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

Abstract

The present disclosure relates to a thermoplastic resin composition, a preparation method therefor, and a molded article comprising same and, more specifically, to a thermoplastic resin composition, a preparation method therefor, and a molded article comprising same, wherein the thermoplastic resin composition comprises: (a) 32.5 to 49 wt% of a polymer; (b) 7 to 20.5 wt% of a ceramic-forming binder; (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor; (d) 13 to 37 wt% of a ceramic-forming nonmetal precursor; and (e) 2 to 8 wt% of a flame retardant. According to the present invention, there is an effect of providing a thermoplastic resin composition, a method of preparing same, and a molded article comprising same, wherein the thermoplastic resin composition has excellent flame retardancy and electrical insulation, and forms ceramics at ultra-high temperatures and upon flame generation to delay flame propagation, thereby providing superior flame-retardant characteristics against thermal runaway, ensuring safety of property and human life, and being environmentally friendly.

Description

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

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

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0053331, dated April 22, 2024, and Korean Patent Application No. 10-2024-0053332, dated April 22, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, which has excellent flame retardancy and electrical insulation properties, and which forms ceramics when an unexpected ultra-high temperature flame and the resulting pressure are generated, thereby delaying flame propagation, thereby ensuring the safety of property and life, and is environmentally friendly.

[0004] Thermoplastic resins have excellent impact resistance, wear resistance, cold resistance, chemical resistance, and electrical insulation properties, and are widely used in various fields such as household goods, electrical and electronic components, automobile parts, building materials, and various industrial materials.

[0005] Recently, thermoplastic resins used in automobile parts, especially electric vehicle batteries, require higher safety against fire, and thus require not only flame retardancy but also flame retardancy in the event of thermal runaway.

[0006] Thermal runaway, a major cause of electric vehicle battery fires, occurs when abnormal stress is applied to battery cells, causing uncontrollable temperature increases and even explosions. When the battery's internal temperature rises above a certain level due to short circuits such as overvoltage or overdischarge, a fire can occur. Lithium-ion batteries are highly reactive with water, making them difficult to extinguish with water. Furthermore, the risk of thermal runaway is increasing as the use of high-capacity batteries increases to improve driving range.

[0007] Conventionally, flame retardancy and flame retardancy properties have been imparted to thermoplastic resins by applying halogen compounds and antimony compounds together. This method of imparting flame retardancy by applying halogen compounds and antimony compounds together can secure flame retardancy grade V-0 or 5V according to the UL 94 test, but flame retardancy properties are significantly inadequate when a flame exceeds 1200℃ and the resulting pressure is generated. In addition, the hydrogen halogen gas generated during the processing and the environmental hormones released during the combustion process are highly likely to have fatal adverse effects on the human body.

[0008] In addition, flame retardants that do not contain halogen are called non-halogen flame retardants, and the most widely used non-halogen flame retardants are phosphorus-based flame retardants. However, in the case of phosphorus-based flame retardants, the flame retardancy is significantly inferior to that of halogen-containing flame retardants, so although a large amount of flame retardant is added to achieve a flame retardancy of grade V-0 or 5V according to the UL 94 test, it lacks flame retardancy properties that can prevent thermal runaway when an unexpected flame exceeds 1200℃ and the resulting pressure is generated.

[0009] Additionally, thermoplastic resins used in electric vehicle battery components require electrical insulation properties as they are exposed to electricity for long periods of time.

[0010] Therefore, there is a need to develop a thermoplastic resin composition that can satisfy the quality required for automobile parts, especially electric vehicle battery parts, by ensuring safety against additional damage through excellent flame retardancy during thermal runaway while also having excellent electrical insulation and flame retardancy.

[0011]

[0012] [Prior Art Literature]

[0013] [Patent Document]

[0014] Japanese Patent Publication No. Hei 2-187456

[0015] In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition that has excellent flame retardancy and electrical insulation properties, forms ceramics in the event of thermal runaway, has excellent flame retardancy properties, ensures high safety for property and life, and is environmentally friendly.

[0016] In addition, the present invention aims to provide a method for producing the above thermoplastic resin composition.

[0017] In addition, the present invention aims to provide a molded product manufactured from the thermoplastic resin composition described above.

[0018]

[0019] The above-mentioned and other purposes of this invention can all be achieved by the invention described below.

[0020] In order to achieve the above object, I) the present invention provides a thermoplastic resin composition characterized by comprising (a) 32.5 to 49 wt% of a polymer, (b) 7 to 20.5 wt% of a ceramic-forming binder, (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor, (d) 13 to 37 wt% of a ceramic-forming non-metal precursor, and (e) 2 to 8 wt% of a flame retardant.

[0021] II) In the above I), the polymer (a) may include at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified resins thereof.

[0022] III) In the above I) or II), the ceramic forming binder (b) may include a metal-based flame retardant.

[0023] IV) In the above I) to III), the (c) ceramic-forming metal precursor may include a metal silicate, or may have a magnesium (provided that it does not contain magnesium oxide) or magnesium oxide content of 3 wt% or less based on the total weight of the ceramic-forming metal precursor.

[0024] V) In the above I) to IV), the metal silicate may include at least one selected from the group consisting of aluminum silicate and calcium silicate.

[0025] VI) In the above I) to V), the aluminum silicate may include at least one selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite.

[0026] VII) In the above I) to VI), the calcium silicate may include wollastonite.

[0027] VIII) In the above I) to VII), the (d) ceramic forming non-metallic precursor may include glass fiber.

[0028] IX) In the above I) to VIII), the flame retardant (e) may include at least one selected from the group consisting of a melamine-based flame retardant, a phosphazene-based flame retardant, and a phosphate-based flame retardant.

[0029] X) In the above I) to IX), the thermoplastic resin composition may have a flame endurance time of 600 seconds or more, which is measured by applying a flame of 1200° C. formed with oxygen and propane gas to a 150 mm x 150 mm x 3 mm specimen until a hole or drip occurs, based on the Torch and Grit evaluation of UL 2596, or may have a grade of 1 or higher by PLC (Performance Level Category) classification by measuring the Comparative Tracking Index (CTI) using a specimen with a thickness of 3 mm based on IEC 60112.

[0030] In addition, XII) The present invention provides a method for producing a thermoplastic resin composition, characterized in that the method comprises the steps of mixing and extruding (a) 32.5 to 49 wt% of a polymer, (b) 7 to 20.5 wt% of a ceramic-forming binder, (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor, (d) 13 to 37 wt% of a ceramic-forming non-metal precursor, and (e) 2 to 8 wt% of a flame retardant, and the mixing and extruding are performed using an extruder having 9 or more mixing blocks.

[0031] In addition, XIII) The present invention provides a flame retardant composition characterized by including a ceramic forming binder, a ceramic forming metal precursor, a ceramic forming non-metal precursor, and a flame retardant.

[0032] XIV) In the above XIII), the flame retardant composition may include 11 to 34 wt% of a ceramic-forming binder, 14.5 to 41 wt% of a ceramic-forming metal precursor, 24 to 59 wt% of a ceramic-forming non-metal precursor, and 4 to 14 wt% of a flame retardant based on the total weight thereof.

[0033] In addition, XV) The present invention provides a molded product characterized in that it includes the thermoplastic resin composition in the above I) to XI).

[0034] According to the present invention, the flame retardancy is V-0 grade or higher according to the UL 94 test, the electrical insulation is excellent, and when a flame of an ultra-high temperature of 1200 ℃ or higher and pressure is generated due to it, the flame propagation is blocked by forming a ceramic, so that the fire resistance performance time is 600 seconds or longer, or the grade by PLC (Performance Level Category) classification is grade 1 or higher by measuring the Comparative Tracking Index (CTI), so that the safety of property and life is secured even in the case of thermal runaway, and it is environmentally friendly, so that the thermoplastic resin composition, a method for producing the same, and a molded product including the same can be applied in high quality to automobile parts, especially electrical parts such as electric vehicle batteries.

[0035] Figure 1 is a schematic diagram of an extruder equipped with nine or more mixing blocks according to the present invention.

[0036] Figure 2 is a schematic diagram showing a measurement method according to the Torch and Grit evaluation of UL 2596.

[0037] Figure 3 is a photograph of an actual measurement scene according to the Torch and Grit evaluation of UL 2596.

[0038] FIG. 4 is a photograph showing an actual measurement scene (left photo) according to the Torch and Grit evaluation of UL 2596 of a thermoplastic resin composition according to Example 1 and a specimen (right photo) after applying a flame for 600 seconds.

[0039] FIG. 5 is a photograph showing an actual measurement scene (left photograph) and a specimen after evaluation (right photograph) according to the Torch and Grit evaluation of UL 2596 of a thermoplastic resin composition according to Example 5.

[0040] Figure 6 shows a specimen of a thermoplastic resin composition according to Comparative Example 6 after the Torch and Grit evaluation of UL 2596. The left side is the front side of the specimen and the right side is the back side of the specimen.

[0041]

[0042]

[0043] Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and a molded article including the same are described in detail.

[0044] The present inventors have confirmed that when a polymer, a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming non-metal precursor, and a flame retardant are included in a predetermined amount, a thermoplastic resin composition is provided that has a flame retardancy of V-0 or higher as measured by the UL 94 test and excellent insulation properties, and that when a flame of an ultra-high temperature of 1200°C or higher and pressure generated thereby are formed to delay flame propagation, thereby significantly improving the safety of property and life even in the event of thermal runaway is provided, and based on this, they have devoted themselves to further research and completed the present invention.

[0045]

[0046] The thermoplastic resin composition according to this invention is examined in detail as follows.

[0047]

[0048] The thermoplastic resin composition of the present invention is characterized by comprising (a) 32.5 to 49 wt% of a polymer, (b) 7 to 20.5 wt% of a ceramic-forming binder, (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor, (d) 13 to 37 wt% of a ceramic-forming non-metal precursor, and (e) 2 to 8 wt% of a flame retardant, and in this case, while having excellent flame retardancy and insulating properties, it forms a ceramic under an unexpected ultra-high temperature flame to delay flame propagation, thereby ensuring safety for property and life, and is environmentally friendly.

[0049]

[0050] Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

[0051]

[0052] In this description, ceramic is not particularly limited as long as it is a ceramic as defined in the technical field or scientific community to which the present invention belongs, and as a specific example, it may refer to a sintering process in which a metal and a non-metal or a metalloid are combined with each other by heat treatment to form crystals, and then the formed crystals come together to form a three-dimensional network structure. According to this definition, a ceramic-forming metal precursor corresponding to a metal in the present invention is defined as an inorganic material containing a metal element, and a ceramic-forming non-metal precursor corresponding to a non-metal or a metalloid is defined as a material containing 50 wt% or more of silicon dioxide.

[0053]

[0054] (a) polymer

[0055] The polymer may include, for example, at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified resins thereof, and preferably may include at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, and polyalkylene terephthalate resin, and in this case, mechanical properties such as impact strength, tensile strength, elongation, flexural strength, and surface hardness, electrical insulation, and flame retardancy are excellent, and flame retardancy characteristics are excellent in the event of thermal runaway, thereby ensuring the safety of property and life.

[0056] The polymer (a) may be, for example, 32.5 to 49 wt%, preferably 34 to 47 wt%, more preferably 35 to 46 wt%, or 36 to 45 wt%, even more preferably 38 to 45 wt%, and even more preferably 38 to 43 wt%, based on the total weight of the components (a) to (e), and within this range, the polymer has excellent mechanical properties, electrical insulation, and flame retardancy, and has excellent flame retardancy characteristics in the event of thermal runaway, thereby ensuring the safety of property and life.

[0057] In this context, thermal runaway refers to a state in which a temperature change alters the environment in a way that further accelerates the temperature change. In other words, thermal runaway occurs when a dynamic process is caused by an increase in temperature, and the energy released as a result of that process increases the temperature, accelerating the process.

[0058]

[0059] In this description, modification is not particularly limited if it is modification by a modification method of a resin commonly used in the technical field to which the present invention belongs, and may mean, for example, grafting by adding at least one compound of an α,β-unsaturated dicarboxylic acid and an anhydride thereof to an unmodified resin, and as another example, may mean copolymerizing by adding at least one compound of an α,β-unsaturated dicarboxylic acid and anhydride thereof as a comonomer when manufacturing an unmodified resin.

[0060]

[0061] polyamide resin

[0062] The above polyamide resin is not particularly limited, but may be, for example, a polyamide manufactured by polycondensation of a single or two or more types of lactam or ω-amino acid, or a polyamide manufactured by polycondensation of a diacid and a diamine.

[0063] Preferably, the polyamide resin is at least one selected from the group consisting of a copolymer of a diamine having 2 to 30 carbon atoms and a dicarboxylic acid having 4 to 30 carbon atoms; a lactam polymer; an aminocarboxylic acid polymer; and a copolymer of a lactam and an aminocarboxylic acid; and in this case, excellent mechanical properties and appearance quality are achieved.

[0064] Additionally, the polyamide resin may be, for example, homopolyamide, copolyamide, or a mixture thereof.

[0065] The above polyamide resin may be, for example, crystalline, semi-crystalline or amorphous.

[0066] The copolymer of the above-mentioned diamine having 2 to 30 carbon atoms and the dicarboxylic acid having 4 to 30 carbon atoms is preferably 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, It may be at least one selected from the group consisting of polyamide resins obtained by polymerization of an aliphatic or aromatic diamine such as aminoethylpiperidine and an aliphatic or aromatic dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, terephthalic acid, 2-chloroterephthalic acid, and 2-methylterephthalic acid.

[0067] The above lactam polymer can preferably be obtained by ring-opening polymerization of a lactam compound such as caprolactam or laurolactam.

[0068] The above aminocarboxylic acid polymer can preferably be obtained by polymerizing an aminocarboxylic acid such as aminocaproic acid, 11-aminoundecanoic acid, or 12-aminododecanoic acid.

[0069]

[0070] The above 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, polyamide 66 / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 9T, polyamide 9I, polyamide 6 / 9T, polyamide 6 / 9I, polyamide 66 / 9T, polyamide 6 / 12 / 9T, polyamide 66 / 12 / 9T, polyamide 6 / 12 / 9I and polyamide It may be at least one selected from the group consisting of 66 / 12 / 6I, and more preferably at least one selected from the group consisting of polyamide 6, polyamide 56, and polyamide 66. In this case, it has the advantage of improving mechanical properties and heat resistance as well as being advantageous in terms of price and processability.

[0071] The polyamide resin may have, for example, 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, the polyamide resin does not cause a problem of overheating due to friction between the screw of the extruder and the molten composition during extrusion molding, and has the advantage of excellent extrusion processability because the tension applied to the molten composition is appropriate.

[0072] In this description, relative viscosity is measured at 20°C using a UFIT-UVS instrument using a solution prepared by dissolving 1 g of polyamide in 100 ml of 96 wt% sulfuric acid, unless otherwise specified.

[0073]

[0074] poly(arylene ether) resin

[0075] The above poly(arylene ether) resin may be, for example, a homopolymer or copolymer comprising a unit of the following chemical formula 1 or chemical formula 2.

[0076] [Chemical Formula 1]

[0077]

[0078] [Chemical Formula 2]

[0079]

[0080] 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 are each independently or simultaneously hydrogen, chlorine, bromine, iodine, alkyl, allyl, phenyl, alkylbenzyl, chloroalkyl, bromoalkyl, cyanoalkyl, cyano, alkoxy, phenoxy, or nitro group, Ar is an arylene group having 6 to 20 carbon atoms, and alkoxy may be an alkoxy having 1 to 4 carbon atoms.

[0081] Preferably, the 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 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.

[0082] The average degree of polymerization of the units of Chemical Formula 1 or Chemical Formula 2 of the above poly(arylene ether) resin is not particularly limited as long as it follows the definition of the present invention.

[0083]

[0084] The homopolymer of the above poly(arylene ether) resin may be, for example, at least one selected from the group consisting of poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-dichloromethyl-1,4-phenylene) ether, poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, and poly(2,5-dimethyl-1,4-phenylene) ether, and in this case It provides the advantage of improved appearance quality due to its excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as excellent processability.

[0085]

[0086] In addition, the copolymer of the poly(arylene ether) resin may be at least one selected from the group consisting of, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, and a copolymer of 2,3,6-trimethylphenol and o-cresol, and in this case, it provides the advantage of having excellent mechanical properties such as impact strength and tensile strength, as well as excellent processability, thereby improving the appearance quality.

[0087] The above poly(arylene ether) resin may preferably be a polyphenylene ether resin.

[0088]

[0089] The poly(arylene ether) resin may have, for example, an intrinsic viscosity of 25 to 55 dl / g, preferably 30 to 50 dl / g, and more preferably 32 to 45 dl / g, and within this range, it has the advantage of maintaining high mechanical properties such as impact strength and tensile strength of the composition while securing fluidity suitable for molding.

[0090] Unless otherwise specified, the intrinsic viscosity of the above poly(arylene ether) resin may be a value measured at 25°C using an Ubbelohde viscometer after dissolving the sample to be measured in a chloroform solvent at a concentration of 0.5 g / dl.

[0091]

[0092] polyalkylene terephthalate resin

[0093] The above polyalkylene terephthalate resin may be, for example, polybutylene terephthalate, polyethylene terephthalate, or a mixture thereof, and preferably polybutylene terephthalate, in which case it has excellent mechanical properties, fluidity, and heat resistance.

[0094] The above polybutylene terephthalate resin is not particularly limited as long as it is a conventional polybutylene terephthalate resin, and for example, a polybutylene terephthalate resin obtained by directly esterifying or transesterifying 1,4-butanediol and terephthalic acid or dimethyl terephthalate and then polycondensing the resin may be used.

[0095] The above polybutylene terephthalate resin may include a repeating unit represented by the following chemical formula 3.

[0096] [Chemical Formula 3]

[0097]

[0098] In the above chemical formula 3, n is an average degree of polymerization in the integer range of 50 to 200.

[0099] The above polybutylene terephthalate resin may have a melting point measured by differential scanning calorimetry (DSC) of, for example, 200 to 240°C, preferably 210 to 230°C, and more preferably 220 to 230°C, and may maintain mechanical properties even under high temperature conditions within this range.

[0100] The above polybutylene terephthalate resin may have a melt flow rate of 7 to 11 g / 10 min, preferably 8 to 10 g / 10 min, measured at 250°C and 2.16 kgf according to ISO 1133, and has the advantage of excellent processability within this range.

[0101]

[0102] The method for producing the above polyalkylene terephthalate resin is not particularly limited if it is a manufacturing method commonly used in the technical field to which the present invention belongs, and if it conforms to the definition of the polyalkylene terephthalate resin according to the present invention, it may be purchased commercially and used.

[0103] 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, and within this range, the melt index is appropriate, so that the resin has excellent processability, moldability, and molding stability.

[0104] Unless otherwise specified, the intrinsic viscosity of the above polyalkylene terephthalate resin can be measured according to ASTM D2857. As a specific example, the sample to be measured is completely dissolved in methylene chloride, and then the filtrate is filtered using a filter, and the filtrate can be measured using an Ubbelohde viscometer at 20°C.

[0105]

[0106] polystyrene resin

[0107] The polystyrene resin may be, for example, general purpose polystyrene, high-impact polystyrene, or a mixture thereof, and preferably may be a high-impact polystyrene resin, in which case it has excellent processability, dimensional stability, and tensile strength.

[0108] The above general-purpose polystyrene resin may be, for example, a polymer obtained by polymerizing styrene alone, in which case it has the effect of excellent processability.

[0109] The above high-impact polystyrene resin may be, for example, a rubber-reinforced polystyrene resin.

[0110] The above rubber may be, for example, at least one selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, and alkyl acrylate rubbers, and is preferably butadiene rubber, in which case there is an advantage of improving impact strength.

[0111] The above rubber may be, for example, 3 to 25 wt%, preferably 6 to 14 wt%, and more preferably 8 to 12 wt%, based on 100 wt% of high-impact polystyrene resin, and within this range, excellent impact strength and fluidity are achieved.

[0112]

[0113] The above rubber may have a volume average particle size of, for example, 0.1 to 20 ㎛, preferably 1.0 to 15 ㎛, and has excellent impact strength and fluidity within this range.

[0114] In this description, the volume average particle size can be measured by dissolving 3 g of high-impact polystyrene resin in 100 ml of methyl ethyl ketone using a Coulter Counter LS230 device and then dispersing the rubber particles in a particle form without dissolving them by the laser scattering method.

[0115]

[0116] The above rubber-reinforced polystyrene resin may preferably be at least one 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, alpha-methylstyrene-butadiene copolymer, styrene-ethylene-propylene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-(ethylene-butylene-styrene copolymer)-styrene copolymer.

[0117]

[0118] The above rubber-reinforced polystyrene resin can be produced, for example, by polymerizing rubber and an aromatic vinyl compound using bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof. The polymerization can be carried out by thermal polymerization or in the presence of a polymerization initiator.

[0119] The polymerization initiator that can be used in the above polymerization may be, for example, a peroxide-based initiator, an azo-based initiator, or a mixture thereof.

[0120] The above peroxide initiator may preferably be at least one selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and the above azo initiator may preferably be azobisisobutyronitrile.

[0121]

[0122] The polystyrene resin may have a flow index of 2 to 20 g / 10 min, preferably 3 to 15 g / 10 min, measured at 200° C. and 5 kg according to ASTM D1238, for example, and has excellent processability and property balance within this range.

[0123]

[0124] polycarbonate resin

[0125] The above polycarbonate resin may be a polymerized resin including, for example, an aromatic diol compound and a carbonate precursor.

[0126] The above aromatic diol compounds include, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, It may be at least one selected from the group consisting of 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3chlorophenyl)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, and preferably bisphenol A.

[0127] The above carbonate precursor may be, for example, at least one 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 bishaloformates, and from the viewpoint of manufacturing efficiency and physical properties, it may be preferable to use triphosgene, phosgene, or a mixture thereof.

[0128] As a specific example, a polycarbonate formed by polymerization of the aromatic diol compound and the carbonate precursor includes a repeating unit represented by the following chemical formula 4.

[0129] [Chemical Formula 4]

[0130]

[0131] In the above chemical formula 4, R'5 to R'8 are each independently hydrogen, C 1-10 Alkyl, C 1-10 Alkoxy, or halogen, and Z' is unsubstituted or C 1-6 Alkyl or C 6-20 C substituted with aryl 1-10 Alkylene, unsubstituted or C 1-10 C substituted with alkyl 3-15 Cycloalkylene, O, S, SO, SO2, or CO.

[0132] Preferably, in the above chemical formula 4, R'5 to R'8 are each independently hydrogen or C 1-3 C is alkyl, and Z' is unsubstituted or substituted with methyl or phenyl. 1-6 It may be alkylene.

[0133] The polycarbonate may have, for example, a melting 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, and within this range, it has excellent mechanical properties and heat resistance.

[0134] In this paper, the melting index is measured at 300°C and under a load of 1.2 kg according to ASTM D1238.

[0135] The average degree of polymerization of the repeating unit of chemical formula 4 of the above polycarbonate resin, i.e., the unit, is not particularly limited as long as it follows the definition of the present invention.

[0136]

[0137] (b) Ceramic forming binder

[0138] In the present invention, a ceramic-forming binder is thermally decomposed when a high-temperature flame and the resulting pressure are generated, thereby generating a metal phosphate component, and the metal phosphate component acts as a bonding agent that binds a ceramic-forming metal precursor and a ceramic-forming non-metal precursor that has reached the Gob Temperature, thereby causing physical and chemical structural changes to form a ceramic, and the formed ceramic delays flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway of a battery, and has the advantage of being environmentally friendly.

[0139] In this description, the Gob temperature refers to the temperature at which a ceramic forming non-metallic precursor melts and changes into a hot lump called a Gob, which can be formed into a desired shape.

[0140]

[0141] In this description, the ultra-high temperature flame and the resulting pressure mean that when a flame of 1200℃ formed with oxygen and propane gas is applied to a specimen based on the Torch and Grit evaluation of UL 2596, the pressure generated from the ultra-high temperature flame is transmitted to the specimen together with the flame.

[0142]

[0143] In the present invention, the ceramic may preferably be formed by including Al, Si, Ca and P components, in which case it has an excellent flame retardation effect during thermal runaway of the battery.

[0144]

[0145] The above (b) ceramic forming binder may be, for example, 7 to 20.5 wt%, preferably 8 to 19 wt%, more preferably 9 to 18 wt%, even more preferably 9 to 17 wt%, and even more preferably 9 to 13 wt%, based on the total weight of the components (a) to (e), and within this range, the ceramic forming binder has excellent flame retardancy and electrical insulation properties, and forms a ceramic when an ultra-high temperature flame and pressure are generated, thereby delaying flame propagation, thereby ensuring safety against additional damage even in the event of thermal runaway and providing an environmentally friendly advantage.

[0146]

[0147] The above (b) ceramic forming binder may include, for example, a metal-based flame retardant, preferably an organic phosphinate metal salt, and more preferably, a dialkylphosphinic acid salt represented by the following chemical formula 5, a diphosphinic acid salt represented by the following chemical formula 6, or a mixture thereof. In this case, the ceramic is formed when an ultra-high temperature flame and pressure are generated, thereby delaying flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway, and is environmentally friendly.

[0148] [Chemical Formula 5]

[0149]

[0150] [Chemical Formula 6]

[0151]

[0152] In the above chemical formulas 5 and 6, R 5 , R 6 , R 7 and R 8 are each independently linear or branched C1-C 10 In alkyl, C3-C 12 Cycloalkyl, C6-C 10 is an aryl group, or H; R9 is linear or branched C1-C 10 In alkylene, C6-C 10 In arylene, C6-C 20 Alkylarylene, or C6-C 20 is 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; and x is an integer from 1 to 4.

[0153] In the above chemical formulas 5 and 6, cycloalkyl may independently preferably be cyclohexyl or cyclohexadimethyl.

[0154] The above R 5 , R 6 , R 7 and R 8 may preferably be independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or phenyl.

[0155] The above R 9 It 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, phenylethylene, phenylpropylene or phenylbutylene.

[0156] The above M1 and M2 may each independently be Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, or K, and more preferably, may each independently be Mg, Ca, Al, Ti, or Zn.

[0157] The above R 5 and R 6 , and R 7 and R 8 can combine with each other to form a ring with adjacent phosphorus atoms. The R 5 and R 6 , and R 7 and R 8 Each of these rings formed by combining with adjacent phosphorus atoms is a heterocycle having the phosphorus atom as a heteroatom constituting the ring, and the number of atoms constituting the ring may be, for example, 4 to 20, preferably 5 to 16. The heterocycle having the phosphorus atom may be a bicyclo ring or may have a substituent.

[0158]

[0159] The dialkylphosphinic acid salt represented by the above chemical formula 5 is preferably 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 methyl-n-propylphosphinate, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. There may be more than one type.

[0160]

[0161] The diphosphinic acid salt represented by the above chemical formula 6 may preferably be at least one selected from the group consisting of methylenebis(methylphosphinic acid)calcium, methylenebis(methylphosphinic acid)magnesium, methylenebis(methylphosphinic acid)aluminum, methylenebis(methylphosphinic acid)zinc, 1,4-phenylenebis(methylphosphinic acid)calcium, 1,4-phenylenebis(methylphosphinic acid)magnesium, 1,4-phenylenebis(methylphosphinic acid)aluminum, and 1,4-phenylenebis(methylphosphinic acid)zinc.

[0162] The above (b) ceramic forming binder may be more preferably at least one 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 may be more preferably aluminum diethylphosphinate. In this case, high flame retardancy can be realized with a small amount of flame retardant while maintaining mechanical properties, and the flame retardancy is excellent even in the event of thermal runaway, ensuring safety for property and life, and having an environmentally friendly effect.

[0163] As a specific example, when aluminum diethylphosphinate is used as the ceramic forming binder (b), the organic component is volatilized into phosphoric acid gas under an ultra-high temperature flame, the remaining component changes from an amorphous structure to a crystalline structure, and AlPO3 changes its structure to AlPO4, which serves to bind the ceramic forming metal and the ceramic forming non-metal.

[0164]

[0165] The above (b) ceramic forming binder may have, for example, an average particle diameter of 0.1 to 100 μm, preferably 0.1 to 80 μm, more preferably 1 to 60 μm, and has the advantage of excellent flame retardancy and mechanical properties within this range.

[0166] In this description, the average particle size of the ceramic forming binder refers to the number average particle size obtained from the particle size and particle number frequency distribution measured using a laser diffraction particle size analyzer, using a dispersion of the binder dispersed in a medium such as acetone as a measurement sample.

[0167]

[0168] The above (b) ceramic forming binder may preferably have a phosphorus content of 20 to 35 wt%, more preferably 22 to 30 wt%, and within this range, it has excellent flame retardancy and electrical insulation properties, while forming ceramics when an ultra-high temperature flame and pressure are generated thereby, thereby delaying flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway.

[0169] In this description, the phosphorus content means the weight % of phosphorus converted from the molecular weight of phosphorus contained in the molecular structure of the phosphorus-based flame retardant.

[0170]

[0171] (c) Ceramic forming metal precursor

[0172] In this invention, a ceramic-forming metal precursor is combined with a ceramic-forming non-metal precursor in a gob state by a metal phosphate component generated by thermal decomposition of a ceramic-forming binder when an ultra-high-temperature flame and the resulting pressure are applied, thereby causing physical and chemical structural changes to form a ceramic, and the formed ceramic retards the flame, thereby ensuring safety for property and life even in the event of thermal runaway of a battery.

[0173]

[0174] The above (c) ceramic-forming metal precursor may be, for example, 6.5 to 20.5 wt%, preferably 8 to 19 wt% or 8 to 18 wt%, more preferably 9 to 18 wt%, even more preferably 10 to 17 wt%, and even more preferably 13 to 17 wt%, based on the total weight of the components (a) to (e), and within this range, the ceramic-forming metal precursor has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, the ceramic is formed by bonding with the ceramic-forming non-metal precursor by the ceramic-forming binder, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway.

[0175]

[0176] The above (c) ceramic-forming metal precursor may, for example, contain metal silicate, or may contain magnesium (but not magnesium oxide) or magnesium oxide in an amount of 3 wt% or less based on the total weight thereof, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, the ceramic is formed by bonding with the ceramic-forming non-metal precursor by the ceramic-forming binder, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway.

[0177]

[0178] The metal silicate may include, for example, at least one selected from the group consisting of aluminum silicate and calcium silicate, and preferably aluminum silicate. In this case, the metal silicate has excellent flame retardancy and electrical insulation properties, and when an ultra-high temperature flame and the resulting pressure are generated, a ceramic is formed by combining with a ceramic-forming non-metallic precursor by a ceramic-forming binder, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway.

[0179]

[0180] The above aluminum silicate may include, for example, at least one selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, and petalite, preferably may include kaolin, mica, or a mixture thereof, and more preferably may include kaolin, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, a ceramic is formed by combining with a ceramic-forming non-metallic precursor by a ceramic-forming binder, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway.

[0181] The above calcium silicate may include, for example, wollastonite, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, a ceramic is formed by bonding with a ceramic-forming non-metallic precursor by a ceramic-forming binder, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway.

[0182]

[0183] The above (c) ceramic forming metal precursor may be, for example, a magnesium-free silicate, in which case, without interference from magnesium, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high temperature flame and the resulting pressure are generated, it forms a ceramic by combining with the ceramic forming non-metal precursor, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0184] The above-mentioned 'magnesium-free silicate' may contain magnesium (except when magnesium oxide is not included) or magnesium oxide in an amount of, for example, 3 wt% or less, preferably 2 wt% or less, more preferably less than 2 wt%, even more preferably 1 wt% or less, even more preferably less than 1 wt%, and particularly preferably 0.01 wt% or more to less than 1 wt%, based on the total weight of the ceramic-forming metal precursor, and within this range, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, a ceramic is formed by bonding with the ceramic-forming non-metal precursor by the ceramic-forming binder, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway. In addition, when the magnesium or magnesium oxide content exceeds the above range, it is difficult to form a ceramic when an ultra-high-temperature flame and the resulting pressure are generated, and even if the ceramic is formed, it is instantly broken, so that the effect of delaying flame propagation is not exhibited.

[0185]

[0186] The above (c) ceramic-forming metal precursor is defined as a material that forms a ceramic by combining a ceramic-forming non-metallic precursor in a gob state with a ceramic-forming binder when an ultra-high-temperature flame and the resulting pressure are applied, and accordingly, talc that cannot form a ceramic does not correspond to a ceramic-forming metal precursor according to the definition of the present invention.

[0187]

[0188] The above (c) ceramic-forming metal precursor may have, for example, an average particle diameter of 0.1 to 170 ㎛, preferably 0.1 to 150 ㎛, more preferably 0.1 to 100 ㎛, and even more preferably 0.1 to 60 ㎛, and within this range, compatibility with the ceramic-forming non-metal precursor is improved, so that mechanical properties, electrical insulation properties, flame retardancy, and flame retardancy properties are excellent.

[0189] In this description, the average particle diameter of the ceramic forming metal precursor can be measured by a measuring method commonly used in the technical field to which this invention belongs, such as electron microscope analysis, and as another specific example, can be measured by an X-ray method.

[0190]

[0191] (d) Ceramic forming non-metallic precursor

[0192] In this invention, the ceramic-forming non-metallic precursor changes into a gob state when an ultra-high-temperature flame and the resulting pressure are generated, and the ceramic-forming non-metallic precursor in the gob state combines with the ceramic-forming metal precursor by a metal phosphate component generated by thermal decomposition of the ceramic-forming binder to cause physical and chemical structural changes to form a ceramic, thereby preventing the formation of holes or drips due to the flame, and ensuring safety with excellent flame retardation characteristics in the event of thermal runaway.

[0193]

[0194] The above (d) ceramic-forming non-metallic precursor may be, for example, 13 to 37 wt%, preferably 18 to 34 wt%, more preferably 19 to 32 wt%, even more preferably 20 to 30 wt%, and even more preferably 25 to 32 wt%, based on the total weight of the components (a) to (e), and within this range, the ceramic has excellent mechanical properties, flame retardancy, and appearance characteristics, and forms a ceramic when an ultra-high-temperature flame and pressure are generated, thereby delaying flame propagation, thereby ensuring safety.

[0195]

[0196] The above (d) ceramic-forming non-metallic precursor may include, for example, glass fiber, and preferably, E-glass fiber, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and the resulting pressure are generated, the ceramic is formed by bonding with the ceramic-forming non-metallic precursor by the ceramic-forming binder, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0197] The above glass fiber may include, for example, chopped glass fiber, in which case it has the advantage of excellent compatibility with the polymer.

[0198] In this description, the chopped glass fiber is not particularly limited as long as it is a chopped glass fiber commonly used in the technical field to which the present invention belongs.

[0199] In this description, E-glass fiber is a glass fiber with excellent electrical properties, and is not particularly limited to E-glass fiber commonly used in the technical field to which the present invention belongs, and includes SiO2, Al2O3, CaO, and B2O3 as upper components.

[0200]

[0201] The above (d) ceramic-forming non-metallic precursor may have, for example, an average particle diameter of 3 to 25 ㎛, preferably 5 to 20 ㎛, and more preferably 7 to 15 ㎛, and within this range, the mechanical strength with the polymer is improved while the appearance characteristics of the final product are excellent.

[0202] The above (d) ceramic forming non-metallic precursor may have an average length of, for example, 1 to 10 mm, preferably 2 to 7 mm, more preferably 2 to 5 mm, and within this range, the mechanical strength with the polymer is improved while the appearance characteristics of the final product are excellent.

[0203] The above (d) ceramic-forming non-metallic precursor may have, for example, an aspect ratio (L / D) of the average length (L) to the average particle diameter (D) of 200 to 550, preferably 220 to 450, more preferably 250 to 350, and even more preferably 270 to 320, and within this range, has excellent compatibility with a polymer and thus has the advantage of an excellent surface appearance.

[0204] In this description, the average particle diameter, average length, aspect ratio, etc. of the ceramic forming non-metallic precursor are measured for 30 times using a microscopic analysis method and calculated as the average value.

[0205]

[0206] The above (d) ceramic-forming non-metallic precursor may be surface-treated with, for example, a silane-based compound or a urethane-based compound, and preferably may be surface-treated with at least one surface-treating agent selected from the group consisting of an amino silane-based compound, an epoxy silane-based compound, and a urethane-based compound, and more preferably, may be surface-treated with an amino silane-based compound, and in this case, by combining with a polymer, dispersibility and surface wettability are improved, and as a result, there is an effect of improving the mechanical properties, including the tensile strength, of the resin composition.

[0207]

[0208] The surface treatment agent may be included in an amount of, for example, 0.1 to 10 wt%, preferably 0.1 to 5 wt%, more preferably 0.1 to 3 wt%, even more preferably 0.1 to 0.8 wt%, and even more preferably 0.2 to 0.5 wt%, based on 100 wt% of the total surface-treated ceramic-forming non-metallic precursor (ceramic-forming non-metallic precursor + surface treatment agent), and within this range, the mechanical properties, property balance, and appearance of the final product are excellent.

[0209] The above amino silane compound is not particularly limited as long as it is an amino silane generally used as a coating agent for glass fiber, but examples thereof include gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyltriethoxy silane, gamma-acetoacetatepropyl trimethoxysilane, acetoacetatepropyl triethoxy silane, gamma-cyanoacetyl trimethoxy silane, It may be at least one selected from the group consisting of gamma-cyanoacetyl triethoxy silane, and acetoxyaceto trimethoxy silane, and in this case, it has the effect of providing excellent mechanical properties and heat resistance as well as excellent surface properties of the injection-molded product.

[0210] The above epoxy silane compound is not particularly limited as long as it is an epoxy silane generally used as a coating agent for glass fibers, but may be at least one selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and in this case, there is an effect of excellent mechanical properties and heat resistance as well as excellent surface properties of the injection-molded product.

[0211]

[0212] The above glass fiber can be appropriately selected and used within the range commonly used in the art as long as it follows the definition of the present invention, and the cross-sectional shape such as cylindrical or oval is not particularly limited.

[0213]

[0214] The total amount of the (c) ceramic-forming metal precursor and (d) ceramic-forming non-metal precursor may be, for example, 30 to 52 wt%, preferably 32 to 50 wt%, more preferably 34 to 48 wt%, and even more preferably 38 to 43 wt% or 40 to 46 wt%, based on the total weight of the components (a) to (e), and within this range, there is an advantage of excellent flame retardancy and electrical insulation while also being capable of forming ceramics when subjected to ultra-high temperature flames and pressure generated thereby.

[0215]

[0216] (e) flame retardants

[0217] The flame retardant in this article provides a thermoplastic resin composition with a high degree of flame retardancy of V-0 or higher according to the UL 94 test and excellent electrical insulation, and is thermally decomposed when a high-temperature flame and the resulting pressure are generated, and does not generate toxic gases or emit environmental hormones during thermal decomposition, so it does not have a harmful effect on the human body or the environment.

[0218]

[0219] The flame retardant (e) may be, for example, 2 to 8 wt%, preferably 2.5 to 7 wt%, more preferably 3 to 6.5 wt%, even more preferably 3 to 6 wt%, and even more preferably 4 to 6 wt%, based on the total weight of the components (a) to (e), and within this range, it provides a high degree of flame retardancy of V-0 grade or higher according to the UL 94 test, and has excellent mechanical properties and electrical insulation properties.

[0220]

[0221] The above (e) flame retardant may include, for example, at least one selected from the group consisting of a melamine-based flame retardant, a phosphazene-based flame retardant, and a phosphate-based flame retardant, and preferably includes a melamine-based flame retardant. In this case, it has the advantage of imparting a high degree of flame retardancy of V-0 grade or higher according to the UL 94 test, excellent mechanical properties and electrical insulation, and not emitting gases or environmental hormones that are harmful to the human body and the environment.

[0222]

[0223] The above melamine-based flame retardant may be, for example, at least one selected from the group consisting of melamine cyanurate, triphenylisocyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine borate, and melamine sulfate, and preferably may be melamine polyphosphate. In this case, it provides a high degree of flame retardancy of V-0 grade or higher according to the UL 94 test and has excellent mechanical properties and electrical insulation.

[0224]

[0225] The above phosphazene-based flame retardant is, for example, an organic compound having a -P=N- bond in the molecule, and may be at least one selected from the group consisting of a cyclic phosphazene compound, a chain phosphazene compound, and a cross-linked phosphazene compound, and may preferably be a cyclic phosphazene compound, in which case it has excellent flame retardancy and mechanical properties.

[0226] The above cyclic phosphazene compound may preferably be a compound represented by the following chemical formula 7.

[0227] [Chemical Formula 7]

[0228]

[0229] In the above chemical formula 7, m is an integer from 3 to 25, and R 13 and R 14are identical or different and represent an aryl group or an alkylaryl group.

[0230] In the above chemical formula 7, m is preferably an integer of 3 to 5.

[0231]

[0232] The cyclic phosphazene compound represented by the above chemical formula 7 is more preferably R 13 and R 14 The cyclic phenoxyphosphazene is a phenyl group, and more preferably, it may be at least one selected from the group consisting of phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decapenoxycyclopentaphosphazene.

[0233]

[0234] The above chain-type phosphazene compound may preferably be a compound represented by the following chemical formula 8.

[0235] [Chemical Formula 8]

[0236]

[0237] In the above chemical formula 8, n is an integer from 3 to 10,000, and X is -N=P(OR 15 )3rd or -N=P(O)OR 15 represents the flag, and Y is -P(OR 16 )4 or -P(O)(OR 16 ) represents the 2nd period. R 15 and R 16 are identical or different and represent an aryl group or an alkylaryl group.

[0238] In the above chemical formula 8, n is preferably an integer from 3 to 100, more preferably an integer from 3 to 25.

[0239] The chain-like phosphazene compound represented by the above chemical formula 8 is preferably R 15 and R 16 This is a chain-type phenoxphosphazene with a phenyl group.

[0240]

[0241] The above cross-linked phosphazene compound is formed by cross-linking at least one phosphazene-based flame retardant selected from the group consisting of, for example, cyclic phosphazene compounds and chain phosphazene compounds, with a cross-linking group represented by the following chemical formula 9.

[0242] [Chemical Formula 9]

[0243]

[0244] In the above chemical formula 9, (A) I is -C(CH3)2-, -SO2-, -S-, or -O-, and I is an integer of 0 or 1, is a bond.

[0245]

[0246] The above-mentioned cross-linked phosphazene compound is preferably R in the above-mentioned chemical formula 7. 13 and R 14 A crosslinked phenoxyphosphazene compound formed by crosslinking a cyclic phenoxyphosphazene compound having a phenyl group by a crosslinking group represented by the above chemical formula 9, wherein in the above chemical formula 8, R 15 and R 16 This phenyl group chain-type phenoxyphosphazene compound may be a crosslinked phenoxyphosphazene compound formed by crosslinking with a crosslinking group represented by the above chemical formula 9, or a mixture thereof, and more preferably, it may be a crosslinked phenoxyphosphazene compound formed by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the above chemical formula 9.

[0247]

[0248] Examples of the above phosphate flame retardants include trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), tricylenyl phosphate (TXP), resorcinolbis(diphenyl phosphate) [RDP], phenyl diresorcinol phosphate, bisphenol diphenyl phosphate (BDP), cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyldi(isopropylphenyl) phosphate, triisophenyl It may be at least one selected from the group consisting of triisophenylphosphate, diphenyl phosphate, resorcinol di phosphate, resorcinol bis (2,6-dixylenyl phosphate), and aromatic polyphosphate.

[0249]

[0250] The thermoplastic resin composition may include, for example, an anti-oxidant, an anti-fungal agent, or a mixture thereof.

[0251] The above-mentioned active agent may be included in an amount of, for example, 0.01 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.2 to 1 wt%, and even more preferably 0.2 to 0.5 wt%, based on the total weight of the components (a) to (e), and within this range, the mechanical properties are excellent while the molding processability is improved.

[0252] The above-mentioned active agent may be, for example, at least one selected from the group consisting of an ester-based active agent, a fatty acid amide-based active agent, an olefin-based active agent, and a montan-based active agent, and preferably may be an ester-based active agent, a fatty acid amide-based active agent, or a mixture thereof, in which case the mechanical properties are excellent while the molding processability is improved.

[0253] The above ester-based lubricant may be, for example, at least one selected from the group consisting of fatty acid esters of alcohol, hardened oil, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester wax, and alkyl phosphate ester, and in this case, there is an effect of improving molding processability while providing excellent mechanical properties.

[0254] The fatty acid amide-based lubricant may be, for example, at least one selected from the group consisting of stearamide, behanamide, ethylene bis(stearamide), ethylene bis 12-hydroxy stearamide, erucamide, oleamide, and ethylene bis oleamide, and in this case, there is an effect of improving molding processability while providing excellent mechanical properties.

[0255] The above olefin-based lubricant may be, for example, polyethylene wax, polypropylene wax, or a mixture thereof, in which case the mechanical properties are excellent while the molding processability is improved.

[0256] The above-mentioned montan-based lubricant may be, for example, a montan wax, a montan ester wax, or a mixture thereof. The above-mentioned montan ester wax may be, for example, at least one selected from a wax obtained by esterifying a montan-based wax with ethylene glycol and montanic acid, a wax obtained by esterifying a montanic wax with glycerin and montanic acid, calcium montanate containing a montanic acid ester, and an ester mixed wax based on montanic acid. In this case, the mechanical properties are excellent and the molding processability is improved.

[0257]

[0258] The antioxidant may be included in an amount of, for example, 0.01 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.2 to 1 wt%, and even more preferably 0.2 to 0.5 wt%, based on the total weight of components (a) to (e), and within this range, it has the effect of preventing oxidation due to heat during the extrusion process and exhibiting excellent mechanical properties and heat resistance.

[0259] The above antioxidant may be, for example, at least one selected from the group consisting of a phosphorus-based antioxidant, a hindered phenol-based antioxidant, and a phenol-based antioxidant, and 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.

[0260] The above-mentioned antioxidants include, for example, bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C 12 -C 15 Mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol)diphosphite, tris(mono- and di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol 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, It may be at least one selected from the group consisting of 2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphepine-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine, and more preferably, it may be tris(2,4-di-tert-butylphenyl) phosphite (IF168). In this case, it has the effect of preventing oxidation due to heat during the extrusion process and has excellent mechanical properties and heat resistance.

[0261] The above hindered phenol antioxidant may be, for example, at least one 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 this case, it has the effect of preventing oxidation due to heat during the extrusion process and having excellent mechanical properties and heat resistance.

[0262] Examples of the above 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-hexanediolbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[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-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, It may be at least one selected from the group consisting of 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-ditert-butyl-4-hydroxyphenyl)propanoate (IR1076). In this case, it has the effect of preventing oxidation due to heat during the extrusion process and having excellent mechanical properties and heat resistance.

[0263]

[0264] The thermoplastic resin composition may further include, for example, one or more additives selected from the group consisting of a plasticizer, a heat stabilizer, an anti-dripping agent, a light stabilizer, a pigment, a dye, an inorganic additive (excluding glass fiber), and carbon fiber.

[0265] The above additive may be included in an amount of, for example, 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 100 parts by weight of the total content of components (a) to (e), and within this range, the thermoplastic resin composition of the present invention has the effect of well implementing the required properties without lowering the original properties.

[0266]

[0267] thermoplastic resin composition

[0268] The thermoplastic resin composition may preferably have a flame retardancy of V-0 or higher as measured by a UL 94 test (Vertical Burning Test) using an injection molded specimen of 127 mm x 12.7 mm x 1.5 mm, and in this case, it has the advantage of excellent physical property balance and excellent flame retardancy.

[0269]

[0270] The thermoplastic resin composition may preferably have a flame endurance time of 600 seconds or more, which is measured by applying a flame of 1200°C formed with oxygen and propane gas to a 150 mm x 150 mm x 3 mm specimen until a hole or drip occurs, based on the Torch and Grit evaluation of UL 2596, and within this range, the composition has an excellent balance of physical properties and forms ceramics when an ultra-high-temperature flame and pressure are generated, thereby delaying flame propagation, thereby ensuring safety.

[0271]

[0272] The thermoplastic resin composition preferably has a grade of 1 or higher, preferably 0 or higher, based on the PLC (Performance Level Category) classification by measuring the Comparative Tracking Index (CTI) with a specimen having a thickness of 3 mm according to IEC 60112, and has an excellent balance of physical properties within this range while exhibiting excellent electrical insulation properties.

[0273]

[0274] Method for producing a thermoplastic resin composition

[0275] The method for producing a thermoplastic resin composition of the present invention comprises the steps of mixing and extruding (a) 32.5 to 49 wt% of a polymer, (b) 7 to 20.5 wt% of a ceramic-forming binder, (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor, (d) 13 to 37 wt% of a ceramic-forming non-metallic precursor, and (e) 2 to 8 wt% of a flame retardant, wherein the mixing and extruding are performed using an extruder having 9 or more mixing blocks, and in this case, the composition has excellent flame retardancy and insulating properties, and at the same time, when an unexpected ultra-high-temperature flame and pressure are generated, ceramics are formed to delay flame propagation, thereby ensuring safety and being environmentally friendly.

[0276] The above mixing and extrusion can be performed 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 which case, sufficient melt mixing is possible while the processing amount per unit time is high, and there is an advantage in that problems such as thermal decomposition of the polymer do not occur.

[0277] The above mixing and extrusion can be performed 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, and within this range, there is an effect of high throughput per unit time and excellent process efficiency.

[0278] The thermoplastic resin composition obtained through the above mixing and extrusion can preferably be provided in the form of pellets.

[0279]

[0280] flame retardant composition

[0281] The flame retardant composition of the present invention is characterized by including a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming non-metal precursor, and a flame retardant, and in this case, while having excellent flame retardancy and insulating properties, it forms a ceramic when an unexpected ultra-high temperature flame and the resulting pressure are generated, thereby delaying flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway, and has an environmentally friendly effect in that it produces almost no toxic gases and does not release environmental hormones during thermal decomposition.

[0282]

[0283] The above flame retardant composition is characterized in that when a high-temperature flame of 1200°C or higher and pressure generated thereby occur, the ceramic-forming binder is thermally decomposed and converted into a metal phosphate component, and the metal phosphate component combines a ceramic-forming metal precursor and a ceramic-forming non-metal precursor that has reached the Gob temperature to cause physical and chemical structural changes to form a ceramic, and the formed ceramic delays flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway of a battery.

[0284]

[0285] The flame retardant composition may comprise, for example, 11 to 34 wt% of a ceramic-forming binder, 14.5 to 41 wt% of a ceramic-forming metal precursor, 24 to 59 wt% of a ceramic-forming non-metal precursor, and 4 to 14 wt% of a flame retardant based on the total weight thereof, preferably 13 to 32 wt% of a ceramic-forming binder, 16 to 35 wt% of a ceramic-forming metal precursor, 30 to 57 wt% of a ceramic-forming non-metal precursor, and 4.5 to 12 wt% of a flame retardant, more preferably 15.5 to 31 wt% of a ceramic-forming binder, 17.5 to 28 wt% of a ceramic-forming metal precursor, 35 to 55 wt% of a ceramic-forming non-metal precursor, and 5 to 9.5 wt% of a flame retardant, even more preferably 15.5 to 25 wt% of a ceramic-forming binder, 20 to 27 wt% of a ceramic-forming metal precursor, and It may contain 43 to 53 wt% of a forming non-metallic precursor and 7 to 9 wt% of a flame retardant, and within this range, it has excellent flame retardancy and insulating properties, and by forming a ceramic when an unexpected ultra-high temperature flame and pressure are generated, flame propagation is delayed, thereby ensuring safety for property and life even in the event of thermal runaway, and has an environmentally friendly effect in that almost no toxic gases are generated during thermal decomposition and no environmental hormones are released.

[0286]

[0287] The present flame retardant composition includes the contents of the thermoplastic resin composition described above, and is omitted here to avoid redundant description.

[0288]

[0289] molded products

[0290] The molded article of the present invention is characterized by including the thermoplastic resin composition of the present invention, and in this case, while having excellent flame retardancy and electrical insulation properties, it forms ceramics when an ultra-high temperature flame and the resulting pressure are generated, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway and having an environmentally friendly effect.

[0291] The above-mentioned molded product may be, for example, an electrical / electronic component or an automobile component, and specifically, an electric vehicle electrical component or a battery component. In this case, the molded product has excellent flame retardancy and electrical insulation properties, and when a high-temperature flame and the resulting pressure are generated, the ceramic is formed to delay flame propagation, thereby ensuring safety even in the event of thermal runaway, and is environmentally friendly.

[0292] The above electric vehicle battery component may be, for example, a plastic upper cover, module housing, or busbar of an electric vehicle battery.

[0293]

[0294] The method for manufacturing a molded article of the present invention preferably comprises the steps of mixing and extruding a thermoplastic resin composition pellet comprising (a) 32.5 to 49 wt% of a polymer, (b) 7 to 20.5 wt% of a ceramic-forming binder, (c) 6.5 to 20.5 wt% of a ceramic-forming metal precursor, (d) 13 to 37 wt% of a ceramic-forming non-metallic precursor, and (e) 2 to 8 wt% of a flame retardant, and the steps of injecting the manufactured pellet to manufacture a molded article, wherein the mixing and extrusion are performed using an extruder having 9 or more mixing blocks. In this case, the flame retardancy and insulating properties are excellent, and the ceramic is formed when an unexpected ultra-high-temperature flame and the resulting pressure are generated, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway, and is environmentally friendly.

[0295]

[0296] The above injection is not particularly limited and can be applied by appropriate selection as needed, if it is based on a method and conditions commonly used in the technical field to which the present invention belongs.

[0297]

[0298] In describing the thermoplastic resin composition, molded article and method for manufacturing the same of the present invention, it is stated that other conditions (e.g., configuration or specifications of an extruder and an injection molding machine, extrusion and injection molding, additives, etc.) that are not specifically stated are not particularly limited and can be appropriately selected and implemented as needed, as long as they are within the scope commonly practiced in the art.

[0299]

[0300] The present invention will be described with reference to the drawings below.

[0301] The following drawing 1 is a schematic diagram of an extruder equipped with nine or more kneading blocks for producing a thermoplastic resin composition of the present invention.

[0302] The type of the extruder is not particularly limited, and can be appropriately selected and used if it is one commonly used in the art. For example, a single-screw extruder with one screw or a multi-screw extruder with multiple screws can be used. Considering uniform mixing of materials, ease of processing, and economy, it may be preferable to use a twin-screw extruder with two screws.

[0303] The extruder is composed of a feeder for supplying materials into a barrel, a screw for transporting and mixing the materials supplied into the barrel, and a die for extruding the mixed materials, and the screw is composed of a plurality of screw elements to provide various functions.

[0304] The above raw material feeder may be one or more, and optionally, two or more may be provided as needed. For example, a main feeder and optionally, an auxiliary feeder may be provided, and two or more auxiliary feeders may be provided as needed.

[0305] As a specific example, an additive including a polymer, a ceramic forming binder, a flame retardant, and a lubricant and an antioxidant may be injected into the main inlet, a ceramic forming metal precursor may be injected into the auxiliary inlet 1, and a ceramic forming non-metal precursor may be injected into the auxiliary inlet 2. In this case, there is an advantage in that they are uniformly mixed, and there is an excellent property balance, electrical insulation, flame retardancy, and flame retardancy characteristics in the event of thermal runaway when a high-temperature flame and pressure are generated.

[0306] As another example, a polymer and an additive may be injected into the main inlet, a ceramic forming binder and a flame retardant may be injected into the auxiliary inlet 1, and a ceramic forming metal precursor and a ceramic forming non-metal precursor may be injected into the auxiliary inlet 2. In this case, they are uniformly mixed, and there is an advantage of excellent physical property balance, electrical insulation, flame retardancy, and flame retardancy characteristics in the event of thermal runaway when an ultra-high temperature flame and pressure are generated accordingly.

[0307] As another example, a polymer may be injected into the main inlet, a ceramic forming binder, a ceramic forming metal precursor, a ceramic forming non-metal precursor, a flame retardant, and some of the additives may be injected into the auxiliary inlet 1, and the remainder may be injected into the auxiliary inlet 2. In this case, the polymer may be uniformly mixed, resulting in excellent properties such as a balance of physical properties, electrical insulation, flame retardancy, and flame retardancy when a high-temperature flame and pressure are generated.

[0308]

[0309] The kneading block of the present invention is an example of the screw element, and specifically comprises a plurality of discs, preferably 3 to 7 discs, 5 to 7 discs, 3 to 5 discs, or 4 to 5 discs, and typically has a cross-section such as a polygon or an ellipse, and is arranged continuously in the direction of material transport. In addition, in the kneading block, the phase angle of the discs (meaning the movement angle between the discs) is preferably 45 to 90°.

[0310] In addition, the mixing block includes a forward mixing block with the ability to transport, distribute, and mix materials, a neutral mixing block with only the ability to distribute and mix materials without the ability to transport materials, and a backward mixing block that transports materials in the opposite direction to the transport direction.

[0311] The thermoplastic resin composition according to the present invention can be manufactured by including a step of kneading and extruding using an extruder having, for example, 9 or more, preferably 10 or more, more preferably 12 or more, preferably 9 to 18, more preferably 10 to 18, and even more preferably 12 to 16 kneading blocks. At this time, it can be effective to use the kneading blocks in combination in the order of forward, orthogonal, and reverse with respect to the resin flow direction, and a continuous or separated block combination 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, thereby providing a thermoplastic resin composition of higher quality.

[0312] The above kneading blocks may be arranged in series, for example, nine or more, or may be arranged discontinuously between the screws, for example. As a specific example, three to six kneading blocks may be arranged in series between the main inlet and the auxiliary inlet 1, three to eight kneading blocks may be arranged in series between the auxiliary inlet 1 and the auxiliary inlet 2, and two to five kneading blocks may be arranged between the auxiliary inlet 2 and the discharge port (not shown). When arranged in this manner, local heat generation is controlled during melt kneading, thereby preventing thermal deformation of the raw material, and excessive cutting of the glass fiber is prevented, so that there is an advantage in that mechanical properties, electrical insulation, flame retardancy, and flame retardancy characteristics during thermal runaway are not deteriorated.

[0313]

[0314] Hereinafter, preferred examples are presented to help understand the present disclosure; however, the following examples are merely illustrative of the present disclosure, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0315]

[0316] [Example]

[0317] The materials used in the following examples and comparative examples are as follows.

[0318] * (a) polymer

[0319] - (a-1) PA6: Polyamide 6 resin (relative viscosity: 2.2)

[0320] - (a-2) PA66: Polyamide 66 resin (relative viscosity: 2.4)

[0321] - (a-3) PA56: Polyamide 56 resin (relative viscosity: 2.5)

[0322] - (a-4) PPE: Poly(2,6-dimethyl-1,4-phenylene) ether (intrinsic viscosity: 35~42 dl / g)

[0323] * (b) Ceramic forming binder

[0324] - (b-1) ADP: Aluminum diethyl phosphinate (Clariant's OP1230)

[0325] * (c) Ceramic forming metal precursor

[0326] - (c-1) Kaolin: Aluminum silicate

[0327] - (c-2) Mica: Aluminum silicate

[0328] - (c-3) Wollastonite: calcium silicate

[0329] * (c') Ceramic-free metal precursor

[0330] - (c'-1) Talc: Magnesium silicate

[0331] * (d) Ceramic forming non-metallic precursor

[0332] - (d-1) Glass fiber: Chopped glass fiber with an average particle size of 10 to 13 ㎛ and an average length of 3 to 4 mm and surface-treated with amino silane.

[0333] * (e) Flame retardant

[0334] - (e-1) MPP: Melamine polyphosphate

[0335] - (e-2) RDX: Resorcinol bis (2,6-dixylenyl phosphate)

[0336] * (f) Additives:

[0337] - Activator: EP184 (Hanyang Chemical) and Sunlube EBS DA-01 (Seongu) 0.25 wt%

[0338] - Antioxidant: 0.25 wt% of a mixture of AO-412S, IR1010, IR1098 and IR68

[0339]

[0340] Examples 1 to 10 and Comparative Examples 1 to 9

[0341] Polymers, ceramic-forming binders, ceramic-forming metal precursors, ceramic-forming non-metal precursors, flame retardants, and additives were melt-mixed and extruded at a temperature of 230 to 310°C and a rotation speed (rpm) of 150 to 300 rpm using a twin-screw extruder (T40 from SM) with nine mixing blocks in the amounts shown in Tables 1 and 2 below to produce pellets. The pellets were then used to produce test specimens for evaluation using an injection molding machine (80 tons from Engel). The properties of the produced specimens were measured after leaving them at room temperature for more than 48 hours, and are shown in Tables 1 and 2 below.

[0342] At this time, the twin-screw extruder has two or more total input ports, and a polymer, a ceramic-forming binder, a flame retardant, and an additive are input into the main input port, a ceramic-forming metal precursor is input into auxiliary input port 1, and a ceramic-forming non-metal precursor is input into auxiliary input port 2.

[0343]

[0344] [Example Exam]

[0345] The characteristics of the specimens manufactured in Examples 1 to 10 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0346]

[0347] measurement method

[0348] * Flame retardancy: Measured according to UL 94 V test (Vertical Burning Test) using injection molded specimens measuring 127 mm x 12.7 mm x 1.5 mm.

[0349] * CTI (Comparative Tracking Index): Based on IEC 60112, the voltage at which a 3-mm thick specimen is short-circuited when 50 drops of electrolyte solution fall is calculated, and the PLC (Performance Level Category) grade is assigned as shown in Table 3 below based on CTI.

[0350] Tracking index (volts) PLC grade 600 ≤ TI 0 400 ≤ TI < 600 1 250 ≤ TI < 400 2 175 ≤ TI < 250 3 100 ≤ TI < 175 4 0 ≤ TI < 100 5

[0351] * Flame Endurance Time (seconds): As shown in FIGS. 2 and 3, based on the Torch and Grit evaluation of UL 2596, a flame at 1200 °C formed by oxygen and propane gas was applied to a 150 mm x 150 mm x 3 mm specimen, and the time until a hole or drip occurred was measured.

[0352] Classification (weight %) Actual example 1 2 3 4 5 6 7 8 9 10 (a-1) PA6 39.5 39.5 39.5 44.5 37.5 42.5 44.5 (a-2) PA66 39.5 23.5 (a-3) PA56 39.5 (a-4) PPE 16 (b-1) ADP 10 10 10 10 10 10 10 10 10 17 (c-1) Kaolin 15 15 15 15 10 17 15 15 (c-2) Mica 15 (c-3) Wollastonite 15 (c'-1) Talc (d-1) Glass fiber 30 30 30 30 30 30 30 30 27 20 (e-1) MPP 5 5 5 5 5 5 5 5 3 (e-2) RDX 5 (f) Additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Physical properties CTI (PLC grade) 0 0 0 1 0 0 0 0 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Flame endurance time (sec.) 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more 600 seconds or more

[0353] Classification (weight %) Comparison Example 123456789 (a-1) PA6 39.5 39.5 54.5 52.5 39.5 49.5 24.5 34.5 (a-2) PA66 39.5 (a-3) PA56 (a-4) PPE (b-1) ADP 314 1010 310 1010 25 (c-1) Kaolin 15 1525 2155 1510 (c-2) Mica (c-3) Wollastonite (c'-1) Talc 15 (d-1) Glass fiber 30 305 3030 3030 4525 (e-1) MPP 12 155 1255 55 (e-2) RDX (f) Additive 0.5 ... Grade)0001000--Flame retardancyV-1V-1V-1V-1V-1V-1V-0--Fire resistance performance time (sec.) 50600 seconds or more10060607080--

[0354] -: Properties cannot be measured because extrusion is not possible.

[0355] As shown in Tables 1 and 2 above, the thermoplastic resin compositions of the present invention (Examples 1 to 10) have excellent flame retardancy and insulating properties compared to Comparative Examples 1 to 9, and when a high-temperature flame of 1200°C and pressure are generated accordingly, ceramics are formed to delay flame propagation, so that the fire resistance performance time is excellent at 600 seconds or more, and no holes are formed, so that safety for property and life is secured even in the event of thermal runaway of the battery, and it was confirmed that there is almost no generation of toxic gases and no emission of environmental hormones, so that there is no harmful effect on the human body and the environment.

[0356] Specifically, Comparative Examples 1 and 5, which contained a small amount of (b-1) ADP, a ceramic forming binder, and an excessive amount of (e-1) MPP, a flame retardant, showed reduced flame retardancy and very poor fire resistance time, and Comparative Example 2, which contained a small amount of (e-1) MPP, showed reduced flame retardancy.

[0357] In addition, Comparative Example 3, which contained a small amount of (d-1) glass fiber, a ceramic-forming non-metallic precursor, and an excessive amount of (c-1) kaolin, a ceramic-forming metal precursor, showed reduced flame retardancy and very poor fire resistance time.

[0358] In addition, Comparative Example 4, which included a small amount of (c-1) kaolin, a ceramic-forming metal precursor, and Comparative Example 6, which included (c'-1) talc, a ceramic-non-forming metal precursor, showed reduced flame retardancy and very poor fire resistance time.

[0359] In addition, (c-1) Comparative Example 7 containing a small amount of kaolin had very poor fire resistance performance time, and (d-1) Comparative Example 8 containing an excessive amount of glass fiber and (b-1) Comparative Example 9 containing an excessive amount of ADP were difficult to extrude.

[0360]

[0361] As shown in the following Figures 4 and 5, when a flame of 1200°C and pressure formed by oxygen and propane gas were applied to a specimen manufactured from a thermoplastic resin composition according to Examples 1 and 5 of the present invention based on the Torch and Grit evaluation of UL 2596, it was confirmed that ceramics were formed and no holes were formed even after 600 seconds or more, indicating that the fire resistance time was greatly improved.

[0362] On the other hand, as shown in Fig. 6 below, when a 1200°C flame formed with oxygen and propane gas and pressure corresponding thereto were applied to a specimen manufactured with a thermoplastic resin composition according to Comparative Example 6 based on the Torch and Grit evaluation of UL 2596, it was confirmed that a hole was created in just 70 seconds without ceramics being formed.

[0363]

[0364] In conclusion, the thermoplastic resin composition comprising a polymer, a ceramic-forming binder, a ceramic-forming metal precursor, a ceramic-forming non-metal precursor, and a flame retardant in a predetermined amount according to the present invention has excellent flame retardancy and electrical insulation properties, and forms a ceramic when an ultra-high-temperature flame and the resulting pressure are generated, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway, and confirming an environmentally friendly effect.

Claims

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

2. In paragraph 1, The above (a) polymer is characterized in that it comprises at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, polyalkylene terephthalate resin, polystyrene resin, polycarbonate resin, and modified polymers thereof. Thermoplastic resin composition.

3. In paragraph 1, The above (b) ceramic forming binder is characterized in that it contains a metal-based flame retardant. Thermoplastic resin composition.

4. In paragraph 1, The above (c) ceramic forming metal precursor is characterized in that it contains metal silicate or has a magnesium (but does not contain magnesium oxide) or magnesium oxide content of 3 wt% or less based on the total weight of the ceramic forming metal precursor. Thermoplastic resin composition.

5. In paragraph 4, The metal silicate is characterized in that it comprises at least one selected from the group consisting of aluminum silicate and calcium silicate. Thermoplastic resin composition.

6. In paragraph 5, The above aluminum silicate is characterized in that it includes at least one selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene and petalite. Thermoplastic resin composition.

7. In paragraph 5, The above calcium silicate is characterized in that it includes wollastonite. Thermoplastic resin composition.

8. In paragraph 1, The above (d) ceramic forming non-metallic precursor is characterized in that it includes glass fiber. Thermoplastic resin composition.

9. In paragraph 1, The above (e) flame retardant is characterized in that it includes at least one selected from the group consisting of melamine-based flame retardants, phosphazene-based flame retardants, and phosphate-based flame retardants. Thermoplastic resin composition.

10. In paragraph 1, The thermoplastic resin composition is characterized in that the flame endurance time, which is measured by applying a flame of 1200°C formed with oxygen and propane gas to a 150 mm x 150 mm x 3 mm specimen until a hole or drip occurs, is 600 seconds or more according to the Torch and Grit evaluation of UL 2596, or the comparative tracking index (CTI) is measured using a specimen with a thickness of 3 mm according to IEC 60112 and the grade by PLC (Performance Level Category) classification is 1 or higher. Thermoplastic resin composition.

11. In paragraph 1, The thermoplastic resin composition is characterized in that it contains an anti-oxidant, an anti-oxidant, or a mixture thereof. Thermoplastic resin composition. 12.(a) A method for producing a composite material comprising: mixing and extruding a polymer comprising 32.5 to 49 wt% of a polymer, 7 to 20.5 wt% of a ceramic-forming binder, 6.5 to 20.5 wt% of a ceramic-forming metal precursor, 13 to 37 wt% of a ceramic-forming non-metal precursor, and 2 to 8 wt% of a flame retardant; characterized in that the mixing and extruding are performed using an extruder having 9 or more mixing blocks. A method for producing a thermoplastic resin composition.

13. Characterized in that it comprises a ceramic forming binder, a ceramic forming metal precursor, a ceramic forming non-metal precursor, and a flame retardant. Flame retardant composition.

14. In paragraph 13, The flame retardant composition is characterized in that it comprises 11 to 34 wt% of a ceramic forming binder, 14.5 to 41 wt% of a ceramic forming metal precursor, 24 to 59 wt% of a ceramic forming non-metal precursor, and 4 to 14 wt% of a flame retardant based on the total weight thereof. Flame retardant composition.

15. Characterized in that it comprises a thermoplastic resin composition of any one of claims 1 to 11. Molded product.

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