.

[0032] The inventors have confirmed that, when a polymer, ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming nonmetal precursor, and flame retardant are included in predetermined amounts, the flame retardancy according to the UL94 test is V-0 or higher, the insulation properties are excellent, and the thermoplastic resin composition provides significantly improved safety for property and human life even during thermal runaway by forming ceramics when ultra-high temperature flames of 1200°C or higher and the pressure generated therefrom are generated, thereby delaying the propagation of the flame. Based on this, the inventors have continued their research and completed the present invention.

[0033] The thermoplastic resin composition described herein is explained in detail as follows:

[0034] The thermoplastic resin composition described herein is characterized by containing (a) 32.5 to 49% by weight of polymer, (b) 7 to 20.5% by weight of ceramic-forming binder, (c) 6.5 to 20.5% by weight of ceramic-forming metal precursor, (d) 13 to 37% by weight of ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of flame retardant. In such cases, while having excellent flame retardancy and insulation properties, it ensures safety for property and human life by forming ceramics under unexpectedly high-temperature flames and delaying the propagation of flames, and is also environmentally friendly.

[0035] The thermoplastic resin composition of the present invention will be described in detail below, component by component.

[0036] In this description, the term "ceramic" is not particularly limited as long as it is a ceramic as defined in the art and scientific community to which this invention belongs. Specifically, it can refer to a material in which a metal and a nonmetal or quasimetallic material are bonded together by heat treatment during a sintering process to produce a crystalline material, and the resulting crystalline material then aggregates to form a three-dimensional network structure. With this definition, in this invention, a ceramic-forming metal precursor corresponding to a metal is defined as an inorganic substance containing a metal element, and a ceramic-forming nonmetallic precursor corresponding to a nonmetal or quasimetallic material is defined as a substance containing 50% by weight or more of silicon dioxide.

[0037] (a) polymer The polymer may, for example, include one or more selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified resins thereof. Preferably, it may include one or more selected from the group consisting of polyamide resin, poly(arylene ether) resin, and polyalkylene terephthalate resin. In this case, it has excellent mechanical properties such as impact strength, tensile strength, elongation, flexural strength, and surface hardness, as well as electrical insulation and flame retardancy, and also has excellent flame delay characteristics in the event of thermal runaway, thus ensuring safety for property and human life.

[0038] The polymer (a) may be, for example, 32.5 to 49% by weight, preferably 34 to 47% by weight, more preferably 35 to 46% by weight, or 36 to 45% by weight, even more preferably 38 to 45% by weight, and even more preferably 38 to 43% by weight, relative to the total weight of components (a) to (e). Within this range, it exhibits excellent mechanical properties, electrical insulation and flame retardancy, as well as excellent flame delay characteristics in the event of thermal runaway, thus ensuring safety for property and human life.

[0039] In this description, thermal runaway refers to a state in which a change in temperature alters the environment in a way that further accelerates that temperature change. In other words, thermal runaway can be described as a situation where the cause of a certain mechanical process is an increase in temperature, but the energy released as a result of that process increases the temperature and accelerates the process.

[0040] In this description, "modification" is not particularly limited as long as it is a modification of resins by a method commonly used in the art to which the present invention belongs. For example, it can mean grafting an unmodified resin with at least one compound from α,β-unsaturated dicarboxylic acid and its anhydride. Another example is copolymerizing an unmodified resin by adding at least one compound from α,β-unsaturated dicarboxylic acid and its anhydride as a copolymer during its production.

[0041] Polyamide resin The polyamide resin is not particularly limited, but as an example, it may be a polyamide produced by condensation polymerization of one or more lactams or ω-amino acids, or a polyamide produced by condensation polymerization of a divalent acid and a diamine.

[0042] Preferably, the polyamide resin is one or more selected from the group consisting of 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 lactam and aminocarboxylic acid. In this case, there is an effect of excellent mechanical properties and appearance quality.

[0043] Furthermore, the polyamide resin may, for example, be homopolyamide, copolyamide, or a mixture thereof.

[0044] The polyamide resin may, for example, be crystalline, semi-crystalline, or amorphous.

[0045] The copolymer of a diamine having 2 to 30 carbon atoms and a dicarboxylic acid having 4 to 30 carbon atoms is preferably a copolymer of an aliphatic or aromatic diamine such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 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, aminoethylpiperidine, etc.; adipic acid, sebacic acid (sebacic It may be one or more selected from the group consisting of polyamide resins obtained by polymerization of aliphatic or aromatic dicarboxylic acids such as azelaic acid, terephthalic acid, 2-chloroterephthalic acid, and 2-methylterephthalic acid.

[0046] The lactam polymer may preferably be obtained by ring-opening polymerization of lactam compounds such as caprolactam and laurolactam.

[0047] The aminocarboxylic acid polymer may preferably be obtained by polymerizing aminocarboxylic acids such as aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0048] The polyamide resin is preferably 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 / 6I, polyamide 66 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide It may be one or more selected from the group consisting of 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, and more preferably one or more selected from the group consisting of polyamide 6, polyamide 56, and polyamide 66, in which case, in addition to being advantageous in terms of price and processability, there is also the advantage of improving mechanical properties and heat resistance.

[0049] The polyamide resin may, for example, have a relative viscosity (RV) of 1.5 to 3.5, preferably 1.7 to 3, and more preferably 2.0 to 2.7. In this case, it does not cause the problem of overheating due to friction between the extruder screw and the molten composition during extrusion molding, and the tension applied to the molten composition is appropriate, thus having the advantage of excellent extrusion processability.

[0050] In this document, unless otherwise specified, relative viscosity is measured using a UFIT-UVS instrument at 20°C with a solution prepared by dissolving 1 g of polyamide in 100 ml of 96 wt% sulfuric acid.

[0051] Poly(arylene ether) resin The aforementioned poly(arylene ether) resin may, for example, be a homopolymer or copolymer containing the units of the following chemical formula 1 or chemical formula 2.

[0052] [ka]

[0053] [ka]

[0054] In the above chemical formulas 1 and 2, R1, R2, R3, R4, R'1, R'2, R'3, and R'4 are substituents of an arylene group (Ar) or a phenylene group, and each is independently or simultaneously a hydrogen, chlorine, bromine, iodine, alkyl, allyl, phenyl, alkylbenzyl, chloroalkyl, bromoalkyl, cyanoalkyl, cyano, alkoxy, phenoxy, or nitro group, where Ar is an arylene group having 6 to 20 carbon atoms, and alkoxy may be an alkoxy having 1 to 4 carbon atoms.

[0055] Preferably, R1, R2, R3, R4, R'1, R'2, R'3, and R'4 are substituents of an arylene group (Ar) or a phenylene group, each independently or simultaneously being hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy, or nitro group, and Ar may be an arylene group having 6 to 20 carbon atoms.

[0056] The average degree of polymerization of the poly(arylene ether) resin with respect to the unit of chemical formula 1 or chemical formula 2 is not particularly limited, as long as it conforms to the definition of the present invention.

[0057] Examples of the aforementioned poly(arylene ether) homopolymers include 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, It may be one or more selected from the group consisting of 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, it offers the advantage of improved appearance quality because it has excellent mechanical properties such as impact strength, tensile strength, and bending strength, as well as excellent processability.

[0058] Furthermore, the copolymer of the poly(arylene ether) resin may be, for example, one or more selected from the group consisting of 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, it offers the advantage of improved appearance quality because it has excellent mechanical properties such as impact strength and tensile strength, as well as excellent processability.

[0059] The poly(arylene ether) resin may preferably be a polyphenylene ether resin.

[0060] The aforementioned poly(arylene ether) resin may, for example, have an intrinsic viscosity of 25 to 55 dl / g, preferably 30 to 50 dl / g, and more preferably 32 to 45 dl / g. Within this range, there is an advantage in ensuring fluidity suitable for molding while maintaining high mechanical properties such as impact strength and tensile strength of the composition.

[0061] The intrinsic viscosity of the poly(arylene ether) resin may be the value measured at 25°C using an Ubbelohde viscometer after dissolving the sample to be measured in chloroform solvent at a concentration of 0.5 g / dl, unless otherwise specified.

[0062] Polyalkylene terephthalate resin The polyalkylene terephthalate resin may, for example, be polybutylene terephthalate, polyethylene terephthalate, or a mixture thereof, and preferably polybutylene terephthalate, in which case it has the effect of having excellent mechanical properties, fluidity and heat resistance.

[0063] The polybutylene terephthalate resin is not particularly limited as long as it is a normal polybutylene terephthalate resin. For example, a polybutylene terephthalate resin obtained by directly esterifying 1,4-butanediol with terephthalic acid or dimethyl terephthalate, or by transesterification and condensation polymerization, may be used.

[0064] The polybutylene terephthalate resin may contain repeating units represented by the following chemical formula 3.

[0065] [ka]

[0066] In the above chemical formula 3, n is the average degree of polymerization in the integer range of 50 to 200.

[0067] The polybutylene terephthalate resin may have a melting point measured by differential scanning calorimeter (DSC) of, for example, 200 to 240°C, preferably 210 to 230°C, and more preferably 220 to 230°C, and within this range, it can maintain its mechanical properties even under high-temperature conditions.

[0068] The aforementioned polybutylene terephthalate resin may have a melt flow velocity of 7 to 11 g / 10 min, preferably 8 to 10 g / 10 min, measured at 250°C and 2.16 kgf in accordance with ISO 1133, and within this range, it has the advantage of excellent processability.

[0069] The method for producing the polyalkylene terephthalate resin is not particularly limited, as long as it is a method commonly used in the art to which the present invention pertains. It may also be commercially purchased and used if it conforms to the definition of polyalkylene terephthalate resin according to the present invention.

[0070] The polyalkylene terephthalate resin may preferably have an intrinsic viscosity of 0.6 to 1.4 dl / g, more preferably 0.8 to 1.4 dl / g, and even more preferably 1.0 to 1.3 dl / g. Within this range, the melt index is appropriate, resulting in excellent processability, moldability, and mold stability.

[0071] The intrinsic viscosity of the polyalkylene terephthalate resin can be measured in accordance with ASTM D2857 unless otherwise specified. Specifically, the sample to be measured can be completely dissolved in methylene chloride, and the filtrate obtained by filtering can be measured at 20°C using an Ubbelohde viscometer.

[0072] Polystyrene resin The polystyrene resin may, for example, be general-purpose polystyrene, high-impact polystyrene, or a mixture thereof, and preferably high-impact polystyrene, in which case it has the effect of excellent processability, dimensional stability, and tensile strength.

[0073] The aforementioned general-purpose polystyrene resin may, for example, be a polymer obtained by polymerizing styrene alone, in which case it has the effect of excellent processability.

[0074] The aforementioned high-impact polystyrene resin may, for example, be a rubber-reinforced polystyrene resin.

[0075] The rubber may be, for example, one or more selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, and alkyl acrylate rubbers, and preferably butadiene rubber, in which case there is an advantage in improving impact strength.

[0076] The rubber may, for example, be present in an amount of 3 to 25% by weight, preferably 6 to 14% by weight, and more preferably 8 to 12% by weight, relative to 100% by weight of the high-impact polystyrene resin, and within this range, it has the effect of having excellent impact strength and fluidity.

[0077] The rubber may have a volume-average particle size of, for example, 0.1 to 20 μm, preferably 1.0 to 15 μm, and within this range, it has the effect of having excellent impact strength and fluidity.

[0078] In this description, the volume-average particle size can be measured using a Coulter Counter LS230 instrument by dissolving 3 g of high-impact polystyrene resin in 100 ml of methyl ethyl ketone, and then measuring the rubber particles that remain undissolved and dispersed in particulate form using the laser scattering method.

[0079] The rubber-reinforced polystyrene resin may preferably be one or more selected from the group consisting of high-impact styrene-butadiene (HIPS) copolymer, styrene-butadiene-styrene (SBS) copolymer, styrene-ethylene-butylene-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-butylene-styrene copolymer)-styrene copolymer.

[0080] The rubber-reinforced polystyrene resin can be produced, for example, by bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof, of rubber and an aromatic vinyl compound. The polymerization may be carried out by thermal polymerization or in the presence of a polymerization initiator.

[0081] The polymerization initiator that can be used for the aforementioned polymerization may, for example, be a peroxide-based initiator, an azo-based initiator, or a mixture thereof.

[0082] The peroxide-based initiator may preferably be one or more selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and the azo-based initiator may preferably be azobisisobutyronitrile.

[0083] For example, the polystyrene resin may have a flow index of 2 to 20 g / 10 min, preferably 3 to 15 g / 10 min, as measured at 200°C and 5 kg in accordance with ASTM D1238, and within this range, it has the effect of having an excellent balance of processability and physical properties.

[0084] Polycarbonate resin The polycarbonate resin may, for example, be a resin polymerized containing an aromatic diol compound and a carbonate precursor.

[0085] Examples of the aforementioned aromatic diol compounds include 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), and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane. It may be one or more selected from the group consisting of 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-(ο-hydroxyphenyl)propyl]polydimethylsiloxane, preferably bisphenol A.

[0086] The carbonate precursor may be one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate, and it is preferable to use triphosgene, phosgene, or a mixture thereof in terms of manufacturing efficiency and physical properties.

[0087] As a specific example, the polycarbonate formed by the polymerization of the aromatic diol compound and the carbonate precursor contains a repeating unit represented by the following chemical formula 4.

[0088] [Chemical Formula]

[0089] In Chemical Formula 4, R’5 to R’8 are each independently hydrogen, C

[0094] , , , alkyl, C 1-10 alkoxy, or halogen, and Z’ is unsubstituted or C 1-6 alkyl or C 6-20 arylene-substituted C 1-10 alkylene, unsubstituted or C 1-10 alkyl-substituted C 3-15 cycloalkylene, O, S, SO, SO2, or CO.

[0090] Preferably, in Chemical Formula 4, R’5 to R’8 are each independently hydrogen or C 1-3 alkyl, and Z’ may be unsubstituted or C 1-6 alkylene substituted with methyl or phenyl.

[0091] As an example, the polycarbonate may have a melt index (300 °C, 1.2 kg) of 3 to 20 g / 10 min, preferably 5 to 17 g / 10 min, more preferably 7 to 15 g / 10 min. Within this range, there is an effect of excellent mechanical properties and heat resistance.

[0092] In this description, the melt index is measured at 300 °C and a load of 1.2 kg in accordance with ASTM D1238.

[0093] [[ID=4५]] The repeating unit of Chemical Formula 4 of the polycarbonate resin, that is, the average degree of polymerization of the unit, is not particularly limited as long as it conforms to the definition of the present invention.

[0094] (b) Ceramic forming binder In this description, the ceramic-forming binder is thermally decomposed when a superheated flame and the resulting pressure are generated, producing a metal phosphate component. This metal phosphate component acts as a bonding agent, binding the ceramic-forming metal precursor to the ceramic-forming non-metallic precursor that has reached the Gob temperature, causing physical and chemical structural changes to form a ceramic. The formed ceramic delays the propagation of the flame, ensuring safety for property and human life even during thermal runaway of batteries, and also has the advantage of being environmentally friendly.

[0095] In this description, the Gob temperature refers to the temperature at which the ceramic-forming nonmetallic precursor melts and transforms into a gob, a hot mass, at which it can be molded into the desired shape.

[0096] In this description, "ultra-high temperature flame and the resulting pressure" means that, in accordance with the Torch and Grit evaluation of UL 2596, when a 1200°C flame formed with oxygen and propane gas is applied to a test specimen, the pressure generated from the ultra-high temperature flame is transmitted to the test specimen along with the flame.

[0097] In this description, the ceramic may preferably contain Al, Si, Ca, and P components, which has the effect of having excellent flame delay characteristics in the event of thermal runaway of the battery.

[0098] The ceramic-forming binder (b) may be, for example, 7 to 20.5% by weight, preferably 8 to 19% by weight, more preferably 9 to 18% by weight, even more preferably 9 to 17% by weight, and even more preferably 9 to 13% by weight, relative to the total weight of components (a) to (e). Within this range, while having excellent flame retardancy and electrical insulation properties, it also has the advantage of being environmentally friendly, as it forms ceramics when extremely high-temperature flames and the resulting pressure are generated, thereby delaying the propagation of flames and ensuring safety against further damage during thermal runaway.

[0099] The ceramic-forming binder (b) may, for example, include a metal phosphorus-based flame retardant, preferably an organic phosphinate metal salt, more preferably a dialkylphosphinate represented by chemical formula 5, a diphosphinate represented by chemical formula 6, or a mixture thereof. In this case, while having excellent flame retardancy and electrical insulation properties, it also has the advantage of ensuring safety for property and human life even during thermal runaway by forming a ceramic when extremely high-temperature flames and the resulting pressure are generated, thereby delaying the propagation of the flame, and is environmentally friendly.

[0100] [ka]

[0101] [ka]

[0102] In the aforementioned chemical formulas 5 and 6, R 5 , R 6 , R 7 and R 8 Each of these is independently linear or branched C1-C 10 alkyl, C3-C 12 Cycloalkyl, C6-C 10 The aryl group of or H; R 9 C1-C is linear or branched. 10 Alkylene, C6-C 10 Arrene, C6-C 20 Alkyl arylene, or C6-C 20It is an 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.

[0103] In chemical formulas 5 and 6, the cycloalkyl may be independently preferably cyclohexyl or cyclohexadimethyl.

[0104] The aforementioned R 5 , R 6 , R 7 and R 8 Preferably, each of these may be independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or phenyl.

[0105] The aforementioned R 9 The material may preferably be 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, phenylpropylene, or phenylbutylene.

[0106] The above M1 and M2 may preferably be independently Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, or K, and more preferably independently Mg, Ca, Al, Ti, or Zn.

[0107] The aforementioned R 5 and R 6 , and R 7 and R 8These can bond with each other to form a ring with adjacent phosphorus atoms. 5 and R 6 , and R 7 and R 8 The rings formed by the bonding of these atoms together with adjacent phosphorus atoms are heterocycles having the phosphorus atoms as heteroatoms constituting the ring, and the number of atoms constituting such a ring may be, for example, 4 to 20, preferably 5 to 16. The heterocycle having the phosphorus atoms may be a bicyclocycle or may have substituents.

[0108] The dialkylphosphinate represented by chemical formula 5 may preferably be one or more selected from the group consisting of calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methylphenylphosphinate, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

[0109] The diphosphinate represented by the chemical formula 6 is preferably one or more selected from the group consisting of methylenebis(methylphosphinate)calcium, methylenebis(methylphosphinate)magnesium, methylenebis(methylphosphinate)aluminum, methylenebis(methylphosphinate)zinc, 1,4-phenylenebis(methylphosphinate)calcium, 1,4-phenylenebis(methylphosphinate)magnesium, 1,4-phenylenebis(methylphosphinate)aluminum, and 1,4-phenylenebis(methylphosphinate)zinc.

[0110] The ceramic-forming binder (b) may more preferably be one or more selected from the group consisting of calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate, and even more preferably aluminum diethylphosphinate. In this case, high flame retardancy can be achieved with a small amount of flame retardant while maintaining mechanical properties, and it also has excellent flame delay characteristics even in the event of thermal runaway, thus ensuring safety for property and human life, and is environmentally friendly.

[0111] As a specific example, when aluminum diethylphosphinate is used as the ceramic-forming binder (b) above, under an ultra-high temperature flame, the organic components volatilize as phosphoric acid gas, and the remaining components change from an amorphous structure to a crystalline structure, with AlPO3 changing structure to AlPO4, which plays a role in bonding the ceramic-forming metal and the ceramic-forming nonmetal.

[0112] The ceramic-forming binder (b) may, for example, have an average particle size of 0.1 to 100 μm, preferably 0.1 to 80 μm, and more preferably 1 to 60 μm, and within this range, it has the advantage of being excellent in flame retardancy and mechanical properties.

[0113] In this description, 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 particle number measured using a laser diffraction particle size analyzer, with the binder dispersion in a medium such as acetone used as the measurement sample.

[0114] The ceramic-forming binder (b) may have a phosphorus content of preferably 20 to 35% by weight, more preferably 22 to 30% by weight. Within this range, while exhibiting excellent flame retardancy and electrical insulation properties, it also has the effect of ensuring safety for property and human life even during thermal runaway by forming a ceramic when an extremely high temperature flame and the resulting pressure are generated, thereby delaying the propagation of the flame.

[0115] In this description, phosphorus content refers to the weight percentage of phosphorus calculated from the molecular weight of phosphorus contained in the molecular structure of the phosphorus-based flame retardant.

[0116] (c) Ceramic forming metal precursor In this description, the ceramic-forming metal precursor combines with a gob-state ceramic-forming nonmetal precursor by metal phosphate components generated by the thermal decomposition of the ceramic-forming binder when a superheated flame and the resulting pressure are generated, causing physical and chemical structural changes to form a ceramic. The formed ceramic delays the flame, thereby ensuring safety for property and human life even in the event of thermal runaway of the battery.

[0117] The (c) ceramic-forming metal precursor may be, for example, 6.5 to 20.5% by weight, preferably 8 to 19% by weight, or 8 to 18% by weight, more preferably 9 to 18% by weight, even more preferably 10 to 17% by weight, and even more preferably 13 to 17% by weight, relative to the total weight of components (a) to (e). Within this range, it has excellent flame retardancy and electrical insulation properties, and when extremely high-temperature flames and the resulting pressure are generated, the ceramic-forming binder combines with the ceramic-forming nonmetal precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety for property and human life even during thermal runaway.

[0118] The (c) ceramic-forming metal precursor may, for example, contain a metal silicate, or the magnesium content (provided that magnesium oxide is not included) or magnesium oxide content may be 3% by weight or less relative to the total weight. In this case, it has excellent flame retardancy and electrical insulation properties, and when extremely high-temperature flames and the pressure generated therefrom are generated, the ceramic-forming binder combines with the ceramic-forming nonmetal precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety for property and human life even in the event of thermal runaway.

[0119] The aforementioned metal silicate may, for example, include one or more selected from the group consisting of aluminum silicate and calcium silicate, and preferably includes aluminum silicate. In this case, it has excellent flame retardancy and electrical insulation properties, and when ultra-high temperature flames and the pressure generated therefrom are generated, the ceramic-forming binder combines with the ceramic-forming nonmetallic precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety for property and human life even during thermal runaway.

[0120] The aluminum silicate may, for example, contain one or more selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite. Preferably, it may contain kaolin, mica, or a mixture thereof, and more preferably, it may contain kaolin. In this case, it has excellent flame retardancy and electrical insulation properties, and when ultra-high temperature flames and the resulting pressure are generated, the ceramic-forming binder combines with the ceramic-forming nonmetallic precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety for property and human life even during thermal runaway.

[0121] The calcium silicate may, for example, contain wollastonite. In this case, it has excellent flame retardancy and electrical insulation properties, and when extremely high-temperature flames and the resulting pressure are generated, it forms ceramics by bonding with a ceramic-forming nonmetallic precursor through a ceramic-forming binder, thereby delaying the propagation of flames and ensuring safety for property and human life even during thermal runaway.

[0122] The ceramic-forming metal precursor (c) may, for example, be a magnesium-free silicate. In this case, without the interference of magnesium, it exhibits excellent flame retardancy and electrical insulation properties, and when ultra-high temperature flames and the resulting pressure are generated, it forms a ceramic by bonding with the ceramic-forming nonmetal precursor, delaying the propagation of the flame and thus ensuring safety even during thermal runaway.

[0123] The aforementioned 'magnesium-free silicate' may contain, for example, 3% by weight or less, preferably 2% by weight or less, more preferably less than 2% by weight, even more preferably 1% by weight or less, even more preferably less than 1% by weight, and particularly preferably 0.01% by weight or more to less than 1% by weight, relative to the total weight of the ceramic-forming metal precursor. Within this range, it exhibits excellent flame retardancy and electrical insulation properties, and when ultra-high temperature flames and the resulting pressure are generated, the ceramic-forming binder combines with the ceramic-forming nonmetallic precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety even during thermal runaway. Furthermore, if the magnesium or magnesium oxide content exceeds the above range, it becomes difficult to form a ceramic when ultra-high temperature flames and the resulting pressure are generated, and even if a ceramic is formed, it breaks instantly, and the effect of delaying the propagation of the flame does not manifest.

[0124] The (c) ceramic-forming metal precursor is defined as a substance that, when a superheated flame and the resulting pressure are generated, combines with a gob-state ceramic-forming nonmetal precursor and a ceramic-forming binder to form a ceramic. Talc, which cannot form a ceramic in this way, does not fall under the definition of a ceramic-forming metal precursor according to the present invention.

[0125] The ceramic-forming metal precursor (c) may, for example, have an average particle size of 0.1 to 170 μm, preferably 0.1 to 150 μm, more preferably 0.1 to 100 μm, and even more preferably 0.1 to 60 μm. Within this range, compatibility with the ceramic-forming nonmetal precursor is improved, and excellent mechanical properties, electrical insulation, flame retardancy, and flame retardancy are achieved.

[0126] In this description, the average particle size of the ceramic-forming metal precursor can be measured by measurement methods commonly used in the art to which the present invention belongs, such as electron microscopy analysis, and as another specific example, it can be measured by the X-ray method.

[0127] (d) Ceramic-forming nonmetallic precursors In this description, the ceramic-forming nonmetallic precursor transforms into a gob state when a superheated flame and the resulting pressure are generated. The gob-state ceramic-forming nonmetallic precursor then combines with the ceramic-forming metal precursor by metal phosphate components generated by the thermal decomposition of the ceramic-forming binder, undergoing physical and chemical structural changes to form a ceramic. This prevents the formation of holes or drips caused by the flame and provides excellent flame delay characteristics during thermal runaway, thus ensuring safety.

[0128] The (d) ceramic-forming nonmetallic precursor may be, for example, 13 to 37% by weight, preferably 18 to 34% by weight, more preferably 19 to 32% by weight, even more preferably 20 to 30% by weight, and even more preferably 25 to 32% by weight, relative to the total weight of components (a) to (e). Within this range, it has excellent mechanical properties, flame retardancy, and appearance characteristics, and also has the effect of ensuring safety by forming ceramics when extremely high-temperature flames and the resulting pressure are generated, thereby delaying the propagation of the flame.

[0129] The (d) ceramic-forming nonmetallic precursor may include, for example, glass fibers, preferably E-glass fibers. In this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high temperature flame and the pressure generated therefrom occur, the ceramic-forming binder combines with the ceramic-forming metal precursor to form a ceramic, delaying the propagation of the flame and thus ensuring safety even during thermal runaway.

[0130] The aforementioned glass fibers may include, for example, chopped glass fibers, which have the advantage of excellent compatibility with polymers.

[0131] In this description, the chopped glass fiber is not particularly limited as long as it is a chopped glass fiber commonly used in the art to which the present invention pertains.

[0132] In this description, E glass fiber is not particularly limited as long as it is a glass fiber with excellent electrical properties and is an E glass fiber commonly used in the art to which the present invention belongs, and contains SiO2, Al2O3, CaO, and B2O3 as major components.

[0133] The (d) ceramic-forming nonmetallic precursor may, for example, have an average particle size of 3 to 25 μm, preferably 5 to 20 μm, and more preferably 7 to 15 μm. Within this range, the mechanical strength with the polymer is improved, and the appearance characteristics of the final product are excellent.

[0134] The (d) ceramic-forming nonmetallic precursor may, for example, have an average length of 1 to 10 mm, preferably 2 to 7 mm, and more preferably 2 to 5 mm. Within this range, the mechanical strength with the polymer is improved, and the appearance characteristics of the final product are excellent.

[0135] The (d) ceramic-forming nonmetallic precursor may, for example, have an aspect ratio (L / D), which is the ratio of the average length (L) to the average particle size (D), of 200 to 550, preferably 220 to 450, more preferably 250 to 350, and even more preferably 270 to 320. Within this range, it has the advantage of excellent compatibility with the polymer, resulting in a superior surface appearance.

[0136] In this description, the average particle size, average length, and aspect ratio of the ceramic-forming nonmetallic precursor are calculated by measuring 30 samples using microscopic analysis and using the average value.

[0137] The (d) ceramic-forming nonmetallic precursor may, for example, be surface-treated with a silane compound or a urethane compound, preferably with one or more surface treatment agents selected from the group consisting of aminosilane compounds, epoxysilane compounds, and urethane compounds, and more preferably with an aminosilane compound. In this case, the dispersibility and surface wettability are improved by bonding with the polymer, and as a result, the mechanical properties of the resin composition, including the tensile strength, are improved.

[0138] The surface treatment agent may be included, for example, in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.1 to 0.8% by weight, and even more preferably 0.2 to 0.5% by weight, relative to 100% by weight of the total surface-treated ceramic-forming nonmetallic precursor (ceramic-forming nonmetallic precursor + surface treatment agent). Within this range, there is an effect of excellent mechanical properties, balance of physical properties, and appearance of the final product.

[0139] The aminosilane compound is not particularly limited as long as it is an aminosilane commonly used as a coating agent for glass fibers. For example, it may be one or more selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanatetopropyltriethoxysilane, γ-acetacetatetopropyltrimethoxysilane, γ-acetacetatetopropyltriethoxysilane, γ-cyanoacetyltrimethoxysilane, γ-cyanoacetyltriethoxysilane, and acetoxyacetotrimethoxysilane. In this case, it has the effect of having excellent mechanical properties and heat resistance while also having excellent surface properties of the injection-molded product.

[0140] The epoxysilane compound is not particularly limited as long as it is an epoxysilane commonly used as a coating agent for glass fibers. For example, it may be one or more selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In this case, it has the effect of having excellent mechanical properties and heat resistance while also having excellent surface properties of the injection-molded product.

[0141] The aforementioned glass fibers can be appropriately selected and used within the range commonly used in the industry, as long as they conform to the definition of the present invention, and their cross-sectional shapes, such as cylindrical or elliptical, are not particularly limited.

[0142] The sum of the ceramic-forming metal precursor (c) and the ceramic-forming nonmetal precursor (d) may be, for example, 30 to 52% by weight, preferably 32 to 50% by weight, more preferably 34 to 48% by weight, even more preferably 38 to 43% by weight, or 40 to 46% by weight, relative to the total weight of components (a) to (e). Within this range, there is an advantage in that the ceramics are formed well when extremely high-temperature flames and the resulting pressure are generated, while maintaining excellent flame retardancy and electrical insulation properties.

[0143] (e) Flame retardants In this description, the flame retardant imparts to the thermoplastic resin composition a high degree of flame retardancy (V-0 or higher according to the UL94 test) and excellent electrical insulation properties. It is thermally decomposed when exposed to extremely high-temperature flames and the resulting pressure, and since there is virtually no generation of toxic gases and no release of endocrine disruptors during thermal decomposition, it does not have harmful effects on the human body or the environment.

[0144] The flame retardant (e) may be, for example, 2 to 8% by weight, preferably 2.5 to 7% by weight, more preferably 3 to 6.5% by weight, even more preferably 3 to 6% by weight, and even more preferably 4 to 6% by weight, relative to the total weight of components (a) to (e). Within this range, it provides a high level of flame retardancy of V-0 grade or higher in accordance with the UL94 test, and has the effect of being excellent in mechanical properties and electrical insulation.

[0145] The aforementioned (e) flame retardant may, for example, include one or more selected from the group consisting of melamine-based flame retardants, phosphazene-based flame retardants, and phosphate-based flame retardants, and preferably may include a melamine-based flame retardant. In this case, it provides a high level of flame retardancy of V-0 or higher according to the UL94 test, has excellent mechanical properties and electrical insulation properties, and has the advantage of not emitting gases or endocrine disruptors that are harmful to the human body and the environment.

[0146] The melamine-based flame retardant may, for example, be one or more selected from the group consisting of melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine borate, and melamine sulfate, and preferably melamine polyphosphate. In this case, it provides a high level of flame retardancy of V-0 or higher according to the UL94 test, and has the effect of excellent mechanical properties and electrical insulation properties.

[0147] The phosphazene-based flame retardant is, for example, an organic compound having a -P=N- bond in its molecule, and is preferably one or more selected from the group consisting of cyclic phosphazene compounds, linear phosphazene compounds, and crosslinked phosphazene compounds, and is preferably a cyclic phosphazene compound, in which case it has the effect of being excellent in flame retardancy and mechanical properties.

[0148] The cyclic phosphazene compound may preferably be a compound represented by the following chemical formula 7.

[0149] [ka]

[0150] In the above chemical formula 7, m is an integer from 3 to 25, and R 13 and R 14 These are identical or different, and represent an aryl group or an alkylaryl group.

[0151] In the above chemical formula 7, m is preferably an integer between 3 and 5.

[0152] The cyclic phosphazene compound represented by the chemical formula 7 is more preferably R 13 and R 14The compound is a cyclic phenoxyphosphazene having a phenyl group, and more preferably one or more selected from the group consisting of phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene.

[0153] The chain-like phosphazene compound may preferably be a compound represented by the following chemical formula 8.

[0154] [ka]

[0155] In the above chemical formula 8, n is an integer between 3 and 10,000, and X is -N=P(OR 15 ) 3 units, or -N=P(O)OR 15 The base is shown, and Y is -P(OR 16 ) 4 units, or -P(O)(OR 16 ) Shows 2 units. R 15 and R 16 These are identical or different, and represent an aryl group or an alkylaryl group.

[0156] In the above chemical formula 8, n is preferably an integer between 3 and 100, and more preferably an integer between 3 and 25.

[0157] The chain-like phosphazene compound represented by the chemical formula 8 is preferably R 15 and R 16 It is a chain-like phenoxyphosphazene in which the phenyl group is located.

[0158] The aforementioned crosslinked phosphazene compound is, for example, one or more phosphazene-based flame retardants selected from the group consisting of cyclic phosphazene compounds and linear phosphazene compounds, which are crosslinked by a crosslinking group represented by the following chemical formula 9.

[0159] [ka]

[0160] In the above chemical formula 9, A is -C(CH3)2-, -SO2-, -S-, or -O-, I is an integer of 0 or 1, and -* is a bond.

[0161] The crosslinked phosphazene compound is preferably, in the chemical formula 7, R 13 and R 14 A cyclic phenoxyphosphazene compound in which is a phenyl group is crosslinked by a crosslinking group represented by the chemical formula 9, in the chemical formula 8, R 15 and R 16 A linear phenoxyphosphazene compound having a phenyl group may be crosslinked with a crosslinking group represented by the chemical formula 9 to form a crosslinked phenoxyphosphazene compound, or a mixture thereof. More preferably, a cyclic phenoxyphosphazene compound may be crosslinked with a crosslinking group represented by the chemical formula 9 to form a crosslinked phenoxyphosphazene compound.

[0162] Examples of the phosphate-based flame retardants include trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), resorcinolbis(diphenyl phosphate) (RDP), phenyl diresorcinol phosphate, bisphenol diphenyl phosphate (BDP), cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyl di(isopropylphenyl) phosphate (Phenyldi(isopropylphenyl)phosphate), triisophenyl phosphate, and diphenyl phosphate (Diphenyl It may be one or more selected from the group consisting of Phosphate, Resorcinol di Phosphate, Resorcinol bis(2,6-dixylenyl phosphate), and Aromatic Polyphosphate.

[0163] The thermoplastic resin composition may, for example, include a lubricant, an antioxidant, or a mixture thereof.

[0164] The lubricant can be present in an amount of, for example, 0.01 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, and even more preferably 0.2 to 0.5% by weight, relative to the total weight of components (a) to (e). Within this range, the lubricant has the effect of improving moldability while maintaining excellent mechanical properties.

[0165] The lubricant may, for example, be one or more selected from the group consisting of ester-based lubricants, fatty acid amide-based lubricants, olefin-based lubricants, and montan-based lubricants. Preferably, it may be an ester-based lubricant, a fatty acid amide-based lubricant, or a mixture thereof. In this case, it has the effect of improving moldability while maintaining excellent mechanical properties.

[0166] The ester-based lubricant may, for example, be one or more selected from the group consisting of fatty acid esters of alcohols, hydrogenated oils, butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, stearyl stearate, ester waxes, and alkyl phosphate esters. In this case, it has the effect of improving moldability while maintaining excellent mechanical properties.

[0167] The fatty acid amide lubricant may be one or more selected from the group consisting of, for example, stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bis oleamide. In this case, it has the effect of improving moldability while maintaining excellent mechanical properties.

[0168] The olefin-based lubricant may, for example, be polyethylene wax, polypropylene wax, or a mixture thereof. In this case, it has the effect of improving moldability while maintaining excellent mechanical properties.

[0169] The montan-based lubricant may, for example, be montan wax, montan ester wax, or a mixture thereof. The montan ester wax may, for example, be one or more selected from a montan-based wax esterified with ethylene glycol and montanic acid, a wax esterified with glycerin and montanic acid, calcium montanate containing montanic acid ester, and a montanic acid-based ester mixture wax. In this case, the effect is to improve moldability while maintaining excellent mechanical properties.

[0170] The antioxidant can be present in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, and even more preferably 0.2 to 0.5% by weight, relative to the total weight of components (a) to (e). Within this range, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0171] The aforementioned antioxidant may be, for example, one or more selected from the group consisting of phosphorus-based antioxidants, hindered phenol-based antioxidants, and phenol-based antioxidants. In this case, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0172] Examples of the phosphorus-based antioxidants include bis(dialkylphenyl)pentaerythritol diphosphite, phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butanediphosphite, and tetra(C 12 -C 15Mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, tris(mono- and di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris[4,4'-isopropylidenebis(2-t-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butylphenol) bis(nonylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2-[{2,4,8,10-tetra It may be one or more selected from the group consisting of -t-butyldibenz[d,f][1.3.2]-dioxaphosfepin-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosfepin-6-yl}oxy]ethyl]-ethaneamine and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosfepin, and more preferably tris(2,4-di-tert-butylphenyl)phosphite (IF168), in which case oxidation due to heat during the extrusion process is prevented and mechanical properties and heat resistance are excellent.

[0173] The aforementioned hindered phenol antioxidant may be, for example, one or more selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and preferably pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], in which case it has the effect of preventing oxidation due to heat during the extrusion process and having excellent mechanical properties and heat resistance.

[0174] Examples of the phenolic antioxidants include 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediol bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 2,2-thiodiethylene bis-[3-( [3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, Tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, Tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-t-butylphenol)terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-teto It may be one or more selected from the group consisting of raoxaspiro[5,5]undecane, 2,2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, and more preferably octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (IR1076), in which case oxidation due to heat during the extrusion process is prevented, and the mechanical properties and heat resistance are excellent.

[0175] The thermoplastic resin composition may further include, as an example, one or more additives selected from the group consisting of plasticizers, heat stabilizers, anti-dripping agents, light stabilizers, pigments, dyes, inorganic additives (excluding glass fibers), and carbon fibers.

[0176] The additive can be included in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 1 part by weight, based on a total content of 100 parts by weight of components (a) to (e). Within this range, the desired physical properties can be achieved without degrading the inherent physical properties of the thermoplastic resin composition described herein.

[0177] thermoplastic resin composition The thermoplastic resin composition may preferably have a flame retardancy of V-0 or higher, as measured in accordance with the UL94 test (Vertical Burning Test) using an injection-molded test piece measuring 127 mm × 12.7 mm × 1.5 mm. In this case, it has the advantage of having a good balance of physical properties and excellent flame retardancy.

[0178] The thermoplastic resin composition may preferably have a flame endurance time of 600 seconds or more, measured in accordance with the UL 2596 Torch and Grit evaluation, where a 1200°C flame formed with oxygen and propane gas is applied to a 150 mm × 150 mm × 3 mm test piece, and the time until a hole or drip occurs is measured. Within this range, it has excellent balance of physical properties and also ensures safety by forming ceramic when an ultra-high temperature flame and the resulting pressure are generated, thereby delaying the propagation of the flame.

[0179] The thermoplastic resin composition is preferably graded 1 or higher, preferably 0 or higher, according to the Performance Level Category (PLC) classification, when the Comparative Tracking Index (CTI) is measured on a 3 mm thick test piece in accordance with IEC 60112. Within this range, it has the effect of having an excellent balance of physical properties as well as excellent electrical insulation properties.

[0180] Method for manufacturing thermoplastic resin compositions The method for producing the thermoplastic resin composition described herein includes the steps of kneading and extruding (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant, wherein the kneading and extrusion are carried out using an extruder with 9 or more kneading blocks. In this case, while having excellent flame retardancy and insulation properties, safety is ensured and the method is environmentally friendly by forming ceramics to delay the propagation of flames when unexpected ultra-high temperature flames and the resulting pressure are generated.

[0181] The aforementioned kneading and extrusion can be carried out within a barrel temperature range of, for example, 200 to 350°C, preferably 220 to 330°C, and more preferably 220 to 310°C. In this case, sufficient melt kneading is possible while maintaining a high processing rate per unit time, and there is the advantage of not causing problems such as thermal decomposition of the polymer.

[0182] The aforementioned kneading and extrusion can be carried out under conditions where the screw rotation speed is, for example, 100 to 500 rpm, preferably 150 to 400 rpm, and more preferably 150 to 300 rpm. Within this range, there is an effect of high processing volume per unit time and excellent process efficiency.

[0183] The thermoplastic resin composition obtained through the aforementioned kneading and extrusion may preferably be provided in pellet form.

[0184] Flame retardant composition The flame retardant composition described herein is characterized by comprising a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming nonmetal precursor, and a flame retardant. In this case, while having excellent flame retardancy and insulating properties, it also ensures safety for property and human life even during thermal runaway by forming ceramics when unexpected ultra-high temperature flames and the resulting pressure are generated, thereby delaying the propagation of flames. Furthermore, it has an environmentally friendly effect as it produces almost no toxic gases during thermal decomposition and does not release endocrine disruptors.

[0185] In the aforementioned flame retardant composition, when subjected to ultra-high temperatures of 1200°C or higher and the resulting pressure, the ceramic-forming binder is thermally decomposed and converted into a metal phosphate component. This metal phosphate component then combines the ceramic-forming metal precursor with the ceramic-forming non-metallic precursor that has reached the Gob temperature, causing physical and chemical structural changes to form a ceramic. The formed ceramic delays the propagation of the flame, thus ensuring safety for property and human life even in the event of thermal runaway of a battery.

[0186] The flame retardant composition may, for example, contain 11-34% by weight of a ceramic-forming binder, 14.5-41% by weight of a ceramic-forming metal precursor, 24-59% by weight of a ceramic-forming nonmetal precursor, and 4-14% by weight of a flame retardant, preferably 13-32% by weight of a ceramic-forming binder, 16-35% by weight of a ceramic-forming metal precursor, 30-57% by weight of a ceramic-forming nonmetal precursor, and 4.5-12% by weight of a flame retardant, more preferably 15.5-31% by weight of a ceramic-forming binder, and The material may contain 17.5-28% by weight of a metal precursor that forms ceramics, 35-55% by weight of a nonmetallic precursor that forms ceramics, and 5-9.5% by weight of a flame retardant. More preferably, it may contain 15.5-25% by weight of a ceramic binder, 20-27% by weight of a metal precursor that forms ceramics, 43-53% by weight of a nonmetallic precursor that forms ceramics, and 7-9% by weight of a flame retardant. Within this range, while having excellent flame retardancy and insulation properties, it ensures safety for property and human life even during thermal runaway by forming ceramics to delay flame propagation when unexpected ultra-high temperature flames and the resulting pressure are generated, and has an environmentally friendly effect as it produces almost no toxic gases during thermal decomposition and does not release endocrine disruptors.

[0187] This flame retardant composition contains the same components as the thermoplastic resin composition described above, and has been omitted here to avoid redundancy.

[0188] molded product The molded article described herein is characterized by containing the thermoplastic resin composition described herein, and in this case, while having excellent flame retardancy and electrical insulation properties, it also has the effect of ensuring safety even in the event of thermal runaway by forming a ceramic when an extremely high temperature flame and the pressure generated thereby are generated, thereby delaying the propagation of the flame, and is environmentally friendly.

[0189] The molded product may, for example, be an electrical or electronic component or an automotive component, specifically an electrical component or battery component for an electric vehicle. In this case, while having excellent flame retardancy and electrical insulation properties, it also has the effect of ensuring safety even during thermal runaway by forming a ceramic when extremely high-temperature flames and the resulting pressure are generated, thereby delaying the propagation of the flame, and is also environmentally friendly.

[0190] The aforementioned battery components of the electric vehicle may, for example, be a plastic upper cover, module housing, or busbar for the electric vehicle battery.

[0191] The method for manufacturing a molded article described herein preferably comprises the steps of kneading and extruding a thermoplastic resin composition pellet containing (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant to produce a thermoplastic resin composition pellet, and injecting the produced pellet to produce a molded article, wherein the kneading and extrusion are carried out using an extruder having 9 or more kneading blocks. In such a case, while having excellent flame retardancy and insulation properties, it also ensures safety during thermal runaway by forming ceramics to delay the propagation of flames when unexpected ultra-high temperature flames and the resulting pressure are generated, and is environmentally friendly.

[0192] The injection is not particularly limited, as long as it is carried out by methods and conditions commonly used in the art to which the present invention pertains, and can be appropriately selected and applied as needed.

[0193] In describing the thermoplastic resin compositions, molded articles, and methods for producing them described herein, it is stated that other conditions not specifically mentioned (for example, the configuration and specifications of the extruder and injection machine, extrusion and injection conditions, additives, etc.) are not particularly limited as long as they are within the range of practices commonly used in this industry, and can be appropriately selected as needed.

[0194] The present invention will be described below with reference to the drawings.

[0195] Figure 1 below is a schematic diagram of an extruder equipped with nine or more kneading blocks for the production of the thermoplastic resin composition described herein.

[0196] The type of extruder is not particularly limited and can be appropriately selected as long as it is commonly used in the industry. For example, a single-screw extruder with one screw or a multi-screw extruder with multiple screws can be used. However, considering the uniform mixing of the material, ease of processing, and economic efficiency, it is preferable to use a twin-screw extruder with two screws.

[0197] The extruder comprises a feeder for supplying material into a barrel, a screw for transporting and kneading the material supplied into the barrel, and a die for extruding the kneaded material. The screw is composed of multiple screw elements to provide various functions.

[0198] The raw material feeder may consist of one or more units, and may be selectively provided with two or more units as needed. For example, it may be provided with a main inlet and optionally an auxiliary inlet, and may be provided with two or more auxiliary inlets as needed.

[0199] As a specific example, a polymer, ceramic-forming binder, flame retardant, and additives containing lubricants and antioxidants can be introduced into the main inlet, a ceramic-forming metal precursor can be introduced into auxiliary inlet 1, and a ceramic-forming non-metal precursor can be introduced into auxiliary inlet 2. In this case, uniform mixing is achieved, which has the advantage of excellent balance of physical properties, electrical insulation, flame retardancy, and flame delay characteristics during thermal runaway when generating ultra-high temperature flames and pressures.

[0200] As another example, polymers and additives can be introduced into the main inlet, ceramic-forming binders and flame retardants into auxiliary inlet 1, and ceramic-forming metal precursors and ceramic-forming non-metal precursors into auxiliary inlet 2. In this case, uniform mixing provides advantages such as a good balance of physical properties, electrical insulation, flame retardancy, and flame delay characteristics during thermal runaway when generating ultra-high temperature flames and the resulting pressure.

[0201] As another example, the polymer can be introduced into the main inlet, and a portion of the ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming non-metal precursor, flame retardant, and additives can be introduced into the auxiliary inlet 1, with the remaining amount then introduced into the auxiliary inlet 2. In this case, uniform mixing is achieved, which has the advantage of excellent balance of physical properties, electrical insulation, flame retardancy, and flame delay characteristics when generating ultra-high temperature flames and the resulting pressure.

[0202] The kneading block of the present invention is an example of the screw element, and specifically consists of a plurality of disks, preferably 3 to 7, 5 to 7, 3 to 5, or 4 to 5 disks, which usually have a polygonal or elliptical cross-section and are arranged continuously in the direction of material transport. Furthermore, the phase angle of the disks in the kneading block (meaning the angle of movement between disks) is preferably 45 to 90°.

[0203] Furthermore, kneading blocks include forward kneading blocks that have the ability to transport, distribute, and mix materials; neutral kneading blocks that have the ability to distribute and mix materials but not the ability to transport them; and backward kneading blocks that transport materials in the opposite direction to the transport direction.

[0204] The thermoplastic resin composition according to the present invention may be manufactured by kneading and extruding using an extruder having, for example, 9 or more kneading blocks, preferably 10 or more, more preferably 12 or more, a preferred example 9 to 18, a more preferred example 10 to 18, and an even more preferred example 12 to 16. In this case, it is effective to use the kneading blocks in combination in the order of forward direction, perpendicular direction, and reverse direction with respect to the resin flow direction, and a combination of continuous or separated blocks can be used depending on the mixing method. In this case, the dispersibility of the ceramic-forming metal precursor and the ceramic-forming non-metal precursor, the compatibility of the composition, etc., are further improved, and an even higher quality thermoplastic resin composition can be provided.

[0205] The aforementioned kneading blocks may, for example, be arranged in a continuous sequence of nine or more blocks, or, as another example, be arranged discontinuously between the screws. Specifically, as an example, three to six kneading blocks may be provided continuously between the main inlet and auxiliary inlet 1, three to eight kneading blocks may be provided continuously between auxiliary inlet 1 and auxiliary inlet 2, and two to five kneading blocks may be provided between auxiliary inlet 2 and discharge port (not shown). When arranged in this manner, localized heat generation during melt kneading can be controlled, preventing thermal deformation of the raw material, and excessive cutting of glass fibers can be prevented, thus preventing a decrease in mechanical properties, electrical insulation, flame retardancy, and flame delay characteristics during thermal runaway.

[0206] The following examples illustrate the description, but these examples are merely illustrative, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the description and the technical concept, and such changes and modifications will naturally fall within the scope of the attached claims.

[0207] [Examples] The substances used in the following examples and comparative examples are as follows: *(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 binder -(b-1)ADP: Aluminum diethyl phosphinate (Clariant OP1230) *(c) Ceramic forming metal precursor -(c-1) Kaolin: Aluminum silicate -(c-2) Mica: Aluminum silicate -(c-3) Wollastonite: Calcium silicate *(c') Ceramic unformed metal precursor -(c'-1) Talc: Magnesium silicate *(d) Ceramic-forming nonmetallic precursor -(d-1) Glass fibers: Chopped glass fibers with an average particle size of 10-13 μm and an average length of 3-4 mm, surface-treated with aminosilane. *(e) Flame retardant -(e-1)MPP: Melamine polyphosphate -(e-2)RDX: Resorcinol bis(2,6-dixylenyl phosphate) *(f) Additives: - Lubricant: EP184 (Hanyang Hwasung Co.) and Sunlube EBS DA-01 (SUNKOO Co.) 0.25% by weight - Antioxidant: 0.25% by weight of a mixture of AO-412S, IR1010, IR1098, and IR68

[0208] Examples 1-10 and Comparative Examples 1-9 Polymers, ceramic-forming binders, ceramic-forming metal precursors, ceramic-forming non-metal precursors, flame retardants, and additives were mixed in the quantities listed in Tables 1 and 2 below using a twin-screw extruder (SM Corporation T40) with 9 mixing blocks, at a temperature of 230-310°C and a rotation speed (rpm) of 150-300 rpm. The mixture was melt-kneaded and extruded to produce pellets, and these pellets were used to produce evaluation test specimens using an injection molding machine (Engel Corporation, 80 tons). After leaving the produced test specimens at room temperature for 48 hours or more, their physical properties were measured and are shown in Tables 1 and 2 below.

[0209] In this case, the twin-screw extruder had a total of two or more inlets. Polymer, ceramic-forming binder, flame retardant, and additives were fed into the main inlet, ceramic-forming metal precursor was fed into auxiliary inlet 1, and ceramic-forming nonmetal precursor was fed into auxiliary inlet 2.

[0210] [Example Test] The properties of the test specimens produced in Examples 1 to 10 and Comparative Examples 1 to 9 were measured by the following method, and the results are shown in Tables 1 and 2 below.

[0211] Measurement method *Flame retardancy: Measured in accordance with the UL94V test (Vertical Burning Test) using an injection-molded test specimen measuring 127mm x 12.7mm x 1.5mm. *CTI (Comparative Tracking Index): In accordance with IEC 60112, the voltage that is short-cut when 50 drops of electrolyte solution are dropped onto a 3 mm thick test specimen was calculated, and the PLC (Performance Level Category) grade was assigned based on the CTI as shown in Table 3 below.

[0212] [Table 3]

[0213] *Flame Endurance Time (seconds): As shown in Figures 2 and 3, in accordance with the Torch and Grit evaluation of UL 2596, a 1200°C flame formed with oxygen and propane gas was applied to a 150mm × 150mm × 3mm test specimen, and the time until a hole or drip occurred was measured.

[0214] [Table 1]

[0215] [Table 2]

[0216] As shown in Tables 1 and 2 above, the thermoplastic resin compositions of the present invention (Examples 1-10) are superior to Comparative Examples 1-9 in terms of flame retardancy and insulation properties. Furthermore, when exposed to ultra-high temperatures of 1200°C and the resulting pressure, ceramics are formed, delaying the propagation of the flame. This results in a fire resistance time of 600 seconds or more, and no holes are formed. Therefore, safety for property and human life is ensured even in the event of battery thermal runaway. In addition, there is virtually no generation of toxic gases and no release of endocrine disruptors, thus ensuring no harmful effects on the human body or the environment.

[0217] Specifically, Comparative Examples 1 and 5, which contained a small amount of the ceramic-forming binder (b-1)ADP and an excessive amount of the flame retardant (e-1)MPP, showed reduced flame retardancy and very poor fire resistance duration, while Comparative Example 2, which contained a small amount of (e-1)MPP, also showed reduced flame retardancy.

[0218] Furthermore, Comparative Example 3, which contained a small amount of (d-1) glass fibers, a nonmetallic precursor for ceramic formation, and an excessive amount of (c-1) kaolin, a metal precursor for ceramic formation, exhibited reduced flame retardancy and extremely poor fire resistance duration.

[0219] Furthermore, Comparative Example 4, which contained a small amount of (c-1) kaolin, a ceramic-forming metal precursor, and Comparative Example 6, which contained (c'-1) talc, a ceramic-unforming metal precursor, exhibited reduced flame retardancy and extremely poor fire resistance duration.

[0220] Furthermore, Comparative Example 7, which contained a small amount of (c-1) kaolin, had very poor fire resistance, while Comparative Example 8, which contained an excessive amount of (d-1) glass fiber, and Comparative Example 9, which contained an excessive amount of (b-1) ADP, were difficult to extrude.

[0221] As shown in Figures 4 and 5 below, when a 1200°C flame and pressure formed from oxygen and propane gas were applied to test specimens made from the thermoplastic resin compositions according to Examples 1 and 5 of the present invention, in accordance with the Torch and Grit evaluation of UL 2596, ceramic material was formed and no holes were formed even after 600 seconds or more, confirming a significant improvement in fire resistance time.

[0222] On the other hand, as shown in Figure 6 below, when a test specimen made with the thermoplastic resin composition of Comparative Example 6 was subjected to a 1200°C flame and pressure generated by oxygen and propane gas, in accordance with the Torch and Grit evaluation of UL 2596, it was confirmed that no ceramic material was formed and a hole was created in 70 seconds.

[0223] In conclusion, the thermoplastic resin composition according to the present invention, containing the polymer, ceramic-forming binder, ceramic-forming metal precursor, ceramic-forming non-metal precursor, and flame retardant in predetermined amounts, exhibits excellent flame retardancy and electrical insulation properties. Furthermore, it ensures safety even during thermal runaway by forming ceramics when extremely high-temperature flames and the resulting pressure are generated, thereby delaying flame propagation, and its environmentally friendly effects have been confirmed.

Claims

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

2. The thermoplastic resin composition according to claim 1, characterized in that the polymer (a) comprises one or more selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified resins thereof.

3. The thermoplastic resin composition according to claim 1, characterized in that the (b) ceramic-forming binder includes a metallic phosphorus-based flame retardant.

4. The thermoplastic resin composition according to claim 1, characterized in that the (c) ceramic-forming metal precursor contains a metal silicate, or the content of magnesium (provided that magnesium oxide is not included) or magnesium oxide is 3% by weight or less relative to the total weight of the ceramic-forming metal precursor.

5. The thermoplastic resin composition according to claim 4, characterized in that the metal silicate comprises one or more selected from the group consisting of aluminum silicate and calcium silicate.

6. The thermoplastic resin composition according to claim 5, characterized in that the aluminum silicate contains one or more selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite.

7. The thermoplastic resin composition according to claim 5, characterized in that the calcium silicate contains wollastonite.

8. The thermoplastic resin composition according to claim 1, characterized in that the (d) ceramic-forming nonmetallic precursor includes glass fibers.

9. The thermoplastic resin composition according to claim 1, characterized in that the (e) flame retardant comprises one or more selected from the group consisting of melamine-based flame retardants, phosphazene-based flame retardants, and phosphate-based flame retardants.

10. The thermoplastic resin composition according to claim 1, characterized in that the flame endurance time is 600 seconds or more, measured by applying a 1200°C flame formed with oxygen and propane gas to a 150 mm × 150 mm × 3 mm test piece in accordance with the Torch and Grit evaluation of UL 2596, and measuring the time until a hole or drip occurs, or the comparative tracking index (CTI) is measured in accordance with IEC 60112 on a 3 mm thick test piece, and the grade according to the PLC (Performance Level Category) classification is 1 or higher.

11. The thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition comprises a lubricant, an antioxidant, or a mixture thereof.

12. A method for producing a thermoplastic resin composition, comprising the steps of kneading and extruding (a) 32.5 to 49% by weight of a polymer, (b) 7 to 20.5% by weight of a ceramic-forming binder, (c) 6.5 to 20.5% by weight of a ceramic-forming metal precursor, (d) 13 to 37% by weight of a ceramic-forming nonmetal precursor, and (e) 2 to 8% by weight of a flame retardant, wherein the kneading and extrusion are carried out using an extruder having 9 or more kneading blocks.

13. A flame retardant composition characterized by 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, characterized in that the flame retardant composition comprises 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, based on its total weight.

15. A molded article characterized by comprising the thermoplastic resin composition described in any one of claims 1 to 11.

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