Poly(arylene ether) resin composition, method for producing same and molded article containing same

Abstract

The present disclosure relates to a poly(arylene ether) resin composition, a method for producing the same, and a molded article containing the same, and more specifically, to a poly(arylene ether) resin composition containing 100 parts by weight of a base resin containing (a-1) 75-95% by weight of a poly(arylene ether) resin and (a-2) 5-25% by weight of a polystyrene resin, (b) 12-17 parts by weight of two or more organic phosphorus-based flame retardants having different phosphorus contents, (c) 10-40 parts by weight of glass fiber, (d) 0.5-5 parts by weight of pulverized mica, and (e) 1-4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05-3 μm, a method for producing the same, and a molded article containing the same. The present invention has the effect of providing a poly(arylene ether) resin composition having excellent mechanical properties such as impact strength, tensile strength, and bending strength, heat resistance, flame retardancy, and flame retardancy, a method for producing the same, and a molded article containing the same.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0110704 filed on September 1, 2022, and Korean Patent Application No. 10-2023-0087697, refiled on July 6, 2023 based thereon, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a poly(arylene ether) resin composition, a method for producing the same, and a molded article containing the same. More specifically, the present invention relates to a poly(arylene ether) resin composition that has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as heat resistance and flame retardancy, and also has excellent flame retardancy during thermal runaway, thereby ensuring safety, a method for producing the same, and a molded article containing the same. [Background technology]

[0003] Poly(arylene ether) resins are thermoplastics that have high glass transition temperatures, high dimensional stability, low specific gravity, hydrolytic stability, and good mechanical performance.

[0004] However, poly(arylene ether) resins, when used alone, have the drawback of requiring high processing temperatures and therefore poor molding properties. For this reason, they are used in the form of a blend with rubber-reinforced polystyrene, which contains rubber, an aromatic vinyl polymer. In particular, polyphenylene ether resins containing rubber-reinforced polystyrene are compatible across the entire range regardless of their respective contents, thus complementing each other's properties. Because of their excellent mechanical properties, they are widely used in various industrial fields, including products used under high heat, such as automotive parts, electrical and electronic parts, and building materials. Furthermore, in some applications requiring even better flexural modulus and flexural strength, poly(arylene ether) resins are reinforced with glass fiber.

[0005] However, molded articles made from these resin compositions have excellent physical properties, such as impact strength, tensile strength, appearance, and heat resistance, but generally suffer from the drawback of being flammable. In particular, when used as components in electric vehicle batteries, they require flame retardancy as well as flame retardancy in the event of thermal runaway for safety reasons. Thermal runaway, the main cause of fires in electric vehicle batteries, is a phenomenon in which stress is applied to battery cells due to various causes, generating heat. When the internal temperature of a battery rises above a certain level due to a short circuit, such as overvoltage or overdischarge, a fire breaks out. However, due to the high reactivity of lithium-ion batteries with water, fires cannot be easily extinguished with water.

[0006] To address this issue, flame retardancy and flame retardancy have been imparted to poly(arylene ether) resin compositions containing poly(arylene ether) resins by incorporating both halogen-based and antimony-based compounds. Examples of halogen-based compounds include polybromodiphenyl ether, tetrabromobisphenol A, bromine-substituted epoxy compounds, and chlorinated polyethylene. Examples of antimony-based compounds include antimony trioxide and antimony pentoxide. While this method of imparting flame retardancy by incorporating both halogen and antimony compounds offers the advantages of easily achieving flame retardancy and causing little deterioration in physical properties, it also suffers from insufficient flame retardancy and the risk of fatal effects on the human body due to the hydrogen halide gas generated during processing. Flame retardants that do not contain halogens are called non-halogen flame retardants, and the most widely used non-halogen flame retardants are phosphorus-based flame retardants containing phosphorus. However, phosphorus-based flame retardants have significantly inferior flame retardancy compared to halogen-containing flame retardants, and therefore, in order to obtain excellent flame retardancy and flame retardancy, a large amount of phosphorus-based flame retardants must be added, which has the disadvantage of deteriorating the physical properties of the resin composition.

[0007] Although the above-mentioned methods can impart flame retardancy to the resin composition, there are problems in that the flame retardancy required to suppress thermal runaway in electric vehicle batteries is insufficient and the mechanical properties are deteriorated.

[0008] Therefore, there is a need to develop a resin composition that has excellent mechanical properties, heat resistance, and flame retardancy, as well as excellent flame retardancy during thermal runaway, and thus can meet the quality requirements for electrical components such as electric vehicle batteries. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2-187456 Summary of the Invention [Problem to be solved by the invention]

[0010] In order to solve the above-mentioned problems of the prior art, the present disclosure aims to provide a poly(arylene ether) resin composition that has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as excellent heat resistance and flame retardancy, and that also has excellent flame retardancy during thermal runaway, thereby ensuring safety.

[0011] Another object of the present disclosure is to provide a method for producing the poly(arylene ether) resin composition.

[0012] The present disclosure also provides molded articles made from the poly(arylene ether) resin compositions.

[0013] The above and other objects of the present disclosure can all be achieved by the disclosure set forth below. [Means for solving the problem]

[0014] In order to achieve the above object, the present disclosure provides I) a poly(arylene ether) resin composition comprising: (a-1) 100 parts by weight of a base resin containing 75 to 95% by weight of a poly(arylene ether) resin and (a-2) 5 to 25% by weight of a polystyrene resin; (b) 12 to 17 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents; (c) 10 to 40 parts by weight of glass fiber; (d) 0.5 to 5 parts by weight of pulverized mica; and (e) 1 to 4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm.

[0015] II) In the above I), the (a-1) poly(arylene ether) resin may preferably have an intrinsic viscosity of 0.2 to 0.8 dl / g.

[0016] III) In the above I) or II), the (a-2) polystyrene resin may preferably be general purpose polystyrene, high-impact polystyrene, or a mixture thereof.

[0017] IV) In the above I) to III), the (b) two or more organic phosphorus flame retardants having different phosphorus contents can preferably include (b-1) an organic phosphorus flame retardant having a phosphorus content of 5 to 15% by weight and (b-2) an organic phosphorus flame retardant having a phosphorus content of 20 to 35% by weight.

[0018] V) In the above I) to IV), the weight ratio (b-1:b-2) of the organophosphorus flame retardant (b-1) to the organophosphorus flame retardant (b-2) may preferably be 6:4 to 8.5:1.5.

[0019] VI) In the above I) to V), the (b-1) organophosphorus flame retardant having a phosphorus content of 5 to 15% by weight may preferably be one or more selected from the group consisting of bisphenol-A-bis(diphenyl phosphate) (BPADP), triphenyl phosphate (TPP), and resorcinol bisdiphenyl phosphate (RDP).

[0020] VII) In the above I) to VI), the (b-2) organophosphorus flame retardant having a phosphorus content of 20 to 35% by weight may preferably be at least one selected from the group consisting of dialkylphosphinates represented by the following chemical formula 3, diphosphinates represented by the following chemical formula 4, and polymers of at least one of these.

[0021] [ka]

[0022] [ka]

[0023] (In the above Chemical Formula 3 and Chemical Formula 4, R 1 , R 2 , R 3 and R 4 are each independently a linear or branched C1-C 10 Alkyl, C1-C 10 or H; R 5 is a linear or branched C1-C 10 Alkylene, C6-C 10 Arylene, C7-C 20 alkylarylene, or C7-C 20 M1 is an aryl alkylene; m+ and M2 m'+are each independently a nitrogen base compound (nitrogen-based compound) in which one or more atoms selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K are cationized, protonated, or cationized and protonated; m is an integer of 1 to 4; n is an integer of 1 to 4; and x is an integer of 1 to 4.

[0024] VIII) In the above I) to VII), the (c) glass fibers may preferably have an average particle size of 3 to 25 μm and an average length of 1 to 15 mm.

[0025] IX) In the above I) to VIII), the (d) pulverized mica may preferably have an average particle size of 50 to 150 μm.

[0026] X) In the above I) to IX), the poly(arylene ether) resin composition may preferably have a flame endurance time of 500 seconds or more, measured as the time it takes for a 100 mm × 100 mm × 1 mm injection test piece to be exposed to a flame of a size (125 mm (500 W)) specified in ASTM D5207 in accordance with the UL94 5V test until a hole or drip occurs in the test piece.

[0027] XI) In the above I) to X), the poly(arylene ether) resin composition preferably has a notched Izod impact strength of 7.7 kJ / m, measured using a 4 mm thick notched test piece in accordance with ISO 180A. 2 It may be more than that.

[0028] XII) In the above I) to XI), the poly(arylene ether) resin composition may preferably have a heat distortion temperature of 120°C or higher, measured on a 4 mm thick test piece under a stress of 1.8 MPa in accordance with ISO 75-2.

[0029] XIII) In the above I) to XII), the poly(arylene ether) resin composition may preferably contain one or more selected from the group consisting of a lubricant, an antioxidant, a compatibilizer, and an impact modifier.

[0030] The present disclosure also provides XIV) a method for producing a poly(arylene ether) resin composition, comprising the steps of kneading and extruding 100 parts by weight of a base resin containing 75 to 95% by weight of (a-1) a poly(arylene ether) resin and 5 to 25% by weight of (a-2) a polystyrene resin, (b) 12 to 17 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents, (c) 10 to 40 parts by weight of glass fiber, (d) 0.5 to 5 parts by weight of pulverized mica, and (e) 1 to 4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm, wherein the kneading and extrusion are carried out using an extruder having 9 or more kneading blocks.

[0031] The present invention also provides XV) a molded article comprising the poly(arylene ether) resin composition according to any one of I) to XIII). [Effects of the Invention]

[0032] According to the present invention, there are provided a poly(arylene ether) resin composition which has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as heat resistance and flame retardancy, and also has excellent flame retardancy during thermal runaway, and therefore can be used with high quality in electrical components such as battery components for electric vehicles, a method for producing the same, and a molded article containing the same.

[0033] In addition, the poly(arylene ether) resin composition of the present invention has excellent flame retardancy and mechanical properties, thereby ensuring safety and minimizing deformation due to vibration or impact of an automobile, and deterioration of physical properties due to changes in temperature or humidity. The present invention also provides a poly(arylene ether) resin composition, a method for producing the same, and a molded article containing the same. [Brief explanation of the drawings]

[0034] [Figure 1] FIG. 1 is a schematic diagram of an extruder equipped with nine or more kneading blocks for producing the poly(arylene ether) resin composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] The poly(arylene ether) resin composition of the present invention, its production method, and molded articles containing the same will be described in detail below.

[0036] The present inventors have confirmed that when a base resin containing predetermined amounts of poly(arylene ether) resin and polystyrene resin is combined with predetermined amounts of two or more organic phosphorus flame retardants having different phosphorus contents, glass fiber, pulverized mica, and an alkaline earth metal sulfate having a predetermined average particle size, a poly(arylene ether) resin composition can be provided that has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, heat resistance, and flame retardancy, as well as significantly improved flame retardancy during thermal runaway. Based on this, they have conducted further research and completed the present invention.

[0037] The poly(arylene ether) resin composition according to the present invention is described in detail below.

[0038] The poly(arylene ether) resin composition of the present invention is characterized by comprising: (a-1) 100 parts by weight of a base resin containing 75 to 95% by weight of a poly(arylene ether) resin and (a-2) 5 to 25% by weight of a polystyrene resin; (b) 12 to 17 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents; (c) 10 to 40 parts by weight of glass fiber; (d) 0.5 to 5 parts by weight of pulverized mica; and (e) 1 to 4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm. In this case, the composition has the advantages of being excellent in mechanical properties such as impact strength, tensile strength, and flexural strength, as well as heat resistance, flame retardancy, and flame retardancy during thermal runaway.

[0039] The poly(arylene ether) resin composition of the present invention will be described in detail below, with respect to each component.

[0040] (a-1) Poly(arylene ether) resin The (a-1) poly(arylene ether) resin may, for example, account for 75 to 95% by weight, preferably 75 to 90% by weight, more preferably 77 to 87% by weight, and even more preferably 77 to 82% by weight, of a total of 100 parts by weight of the base resin. Within this range, the resin has excellent mechanical properties, heat resistance, and flame retardancy, and also has excellent flame retardancy in the event of thermal runaway, thereby ensuring safety.

[0041] As used herein, thermal runaway refers to a condition in which a change in temperature causes changes in the environment that further accelerate that temperature change. That is, thermal runaway occurs when a mechanical process is caused by an increase in temperature, but the energy released as a result of that process increases the temperature, accelerating the process.

[0042] The (a-1) poly(arylene ether) resin may be, for example, a homopolymer or copolymer containing units of the following Chemical Formula 1 or Chemical Formula 2:

[0043] [ka]

[0044] [ka]

[0045] 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, and each independently or simultaneously represents hydrogen, chlorine, bromine, iodine, alkyl, allyl, phenyl, alkylbenzyl, chloroalkyl, bromoalkyl, cyanoalkyl, cyano, alkoxy, phenoxy, or a nitro group, and Ar is an arylene group having 7 to 20 carbon atoms, and the alkoxy may be an alkoxy having 1 to 4 carbon atoms.

[0046] Preferably, R1, R2, R3, R4, R'1, R'2, R'3, and R'4 are substituents of an arylene group (Ar) or a phenylene group, each independently or simultaneously representing hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy, or a nitro group, and Ar is an arylene group having 7 to 20 carbon atoms.

[0047] Examples of the homopolymer of the (a-1) poly(arylene ether) resin include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, and poly(2,6-dimethoxy-1,4-phenylene) ether. The poly(2,6-dichloromethyl-1,4-phenylene)ether may be one or more selected from the group consisting of poly(2,6-dibromomethyl-1,4-phenylene)ether, poly(2,6-diphenyl-1,4-phenylene)ether, poly(2,6-diphenyl-1,4-phenylene)ether, and poly(2,5-dimethyl-1,4-phenylene)ether. In this case, the poly(2,6-dichloromethyl-1,4-phenylene)ether has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, and also has excellent processability, thereby providing the advantage of improved appearance quality.

[0048] In addition, the poly(arylene ether) resin copolymer may be, for example, one or more selected from the group consisting of 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. In this case, the copolymer has excellent mechanical properties such as impact strength and tensile strength, and is also excellent in processability, thereby providing the advantage of improved appearance quality.

[0049] The (a-1) poly(arylene ether) resin may preferably be a polyphenylene ether resin.

[0050] The (a-1) poly(arylene ether) resin may have a weight-average molecular weight of, for example, 10,000 to 100,000 g / mol, preferably 10,000 to 70,000 g / mol, and more preferably 15,000 to 45,000 g / mol. Within this range, the resin has the effect of providing excellent processability and a good balance of physical properties.

[0051] In this description, unless otherwise specified, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, water breeze), and specifically, can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using chloroform as an eluent. In this case, as a specific measurement example, the following conditions can be used: solvent: chloroform, column temperature: 40°C, flow rate: 0.3 ml / min, sample concentration: 20 mg / ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35°C, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): Measurement can be performed under the conditions of OECD TG 118.

[0052] The (a-1) poly(arylene ether) resin may have an intrinsic viscosity of, for example, 0.2 to 0.8 dL / g, preferably 0.3 to 0.6 dL / g, and more preferably 0.35 to 0.5 dL / g. Within this range, the composition can maintain high mechanical properties such as impact strength and tensile strength while ensuring fluidity suitable for molding, and has the effect of having excellent compatibility with polystyrene resins.

[0053] In this description, unless otherwise specified, the intrinsic viscosity is a value measured at 25°C using an Ubbelohde viscometer after dissolving a sample to be measured in chloroform solvent at a concentration of 0.5 g / dl.

[0054] The (a-1) poly(arylene ether) resin may preferably be in the form of flakes or powder. In this case, it has the effect of providing excellent mechanical properties such as impact strength and tensile strength, as well as excellent processability and appearance quality.

[0055] In this description, the term "flake" refers to a thin flake shape broadly including scale-like and granular shapes, and as a specific example, the flake may be 1 to 20 μm thick and 0.05 to 1 mm long. As another example, the flake may be 1.5 to 500, preferably 2 to 100, more preferably 10 to 50, in terms of the ratio of length to depth (L / D).

[0056] The flakes described herein can be produced by conventional flake production methods in the art.

[0057] In this description, the thickness and length of the flakes can be measured through microscopic analysis.

[0058] The powder form can be produced by a conventional powder production method known in the art.

[0059] (a-2) Polystyrene resin The (a-2) polystyrene resin may be, for example, 5 to 25% by weight, preferably 10 to 25% by weight, more preferably 13 to 23% by weight, and even more preferably 18 to 23% by weight, based on 100 parts by weight of the base resin. Within this range, excellent mechanical properties such as impact strength, tensile strength, and flexural strength can be obtained.

[0060] The (a-2) polystyrene resin may be, for example, a general-purpose polystyrene resin, a high-impact polystyrene resin, or a mixture thereof, and preferably a high-impact polystyrene resin, which has the effects of being excellent in processability, dimensional stability, and tensile strength.

[0061] The general-purpose polystyrene resin may be, for example, a polymer obtained by polymerizing styrene alone, which has the effect of being excellent in processability.

[0062] The high impact polystyrene resin may be, for example, a rubber-reinforced polystyrene resin.

[0063] The rubber may be, for example, one or more selected from the group consisting of butadiene rubbers, isoprene rubbers, butadiene-styrene copolymers, and alkyl acrylate rubbers, and is preferably butadiene rubber, which has the advantage of improving impact strength.

[0064] For example, the rubber may be 3 to 25% by weight, preferably 6 to 14% by weight, and more preferably 8 to 12% by weight, relative to 100% by weight of the high-impact polystyrene resin. Within this range, the rubber has the effect of providing excellent impact strength and fluidity.

[0065] The rubber may have a volume average particle diameter of, for example, 0.1 to 20 μm, preferably 1.0 to 15 μm, and within this range, the rubber has the effect of being excellent in impact strength and flowability.

[0066] The rubber-reinforced polystyrene resin may preferably be at least one selected from the group consisting of high-impact styrene-butadiene copolymer (HIPS), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene copolymer (SB), styrene-isoprene copolymer (SI), styrene-isoprene-styrene copolymer (SIS), α-methylstyrene-butadiene copolymer, styrene-ethylene-propylene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-(ethylene-butylene / styrene copolymer)-styrene copolymer.

[0067] The rubber-reinforced polystyrene resin can be produced by, for example, bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof of rubber and an aromatic vinyl compound. The polymerization can be performed thermally or in the presence of a polymerization initiator. The polymerization initiator can be, for example, a peroxide initiator, an azo initiator, or a mixture thereof. The peroxide initiator can be preferably at least one selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and the azo initiator can be preferably azobisisobutyronitrile.

[0068] In this description, the volume average particle size can be measured by dissolving 3 g of high impact polystyrene resin in 100 ml of methyl ethyl ketone using a Coulter Counter LS230 instrument, and then measuring the dispersed rubber particles that are not dissolved in the resin by laser scattering.

[0069] The (a-2) polystyrene resin may have a flow index of, for example, 2 to 20 g / 10 min, preferably 3 to 15 g / 10 min, measured at 200°C under 5 kg in accordance with ASTM D1238. Within this range, the resin has the effect of exhibiting excellent processability and a good balance of physical properties.

[0070] (b) Two or more organic phosphorus flame retardants with different phosphorus contents The (b) two or more organic phosphorus-based flame retardants having different phosphorus contents may be, for example, 12 to 17 parts by weight, preferably 12.5 to 16 parts by weight, and more preferably 12.7 to 15.5 parts by weight, based on 100 parts by weight of the base resin. In this case, the effect of having excellent flame retardancy and excellent mechanical properties is achieved.

[0071] The (b) two or more organic phosphorus-based flame retardants having different phosphorus contents may, for example, include (b-1) an organic phosphorus-based flame retardant having a phosphorus content of 5 to 15 wt % and (b-2) an organic phosphorus-based flame retardant having a phosphorus content of 20 to 35 wt %, and preferably include (b-1) an organic phosphorus-based flame retardant having a phosphorus content of 7 to 12 wt % and (b-2) an organic phosphorus-based flame retardant having a phosphorus content of 22 to 30 wt %. In this case, the amount of flame retardant used can be reduced, while achieving excellent flame retardancy, excellent flame retardancy during thermal runaway, and excellent impact resistance.

[0072] In this description, the phosphorus content means the weight % of phosphorus calculated from the molecular weight of phosphorus contained in the molecular structure of the organophosphorus flame retardant.

[0073] The weight ratio (b-1:b-2) of the (b-1) organic phosphorus flame retardant to the (b-2) organic phosphorus flame retardant may be, for example, 6:4 to 8.5:1.5, preferably 7:3 to 8:2, and more preferably 7.5:2.5 to 8:2. Within this range, the flame retardancy, flame retardancy during thermal runaway, and mechanical properties are further improved.

[0074] The (b-1) organophosphorus flame retardant having a phosphorus content of 5 to 15 wt % may be, for example, one or more selected from the group consisting of bisphenol-A-bis(diphenyl phosphate) (BPADP), triphenyl phosphate (TPP), and resorcinol bisdiphenyl phosphate (RDP), and is preferably bisphenol-A-bis(diphenyl phosphate). In this case, it has the effect of imparting high flame retardancy with a small amount while maintaining mechanical properties.

[0075] The (b-2) organophosphorus flame retardant having a phosphorus content of 20 to 35 wt % may be, for example, one or more selected from the group consisting of dialkylphosphinate salts represented by the following chemical formula 3, diphosphinate salts represented by the following chemical formula 4, and polymers of any one or more thereof. In this case, high flame retardancy can be achieved with a small amount of flame retardant while maintaining mechanical properties, and there is an effect of excellent flame retardancy.

[0076] [ka]

[0077] [ka]

[0078] (In the above Chemical Formula 3 and Chemical Formula 4, R 1 , R 2 , R 3 and R 4 are each independently a linear or branched C1-C 10 Alkyl, C1-C 10 or H; R 5 is a linear or branched C1-C 10 Alkylene, C6-C 10 Arylene, C7-C20 alkylarylene, or C7-C 20 M1 is an aryl alkylene; m+ and M2 m'+ are each independently a nitrogen base compound in which one or more atoms selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K are cationized, protonated, or cationized and protonated; m is an integer of 1 to 4; n is an integer of 1 to 4; and x is an integer of 1 to 4.

[0079] In the above formulas 3 and 4, cycloalkyl may independently be preferably cyclohexyl or cyclohexadimethyl.

[0080] R 1 , R 2 , R 3 and R 4 may preferably each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or phenyl.

[0081] R 5 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.

[0082] M1 m+ and M2 m'+ may each preferably be independently one or more elements selected from the group consisting of Mg, Ca, Al, Ti and Zn.

[0083] R 1 and R 2 , and R3 and R 4 can be bonded to each other to form a ring with the adjacent phosphorus atom. 1 and R 2 , and R 3 and R 4 are bonded to each other to form a ring together with the adjacent phosphorus atom is a heterocycle having the phosphorus atom as a heteroatom constituting the ring, and the number of atoms constituting such a ring may be, for example, 4 to 20, preferably 5 to 16. The heterocycle having a phosphorus atom may be a bicyclo ring or may have a substituent.

[0084] The dialkylphosphinate salt represented by Chemical Formula 3 may preferably be at least one 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.

[0085] The diphosphinate salt represented by Chemical Formula 4 may preferably be at least one selected from the group consisting of calcium methylenebis(methylphosphinate), magnesium methylenebis(methylphosphinate), aluminum methylenebis(methylphosphinate), zinc methylenebis(methylphosphinate), calcium 1,4-phenylenebis(methylphosphinate), magnesium 1,4-phenylenebis(methylphosphinate), aluminum 1,4-phenylenebis(methylphosphinate), and zinc 1,4-phenylenebis(methylphosphinate).

[0086] The (b-2) organophosphorus flame retardant may more preferably be 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 further preferably be aluminum diethylphosphinate. In this case, high flame retardancy can be achieved with a small amount of flame retardant while maintaining mechanical properties, and excellent flame retardancy can be achieved.

[0087] The (b-2) organophosphorus flame retardant may have an average particle size of, for example, 0.1 to 100 μm, preferably 0.5 to 50 μm, and more preferably 1 to 40 μm. Within this range, there is an advantage in that the flame retardancy and mechanical properties are excellent.

[0088] In this description, the average particle size of an organophosphorus flame retardant means the number-average particle size determined from the frequency distribution of particle size and particle number measured using a laser diffraction particle size distribution analyzer, using a dispersion of the organophosphorus flame retardant dispersed in a medium such as water as a measurement sample.

[0089] The (b-1) organophosphorus flame retardant having a phosphorus content of 5 to 15% by weight may preferably be bisphenol A bis(diphenyl phosphate), and the (b-2) organophosphorus flame retardant having a phosphorus content of 20 to 35% by weight may preferably be aluminum diethyl phosphinate. In this case, a synergistic effect is achieved in which excellent flame retardancy is exhibited even with a small amount of the flame retardant.

[0090] (c) Glass fiber The (c) glass fiber may be, for example, 10 to 40 parts by weight, preferably 15 to 35 parts by weight, and more preferably 20 to 30 parts by weight, based on 100 parts by weight of the base resin. Within this range, the resin has the advantages of excellent mechanical properties, excellent heat resistance, flame retardancy, and flame retardancy during thermal runaway, as well as excellent appearance properties of the final product.

[0091] The (c) glass fiber may have an average particle size of, for example, 3 to 25 μm, preferably 5 to 20 μm, and more preferably 7 to 15 μm. Within this range, the mechanical strength with the resin is improved, and the appearance characteristics of the final product are excellent.

[0092] The (c) glass fiber may have an average length of, for example, 1 to 15 mm, preferably 2 to 10 mm, and more preferably 3 to 6 mm. Within this range, the mechanical strength with the resin is improved, and the appearance characteristics of the final product are excellent.

[0093] The (c) glass fiber may be, for example, chopped glass fiber, which has the advantage of excellent compatibility.

[0094] In this description, the chopped glass fiber is not particularly limited as long as it is chopped fiber glass commonly used in the technical field to which the present invention pertains.

[0095] The (c) glass fiber may have, for example, an aspect ratio (L / D), which is the ratio of the average length (L) to the average diameter (D), of 200 to 550, preferably 220 to 450, more preferably 250 to 350, and even more preferably 270 to 320. Within this range, the fiber has excellent compatibility with resins, which has the advantage of providing excellent surface appearance.

[0096] In this description, the average particle size, average length, aspect ratio, etc. of glass fibers are calculated by measuring 30 pieces through a microscopic analysis method and averaging the results.

[0097] The (c) glass fiber may be surface-treated with, for example, a silane-based compound or a urethane-based compound, and preferably, surface-treated with one or more surface treatment agents selected from the group consisting of aminosilane-based compounds, epoxysilane-based compounds, and urethane-based compounds. More preferably, the glass fiber is surface-treated with an aminosilane-based compound. In this case, a chemical bond is formed with the poly(arylene ether) resin, improving dispersibility and surface wettability. As a result, the mechanical properties of the resin composition, including the tensile strength, are improved.

[0098] For example, the surface treatment agent may be contained in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.1 to 0.8% by weight, and even more preferably 0.2 to 0.5% by weight, relative to a total of 100% by weight of the surface-treated glass fiber (glass fiber + surface treatment agent). Within this range, the effect of achieving excellent mechanical properties, balance of physical properties, and appearance of the final product is achieved.

[0099] The aminosilane compound is not particularly limited as long as it is an aminosilane that is generally used as a coating agent for glass fibers. For example, it may be at least one selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, γ-acetoacetatepropyltrimethoxysilane, γ-acetoacetatepropyltriethoxysilane, γ-cyanoacetyltrimethoxysilane, γ-cyanoacetyltriethoxysilane, and acetoxyacetotrimethoxysilane. In this case, the compound has the effect of providing excellent mechanical properties and heat resistance, as well as excellent surface properties of the injection molded product.

[0100] The epoxy silane compound is not particularly limited as long as it is an epoxy silane that is generally used as a coating agent for glass fibers. For example, it 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. In this case, it has the effect of providing excellent mechanical properties and heat resistance, as well as excellent surface properties of the extruded product.

[0101] The (c) glass fiber may be appropriately selected and used within the range commonly used in the art, as long as it complies with the definition of the present invention, and the cross-sectional shape, such as cylindrical or elliptical, is not particularly limited.

[0102] (d) Crushed mica The (d) crushed mica may be, for example, 0.5 to 5 parts by weight, preferably 0.7 to 4 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1 to 3 parts by weight, based on 100 parts by weight of the base resin. Within this range, excellent mechanical properties, heat resistance, flame retardancy, and flame retardancy during thermal runaway can be achieved.

[0103] For purposes of this description, crushed mica may be defined as mica that has been crushed one or more times to an average particle size of 500 μm or less.

[0104] The (d) pulverized mica may have an average particle size of, for example, 50 to 150 μm, preferably 70 to 130 μm, and more preferably 80 to 110 μm. Within this range, the compatibility with resins is excellent, improving all of the mechanical properties, heat resistance, flame retardancy, and flame retardancy during thermal runaway, and providing the effect of excellent appearance quality of molded products.

[0105] The (d) crushed mica may have an aspect ratio of, for example, 40 to 60, preferably 45 to 55, and within this range, the molded product has the effect of being excellent in appearance quality.

[0106] In this description, the aspect ratio of crushed mica refers to the ratio of the major axis to the minor axis in a two-dimensional model.

[0107] In this description, the average particle size, average length, and aspect ratio of pulverized mica are calculated as the average value of 30 particles measured by microscopic analysis.

[0108] (e) Alkaline earth metal sulfates with an average particle size of 0.05 to 3 μm The alkaline earth metal sulfate (e) having an average particle size of 0.05 to 3 μm may be, for example, 1 to 4 parts by weight, preferably 1.2 to 3.8 parts by weight, and more preferably 1.4 to 3.6 parts by weight, based on 100 parts by weight of the base resin. Within this range, the flame retardancy during thermal runaway is improved, while excellent impact resistance is achieved.

[0109] The (e) alkaline earth metal sulfate may have an average particle size of, for example, 0.05 to 3 μm, preferably 0.1 to 2.5 μm, more preferably 0.5 to 2 μm, and even more preferably 0.7 to 1.5 μm. Within this range, the compatibility is excellent, and this has the effect of improving mechanical properties, heat resistance, flame retardancy, and flame retardancy during thermal runaway.

[0110] The alkaline earth metal of the (e) alkaline earth metal sulfate is, for example, one or more elements selected from the group consisting of elements in Group II of the periodic table, preferably one or more elements selected from the group consisting of calcium, barium, strontium, and magnesium, more preferably calcium, barium, or a mixture thereof, and even more preferably barium, which has the effect of improving mechanical properties.

[0111] As a preferred example, the (e) alkaline earth metal sulfate may be barium sulfate, in which case there is an effect of improving mechanical properties.

[0112] The (e) alkaline earth metal sulfate may be contained in an amount greater than that of the (d) pulverized mica, and in this case, the mechanical properties such as tensile strength, flexural strength, and impact strength, and heat resistance may be further improved.

[0113] Poly(arylene ether) resin composition The poly(arylene ether) resin composition preferably has a flame endurance time of 500 seconds or more, more preferably 550 seconds or more, and even more preferably 600 seconds or more, as measured by applying a flame of 125 mm (500 W) as specified in ASTM D5207 to an injection test specimen of 100 mm × 100 mm × 1 mm in accordance with the UL94 5V test, as the time it takes for the flame to develop a hole or drip in the test specimen. Within this range, the composition has an excellent balance of physical properties and excellent flame retardancy during thermal runaway in electrical components such as battery components for electric vehicles, thereby ensuring safety.

[0114] The poly(arylene ether) resin composition preferably has a notched Izod impact strength of 7.7 kJ / m, measured at room temperature using a 4 mm thick notched test piece in accordance with ISO 180A. 2 More preferably, 8.5 kJ / m 2 More preferably, 9 kJ / m 2 More preferably, 9 to 13 kJ / m 2 Within this range, the material has an excellent balance of physical properties and excellent mechanical strength, and therefore, when applied to electrical components, it is possible to minimize changes due to external environments such as automobile vibrations.

[0115] In this description, the notched Izod impact strength is measured in accordance with ISO 180A using an IT from Toyoseiki Co., Ltd. on a notched test specimen having a thickness of 4 mm.

[0116] In this description, normal temperature may be a point within the range of 20±5°C.

[0117] The poly(arylene ether) resin composition preferably has a tensile strength of 67 MPa or more, more preferably 73 MPa or more, even more preferably 80 MPa or more, still more preferably 90 MPa or more, and particularly preferably 90 to 120 MPa, as measured in accordance with ISO 527 using a test piece 4 mm thick at a measurement speed of 5 mm / min. Within this range, the composition has an excellent balance of physical properties and excellent mechanical strength, and therefore, when applied to electrical components, it is possible to minimize deformation due to vibrations and impacts of an automobile and deterioration of physical properties due to changes in temperature and humidity.

[0118] In this description, the tensile strength is measured in accordance with ISO 527 using a UTM (manufacturer: Instron, model name: 4466) at a cross head speed of 5 mm / min.

[0119] The poly(arylene ether) resin composition preferably has a flexural strength of 110 MPa or more, more preferably 115 MPa or more, even more preferably 125 MPa or more, still more preferably 130 MPa or more, and particularly preferably 130 to 170 MPa, as measured in accordance with ISO 527 using a test piece 4 mm thick at a measurement speed of 2 mm / min. Within this range, the composition has an excellent balance of physical properties and excellent mechanical strength, which has the effect of minimizing changes due to external environments such as automobile vibrations when used in electrical components.

[0120] The poly(arylene ether) resin composition may preferably have a heat distortion temperature of 120°C or higher, more preferably 125°C or higher, even more preferably 130°C or higher, still more preferably 135°C or higher, and particularly preferably 135 to 150°C, as measured on a 4 mm thick test piece under a stress of 1.8 MPa in accordance with ISO 75-2. Within this range, the composition has the advantage of having excellent balance of physical properties and heat resistance.

[0121] For example, the poly(arylene ether) resin composition may have a flame retardancy of V-0 or higher as measured in accordance with the UL94 standard (Vertical Burning Test) using an injection molded specimen measuring 127 mm × 12.7 mm × 1.5 mm. In this case, the composition has the advantages of having an excellent balance of physical properties, heat resistance, and flame retardancy during thermal runaway.

[0122] The poly(arylene ether) resin composition may contain, for example, one or more additives selected from the group consisting of lubricants, antioxidants, compatibilizers, and impact modifiers.

[0123] The total amount of the above additives may be, for example, 5 to 10 parts by weight, preferably 6 to 9.5 parts by weight, and more preferably 7 to 9 parts by weight, per 100 parts by weight of the base resin. Within this range, the mechanical properties, heat resistance, and flame retardancy are excellent, as well as the flame retardancy during thermal runaway is advantageously excellent.

[0124] In addition to the additives, the poly(arylene ether) resin composition may further contain one or more selected from the group consisting of a flame retardant aid, a plasticizer, a heat stabilizer, an anti-dripping agent, a light stabilizer, a pigment, a dye, an inorganic additive (excluding glass fiber), and a carbon fiber, in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the base resin. Within this range, the inherent physical properties of the poly(arylene ether) resin composition described herein are not impaired, and the required physical properties can be effectively achieved.

[0125] Method for producing poly(arylene ether) resin composition The present invention provides a method for producing a poly(arylene ether) resin composition, comprising the steps of: (a-1) 100 parts by weight of a base resin containing 75 to 95% by weight of a poly(arylene ether) resin and 5 to 25% by weight of a polystyrene resin; (b) 12 to 17 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents; (c) 10 to 40 parts by weight of glass fiber; (d) 0.5 to 5 parts by weight of pulverized mica; and (e) 1 to 4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm; wherein the extrusion is carried out using an extruder having nine or more kneading blocks. This method offers the advantages of excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as excellent heat resistance, flame retardancy, and flame retardancy during thermal runaway.

[0126] The kneading and extrusion can be carried out at a barrel temperature within a range of, for example, 200 to 350°C, preferably 220 to 330°C, and more preferably 240 to 320°C. In this case, there are advantages that sufficient melt-kneading is possible while the throughput per unit time is high, and problems such as thermal decomposition of the resin component do not occur.

[0127] The kneading and extrusion can be carried out under conditions where the screw rotation speed is, for example, 100 to 500 rpm, preferably 150 to 400 rpm, and more preferably 200 to 350 rpm. Within this range, the throughput per unit time is high and the process efficiency is excellent.

[0128] The poly(arylene ether) resin composition obtained through the kneading and extrusion may be provided preferably in the form of pellets.

[0129] Molded product The molded article of the present invention is characterized by containing the poly(arylene ether) resin composition of the present invention, and in this case, has the advantages of being excellent in all of mechanical properties such as impact strength and tensile strength, heat resistance, electrical insulation, and flame retardancy.

[0130] The molded product may be formed by, for example, injection molding or extrusion molding.

[0131] The molded article can be used, for example, as an electrical component or a battery component.

[0132] The battery component may be, for example, a plastic upper cover, a module housing, or a busbar of an electric vehicle battery.

[0133] The method for producing a molded article described herein preferably includes the steps of kneading and extruding 100 parts by weight of a base resin containing (a-1) 75 to 95% by weight of a poly(arylene ether) resin and (a-2) 5 to 25% by weight of a polystyrene resin, (b) 12 to 17 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents, (c) 10 to 40 parts by weight of glass fiber, (d) 0.5 to 5 parts by weight of pulverized mica, and (e) 1 to 4 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm to produce poly(arylene ether) resin composition pellets, and injecting the produced pellets into a molded article, wherein the kneading and extrusion are carried out using an extruder with nine or more kneading blocks. This method has the advantages of excellent mechanical properties such as impact strength, tensile strength, and flexural strength, as well as excellent heat resistance, flame retardancy, and flame retardancy during thermal runaway.

[0134] The injection may be carried out by any method and under any conditions commonly used in the technical field to which the present invention pertains, and is not particularly limited, and may be appropriately selected and applied as needed.

[0135] In the description of the poly(arylene ether) resin composition, molded article, and method for producing the same described herein, other conditions not specifically stated (e.g., the configuration and specifications of the extruder and injector, extrusion and injection conditions, additives, etc.) are not particularly limited as long as they are within the range commonly used in the art, and can be appropriately selected as needed.

[0136] The present invention will now be described with reference to the drawings.

[0137] FIG. 1 below is a schematic diagram of an extruder equipped with nine or more kneading blocks for producing the poly(arylene ether) resin compositions described herein.

[0138] The type of extruder is not particularly limited, and any extruder commonly used in the industry may be appropriately selected. For example, a single-screw extruder having one screw or a multi-screw extruder having multiple screws may be used. In consideration of uniform mixing of materials, ease of processing, and economy, it is preferable to use a twin-screw extruder having two screws.

[0139] The extruder is composed of a feeder for supplying materials into a barrel, a screw for transporting and kneading the materials supplied into the barrel, and a die for extruding the kneaded materials, and the screw is composed of multiple screw elements to provide various functions.

[0140] The number of the raw material supplier may be one or more, and two or more may be provided selectively as needed. For example, a main inlet and a selective auxiliary inlet may be provided, and two or more auxiliary inlets may be provided as needed.

[0141] As a specific example, the base resin, two or more organic phosphorus flame retardants with different phosphorus contents, glass fiber, pulverized mica, and alkaline earth metal sulfate may be charged all at once into the main charging port. As another example, all of the components except for the two or more organic phosphorus flame retardants with different phosphorus contents may be charged into the main charging port, and the flame retardant may be charged into the auxiliary charging port.

[0142] As another example, all components except for two or more organic phosphorus flame retardants with different phosphorus contents may be fed into the main inlet, the two or more organic phosphorus flame retardants with different phosphorus contents may be fed into auxiliary inlet 1, and additives such as lubricants, antioxidants, compatibilizers, and impact modifiers may be fed into auxiliary inlet 2.

[0143] As yet another example, it is possible to charge the base resin into the main inlet, charge two or more organic phosphorus flame retardants with different phosphorus contents, glass fiber, crushed mica, and a portion of the alkaline earth metal sulfate into auxiliary inlet 1, and then charge the remaining amount into auxiliary inlet 2.

[0144] As another example, the base resin and alkaline earth metal sulfate may be fed into the main inlet, two or more organic phosphorus flame retardants with different phosphorus contents and crushed mica may be fed into auxiliary inlet 1, and glass fiber may be fed into auxiliary inlet 2.

[0145] The kneading block of the present invention is an example of the screw element, and specifically, is composed of a plurality of disks, preferably 3 to 7, 5 to 7, 3 to 5, or 4 to 5 disks, usually with a polygonal or elliptical cross section, and arranged continuously in the material transport direction. Furthermore, the phase angle of the disks in the kneading block (meaning the movement angle between the disks) is preferably 45 to 90°.

[0146] In addition, kneading blocks include forward kneading blocks that have the ability to transport, distribute, and mix materials, neutral kneading blocks that have only the ability to distribute and mix materials without the ability to transport materials, and backward kneading blocks that transport materials in the opposite direction to the transport direction.

[0147] The poly(arylene ether) resin composition according to the present invention may be produced by kneading and extruding the composition 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. It is effective to use kneading blocks in combination in the order of forward, perpendicular, and reverse flow relative to the resin flow direction. Depending on the mixing method, a combination of continuous or separated blocks can be used. In this case, the dispersibility of the glass fiber and pulverized mica, the compatibility of the composition, and the like can be further improved, thereby providing a poly(arylene ether) resin composition of even higher quality.

[0148] For example, nine or more of the kneading blocks may be arranged continuously, or, for another example, they may be arranged discontinuously between the screws. Specifically, three to six kneading blocks may be arranged continuously between the main inlet and auxiliary inlet 1, three to eight kneading blocks may be arranged continuously between auxiliary inlet 1 and auxiliary inlet 2, and two to five kneading blocks may be arranged between auxiliary inlet 2 and a discharge port (not shown). This arrangement offers the advantages of controlling local heat generation during melt-kneading, preventing thermal deformation of the raw materials, and preventing excessive breakage of the glass fibers, thereby preventing deterioration of mechanical properties, flame retardancy, and flame retardancy during thermal runaway.

[0149] Below, preferred examples are presented to help understand the present description, but the following examples are merely illustrative of the present description, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present description, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0150] [Example] The materials used in the following examples and comparative examples are as follows. *(a-1) Poly(arylene ether) resin: Poly(2,6-dimethyl-1,4-phenylene) ether (PPE; Bluestar LXR040) *(a-2): Polystyrene resin: HIPS (High Impact polystyrene) resin (Kumho Petrochemical Co., Ltd. HI450PG) *(b) Two or more organic phosphorus flame retardants with different phosphorus contents: (b-1) bisphenol A bis(diphenyl phosphate) (FCA's BPADP) with a phosphorus content of 9% by weight, (b-2) aluminum diethylphosphinate (Clariant's OP1230) with a phosphorus content of 25% by weight. *(c) Glass fiber: Chopped glass fiber with an average particle size of 10-13 μm and an average length of 3-4 mm, surface-treated with aminosilane (Owens Corning, 910A-13P) *(d) Crushed mica: Crushed mica with an average particle size of 90 μm and an aspect ratio of 50 (Kurary 200D) *(e-1) Sulfates of alkaline earth metals with an average particle size of 0.05 to 3 μm: Barium sulfate with an average particle size of 1 μm (Solvay's HD80) *(e-2) Sulfates of alkaline earth metals: Barium sulfate with an average particle size of 4 μm (Solvay's Blanc FIX G) *(f) Additives: A mixture of lubricant (Pentaerythritol Fatty Acid Ester), antioxidant (Tris(2,4-di-tert-butyl-phenyl)Phosphite and Pentaeryl thritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), compatibilizer (Fumari acid PPO), and impact modifier (Maleated, Styrene-ethylene-butylene Block copolymer rubber).

[0151] Examples 1 to 15 and Comparative Examples 1 to 14 (a-1) poly(arylene ether) resin, (a-2) polystyrene resin, (b-1) organophosphorus flame retardant with a phosphorus content of 9 wt%, (b-2) organophosphorus flame retardant with a phosphorus content of 25 wt%, (c) glass fiber, (d) crushed mica, (e) alkaline earth metal sulfate, and (f) additives were melt-blended and extruded into pellets in the amounts listed in Tables 1 to 4 using a twin-screw extruder (SM T40) with 10 mixing blocks at a temperature of 250 to 310°C and a rotation speed of 300 rpm. The pellets were then used to prepare test specimens for evaluation using an injector (Engel, 80 ton). The test specimens were left at room temperature for at least 48 hours, and their physical properties were measured. The results are shown in Tables 1 to 4.

[0152] In this case, the twin-screw extruder had a total of two or more inlets, and the base resin and alkaline earth metal sulfate were fed into the main inlet, two or more organic phosphorus flame retardants with different phosphorus contents and crushed mica were fed into auxiliary inlet 1, and glass fiber was fed into auxiliary inlet 2.

[0153] [Test example] The properties of the test specimens prepared in Examples 1 to 15 and Comparative Examples 1 to 14 were measured by the following methods, and the results are shown in Tables 1 to 4 below.

[0154] Measurement method *Tensile strength (MPa): According to ISO 527, a 4 mm thick test piece was measured at the break point after being pulled at a crosshead speed of 5 mm / min using a UTM (manufacturer: Instron, model name: 4466). *Flexural strength (MPa): Measured in accordance with ISO 527 using a UTM (manufacturer: Instron, model name: 4466) at a crosshead speed of 2 mm / min using a 4 mm thick test piece. *Impact strength (kJ / m 2): Izod impact strength was measured under standard conditions of constant temperature and humidity using IT equipment from Toyoseiki Co., Ltd. in accordance with ISO 180A. The test specimens were 4 mm thick and notched. *Heat distortion temperature (℃): The heat distortion temperature was measured in accordance with ISO 75-2 using a 4 mm thick test piece under a stress of 45 MPa. *Flame retardancy: Measured in accordance with the UL94 standard (Vertical Burning Test) using an injection test piece measuring 127mm x 12.7mm x 1.5mm. *Flame Endurance Time (seconds): A flame of the size specified in ASTM D5207 (125mm (500W)) was applied to a 100mm x 100mm x 1mm injection test specimen in accordance with the UL94 5V test, and the time it took for the flame to be applied until a hole or drip occurred in the specimen was measured. *Appearance evaluation: The appearance of the molded product was evaluated visually after injection at an injection temperature of 290-300°C, an injection speed of 50mm / sec, a holding pressure of 60bar, a holding time of 5sec, and a cooling time of 20sec. If there were no gas marks or unformed areas and the product was completely molded, it was evaluated as "excellent." If there were unformed areas or gas marks, and the appearance quality was reduced, it was evaluated as "poor."

[0155] [Table 1]

[0156] [Table 2]

[0157] [Table 3]

[0158] [Table 4]

[0159] As shown in Tables 1 to 4, the poly(arylene ether) resin compositions of the present invention (Examples 1 to 15) have excellent mechanical properties such as tensile strength, flexural strength, and impact strength, heat distortion temperature, heat resistance, and flame retardancy, as well as excellent fire resistance times of 500 seconds or more, compared to Comparative Examples 1 to 14, confirming the effect of excellent flame retardancy during thermal runaway of batteries.

[0160] Specifically, Comparative Example 1, which contained 3.13 parts by weight of one phosphorus-based flame retardant, had low flame retardancy and fire resistance time, while Comparative Example 2, which contained 7.5 parts by weight of one phosphorus-based flame retardant, had poor mechanical properties.

[0161] In addition, (d) Comparative Examples 3 and 4, which did not contain crushed mica, and Comparative Example 5, in which the contents of the two phosphorus-based flame retardants were below the range of the present invention, had poor flame retardancy and fire resistance time.

[0162] In addition, Comparative Example 6, in which the composition ratio of the base resin was outside the range of the present invention, had a reduced heat distortion temperature and fire resistance time, while Comparative Example 7, in which the content of the two flame retardants was excessive, had a very short fire resistance time and a low heat distortion temperature.

[0163] Furthermore, Comparative Example 8, which contained less (d) pulverized mica than the range of the present invention, had a very short fire resistance time and reduced flame retardancy, while Comparative Example 9, which contained more (d) pulverized mica than the range of the present invention, had reduced impact strength.

[0164] In addition, (e-1) Comparative Examples 10 and 11, in which the content of barium sulfate was outside the range of the present invention, also showed a shortened fire resistance time and were unable to prevent thermal runaway when applied to battery parts of electric vehicles.

[0165] In addition, Comparative Example 12 containing barium sulfate (e-2) whose average particle size was outside the range of the present invention, showed a shortened fire resistance time.

[0166] In addition, Comparative Example 13, which contained less than the range of (C) glass fiber within the range of the present invention, showed deterioration in all of the mechanical properties, heat distortion temperature, flame retardancy, and fire resistance time. Comparative Example 14, which contained more than the range of (C) glass fiber within the range of the present invention, showed excellent mechanical properties, heat distortion temperature, flame retardancy, and fire resistance time, but showed deterioration in fluidity, resulting in poor moldability and poor appearance of the molded product.

[0167] In conclusion, the poly(arylene ether) resin composition according to the present invention, which comprises a base resin containing predetermined amounts of poly(arylene ether) resin and polystyrene resin, two or more organic phosphorus flame retardants with different phosphorus contents, glass fiber, pulverized mica, and predetermined amounts of alkaline earth metal sulfates having a predetermined average particle size, has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, heat resistance, and flame retardancy, as well as excellent flame retardancy during thermal runaway, and has been confirmed to meet the physical properties required for electrical parts such as electric vehicle batteries.

Claims

1. 100 parts by weight of a base resin containing 75 to 85% by weight of (a-1) a poly(arylene ether) resin and 15 to 25% by weight of (a-2) a polystyrene resin; (b) 13.13 to 15 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents; (c) 12.5 to 37.5 parts by weight of glass fibers; (d) 1.25 to 4 parts by weight of crushed mica; (e) 1.5 to 3.5 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm, The poly(arylene ether) resin composition has a flame endurance time of 500 seconds or more, measured by applying a flame of 125 mm (500 W) as specified in ASTM D5207 to a 100 mm x 100 mm x 1 mm injection test specimen in accordance with the UL94 5V test, as the time it takes for a hole or drip to appear in the test specimen. Poly(arylene ether) resin compositions.

2. 2. The poly(arylene ether) resin composition according to claim 1, wherein the (a-1) poly(arylene ether) resin has an intrinsic viscosity of 0.2 to 0.8 dl / g.

3. The poly(arylene ether) resin composition according to claim 1, wherein the (a-2) polystyrene resin is general-purpose polystyrene, high-impact polystyrene, or a mixture thereof.

4. 2. The poly(arylene ether) resin composition according to claim 1, wherein the (b) two or more organic phosphorus-based flame retardants having different phosphorus contents include (b-1) an organic phosphorus-based flame retardant having a phosphorus content of 5 to 15 wt % and (b-2) an organic phosphorus-based flame retardant having a phosphorus content of 20 to 35 wt %.

5. The poly(arylene ether) resin composition according to claim 4, wherein the weight ratio (b-1:b-2) of the organic phosphorus flame retardant (b-1) to the organic phosphorus flame retardant (b-2) is 6:4 to 8.5:1.

5.

6. 5. The poly(arylene ether) resin composition according to claim 4, wherein the (b-1) organophosphorus flame retardant having a phosphorus content of 5 to 15 wt % is at least one selected from the group consisting of bisphenol-A-bis(diphenyl phosphate) (BPADP), triphenyl phosphate (TPP), and resorcinol bis diphenyl phosphate (RDP).

7. The poly(arylene ether) resin composition according to claim 4, wherein the (b-2) organophosphorus flame retardant having a phosphorus content of 20 to 35 wt % is at least one selected from the group consisting of a dialkylphosphinate represented by the following Chemical Formula 3, a diphosphinate represented by the following Chemical Formula 4, and polymers of at least one thereof: 【Transformation 7】 【Transformation 8】 (In the above Chemical Formula 3 and Chemical Formula 4, R 1 , R 2 , R 3 and R 4 are each independently a linear or branched C 1 -C 10 Alkyl, C 1 -C 10 or H; R 5 is a linear or branched C 1 -C 10 Alkylene, C 6 -C 10 Arylene, C 7 -C 20 alkylarylene of C 7 -C 20 is an aryl alkylene of the formula M 1 m+ and M 2 m'+ are each independently a cationized, protonated, or cationized and protonated nitrogen base compound of one or more atoms selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K; m is an integer of 1 to 4; n is an integer of 1 to 4; and x is an integer of 1 to 4.

8. 2. The poly(arylene ether) resin composition according to claim 1, wherein the (c) glass fibers have an average particle size of 3 to 25 μm and an average length of 1 to 15 mm.

9. 2. The poly(arylene ether) resin composition according to claim 1, wherein the (d) crushed mica has an average particle size of 50 to 150 μm.

10. The poly(arylene ether) resin composition has a notched Izod impact strength of 7.7 kJ / m as measured on a 4 mm thick notched test specimen in accordance with ISO 180A. 2 The poly(arylene ether) resin composition according to claim 1 , wherein

11. 2. The poly(arylene ether) resin composition of claim 1, wherein the poly(arylene ether) resin composition has a heat distortion temperature of 120°C or higher, as measured on a 4 mm thick test specimen under a stress of 1.8 MPa in accordance with ISO 75-2.

12. (a-1) 100 parts by weight of a base resin containing 75 to 85% by weight of a poly(arylene ether) resin and (a-2) 15 to 25% by weight of a polystyrene resin, (b) 13.13 to 15 parts by weight of two or more organic phosphorus flame retardants having different phosphorus contents, (c) 12.5 to 37.5 parts by weight of glass fiber, (d) 1.25 to 4 parts by weight of pulverized mica, and (e) 1.5 to 3.5 parts by weight of an alkaline earth metal sulfate having an average particle size of 0.05 to 3 μm, and then kneading and extruding the resulting mixture to obtain a poly(arylene ether) resin composition; The poly(arylene ether) resin composition has a flame endurance time of 500 seconds or more, measured by applying a flame of 125 mm (500 W) as specified in ASTM D5207 to a 100 mm x 100 mm x 1 mm injection test specimen in accordance with the UL94 5V test, as the time it takes for a flame to develop a hole or drip in the test specimen; The method for producing a poly(arylene ether) resin composition, wherein the kneading and extrusion are carried out using an extruder having 9 or more kneading blocks.

13. A molded article comprising the poly(arylene ether) resin composition of any one of claims 1 to 11.

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