Thermoplastic resin composition, preparation method therefor 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, the composition comprising: (a) 15.5 to 26 wt% of a polyamide resin; (b) 9.5 to 17 wt% of a poly(arylene ether) resin; (c) 2 to 5.5 wt% of a modified poly (arylene ether) resin; (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of an aromatic vinyl-based elastomer and an olefin-based elastomer; (e) 5.5 to 12.5 wt% of a metal phosphorus-based flame retardant; (f) 6.5 to 20.5 wt% of a metal silicate; (g) 15.5 to 38.5 wt% of glass fibers; and (h) 4.5 to 10 wt% of a flame retardant. According to the present invention the thermoplastic resin composition, which has excellent flame retardancy and electrical insulation, and delays flame propagation by forming ceramic during the occurrence of extreme heat or flames, thereby having excellent flame delay characteristics during thermal runaway so as to ensure safety of property and human life and being eco-friendly, the preparation method therefor, and the molded article comprising same are provided.

Description

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

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

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2024-0053333, filed 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, there is a high possibility that the hydrogen halogen gas generated during the processing or the environmental hormones released during the combustion process can have fatal adverse effects on the human body.

[0008] Additionally, 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, phosphorus-based flame retardants have significantly lower flame retardancy than halogen-containing flame retardants, so although they achieve a V-0 or 5V flame retardancy rating according to the UL 94 test by adding a large amount of flame retardant, they lack the flame retardancy properties to prevent thermal runaway when an unexpected ultra-high-temperature flame and the resulting pressure are 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] To achieve the above object, I) the present invention provides a thermoplastic resin composition characterized by comprising (a) 15.5 to 26 wt% of a polyamide resin; (b) 9.5 to 17 wt% of a poly(arylene ether) resin; (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin; (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers; (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant; (f) 6.5 to 20.5 wt% of a metal silicate; (g) 15.5 to 38.5 wt% of glass fiber; and (h) 4.5 to 10 wt% of a flame retardant.

[0021] II) In the above I), the (c) modified poly(arylene ether) resin may include a poly(arylene ether) resin modified with an unsaturated carboxylic acid or an anhydride thereof.

[0022] III) In the above I) or II), the aromatic vinyl elastomer may include at least one selected from a styrene-butadiene-styrene (SBS) copolymer, a styrene-ethylene-butylene-styrene (SEBS) copolymer, a styrene-butadiene (SB) copolymer, a styrene-isoprene (SI) copolymer, a styrene-isoprene-styrene (SIS) copolymer, an alpha-methylstyrene-butadiene copolymer, a styrene-ethylene-propylene copolymer, a styrene-ethylene-propylene-styrene (SEPS) copolymer, a styrene-ethylene-ethylene-butadiene-styrene (SEEBS), a styrene-ethylene-ethylene-propylene-styrene (SEEPS), a styrene-isoprene-butadiene (SIBS), and modified polymers thereof.

[0023] IV) In the above I) to III), the olefin-based elastomer may include at least one selected from among high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-butene copolymer, ethylene-octene copolymer, and modified polymers thereof.

[0024] V) In the above I) to IV), the metal silicate (f) may include Al, Ca or a mixture thereof.

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

[0026] VII) In the above I) to VI), the (f) metal silicate may be a magnesium-free silicate.

[0027] VIII) In the above I) to VII), the (g) glass fiber may have an average particle diameter of 3 to 25 ㎛ and an average length of 1 to 10 mm.

[0028] IX) In the above I) to VIII), the flame retardant (h) 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.

[0030] XI) In the above I) to X), the thermoplastic resin composition may have a grade of 1 or higher according to the PLC (Performance Level Category) classification by measuring the comparative tracking index (CTI) using a specimen having a thickness of 3 mm according to IEC 60112.

[0031] In addition, XII) the present invention provides a method for producing a thermoplastic resin composition, comprising the steps of mixing and extruding (a) 15.5 to 26 wt% of a polyamide resin, (b) 9.5 to 17 wt% of a poly(arylene ether) resin, (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin, (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers, (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant, (f) 6.5 to 20.5 wt% of a metal silicate, (g) 15.5 to 38.5 wt% of glass fibers, and (h) 4.5 to 10 wt% of a flame retardant, wherein the mixing and extrusion are performed using an extruder having 9 or more mixing blocks.

[0032] In addition, XIII) The present invention provides a flame retardant composition characterized by including a metal-based flame retardant, a metal silicate, glass fiber, and a flame retardant.

[0033] XVI) In the above XIII), the flame retardant composition may include 8.5 to 21.3 wt% of a metal-based flame retardant, 11.5 to 40 wt% of a metal silicate, 27 to 56 wt% of a glass fiber, and 6.5 to 17 wt% of a flame retardant based on the total weight thereof.

[0034] In addition, XV) The present invention provides a molded article characterized by including a thermoplastic resin composition of any one of the above I) to XI).

[0035] 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 the pressure generated thereby are formed, the flame propagation is blocked, thereby ensuring the safety of property and life even in the event of thermal runaway, and is environmentally friendly, so that it can be applied with high quality to automobile parts, especially electric vehicle battery and other electrical parts, a method for producing the same, and a molded product including the same are provided.

[0036] Figure 1 is a schematic diagram of an extruder equipped with nine or more mixing blocks according to the present invention.

[0037] Figure 2 is a schematic diagram showing a measurement method according to the Torch and Grit evaluation of UL 2596.

[0038] Figure 3 is a photograph of an actual measurement scene according to the Torch and Grit evaluation of UL 2596.

[0039] FIG. 4 is a photograph showing a specimen of a thermoplastic resin composition according to Example 1 after the Torch and Grit evaluation of UL 2596.

[0040] Figure 5 shows a specimen of a thermoplastic resin composition according to Comparative Example 5 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] Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and a molded article including the same are described in detail.

[0042] The present inventors have confirmed that when a thermoplastic resin composition is included in a predetermined amount of a polyamide resin; a poly(arylene ether) resin; a modified poly(arylene ether) resin; at least one selected from the group consisting of an aromatic vinyl elastomer and an olefin elastomer; a metal phosphorus flame retardant; a metal silicate; glass fiber; and a flame retardant, the composition has a flame retardancy of V-0 or higher as determined by the UL 94 test and has excellent insulation properties, and forms a ceramic when a flame of an ultra-high temperature of 1200°C or higher and pressure generated thereby are generated to delay flame propagation, thereby significantly improving the safety of property and life even in the event of thermal runaway, and is environmentally friendly, and based on this, they have devoted themselves to further research and completed the present invention.

[0043]

[0044] The thermoplastic resin composition according to this invention is examined in detail as follows.

[0045]

[0046] The thermoplastic resin composition of the present invention comprises: (a) 15.5 to 26 wt% of a polyamide resin; (b) 9.5 to 17 wt% of a poly(arylene ether) resin; (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin; (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers; (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant; (f) 6.5 to 20.5 wt% of a metal silicate; (g) 15.5 to 38.5 wt% of glass fiber; And (h) 4.5 to 10 wt% of a flame retardant; characterized in that 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 has an environmentally friendly effect.

[0047]

[0048] Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

[0049]

[0050] (a) polyamide resin

[0051] The polyamide resin (a) may be, for example, 15.5 to 26 wt%, preferably 17 to 25 wt%, more preferably 18 to 24 wt%, even more preferably 19 to 23 wt%, and even more preferably 19 to 22 wt%, based on the total weight of the components (a) to (h), and within this range, the polyamide resin 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.

[0052] 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.

[0053]

[0054] The above (a) 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.

[0055] Preferably, the (a) 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, the mechanical properties and appearance quality are excellent.

[0056] Additionally, the polyamide resin may be, for example, homopolyamide, copolyamide, or a mixture thereof.

[0057] The above (a) polyamide resin may be, for example, crystalline, semi-crystalline or amorphous.

[0058] 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.

[0059] The above lactam polymer can preferably be obtained by ring-opening polymerization of a lactam compound such as caprolactam or laurolactam.

[0060] 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.

[0061]

[0062] The above (a) 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.

[0063] The above (a) 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 which case, the problem of overheating due to friction between the screw of the extruder and the molten composition during extrusion molding is not caused, and the tension applied to the molten composition is appropriate, so there is an advantage of excellent extrusion processability.

[0064] 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.

[0065]

[0066] (b) poly(arylene ether) resin

[0067] The above (b) poly(arylene ether) resin may be, for example, 9.5 to 17 wt%, preferably 10 to 16 wt%, more preferably 10 to 15.5 wt%, even more preferably 11 to 15.5 wt%, and even more preferably 11.5 to 15.5 wt%, based on the total weight of the components (a) to (h), and within this range, the resin 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.

[0068] 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.

[0069] [Chemical Formula 1]

[0070]

[0071] [Chemical Formula 2]

[0072]

[0073] 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.

[0074] 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.

[0075] 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.

[0076]

[0077] The above (b) homopolymer of 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 excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as excellent processability.

[0078]

[0079] In addition, the copolymer of the above (b) 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.

[0080] The above (b) poly(arylene ether) resin may preferably be a polyphenylene ether resin.

[0081]

[0082] The above (b) 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 has the advantage of maintaining high mechanical properties such as impact strength and tensile strength of the composition within this range while securing fluidity suitable for molding.

[0083] The intrinsic viscosity of the above (b) poly(arylene ether) resin is 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, unless otherwise specified.

[0084]

[0085] The total amount of the above (a) polyamide resin and (b) poly(arylene ether) resin may be, for example, 25 to 42 wt%, preferably 28 to 41 wt%, more preferably 29 to 40 wt%, even more preferably 31 to 39 wt%, and even more preferably 31 to 36 wt%, based on the total weight of the components (a) to (h), and within this range, the mechanical properties, electrical insulation, and flame retardancy are excellent, and the flame retardancy during thermal runaway is excellent, so that the safety of property and life is secured.

[0086]

[0087] The above (a) polyamide resin may be included in an amount greater than, for example, the (b) poly(arylene ether) resin, and preferably, the weight ratio (a:b) of the (a) polyamide resin and the (b) poly(arylene ether) resin may be 1:0.4 to 1:0.75, preferably 1:0.45 to 1:0.7, and more preferably 1:0.5 to 1:0.7, and within this range, the mechanical properties, electrical insulation, and flame retardancy are excellent, and the flame retardancy characteristics in the event of thermal runaway are excellent, so that the safety of property and life is secured.

[0088]

[0089] (c) modified poly(arylene ether) resin

[0090] The above (c) modified poly(arylene ether) resin may be, for example, 2 to 5.5 wt%, preferably 2.3 to 5 wt%, more preferably 2.5 to 4.5 wt%, even more preferably 2.7 to 4.3 wt%, and even more preferably 3 to 4 wt%, based on the total weight of the components (a) to (h), and within this range, compatibility with glass fiber is enhanced, so that mechanical properties, electrical insulation, and flame retardancy are excellent, and flame retardancy characteristics are excellent during thermal runaway, thereby ensuring the safety of property and life.

[0091]

[0092] The above (c) modified poly(arylene ether) resin may include, for example, a poly(arylene ether) resin modified with an unsaturated carboxylic acid or an anhydride thereof, in which case compatibility with glass fiber is improved, and mechanical properties, electrical insulation, and flame retardancy are excellent, while flame retardancy characteristics during thermal runaway are excellent, thereby ensuring safety.

[0093] The above unsaturated carboxylic acid or anhydride thereof may be, for example, at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylic acid, citric acid, malic acid, agaric acid, fumaric acid, maleic acid, itaconic acid, citric acid, aconitic acid, and anhydrides thereof.

[0094]

[0095] The poly(arylene ether) resin modified with the above unsaturated carboxylic acid or its anhydride may be, for example, one manufactured by grafting a poly(arylene ether) resin and an unsaturated carboxylic acid or its anhydride in a molten, solution or slurry state.

[0096]

[0097] As a specific example, the poly(arylene ether) resin modified with the unsaturated carboxylic acid or its anhydride may be manufactured by mixing the poly(arylene ether) resin and the unsaturated carboxylic acid or its anhydride, melt-mixing them using a mixing device at a temperature of 250 to 350°C for 0.1 to 10 minutes, and then performing a graft reaction.

[0098]

[0099] The above unsaturated carboxylic acid or its anhydride may be included in an amount of, for example, 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the poly(arylene ether) resin used in the graft reaction, and within this range, the interfacial tension between the poly(arylene ether) and the glass fiber is lowered, thereby improving dispersibility and providing excellent mechanical strength and physical property balance.

[0100]

[0101] The poly(arylene ether) resin modified with the above unsaturated carboxylic acid or its anhydride may preferably be a poly(arylene ether) resin grafted with maleic anhydride, in which case compatibility with glass fiber is improved, and mechanical properties, heat resistance, and flame retardancy are all excellent.

[0102]

[0103] The above (c) modified poly(arylene ether) resin may have, for example, a glass transition temperature (Tg) of 160 to 220°C, preferably 170 to 210°C, and more preferably 180 to 200°C, and within this range, it has excellent mechanical properties and property balance.

[0104] In this paper, the glass transition temperature (Tg) can be measured at a heating rate of 10℃ / min using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument).

[0105]

[0106] The above (c) modified poly(arylene ether) resin may have, for example, an intrinsic viscosity of 0.1 to 0.9 dl / g, preferably 0.3 to 0.6 dl / g, and has excellent moldability within this range.

[0107] The intrinsic viscosity of the above (c) modified 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, unless otherwise specified.

[0108]

[0109] (d) at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers;

[0110] The thermoplastic resin composition of the present invention may include, for example, (d) at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers, preferably an aromatic vinyl elastomer and an olefin elastomer, more preferably an aromatic vinyl elastomer or an olefin elastomer, and even more preferably an olefin elastomer, and in this case, there is an excellent effect in mechanical properties such as impact strength and tensile strength.

[0111]

[0112] The above (d) at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers may be present in an amount of, for example, 0.5 to 4.5 wt%, preferably 0.6 to 4 wt%, more preferably 0.7 to 3.5 wt%, even more preferably 0.8 to 3 wt%, and even more preferably 1 to 2.5 wt%, based on the total weight of the components (a) to (h), and within this range, excellent mechanical properties such as impact strength and tensile strength are achieved.

[0113]

[0114] The above aromatic vinyl elastomer may include, for example, at least one selected from a styrene-butadiene-styrene (SBS) copolymer, a styrene-ethylene-butylene-styrene (SEBS) copolymer, a styrene-butadiene (SB) copolymer, a styrene-isoprene (SI) copolymer, a styrene-isoprene-styrene (SIS) copolymer, an alpha-methylstyrene-butadiene copolymer, a styrene-ethylene-propylene copolymer, a styrene-ethylene-propylene-styrene (SEPS) copolymer, a styrene-ethylene-ethylene-butadiene-styrene (SEEBS), a styrene-ethylene-ethylene-propylene-styrene (SEEPS), a styrene-isoprene-butadiene (SIBS), and modified polymers thereof, and preferably a styrene-butadiene-styrene copolymer, a styrene-ethylene-butylene-styrene It may be at least one selected from the group consisting of copolymers and maleic anhydride-modified styrene-ethylene-butylene-styrene copolymers, and in this case, it has excellent effects in processability, impact strength, and tensile strength.

[0115] In the present invention, a modified polymer means a polymer that is modified into an unsaturated carboxylic acid or an anhydride thereof by reacting with a reactive monomer such as an unsaturated carboxylic acid or an anhydride thereof.

[0116] The above reactive monomer may be, for example, at least one selected from the group consisting of citric acid, maleic acid, malic acid, agaric acid, itaconic acid, fumaric acid, (meth)acrylic acid, anhydrides thereof, and (meth)acrylic acid esters.

[0117] The above aromatic vinyl elastomer may preferably contain 20 to 40 wt%, preferably 25 to 35 wt%, and more preferably 27 to 33 wt% of an aromatic vinyl compound based on its total weight, and within this range, excellent processability, impact strength, and tensile strength are achieved.

[0118] The above aromatic vinyl elastomer may have, for example, a weight average molecular weight of 50,000 to 400,000 g / mol, preferably 70,000 to 350,000 g / mol, more preferably 100,000 to 300,000 g / mol, and within this range, has excellent processability, impact strength, and tensile strength.

[0119] In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, the solvent is THF, the column temperature is 40℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection amount is 5㎕, the column model is 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), the measuring device is Agilent 1200 series system, the refractive index detector: Agilent G1362 RID, the RI temperature is 35℃, the data processing is Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

[0120]

[0121] The above aromatic vinyl elastomer may have a Shore A hardness of 50 to 75, preferably 60 to 72, as measured according to ASTM D2240, for example, and has excellent processability, impact strength, and tensile strength within this range.

[0122] The above aromatic vinyl elastomer may have a tensile strength of, for example, 20 MPa or more, preferably 25 MPa or more, more preferably 30 MPa or more, and even more preferably 30 to 50 MPa as measured according to ASTM D638, and within this range, has excellent processability, impact strength, and tensile strength.

[0123]

[0124] The above olefin-based elastomer may be, for example, a copolymer polymerized solely with an olefin-based compound or including the same, and the olefin-based compound may be, for example, at least one selected from among ethylene, propylene, isopropylene, butylene, isobutylene, and octene.

[0125] As a more specific example, the olefin-based elastomer may be at least one selected from among high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-butene copolymer, ethylene-octene copolymer, and modified polymers thereof. In terms of ensuring compatibility with the polyamide resin, it may be preferable to use a modified polyolefin, and in this case, there is an advantage in that physical properties such as heat resistance and impact strength are further improved.

[0126] The above-mentioned modified polyolefin may be, for example, a reaction product of an unsaturated carboxylic acid, an anhydride thereof, or an epoxy compound and a polyolefin polymer, and specifically, may be at least one selected from maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified ethylene-propylene copolymer. In this case, there is an advantage in that the compatibility between the olefin-based impact modifier and the polyamide resin is increased, thereby further improving physical properties such as heat resistance and impact strength.

[0127]

[0128] The weight ratio of the aromatic vinyl elastomer and the olefin elastomer may be preferably 1:9 to 9:1, more preferably 2:8 to 8:2, even more preferably 3:7 to 7:3, and even more preferably 4:6 to 6:4, and within this range, excellent mechanical properties such as impact strength and tensile strength are achieved.

[0129]

[0130] There is an advantage in that the extrusion performance is improved while the flame retardancy, insulation properties, and flame retardancy properties are excellent due to the synergistic effect of the combination of at least one selected from the group consisting of the above (c) modified poly(arylene ether) resin and (d) aromatic vinyl elastomer and olefin elastomer.

[0131]

[0132] (e) Metal-based flame retardants

[0133] In this invention, the metal phosphorus flame retardant 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 the metal silicate and glass fiber that have 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 the battery, and has the advantage of being environmentally friendly.

[0134] In this description, the gob temperature refers to the temperature at which the glass fiber is melted and turned into a hot lump called a gob, which can be formed into a desired shape.

[0135]

[0136] In this description, the ultra-high temperature flame and pressure means that when a flame of 1200℃ formed with oxygen and propane gas is applied to the 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.

[0137]

[0138] 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.

[0139]

[0140] The above (e) metal-based flame retardant may be, for example, 5.5 to 12.5 wt%, preferably 6 to 12 wt%, more preferably 6.5 to 12 wt%, even more preferably 7 to 12 wt%, and even more preferably 7 to 11 wt%, based on the total weight of the components (a) to (h), and within this range, the flame retardancy and electrical insulation are excellent, and when ultra-high temperature and flame pressure are generated, ceramics are formed to delay flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway, and providing an environmentally friendly advantage.

[0141]

[0142] The above (e) metal-based flame retardant may be, for example, an organic phosphinate metal salt, preferably a dialkylphosphinic acid salt represented by the following chemical formula 3, a diphosphinic acid salt represented by the following chemical formula 4, or a mixture thereof. In this case, while having excellent flame retardancy and electrical insulation properties, it forms a ceramic when ultra-high temperature and flame pressure are generated, thereby delaying flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway, and has the advantage of being environmentally friendly.

[0143] [Chemical Formula 3]

[0144]

[0145] [Chemical Formula 4]

[0146]

[0147] In the above chemical formulas 3 and 4, R 5 , R 6 , R 7 and R 8 are each independently linear or branched C1-C 10 In alkyl, C3-C 12 Cycloalkyl, or H; R 9 is linear or branched C1-C 10 In alkylene, C6-C 10In 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.

[0148] In the above chemical formulas 3 and 4, cycloalkyl may independently preferably be cyclohexyl or cyclohexadimethyl.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] The above R 5 and R 6 , and R 7 and R8 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.

[0153]

[0154] The dialkylphosphinic acid salt represented by the above chemical formula 3 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.

[0155]

[0156] The diphosphinic acid salt represented by the above chemical formula 4 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.

[0157] The above (e) metal-based flame retardant 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.

[0158] As a specific example, when aluminum diethylphosphinate is used as the above (e) metal-based flame retardant, the organic component volatilizes 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 acts to bind the metal silicate and glass fiber.

[0159]

[0160] The above (e) metal-based flame retardant may have, for example, an average particle diameter of 0.1 to 100 μm, preferably 0.5 to 80 μm, more preferably 1 to 60 μm, and has the advantage of excellent flame retardancy and mechanical properties within this range.

[0161] 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.

[0162]

[0163] The above (e) metal-based flame retardant may preferably have a phosphorus content of 20 to 35 wt%, more preferably 22 to 30 wt%, and within this range, has excellent flame retardancy and electrical insulation properties, while forming ceramics 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.

[0164] 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 organic phosphorus flame retardant.

[0165]

[0166] (f) metal silicates

[0167] In this invention, metal silicate is combined with glass fibers in a gob state by a metal phosphate component generated by thermal decomposition of a metal phosphorus flame retardant when an ultra-high temperature flame and pressure are generated, causing physical and chemical structural changes to form a ceramic, and the formed ceramic retards the flame, thereby ensuring the safety of property and life even in the event of thermal runaway of the battery.

[0168]

[0169] The above (f) metal silicate may be, for example, 6.5 to 20.5 wt%, preferably 7.5 to 19 wt%, more preferably 8 to 18 wt%, even more preferably 9 to 18 wt%, and even more preferably 10 to 17 wt%, based on the total weight of the components (a) to (h), and within this range, the metal silicate has excellent flame retardancy and electrical insulation properties, and forms a ceramic by bonding with glass fibers using a metal-based flame retardant under an ultra-high temperature flame to delay flame propagation, thereby ensuring safety for property and life even in the event of thermal runaway.

[0170] The above (f) metal silicate can be defined as a material that forms a ceramic by combining glass fibers in a gob state and a metal-based flame retardant under an ultra-high temperature flame, i.e., a ceramic-forming metal silicate, and accordingly, talc that does not form a ceramic under an ultra-high temperature flame does not correspond to a metal silicate according to the definition of the present invention.

[0171]

[0172] The above (f) metal silicate may include, for example, Al, Ca or a mixture thereof, and in this case, it has excellent flame retardancy and electrical insulation properties, and when a high-temperature flame and pressure are generated, it forms a ceramic by combining with glass fibers to delay flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0173]

[0174] The above (f) metal silicate may include, for example, at least one selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, petalite, and wollastonite, preferably at least one selected from the group consisting of kaolin, mica, and wollastonite, more preferably kaolin, mica, or a mixture thereof, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high-temperature flame and pressure are generated, it forms a ceramic by combining with glass fibers to delay flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0175]

[0176] The above (f) metal silicate 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 a high-temperature flame and pressure are generated, it forms a ceramic by combining with glass fibers to delay flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0177] In this description, 'magnesium-free silicate' refers to one containing magnesium (but not containing magnesium oxide) 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 metal silicate. If the magnesium or magnesium oxide content in the metal silicate 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 and does not exhibit the effect of delaying flame propagation.

[0178]

[0179] The above (f) metal silicate may have, for example, an average particle size of 0.1 to 100 ㎛, preferably 0.1 to 70 ㎛, more preferably 0.1 to 60 ㎛, and within this range, compatibility with glass fiber is improved, resulting in excellent mechanical properties, electrical insulation, flame retardancy, and flame retardancy properties.

[0180] In this description, the average particle diameter can be measured by a measurement 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.

[0181]

[0182] (g) glass fiber

[0183] In this invention, glass fibers change into a gob state when subjected to ultra-high temperature flame and pressure, and the gob state glass fibers combine with metal silicates by the metal phosphate component generated by thermal decomposition of a metal phosphorus flame retardant to cause physical and chemical structural changes to form ceramics, thereby preventing the formation of holes or drips due to flames, thereby ensuring safety with excellent flame retardancy characteristics in the event of thermal runaway.

[0184]

[0185] The above (g) glass fiber may be, for example, 15.5 to 38.5 wt%, preferably 20 to 36 wt%, more preferably 22 to 34 wt%, even more preferably 24 to 34 wt%, and even more preferably 25 to 33 wt%, based on the total weight of the components (a) to (h), and within this range, the glass fiber 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.

[0186]

[0187] The above (g) glass fiber may preferably include E-glass fiber, and in this case, it has excellent flame retardancy and electrical insulation properties, and when an ultra-high temperature flame and pressure are generated, a ceramic is formed by bonding with the glass fiber by a metal-based flame retardant, thereby delaying flame propagation, thereby ensuring safety even in the event of thermal runaway.

[0188] 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.

[0189]

[0190] The above (g) glass fiber may include, for example, chopped glass fiber, in which case it has the advantage of excellent compatibility.

[0191] 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.

[0192]

[0193] The above (g) glass fiber may have, for example, an average particle size of 3 to 25 ㎛, preferably 5 to 20 ㎛, and more preferably 7 to 15 ㎛, and within this range, the mechanical strength with respect to the polyamide resin is improved, while the appearance characteristics of the final product are excellent.

[0194] The above (g) glass fiber may have an average length of, for example, 1 to 10 mm, preferably 2 to 7 mm, and more preferably 2 to 5 mm, and within this range, the mechanical strength with the polyamide resin is improved while the appearance characteristics of the final product are excellent.

[0195] The above (g) glass fiber may have an aspect ratio (L / D), which is the ratio of the average length (L) to the average diameter (D), of, for example, 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 polyamide resin, thereby providing an advantage of an excellent surface appearance.

[0196] In this description, the average particle diameter, average length, aspect ratio, etc. of the glass fibers are calculated as the average value by measuring 30 pieces using a microscopic analysis method.

[0197]

[0198] The above (g) glass fiber may be surface-treated with, for example, a silane-based compound or a urethane-based compound, and preferably, one 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 may be used, and more preferably, one surface-treated with an amino silane-based compound, and in this case, by combining with a polyamide resin, 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.

[0199]

[0200] 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 glass fiber (glass fiber + surface treatment agent), and within this range, the mechanical properties, property balance, and appearance of the final product are excellent.

[0201] 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.

[0202] 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.

[0203]

[0204] The above (g) 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.

[0205]

[0206] The total amount of the metal silicate and glass fibers may be, for example, 30 to 54 wt%, preferably 35 to 51 wt%, more preferably 37 to 48 wt%, and even more preferably 39 to 45 wt%, based on the total weight of the thermoplastic resin composition, and within this range, there is an advantage of excellent flame retardancy and electrical insulation while also being excellent in ceramic formation when a high-temperature flame and the resulting pressure are generated.

[0207]

[0208] (h) flame retardants

[0209] 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.

[0210] The flame retardant (h) may be, for example, 4.5 to 10 wt%, preferably 5 to 9 wt%, more preferably 5.5 to 8.5 wt%, even more preferably 5.5 to 8 wt%, and even more preferably 6 to 8 wt%, based on the total weight of the components (a) to (h), 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.

[0211]

[0212] The 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 harmful to the human body and the environment.

[0213]

[0214] 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.

[0215]

[0216] 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, preferably a cyclic phosphazene compound, and in this case, it has excellent flame retardancy and mechanical properties.

[0217] The above cyclic phosphazene compound may preferably be a compound represented by the following chemical formula 5.

[0218] [Chemical Formula 5]

[0219]

[0220] In the above chemical formula 5, m is an integer from 3 to 25, and R 13 and R 14 are identical or different and represent an aryl group or an alkylaryl group.

[0221] In the above chemical formula 5, m is preferably an integer of 3 to 5.

[0222]

[0223] The cyclic phosphazene compound represented by the above chemical formula 5 is more preferably R 13 and R 14Each independently phenyl group is a cyclic phenoxyphosphazene, and more preferably, it may be at least one selected from the group consisting of phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decapenoxycyclopentaphosphazene.

[0224]

[0225] The above chain-type phosphazene compound may preferably be a compound represented by the following chemical formula 6.

[0226] [Chemical Formula 6]

[0227]

[0228] In the above chemical formula 6, 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.

[0229] In the above chemical formula 6, n is preferably an integer from 3 to 100, more preferably an integer from 3 to 25.

[0230] The chain-like phosphazene compound represented by the above chemical formula 6 is preferably R 15 and R 16 This is a chain-type phenoxphosphazene with a phenyl group.

[0231]

[0232] The above-mentioned 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 7.

[0233] [Chemical Formula 7]

[0234]

[0235] In the above chemical formula 7, (A) I is -C(CH3)2-, -SO2-, -S-, or -O-, and I is an integer of 0 or 1, is a bond.

[0236]

[0237] The above cross-linked phosphazene compound is preferably R in the above chemical formula 5. 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 7, wherein in the above chemical formula 6, 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 7, 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 7.

[0238]

[0239] Examples of the above phosphate flame retardants include trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), tricxylenyl 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.

[0240]

[0241] The thermoplastic resin composition may include, for example, an anti-oxidant, an anti-fungal agent, or a mixture thereof.

[0242] 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 thermoplastic resin composition, and within this range, the mechanical properties are excellent while the molding processability is improved.

[0243] The above-mentioned active agent may be, for example, at least one selected from the group consisting of a fatty acid ester active agent, an olefin active agent, a fatty acid amide active agent, and a montan active agent, and preferably a fatty acid ester active agent. In this case, there is an effect of improving molding processability while providing excellent mechanical properties.

[0244] The above fatty acid ester-based active agent may include, for example, pentaerythritol fatty acid ester (PETS-AHS).

[0245] The above olefin-based lubricant may be, for example, polyethylene wax, polypropylene wax, or a mixture thereof.

[0246] 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.

[0247] The above-mentioned montan-based lubricant may be, for example, a montan wax, a montan ester wax, or a mixture thereof. The 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 glycerin and montanic acid, calcium montanate containing a montanic acid ester, and an ester mixed wax based on montanic acid.

[0248]

[0249] The above 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 the thermoplastic resin composition, and within this range, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties and heat resistance.

[0250] 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 preferably a phosphorus-based antioxidant, a hindered phenol-based antioxidant, or a mixture thereof, in which case it has the effect of preventing oxidation due to heat during the extrusion process and having excellent mechanical properties and heat resistance.

[0251] 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(C12-C15 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). there is.

[0252]

[0253] 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].

[0254] 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).

[0255]

[0256] The thermoplastic resin composition may further include 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.

[0257] 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 thermoplastic resin composition, and within this range, the thermoplastic resin composition of the present invention has the effect of well realizing the required properties without lowering the original properties thereof.

[0258]

[0259] thermoplastic resin composition

[0260] 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.

[0261]

[0262] 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.

[0263]

[0264] 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.

[0265]

[0266] Method for producing a thermoplastic resin composition

[0267] The method for producing a thermoplastic resin composition of the present invention comprises the steps of mixing and extruding (a) 15.5 to 26 wt% of a polyamide resin, (b) 9.5 to 17 wt% of a poly(arylene ether) resin, (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin, (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers, (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant, (f) 6.5 to 20.5 wt% of a metal silicate, (g) 15.5 to 38.5 wt% of glass fiber, and (h) 4.5 to 10 wt% of a flame retardant, characterized in that 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. It forms ceramics in the event of an unexpected high-temperature flame and the resulting pressure, thereby delaying flame propagation, thereby ensuring the safety of property and life, and is environmentally friendly.

[0268] 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 polyamide resin do not occur.

[0269] 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.

[0270] The thermoplastic resin composition obtained through the above mixing and extrusion can preferably be provided in the form of pellets.

[0271]

[0272] flame retardant composition

[0273] The flame retardant composition of the present invention is characterized by including a metal phosphorus flame retardant, a metal silicate, glass fiber, and a flame retardant, and in this case, while having excellent flame retardancy and insulating properties, it forms ceramics 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 has an environmentally friendly effect in that it produces almost no toxic gases during thermal decomposition and does not release environmental hormones.

[0274]

[0275] The flame retardant composition may include, for example, 8.5 to 21.3 wt% of a metal phosphorus-based flame retardant, 11.5 to 40 wt% of a metal silicate, 27 to 56 wt% of a glass fiber, and 6.5 to 17 wt% of a flame retardant based on the total weight thereof, preferably 9.5 to 21 wt% of a metal phosphorus-based flame retardant, 14 to 35 wt% of a metal silicate, 33 to 55.5 wt% of a glass fiber, and 7.5 to 16 wt% of a flame retardant, and more preferably 11 to 20.5 wt% of a metal phosphorus-based flame retardant, 17 to 30 wt% of a metal silicate, 40 to 55 wt% of a glass fiber, and 9 to 14 wt% of a flame retardant, and within this range, a ceramic having excellent flame retardancy and insulating properties is formed when an unexpected ultra-high temperature flame and pressure are generated, thereby preventing flame retardancy. By delaying propagation, safety is ensured even in the event of thermal runaway, and it has an environmentally friendly effect as it produces almost no toxic gases and does not release environmental hormones during thermal decomposition.

[0276]

[0277] The above flame retardant composition is thermally decomposed into a metal phosphate component when a high-temperature flame of 1200°C or higher and pressure generated thereby occur, and the metal phosphate component combines with metal silicate and glass fiber 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.

[0278]

[0279] The present flame retardant composition includes the contents of the thermoplastic resin composition described above, and is omitted here to avoid redundant description.

[0280]

[0281] molded products

[0282] 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.

[0283] 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.

[0284] The above electric vehicle battery component may be, for example, a plastic upper cover, module housing, or busbar of an electric vehicle battery.

[0285]

[0286] 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) 15.5 to 26 wt% of a polyamide resin, (b) 9.5 to 17 wt% of a poly(arylene ether) resin, (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin, (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of an aromatic vinyl elastomer and an olefin elastomer, (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant, (f) 6.5 to 20.5 wt% of a metal silicate, (g) 15.5 to 38.5 wt% of a glass fiber, and (h) 4.5 to 10 wt% of a flame retardant, and the step of injecting the manufactured pellet to manufacture a molded article, wherein the mixing and extrusion are performed by mixing a mixing block. It is characterized by the use of extruders with nine or more extruders. In this case, while possessing excellent flame retardancy and insulation properties, it forms a ceramic in the event of unexpected ultra-high-temperature flames and resulting pressure, thereby delaying flame propagation, thereby ensuring the safety of property and life even in the event of thermal runaway, and is environmentally friendly.

[0287]

[0288] 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.

[0289]

[0290] 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.

[0291]

[0292] The present invention will be described with reference to the drawings below.

[0293] 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.

[0294] 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.

[0295] 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.

[0296] 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.

[0297] As a specific example, at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, modified poly(arylene ether) resin, aromatic vinyl elastomer and olefin elastomer, a metal phosphorus flame retardant, a flame retardant, and an additive including a lubricant and an antioxidant may be injected into the main inlet, metal silicate may be injected into the auxiliary inlet 1, and glass fiber may be injected into the auxiliary inlet 2. In this case, there is an advantage in that the mixture is uniformly mixed, and there is an excellent property balance, electrical insulation, flame retardancy, and flame retardancy during thermal runaway when an ultra-high temperature flame and pressure are generated accordingly.

[0298] As another example, at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, modified poly(arylene ether) resin, aromatic vinyl elastomer, and olefin elastomer, and an additive may be injected into the main inlet, a metal phosphorus flame retardant and a flame retardant may be injected into the auxiliary inlet 1, and a metal silicate and glass fiber may be injected into the auxiliary inlet 2. In this case, there is an advantage in that they are uniformly mixed, and thus have excellent properties such as a balance of physical properties, electrical insulation, flame retardancy, and flame retardancy in the event of thermal runaway when an ultra-high temperature flame and pressure are generated accordingly.

[0299] As another example, at least one selected from the group consisting of polyamide resin, poly(arylene ether) resin, modified poly(arylene ether) resin, and aromatic vinyl elastomer and olefin elastomer may be injected into the main inlet, and a portion of a metal phosphorus flame retardant, metal silicate, glass fiber, flame retardant, and additives may be injected into the auxiliary inlet 1, and the remainder may be injected into the auxiliary inlet 2. In this case, there is an advantage of uniform mixing, excellent physical property balance, electrical insulation, flame retardancy, and flame retardancy when ultra-high temperature flames and pressure are generated accordingly.

[0300]

[0301] 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°.

[0302] 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.

[0303] 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 metal silicate and glass fiber, the compatibility of the composition, etc. are further improved, thereby providing a thermoplastic resin composition of higher quality.

[0304] 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.

[0305]

[0306] 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.

[0307]

[0308] [Example]

[0309] The materials used in the following examples and comparative examples are as follows.

[0310] * (a) polyamide resin

[0311] - (a-1) PA6: Polyamide 6 resin (relative viscosity: 2.2)

[0312] - (a-2) PA66: Polyamide 66 resin (relative viscosity: 2.4)

[0313] - (a-3) PA56: Polyamide 56 resin (relative viscosity: 2.5)

[0314] * (b) poly(arylene ether) resin

[0315] - (b-1) PPE: Poly(2,6-dimethyl-1,4-phenylene) ether (intrinsic viscosity: 35~42 dl / g)

[0316] * (c) Modified poly(arylene ether) resin

[0317] - (c-1) FA-g-PPO: Fumaric acid grafted polyphenylene ether (g-farm, SPO2-ZA)

[0318] * (d) Olefin elastomer

[0319] - (d-1) MAH-g-POE: Maleic anhydride graft olefin elastomer (DOW, FUSABOND MN493D)

[0320] * (e) Metal-based flame retardants

[0321] - (e-1) ADP: Aluminum diethyl phosphinate (Clariant's OP1230)

[0322] * (f) metal silicates

[0323] - (f-1) Kaolin: Silicate containing Al

[0324] - (f-2) Mica: Silicate containing Al

[0325] - (f-3) Wollastonite: Silicate containing Ca

[0326] * (f') Ceramic unformed metal silicate

[0327] - (f'-1) Talc: Silicate containing Mg

[0328] * (g) glass fiber

[0329] - (g-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.

[0330] * (h) Flame retardant

[0331] - (h-1) RDX: Resorcinol bis (2,6-dixylenyl phosphate)

[0332] * (i) Additives

[0333] - Active ingredient: EP184 (Hanyang Chemical) 0.25 wt%

[0334] - Antioxidant: 0.25 wt% of a mixture of IR1010 and AO-412S

[0335]

[0336] Examples 1 to 10 and Comparative Examples 1 to 8

[0337] Polyamide resin, poly(arylene ether) resin, modified poly(arylene ether) resin, olefin elastomer, metal phosphorus flame retardant, metal silicate, glass fiber, flame retardant, and additives were melt-mixed and extruded at a temperature of 220 to 310°C and a rotation speed (rpm) of 150 to 300 rpm using a twin-screw extruder (T40 from SM) with 9 or more mixed blocks in the amounts shown in Tables 1 and 2 below to produce pellets, and the pellets were then used to produce test specimens for evaluation using an injection molding machine (80 tons from Engel). The physical properties of the produced specimens were measured after leaving them at room temperature for 48 hours or more, and are shown in Tables 1 and 2 below.

[0338] At this time, the twin-screw extruder has two or more total input ports, and polyamide resin, poly(arylene ether) resin, modified poly(arylene ether) resin, olefin elastomer, metal phosphorus flame retardant, flame retardant, and additives are input into the main input port, metal silicate is input into auxiliary input port 1, and glass fiber is input into auxiliary input port 2.

[0339]

[0340] [Example Exam]

[0341] The properties of the specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 8 were measured in the following manner, and the results are shown in Tables 1 and 2 below.

[0342]

[0343] Measurement method

[0344] * Flame retardancy: Measured by the UL 94 V test (Vertical Burning Test) using injection specimens of 127 mm x 12.7 mm x 1.5 mm.

[0345] * CTI (Comparative Tracking Index): Based on IEC 60112, the voltage at which a short - cut occurs when 50 drops of electrolyte solution fall on a 3 - mm - thick specimen was calculated, and the PLC (Performance Level Category) grade was assigned as shown in Table 3 below based on CTI.

[0346] Tracking index(volts)PLC grade600 ≤ TI0400 ≤ TI <6001250> ≤ TI <4002175> ≤ TI <2503100> ≤ TI < 17540 ≤ TI < 1005

[0347] * 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.

[0348] Classification (weight%) Example 12345678910 (a-1) PA620 (a-2) PA6620 2020 2319.5 212220 (a-3) PA5620 (b-1) PPE 13.5 13.5 13.5 13.5 13.5 13.5 15.5 1213.5 11.5 13.5 (c-1) FA-g-PPO 3333333334 (d-1) MAH-g-POE 2222222221 (e-1) ADP 101010101010101012710 (f-1) Kaolin 1515151017151515 (f-2) Mica 15 (f-3) Wollastonite 15 (f'-1) Talc (g-1) Glass fiber 30303030303030253330(h-1) RDX 6666666866(i) Additive 0.50.50.50.50.50.50.50.50.50.50.5 Water resistance CTI (PLC grade) 1111111111 Flame retardancy V-0V-0V-0V-0V-0V-0V-0V-0V-0V-0 Fire resistance performance Time (sec.) 600 sec or more 600 sec or more 600 sec or more 600 sec or more 600 sec or more 600 sec or more 600 sec or more 600 sec or more 600 sec or more

[0349] Classification (weight %) Comparison Example 12345678 (a-1) PA6 (a-2) PA66 2020 29.128.12011.119.520.5 (a-3) PA56 (b-1) PPE 13.513.519.418.413.57.41314 (c-1) FA-g-PPO 33333380 (d-1) MAH-g-POE 22222208 (e-1) ADP 314101010101010 (f-1) Kaolin 1515252151311 (f-2) Mica (f-3) Wollastonite (f'-1) Talc 15 (g-1) Glass fiber 303053030453030 (h-1) RDX132666666(i) Additive 0.50.50.50.50.50.50.50.5 Water CTI (PLC grade) 00011---Flame retardancy V-1V-2V-0V-1V-1---Fire resistance performance time (sec.) 50600 seconds or more 10030060---

[0350] -: Properties cannot be measured because extrusion is not possible.

[0351] As shown in Tables 1 and 2 above, the thermoplastic resin compositions of the present invention (Examples 1 to 10) have excellent flame retardancy of V-0 grade or higher compared to Comparative Examples 1 to 8, and have excellent insulation properties of PLC grade 1 or higher as evaluated based on CTI, and when a high-temperature flame of 1200 ℃ and the resulting pressure are generated, 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 the safety of 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.

[0352] Specifically, Comparative Example 1, which contained a small amount of (e-1) ADP and an excessive amount of (h-1) RDX, had poor flame retardancy and very poor fire resistance time, and Comparative Example 2, which contained an excessive amount of (e-1) ADP and a small amount of (h-1) RDX, had poor flame retardancy.

[0353] In addition, Comparative Example 3, which contained an excessive amount of (f-1) kaolin and a small amount of (g-1) glass fiber, had poor fire resistance time, and Comparative Example 4, which contained a small amount of (f-1) kaolin, had reduced flame retardancy and fire resistance time.

[0354] In addition, Comparative Example 5 including (f'-1) talc had poor flame retardancy and no ceramic formation, resulting in very poor fire resistance time.

[0355] In addition, Comparative Example 6 containing an excess of (g-1) glass fiber, Comparative Example 7 containing an excess of (c-1) fumaric acid grafted polyphenylene ether resin and not containing (d-1) maleic anhydride grafted olefin elastomer, and Comparative Example 8 containing an excess of (d-1) maleic anhydride grafted olefin elastomer and not containing (c-1) fumaric acid grafted polyphenylene ether resin were difficult to extrude.

[0356]

[0357] As shown in the following Figure 4, when a 1200°C flame formed with oxygen and propane gas was applied to a specimen manufactured from a thermoplastic resin composition according to Example 1 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 for 600 seconds or more, indicating that the fire resistance time was greatly improved.

[0358] On the other hand, as shown in Fig. 5 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 5 based on the Torch and Grit evaluation of UL 2596, it was confirmed that a hole was created in just 60 seconds without ceramics being formed.

[0359]

[0360] In conclusion, the thermoplastic resin composition comprising a polyamide resin according to the present invention; a poly(arylene ether) resin; a modified poly(arylene ether) resin; at least one selected from the group consisting of an aromatic vinyl elastomer and an olefin elastomer; a metal phosphorus flame retardant; a metal silicate; glass fiber; and a flame retardant in a predetermined amount 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 for property and life even in the event of thermal runaway, and confirming an environmentally friendly effect.

Claims

1. (a) 15.5 to 26 wt% of polyamide resin; (b) 9.5 to 17 wt% of poly(arylene ether) resin; (c) 2 to 5.5 wt% of modified poly(arylene ether) resin; (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers; (e) 5.5 to 12.5 wt% of a metal-based flame retardant; (f) 6.5 to 20.5 wt% of metal silicate; (g) 15.5 to 38.5 wt% of glass fiber; and (h) characterized by comprising 4.5 to 10 wt% of a flame retardant; Thermoplastic resin composition.

2. In paragraph 1, The above (c) modified poly(arylene ether) resin is characterized in that it includes a poly(arylene ether) resin modified with an unsaturated carboxylic acid or an anhydride thereof. Thermoplastic resin composition.

3. In paragraph 1, The above aromatic vinyl elastomer is characterized in that it includes at least one selected from 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 (SEPS) copolymer, styrene-ethylene-ethylene-butadiene-styrene (SEEBS), styrene-ethylene-ethylene-propylene-styrene (SEEPS), styrene-isoprene-butadiene (SIBS), and modified polymers thereof. Thermoplastic resin composition.

4. In paragraph 1, The above olefin elastomer is characterized in that it is at least one selected from among high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-butene copolymer, ethylene-octene copolymer, and modified polymers thereof. Thermoplastic resin composition.

5. In paragraph 1, The above (f) metal silicate is characterized in that it contains Al, Ca or a mixture thereof. Thermoplastic resin composition.

6. In paragraph 1, The above (f) metal silicate is characterized in that it includes at least one selected from the group consisting of kaolin, kaolinite, pyrophyllite, mica, feldspar, spodumene, petalite, and wollastonite. Thermoplastic resin composition.

7. In paragraph 1, The above (f) metal silicate is characterized in that it is a magnesium-free silicate. Thermoplastic resin composition.

8. In paragraph 1, The above (g) glass fiber is characterized in that it has an average particle diameter of 3 to 25 ㎛ and an average length of 1 to 10 mm. Thermoplastic resin composition.

9. In paragraph 1, The above (h) 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. [Correction pursuant to Article 91 of the Rules, July 4, 2025] In the first paragraph, 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. Thermoplastic resin composition.

11. In paragraph 1, The thermoplastic resin composition is characterized in that the comparative tracking index (CTI) is measured using a specimen with a thickness of 3 mm according to IEC 60112 and the grade according to the PLC (Performance Level Category) classification is 1 or higher. Thermoplastic resin composition.

12. (a) a step of mixing and extruding 15.5 to 26 wt% of a polyamide resin, (b) 9.5 to 17 wt% of a poly(arylene ether) resin, (c) 2 to 5.5 wt% of a modified poly(arylene ether) resin, (d) 0.5 to 4.5 wt% of at least one selected from the group consisting of aromatic vinyl elastomers and olefin elastomers, (e) 5.5 to 12.5 wt% of a metal phosphorus flame retardant, (f) 6.5 to 20.5 wt% of a metal silicate, (g) 15.5 to 38.5 wt% of glass fiber, and (h) 4.5 to 10 wt% of a flame retardant, The above mixing and extrusion are characterized in that they 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 metal-based flame retardant, a metal silicate, glass fiber, and a flame retardant. Flame retardant composition.

14. In paragraph 13, The flame retardant composition is characterized in that it comprises 8.5 to 21.3 wt% of a metal-based flame retardant, 11.5 to 40 wt% of a metal silicate, 27 to 56 wt% of a glass fiber, and 6.5 to 17 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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