CN117999317A

CN117999317A - Poly (arylene ether) resin composition, method of preparing the same, and molded article manufactured using the same

Info

Publication number: CN117999317A
Application number: CN202380013110.9A
Authority: CN
Inventors: 金炫兑; 咸惠升; 徐仁锡; 朴在燦
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2022-09-01
Filing date: 2023-07-11
Publication date: 2024-05-07

Abstract

The present disclosure relates to a poly (arylene ether) resin composition, a method of preparing the poly (arylene ether) resin composition, and a molded article manufactured using the poly (arylene ether) resin composition; and more particularly, to a poly (arylene ether) resin composition comprising 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fiber (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm; to a method of preparing the poly (arylene ether) resin composition and a molded article manufactured using the poly (arylene ether) resin composition. According to the present invention, it is possible to provide a poly (arylene ether) resin composition capable of providing excellent mechanical properties such as excellent impact strength, tensile strength and flexural strength, excellent heat resistance, excellent flame retardancy, and excellent flame retardation properties, a method of preparing the poly (arylene ether) resin composition, and a molded article manufactured using the poly (arylene ether) resin composition.

Description

Poly (arylene ether) resin composition, method of preparing the same, and molded article manufactured using the same

Technical Field

Cross Reference to Related Applications

The present application claims priority from korean patent application No. 10-2022-010704 filed in the korean intellectual property office at 1 of 9 of 2022 and korean patent application No.10-2023-0087697 filed again based on 6 of 7 of 2023, the disclosures of which are incorporated herein by reference.

The present disclosure relates to a poly (arylene ether) resin composition, a method of preparing the poly (arylene ether) resin composition, and a molded article manufactured using the poly (arylene ether) resin composition; and more particularly to: a poly (arylene ether) resin composition having excellent mechanical properties such as excellent impact strength, tensile strength and flexural strength, heat resistance and flame retardancy, and ensuring safety due to excellent flame retardation properties during thermal runaway, a method of preparing the poly (arylene ether) resin composition, and a molded article manufactured using the poly (arylene ether) resin composition.

Background

Poly (arylene ether) resins are thermoplastic materials having high glass transition temperatures, high dimensional stability, low specific gravity, hydrolytic stability, and good mechanical properties.

However, when the poly (arylene ether) resin is used alone, it requires a high processing temperature and thus has poor moldability. It is therefore used in the form of a mixture with rubber-reinforced polystyrene comprising rubber, which is an aromatic vinyl polymer. In particular, since the polyphenylene ether resins comprising rubber-reinforced polystyrene have compatibility in all regions regardless of their respective contents, they exhibit excellent mechanical properties. Therefore, it is widely used in various industrial fields such as products used under high heat, for example, automobile parts, electric or electronic parts, and building materials. In addition, poly (arylene ether) resins reinforced with glass fibers are used in some applications where better flexural modulus and flexural strength are desired.

However, molded articles made from the resin composition have excellent physical properties such as excellent impact strength, tensile strength, appearance and heat resistance, but generally have the disadvantage of flammability. In particular, when used as a component of an electric vehicle battery, flame retardation performance during thermal runaway is also necessary for safety in addition to flame retardancy. Thermal runaway is a major cause of fire of an electric vehicle battery, and is a phenomenon in which heat is generated due to stress applied to a battery cell for various reasons. When the internal temperature of the battery rises above a certain level due to short circuits such as overvoltage and overdischarge, flames occur. Lithium ion batteries have a high reactivity with water, making it difficult to easily extinguish with water in case of fire.

To solve this problem, flame retardancy and flame retardation properties are imparted by applying both a halogenated compound and an antimony compound to a poly (arylene ether) resin composition comprising a poly (arylene ether) resin. As the halogenated compound, polybrominated diphenyl ether, tetrabromobisphenol a, brominated epoxy compound, chlorinated polyethylene, and the like are mainly used. As the antimony compound, antimony trioxide and antimony pentoxide are mainly used. The method of imparting flame retardancy by using halogen and antimony compounds together has advantages of ensuring flame retardancy and hardly deteriorating physical properties, but it lacks flame retardant properties and is highly likely to have a fatal influence on the human body due to hydrogen halide gas generated during processing. The halogen-free flame retardant is called a non-halogen flame retardant, and the most widely used non-halogen flame retardant is a phosphorus-based flame retardant containing phosphorus. However, in the case of the phosphorus-based flame retardant, the flame retardancy is significantly reduced as compared with the halogen-containing flame retardant. Therefore, in order to obtain excellent flame retardancy and flame retardation performance, a large amount of phosphorus-based flame retardant needs to be added, so that the physical properties of the resin composition are deteriorated.

Flame retardancy can be imparted to the resin composition in the same manner as above, but there is a problem in that insufficient flame retardant properties and deterioration in mechanical properties, which can suppress thermal runaway of the electric vehicle battery, can be provided.

Therefore, there is an urgent need to develop a resin composition having excellent mechanical properties, heat resistance and flame retardancy, and excellent flame retardation properties during thermal runaway, so as to be able to meet the quality required for electronic parts such as electric vehicle batteries.

[ Related art literature ]

[ Patent literature ]

Japanese patent laid-open No. Hei 2-187456

Disclosure of Invention

Technical problem

Accordingly, the present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a poly (arylene ether) resin composition having excellent mechanical properties such as excellent impact strength, tensile strength, and bending strength, and excellent heat resistance and flame retardancy, and capable of ensuring safety due to excellent flame retardation properties during thermal runaway.

It is another object of the present disclosure to provide a method of preparing the poly (arylene ether) resin composition.

It is yet another object of the present disclosure to provide a molded article made from a poly (arylene ether) resin composition.

The above and other objects can be accomplished by the present disclosure described below.

Technical proposal

In accordance with one aspect of the present invention, the above and other objects can be accomplished by the provision of I) a poly (arylene ether) resin composition comprising: 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2); 12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents; 10 to 40 parts by weight of glass fiber (c); 0.5 to 5 parts by weight of mica powder (d); and 1 to 4 parts by weight of a sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm.

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

III) in I) or II), the polystyrene resin (a-2) may preferably be a general-purpose polystyrene, a high impact polystyrene, or a mixture thereof.

IV) in I) to III), the two or more types of organophosphorus flame retardants (b) having different phosphorus contents may preferably include an organophosphorus flame retardant (b-1) containing 5 to 15 wt% of phosphorus and an organophosphorus flame retardant (b-2) containing 20 to 35 wt% of phosphorus.

V) in 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.

VI) in I) to V), the organophosphorus flame retardant (b-1) containing 5 to 15 wt% of phosphorus may preferably be selected from one or more of bisphenol a bis (diphenyl phosphate) (BPADP), triphenyl phosphate (TPP) and resorcinol bis (diphenyl phosphate) (RDP).

VII) in I) to VI), the organophosphorus flame retardant (b-2) comprising 20% to 35% by weight of phosphorus may preferably be selected from one or more of the following: a dialkylphosphinate represented by the following formula 3, a diphosphinate represented by the formula 4, and a polymer of one or more thereof:

[ 3]

[ 4]

In formulas 3 and 4, R ¹、R²、R³ and R ⁴ are each independently a straight or branched C ₁-C₁₀ alkyl, C ₁-C₁₀ cycloalkyl or H; r ⁵ is a straight or branched chain C ₁-C₁₀ alkylene, C ₆-C₁₀ arylene, C ₇-C₂₀ alkylarylene, or C ₇-C₂₀ arylalkylene; m ₁ ^m+ and M ₂ ^m′+ are each independently nitrogen-based compounds in which one or more atoms selected from 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 from 1 to 4; n is an integer from 1 to 4; x is an integer from 1 to 4.

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

IX) in I) to VIII), the mica powder (d) may preferably have an average particle diameter of 50 μm to 150 μm.

X) in I) to IX), after flame having a size (125 mm (500W)) specified in ASTM D5207 according to UL 94 5v test is applied to an injection molded specimen having a size of 100mm X1 mm made from the poly (arylene ether) resin composition, flame endurance time used until holes or drops are generated in the specimen may be preferably 500 seconds or more.

XI) in I) to X), the notched Izod impact strength of a notched specimen made from the poly (arylene ether) resin composition and having a thickness of 4mm, measured according to ISO 180A, may preferably be 7.7kJ/m ² or more.

XII) in I) to XI), the heat distortion temperature of a specimen made of the poly (arylene ether) resin composition and having a thickness of 4mm may preferably be 120℃or higher, measured under a stress of 1.8MPa according to ISO 75-2.

XIII) in I) to XII), the poly (arylene ether) resin composition may preferably comprise one or more selected from the group consisting of lubricants, antioxidants, compatibilizers, and impact modifiers.

According to another aspect of the present invention, there is provided XIV) a method of preparing a poly (arylene ether) resin composition, the method comprising: 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fibers (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of a sulfate of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm are kneaded and extruded, wherein the kneading and extrusion are performed using an extruder equipped with 9 or more kneading blocks.

According to yet another aspect of the present invention, there is provided XV) a molded article comprising the poly (arylene ether) resin composition of any of I) to XIII).

Advantageous effects

As is apparent from the above description, there is provided: a high quality poly (arylene ether) resin composition having excellent mechanical properties such as excellent impact strength, tensile strength and flexural strength, excellent heat resistance and flame retardancy, and excellent flame retardation properties during thermal runaway, and thus, being applicable to electronic parts such as electric vehicle battery packs; a method of preparing the poly (arylene ether) resin composition; and a molded article manufactured using the poly (arylene ether) resin composition.

Furthermore, the present invention provides: a poly (arylene ether) resin composition having excellent mechanical properties together with excellent flame retardant properties, thus being capable of minimizing deformation of an automobile caused by vibration or impact and deterioration of physical properties of the automobile caused by variation in temperature and humidity while securing safety; a method of preparing the poly (arylene ether) resin composition; and a molded article manufactured using the poly (arylene ether) resin composition.

Drawings

FIG. 1 shows a schematic diagram of an extruder equipped with 9 or more kneading blocks for preparing the poly (arylene ether) resin composition of the present invention.

Detailed Description

Hereinafter, the poly (arylene ether) resin composition of the present disclosure, the method of preparing the poly (arylene ether) resin composition, and the molded article manufactured using the poly (arylene ether) resin composition are described in detail.

The present inventors confirmed that when the poly (arylene ether) resin composition comprises a predetermined content of a base resin comprising a poly (arylene ether) resin and a polystyrene resin, two or more types of organic phosphorus flame retardants having different phosphorus contents, glass fibers, mica powder, and a predetermined content of sulfate of alkaline earth metal having a predetermined average particle diameter, mechanical properties such as impact strength, tensile strength, and flexural strength are excellent, heat resistance and flame retardancy are excellent, and flame retardation properties during thermal runaway are greatly improved. Based on this, further studies have been conducted, thereby completing the present invention.

The poly (arylene ether) resin composition according to the present disclosure is described in detail.

The poly (arylene ether) resin composition of the present disclosure comprises 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organophosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fibers (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm. In this case, mechanical properties such as impact strength, tensile strength and bending strength, heat resistance, flame retardancy, and flame retardation properties during thermal runaway are all excellent.

Hereinafter, each component of the poly (arylene ether) resin composition of the present invention is described in detail.

(A-1) Poly (arylene ether) resin

The poly (arylene ether) resin (a-1) may be present in an amount of, for example, 75 to 95 weight percent, preferably 75 to 90 weight percent, more preferably 77 to 87 weight percent, still more preferably 77 to 82 weight percent, based on 100 parts by weight of the total amount of base resin. Within these ranges, mechanical properties, heat resistance, and flame retardancy are excellent, and safety can be ensured due to excellent flame retardation performance during thermal runaway.

In the present disclosure, thermal runaway refers to a state in which a change in temperature changes the environment in a direction to further accelerate the temperature change. That is, thermal runaway means that the cause of a certain mechanical process is a temperature rise, and the energy released by the process raises the temperature, so that the process is accelerated.

The poly (arylene ether) resin (a-1) may be, for example, a homopolymer or copolymer comprising units of the following formula 1 or formula 2:

[ 1]

[ 2]

Wherein R ₁、R₂、R₃、R₄、R′₁、R′₂、R′₃ and R' ₄ are substituents of arylene (Ar) or phenylene and are each independently or simultaneously hydrogen, chloro, bromo, iodo, alkyl, allyl, phenyl, alkylbenzyl, chloroalkyl, bromoalkyl, cyanoalkyl, cyano, alkoxy, phenoxy or nitro. Here, ar may be an arylene group having 7 to 20 carbon atoms, and an alkoxy group may be an alkoxy group having 1 to 4 carbon atoms.

Preferably, R ₁、R₂、R₃、R₄、R′₁、R′₂、R′₃ and R' ₄ are substituents of arylene (Ar) or phenylene and are each independently or simultaneously hydrogen, chloro, bromo, iodo, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro and Ar is arylene having 7 to 20 carbon atoms.

The homopolymer of the poly (arylene ether) resin (a-1) may be selected from one or more of the following: for example, poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2, 6-dipropyl-1, 4-phenylene) ether, poly (2-ethyl-6-propyl-1, 4-phenylene) ether, poly (2, 6-dimethoxy-1, 4-phenylene) ether, poly (2, 6-dichloromethyl-1, 4-phenylene) ether, poly (2, 6-dibromomethyl-1, 4-phenylene) ether, poly (2, 6-diphenyl-1, 4-phenylene) ether, and poly (2, 5-dimethyl-1, 4-phenylene) ether. In this case, mechanical properties such as impact strength, tensile strength, and bending strength are excellent, and processability is excellent, thereby improving appearance quality.

Further, the copolymer of the poly (arylene ether) resin 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, mechanical properties such as impact strength and tensile strength are excellent, and processability is excellent, thereby improving appearance quality.

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

The poly (arylene ether) resin (a-1) may have a weight average molecular weight of, for example, 10,000g/mol to 100,000g/mol, preferably 10,000g/mol to 70,000g/mol, more preferably 15,000g/mol to 45,000 g/mol. Within these ranges, the balance of processability and physical properties is excellent.

In the present disclosure, unless otherwise defined, gel permeation chromatography (GPC, waters Breeze) may be used to measure weight average molecular weights. As a specific example, the weight average molecular weight can be measured by GPC using chloroform as an eluent. In this case, the weight average molecular weight is obtained as a relative value to a Polystyrene (PS) standard sample. As a specific measurement example, the weight average molecular weight can be measured under the following conditions: solvent: chloroform; column temperature: 40 ℃; flow rate: 0.3ml/min; sample concentration: 20mg/ml; injection amount: 5 μl; column model ：1×PLgel 10μm MiniMix-B(250×4.6mm)+1×PLgel 10μm MiniMix-B(250×4.6mm)+1×PLgel 10μm MiniMix-B Guard(50×4.6mm); device name: agilent 1200 series system; refractive index detector: agilent G1362 RID; RI temperature: 35 ℃; and (3) data processing: agilent ChemStation S/W; test methods (Mn, mw, and PDI): OECD TG 118.

The poly (arylene ether) resin (a-1) may have an intrinsic viscosity of, for example, 0.2dl/g to 0.8dl/g, preferably 0.3dl/g to 0.6dl/g, more preferably 0.35dl/g to 0.5 dl/g. Within these ranges, mechanical properties such as impact and flowability suitable for molding can be ensured, and compatibility with polystyrene resin can be excellent.

In the present specification, after dissolving a sample to be tested to a concentration of 0.5g/dl in a chloroform solvent, the intrinsic viscosity was measured at 25℃using an Ubbelohde viscometer, unless otherwise specified.

The poly (arylene ether) resin (a-1) may preferably be used in the form of flakes or powder. In this case, mechanical properties such as impact strength and tensile strength are excellent, and processability and appearance quality are excellent.

In the present disclosure, a flake refers to a flake shape including a wide range of flakes and particles, and as a specific example, may be flakes having a thickness of 1 μm to 20 μm and a length of 0.05mm to 1 mm. As another example, the flakes may have a flake shape with a length to depth ratio (L/D) of 1.5 to 500, preferably 2 to 100, more preferably 10 to 50.

The sheet shape of the present invention can be prepared by existing sheet preparation methods.

In the present disclosure, the depth and length of the sheet may be measured by microscopic analysis.

The powder form may be prepared by powder preparation methods well known in the art.

(A-2) polystyrene resin

The content of the polystyrene resin (a-2) may be, for example, 5 to 25 wt%, preferably 13 to 23 wt%, more preferably 10 to 25 wt%, even more preferably 13 to 23 wt%, even more preferably 18 to 23 wt%, based on 100 parts by weight of the base resin. Within these ranges, mechanical properties such as impact strength, tensile strength, and bending strength are excellent.

The polystyrene resin (a-2) may be, for example, a general-purpose polystyrene resin, a high impact polystyrene, or a mixture thereof, preferably a high impact polystyrene. In this case, processability, dimensional stability and tensile strength are excellent.

The general-purpose polystyrene resin may be, for example, a polymer prepared by polymerizing styrene alone. In this case, the processability is excellent.

The high impact polystyrene may be, for example, a rubber reinforced polystyrene resin.

The rubber may be, for example, one or more selected from butadiene-based rubbers, isoprene-based rubbers, copolymers of butadiene and styrene, and alkyl acrylate rubbers, with butadiene rubber being preferred. In this case, the impact strength is improved.

The rubber content may be, for example, 3 to 25 wt%, preferably 6 to 14 wt%, more preferably 8 to 12 wt%, based on 100 wt% of the high impact polystyrene. Within these ranges, impact strength and flowability are excellent.

The rubber may have, for example, a volume average particle diameter of 0.1 μm to 20 μm, preferably 1.0 μm to 15 μm. Within these ranges, impact strength and flowability are excellent.

Preferably, the rubber-reinforced polystyrene resin may be selected from one or more of the following: 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), alpha-methylstyrene-butadiene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene- (ethylene-butylene/styrene copolymer) -styrene copolymer.

For example, the rubber-reinforced polystyrene resin may be prepared by polymerizing rubber and an aromatic vinyl compound using bulk polymerization, suspension polymerization, emulsion polymerization, or a combination thereof. The polymerization may be carried out in the presence of a thermal polymerization initiator or a polymerization initiator. The polymerization initiator used in the polymerization may be, for example, a peroxide-based initiator, an azo-based initiator, or a mixture thereof. The peroxide-based initiator may preferably be selected from one or more of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide and cumene hydroperoxide, and the azo-based initiator may preferably be azobisisobutyronitrile.

In the present disclosure, the volume average particle size of the particulate undissolved and dispersed rubber particles can be measured using laser scattering after 3g of high impact polystyrene resin is dissolved in 100ml of methyl ethyl ketone using Coulter Counter LS230,230.

The polystyrene resin (a-2) may have a melt flow index of, for example, 2g/10min to 20g/10min, preferably 3g/10min to 15g/10min, measured at 200℃under 5kg according to ASTM D1238. Within these ranges, the balance of processability and physical properties is excellent.

(B) Two or more types of organophosphorus flame retardants having different phosphorus contents

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

Two or more types of organophosphorus flame retardants (b) having different phosphorus contents may include, for example, an organophosphorus flame retardant (b-1) containing 5 to 15 wt% of phosphorus and an organophosphorus flame retardant (b-2) containing 20 to 35 wt% of phosphorus, preferably an organophosphorus flame retardant (b-1) containing 7 to 12 wt% of phosphorus and an organophosphorus flame retardant (b-2) containing 22 to 30 wt% of phosphorus. In this case, the flame retardancy can be further improved while the content of the flame retardant can be reduced. In addition, flame retardant performance during thermal runaway is excellent, and impact resistance is excellent.

In the present disclosure, the phosphorus content refers to the content (wt%) of phosphorus converted by the molecular weight of phosphorus contained in the molecular structure of the organic phosphorus flame retardant.

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

The organophosphorus flame retardant (b-1) containing 5 to 15 wt% of phosphorus may, for example, be one or more selected from bisphenol a bis (diphenyl phosphate) (BPADP), triphenyl phosphate (TPP) and resorcinol bis (diphenyl phosphate) (RDP), preferably bisphenol a bis (diphenyl phosphate). In this case, even if a small amount of flame retardant is used, high flame retardancy can be imparted while maintaining mechanical properties.

The organophosphorus flame retardant (b-2) containing 20 to 35% by weight of phosphorus may, for example, be selected from one or more of the following: a dialkylphosphinate represented by the following formula 3, a diphosphinate represented by the following formula 4, and one or more polymers thereof. In this case, even if a small amount of flame retardant is used, high flame retardancy can be achieved while maintaining mechanical properties, and flame retardation properties are excellent.

[ 3]

[ 4]

( In formulas 3 and 4, R ¹、R²、R³ and R ⁴ are each independently a straight or branched C1-C1 ₀ alkyl, C ₁-C₁₀ cycloalkyl or H; r ⁵ is a straight or branched chain C ₁-C₁₀ alkylene, C ₆-C₁₀ arylene, C ₇-C₂₀ alkylarylene, or C ₇-C₂₀ arylalkylene; m ₁ ^m+ and M ₂ ^m′+ are each independently nitrogen-based compounds in which one or more atoms selected from 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 from 1 to 4; n is an integer from 1 to 4; x is an integer from 1 to 4. )

Preferably, the cycloalkyl groups in formulas 3 and 4 may be independently cyclohexyl or cyclohexyldimethyl.

Preferably, R ¹、R²、R³ and R ⁴ may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl or phenyl.

Preferably, R ⁵ may be methylene, ethylene, n-propylene, isopropylene, n-butylene, t-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, t-butylphenylene, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

Preferably, M ₁ ^m+ and M ₂ ^m′+ may each be independently selected from one or more of Mg, ca, al, ti and Zn.

R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring with adjacent phosphorus atoms. The ring formed by the bonded R ¹ and R ² and R ³ and R ⁴ together with the adjacent phosphorus atom is a heterocyclic ring having a phosphorus atom as a hetero atom constituting the ring, and the number of atoms constituting the ring may be, for example, 4 to 20, preferably 5 to 16. The heterocyclic ring having a phosphorus atom may be a bicyclic ring or may have a substituent.

Preferably, the dialkylphosphinic salt represented by the formula 3 may be selected from one or more of the following: 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 methylphenyl phosphinate, magnesium methylphenyl phosphinate, aluminum methylphenyl phosphinate, zinc methylphenyl phosphinate, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate.

Preferably, the bisphosphonate represented by formula 4 may be selected from one or more of the following: calcium methylenebis (methylphosphinate), magnesium methylenebis (methylphosphinate), aluminum methylenebis (methylphosphinate), zinc methylenebis (methylphosphinate), calcium 1, 4-phenylenediphenylbis (methylphosphinate), magnesium 1, 4-phenylenediphenylbis (methylphosphinate), aluminum 1, 4-phenylenediphenylbis (methylphosphinate) and zinc 1, 4-phenylenediphenylbis (methylphosphinate).

More preferably, the organophosphorus flame retardant (b-2) may be selected from one or more of the following: calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate. Even more preferably, the organophosphorus flame retardant (b-2) may be an aluminum diethylphosphinate salt. In this case, a small amount of flame retardant is used, high flame retardancy can be achieved while maintaining mechanical properties, and flame retardation properties are excellent.

The organophosphorus flame retardant (b-2) may have, for example, an average particle diameter of 0.1 μm to 100 μm, preferably 0.5 μm to 50 μm, more preferably 1 μm to 40 μm. Within these ranges, flame retardancy and mechanical properties are excellent.

In the present disclosure, the average particle diameter of the organic phosphorus flame retardant refers to a number average particle diameter obtained by using a dispersion of the organic phosphorus flame retardant dispersed in a medium such as water as a measurement sample, the particle diameter measured with a laser diffraction type particle size distribution analyzer, and the number of particles.

The organophosphorus flame retardant (b-1) containing 5 to 15 wt% of phosphorus may preferably be bisphenol a bis (diphenyl phosphate), and the organophosphorus flame retardant (b-2) containing 20 to 35 wt% of phosphorus may preferably be aluminum diethylphosphinate. In this case, there is a synergistic effect in which excellent flame retardancy is exhibited even if a small amount of flame retardant is used.

(C) Glass fiber

The content of the glass fiber (c) may be, for example, 10 to 40 parts by weight, preferably 15 to 35 parts by weight, more preferably 20 to 30 parts by weight, based on 100 parts by weight of the base resin. Within these ranges, mechanical properties are excellent, heat resistance, flame retardancy and flame retardation properties during thermal runaway are excellent, and appearance characteristics of the final product are excellent.

The glass fibers (c) may have, for example, an average particle diameter of 3 μm to 25 μm, preferably 5 μm to 20 μm, more preferably 7 μm to 15 μm. Within these ranges, the mechanical strength of the resin is improved, and the appearance characteristics of the final product are excellent.

The glass fibers (c) may have an average length of, for example, 1mm to 15mm, preferably 2mm to 10mm, more preferably 3mm to 6 mm. Within these ranges, the mechanical strength of the resin is improved, and the appearance characteristics of the final product are excellent.

The glass fibers (c) may be, for example, chopped glass fibers. In this case, the compatibility is excellent.

In the present disclosure, the chopped glass fibers are not particularly limited as long as they are chopped glass fibers commonly used in the art to which the present invention pertains.

The ratio of the average length (L) to the average diameter (D), i.e. the aspect ratio (L/D), of the glass fibers (c) may be, for example, 200 to 550, preferably 220 to 450, more preferably 250 to 350, even more preferably 270 to 320. Within these ranges, compatibility with the resin is excellent, so that the surface appearance is excellent.

In the present disclosure, in order to obtain the average particle diameter, average length and aspect ratio of the glass fiber, 30 samples were measured by microscopic analysis and the average value thereof was calculated.

The glass fiber (c) may be surface-treated with, for example, a silane-based compound or a urethane-based compound, preferably with one or more surface-treating agents selected from an aminosilane-based compound, an epoxysilane-based compound and a urethane-based compound, more preferably with an aminosilane-based compound. In this case, dispersibility and surface wettability are improved by forming chemical bonds with the poly (arylene ether) resin, and thus, mechanical properties of the resin composition, including tensile strength, are improved.

The content of the surface treatment agent may be, for example, 0.1 to 10 wt%, preferably 0.1 to 5wt%, more preferably 0.1 to 3 wt%, even more preferably 0.1 to 0.8 wt%, even more preferably 0.2 to 0.5 wt%, based on 100 wt% of the total surface-treated glass fibers (glass fibers+surface treatment agent). Within these ranges, the mechanical properties, balance of physical properties and appearance of the final product are excellent.

The aminosilane-based compound is not particularly limited as long as it is aminosilane generally used as a coating agent for glass fibers, and may, for example, be selected from one or more of the following: gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, 3-mercaptopropyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, 3-isocyanatopropyl triethoxysilane, gamma-acetoacetic propyl trimethoxysilane, acetoacetic propyl triethoxysilane, gamma-cyanoacetyl trimethoxysilane, gamma-cyanoacetyl triethoxysilane, and acetoxyacetyl trimethoxysilane. In this case, mechanical properties and heat resistance are excellent, and surface characteristics of the injection molded product are excellent.

The epoxysilane-based compound is not particularly limited as long as it is epoxysilane that is generally used as a coating agent for glass fibers, and may be, for example, one or more selected from the following: 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane. In this case, mechanical properties and heat resistance are excellent, and surface characteristics of the injection molded product are excellent.

The glass fiber (c) may be appropriately selected and used within a range commonly used in the art, as long as it is within the scope of the definition of the present invention, and its cross-sectional shape is not particularly limited to a cylindrical shape or an elliptical shape.

(D) Mica powder

The content of the mica powder (d) 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, even more preferably 1 to 3 parts by weight, based on 100 parts by weight of the base resin. Within these ranges, mechanical properties, heat resistance, flame retardancy, and flame retardation properties during thermal runaway are excellent.

In the present disclosure, mica powder may be defined as mica powder having an average particle diameter of 500 μm or less obtained by pulverizing mica one or more times.

The mica powder (d) may have, for example, an average particle diameter of 50 μm to 150 μm, preferably 70 μm to 130 μm, more preferably 80 μm to 110 μm. Within these ranges, compatibility with the resin is excellent, so that all of mechanical properties, heat resistance, flame retardancy, and flame retardation during thermal runaway can be improved, and appearance quality of the molded article is excellent.

The mica powder (d) may have an aspect ratio of, for example, 40 to 60, preferably 45 to 55. Within these ranges, the appearance quality of the molded article is excellent.

In the present disclosure, the aspect ratio of mica powder refers to the length ratio of the major axis to the minor axis in a two-dimensional model.

In the present disclosure, in order to obtain the average particle diameter, average length and aspect ratio of the mica powder, 30 samples were measured by microscopic analysis and the average value thereof was calculated.

(E) Alkaline earth metal sulfate having an average particle diameter of 0.05 μm to 3 μm

The content of the sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 μm to 3 μm may be, for example, 1 part by weight to 4 parts by weight, preferably 1.2 parts by weight to 3.8 parts by weight, more preferably 1.4 parts by weight to 3.6 parts by weight, based on 100 parts by weight of the base resin. Within these ranges, flame retardant performance during thermal runaway is improved, and impact resistance is excellent.

The sulfate (e) of an alkaline earth metal may have, for example, an average particle diameter of 0.05 μm to 3 μm, preferably 0.1 μm to 2.5 μm, more preferably 0.5 μm to 2 μm, even more preferably 0.7 μm to 1.5 μm. Within these ranges, compatibility is superior, so that mechanical properties, heat resistance, flame retardance, and flame retardation properties during thermal runaway are improved.

The alkaline earth metal of sulfate (e) may be, for example, one or more selected from the elements contained in group II of the periodic table; preferably one or more selected from calcium, barium, strontium and magnesium; more preferably calcium, barium or mixtures thereof; still more preferably barium. In this case, the mechanical properties are improved.

As a preferred example, the sulfate of alkaline earth metal (e) may be barium sulfate. In this case, all mechanical properties are improved.

Preferably, the content of the sulfate of alkaline earth metal (e) may be greater than that of the mica powder (d). In this case, mechanical properties such as tensile strength, bending strength and impact strength, and heat resistance are superior.

Poly (arylene ether) resin composition

Flame according to UL 94 5v test having a size specified in ASTM D5207 (125 mm (500W)) is applied to an injection molded specimen having a size of preferably 100mm x 1mm made of a poly (arylene ether) resin composition, and the flame endurance time used until holes or drops are generated in the specimen may be 500 seconds or more, more preferably 550 seconds or more, still more preferably 600 seconds or more. Within these ranges, the physical property balance is excellent, and flame retardation performance during thermal runaway of an electronic component such as an electric vehicle battery component is excellent, so that safety can be ensured.

The notched Izod impact strength measured at room temperature according to ISO 180A using notched samples made from poly (arylene ether) resin compositions and having a thickness of 4mm may be 7.7kJ/m ² or greater, more preferably 8.5kJ/m ² or greater, even more preferably 9kJ/m ² or greater, even more preferably 9kJ/m ² to 13kJ/m ². Within these ranges, the physical property balance is superior and the mechanical strength is excellent, so that when applied to an electronic component, variations caused by external environments such as automobile vibration can be minimized.

In the present disclosure, notched Izod impact strength was measured according to ISO 180A with the aid of IT manufactured by Toyoseiki using a notched specimen having a thickness of 4 mm.

In the present disclosure, room temperature may be a point in the range of 20±5 ℃.

The tensile strength of the poly (arylene ether) resin composition measured according to ISO 527 under conditions such as a sample thickness of 4mm and a measurement speed of 5mm/min may preferably be 67MPa or more, more preferably 73MPa or more, even more preferably 80MPa or more, even more preferably still 90MPa or more, particularly preferably 90MPa to 120MPa. Within these ranges, the physical property balance is superior and the mechanical strength is excellent, so that when applied to an electronic component, deformation caused by vibration or impact of an automobile and deterioration of physical properties due to temperature and humidity changes can be minimized.

In the present disclosure, tensile strength was measured at a crosshead speed of 5mm/min according to ISO527 using U.T.M. (manufacturer: instron, model name: 4466).

The flexural strength of the poly (arylene ether) resin composition measured according to ISO 527 under conditions such as a sample thickness of 4mm and a measurement speed of 2mm/min may preferably be 110MPa or more, more preferably 115MPa or more, even more preferably 125MPa or more, even more preferably 130MPa or more, particularly preferably 130MPa to 170MPa. Within these ranges, the physical property balance is superior and the mechanical strength is excellent, so that when applied to an electronic component, variations caused by external environments such as automobile vibration can be minimized.

The heat distortion temperature of a sample made of the poly (arylene ether) resin composition and having a thickness of 4mm, measured according to ISO 75-2 under a stress of 1.8MPa, may preferably be 120 ℃ or higher, more preferably 125 ℃ or higher, even more preferably 130 ℃ or higher, even more preferably 135 ℃ or higher, particularly preferably 135 ℃ to 150 ℃. Within these ranges, the balance of physical properties and heat resistance are excellent.

The flame retardancy of an injection molded specimen having a size of, for example, 127mm x 12.7mm x 1.5mm, as measured according to the UL 94 standard (vertical burn test), made of a poly (arylene ether) resin composition may be V-0 or more. In this case, the physical property balance is superior, and the heat resistance and flame retardant property during thermal runaway are excellent.

The poly (arylene ether) resin composition may comprise, for example, at least one additive selected from the group consisting of lubricants, antioxidants, compatibilizers, and impact modifiers.

The total amount of the additives may be, for example, 5 to 10 parts by weight, preferably 6 to 9.5 parts by weight, more preferably 7 to 9 parts by weight, based on 100 parts by weight of the base resin. Within these ranges, mechanical properties, heat resistance and flame retardancy are excellent, and flame retardation properties during thermal runaway are excellent.

The poly (arylene ether) resin composition may further comprise, based on 100 parts by weight of the base resin, 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight of each of one or more selected from the group consisting of: flame retardant aids, plasticizers, heat stabilizers, anti-drip agents, light stabilizers, pigments, dyes, inorganic additives (excluding glass fibers), and carbon fibers. Within these ranges, the necessary physical properties can be well achieved without deteriorating the inherent physical properties of the poly (arylene ether) resin composition of the present disclosure.

Method for preparing poly (arylene ether) resin composition

The method of preparing a poly (arylene ether) resin composition of the present disclosure includes the step of kneading and extruding 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organophosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fiber (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of sulfate of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm, wherein the kneading and extruding are performed using an extruder having 9 or more kneading segments. In this case, mechanical properties such as impact strength, tensile strength and bending strength, heat resistance, flame retardancy, and flame retardation properties during thermal runaway are all excellent.

Kneading and extrusion may be performed, for example, in a barrel temperature range of 200 ℃ to 350 ℃, preferably 220 ℃ to 330 ℃, more preferably 240 ℃ to 320 ℃. In this case, there are advantages in that: sufficient melt kneading can be performed while the production amount per unit time is high, and problems such as thermal decomposition of the resin component are not caused.

Kneading and extrusion may be performed at a screw rotation speed of, for example, 100rpm to 500rpm, preferably 150rpm to 400rpm, more preferably 200rpm to 350 rpm. Within these ranges, the production amount per unit time is high, and the process efficiency is excellent.

The poly (arylene ether) resin composition obtained by kneading and extruding may preferably be provided in the form of particles.

Molded article

Molded articles of the present disclosure are characterized by comprising the poly (arylene ether) resin compositions of the present disclosure. In this case, all of mechanical properties such as impact strength and tensile strength, heat resistance, electrical insulation, and flame retardancy are excellent.

The molded article may be formed by, for example, injection molding or extrusion molding.

The molded article can be used, for example, as an electronic component or a battery component.

The battery assembly may be, for example, a plastic upper cover, a module housing, or a bus bar of an electric vehicle battery.

The method of manufacturing the molded article of the present disclosure includes a step of kneading and extruding preferably 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fibers (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of a sulfate of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm to manufacture pellets of the poly (arylene ether) resin composition, and a step of injection molding the manufactured pellets to manufacture the molded article, wherein kneading and extrusion are performed using an extruder having 9 or more kneading sections. In this case, mechanical properties such as impact strength, tensile strength and bending strength, heat resistance, flame retardancy, and flame retardation properties during thermal runaway are all excellent.

The injection molding is not particularly limited as long as it is performed according to methods and conditions commonly used in the art to which the present invention pertains and may be appropriately selected and applied as needed.

In describing the poly (arylene ether) resin composition, the molded article, the method of preparing the conductive resin composition, and the method of manufacturing the molded article of the present disclosure, when the conditions are within the range of common practice in the art, other conditions (e.g., configuration and specifications of an extruder and an injection molding machine, extrusion and injection molding conditions, additives, etc.) may be appropriately selected and implemented as needed, without particular limitation, unless otherwise specified.

Hereinafter, the present invention will be described with reference to the accompanying drawings.

The type of the extruder is not particularly limited, and an extruder commonly used in the art may be appropriately selected and used. For example, a single screw extruder equipped with one screw or a multi-screw extruder equipped with a plurality of screws may be used. In view of uniform kneading of materials, easiness of processing, and economic efficiency, a twin-screw extruder equipped with two screws is preferably used.

The extruder comprises: a raw material feeder for feeding material into the cartridge; a screw for conveying and kneading the fed material; and a die for extruding the kneaded material. In this case, the screw is composed of a plurality of screw elements for various functions.

The extruder may include one or more raw material feeders, and may optionally include more than two raw material feeders, as desired. For example, a primary inlet and optionally a secondary inlet may be included, and more than two secondary inlets may be included as desired.

As a specific example, a base resin, two or more types of organic phosphorus flame retardants having different phosphorus contents, glass fibers, mica powder, and sulfate of alkaline earth metal may be fed batchwise into the main inlet. As another example, all components except for two or more types of organophosphorus flame retardant having different phosphorus contents may be fed into the main inlet, and the flame retardant may be fed into the auxiliary inlet.

As yet another example, all components except for two or more types of organophosphorus flame retardants having different phosphorus contents may be fed into the main inlet, two or more types of organophosphorus flame retardants having different phosphorus contents may be fed into the auxiliary inlet 1, and additives such as lubricants, antioxidants, compatibilizers, and impact modifiers may be fed into the auxiliary inlet 2.

As yet another example, the base resin may be fed into the main inlet, and some of two or more types of organophosphorus flame retardant having different phosphorus contents, glass fiber, mica powder, and sulfate of alkaline earth metal may be fed into the auxiliary inlet 1, followed by feeding the remaining portion into the auxiliary inlet 2.

As yet another example, a base resin and sulfate of an alkaline earth metal may be fed into the main inlet, two or more types of organic phosphorus flame retardant having different phosphorus contents and mica powder may be fed into the auxiliary inlet 1, and glass fiber may be fed into the auxiliary inlet 2.

The kneading blocks of the present invention correspond to the screw elements. Specifically, each kneading block is composed of a plurality of disks, preferably 3 to 7 disks, 5 to 7 disks, 3 to 5 disks or 4 to 5 disks, and has a polygonal cross section or an elliptical cross section. The kneading blocks are arranged continuously in the direction of material transport. Furthermore, in the kneading section, the phase angle of the disks (representing the stroke angle (TRAVEL ANGLE) between the disks) is preferably 45 ° to 90 °.

In addition, the kneading blocks include forward kneading blocks capable of transporting, distributing and mixing materials, neutral kneading blocks capable of distributing and mixing materials without transporting materials, and backward kneading blocks capable of transporting materials in a direction opposite to the transporting direction.

The method of preparing the poly (arylene ether) resin composition according to the present invention may include the step of kneading and extruding using an extruder equipped with, for example, 9 or more kneading blocks, preferably 10 or more kneading blocks, more preferably 12 or more kneading blocks, 9 to 18 kneading blocks as a preferred example, 10 to 18 kneading blocks as a more preferred example, 12 to 16 kneading blocks as an even more preferred example. In this case, it may be effective to arrange the kneading blocks in the order of the forward kneading block, the neutral kneading block, and the backward kneading block with respect to the resin flow direction. Depending on the manner of combination, continuous or individual segment combinations may be used. In this case, dispersibility of the glass fiber and the mica powder, compatibility of the composition, and the like can be further improved, so that a higher quality poly (arylene ether) resin composition can be provided.

More than 9 kneading blocks may be arranged continuously, or may be arranged discontinuously between the screws. As a specific example, 3 to 6 kneading blocks may be continuously provided between the main inlet and the auxiliary inlet 1,3 to 8 kneading blocks may be continuously provided between the auxiliary inlet 1 and the auxiliary inlet 2, and 2 to 5 kneading blocks may be provided between the auxiliary inlet 2 and the outlet (not shown). With this structure, local heat generation during melt kneading can be controlled to prevent thermal deformation of the raw material. In addition, excessive cutting of the glass component can be prevented so that mechanical properties, flame retardancy, and flame retardation performance during thermal runaway are not degraded.

Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only and should not be construed as limiting the scope and spirit of the invention. Further, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and that such changes and modifications are also within the scope of the appended claims.

Examples (example)

The materials used in the following examples and comparative examples are as follows:

* (a-1) a poly (arylene ether) resin: poly (2, 6-dimethyl-1, 4-phenylene) ether (PPE; LXR040 manufactured by Bluestar)

* (A-2) polystyrene resin: HIPS (high impact polystyrene) resin (HI 450PG manufactured by KUMHO PETROCHEMICAL)

* (B) two or more types of organophosphorus flame retardants having different phosphorus contents: (b-1) bisphenol A bis (diphenyl phosphate) (BPADP manufactured by FCA) containing 9% by weight of phosphorus, and (b-2) aluminum diethylphosphinate (OP 1230 manufactured by Clariant) containing 25% by weight of phosphorus

* (C) glass fibers: chopped glass fibers having an average particle diameter of 10 μm to 13 μm and an average length of 3mm to 4mm and surface-treated with an aminosilane (910A-13P manufactured by Owens Corning)

* (D) mica powder: mica powder having an average particle diameter of 90 μm and an aspect ratio of 50 (200D manufactured by Kurary)

* (E-1) a sulfate of an alkaline earth metal having an average particle diameter of 0.05 μm to 3 μm: barium sulfate having an average particle diameter of 1 μm (HD 80 manufactured by Solvay)

* (E-2) alkaline earth metal sulfate: barium sulfate having an average particle diameter of 4 μm (Blanc FIX G manufactured by Solvay)

* (F) additives: mixtures of lubricants (pentaerythritol fatty acid esters), antioxidants (tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate)), compatibilizers (PPO fumarate) and impact modifiers (maleated styrene-ethylene-butylene block copolymer rubber)

Examples 1 to 15 and comparative examples 1 to 14

Using a twin screw extruder (T40, manufactured by SM) equipped with 10 mixing sections set at 250 ℃ to 310 ℃ and a rotational speed of 300rpm, the poly (arylene ether) resin (a-1), the polystyrene resin (a-2), the organophosphorus flame retardant (b-1) containing 9 wt% of phosphorus, the organophosphorus flame retardant (b-2) containing 25 wt% of phosphorus, the glass fiber (c), the mica powder (d), the sulfate of alkaline earth metal (e), and the additive (f) were melt-kneaded and extruded according to the contents shown in tables 1 to 4 below, thereby manufacturing pellets. Pellets were produced into test pieces for evaluation using an injection molding machine (80 tons manufactured by ENGEL). Each of the fabricated samples was allowed to stand at room temperature for more than 48 hours, and then the properties thereof were measured. The results are summarized in tables 1 to 4 below.

Here, the twin screw extruder is provided with a total of 2 or more inlets, a base resin and sulfate of alkaline earth metal are fed into its main inlet, two or more types of organic phosphorus flame retardant having different phosphorus contents and mica powder are fed into the auxiliary inlet 1, and glass fiber is fed into the auxiliary inlet 2.

Test example

Characteristics of the samples manufactured in each of examples 1 to 15 and comparative examples 1 to 14 were measured according to the following methods. The results are summarized in tables 1 to 4 below.

Measurement method

* Tensile strength (MPa): samples of thickness 4mm were pulled at a crosshead speed of 5mm/min according to ISO 527 using U.T.M. (manufacturer: instron, model name: 4466), and then the cut points of the samples were measured.

* Flexural strength (MPa): the flexural strength of a specimen having a thickness of 4mm was measured according to ISO 527 at a crosshead speed of 2mm/min using U.T.M. (manufacturer: instron, model name: 4466).

* Impact strength (kJ/m ²): the cantilever impact strength was measured under standard conditions of constant temperature and humidity using IT equipment manufactured by Toyoseiki according to ISO 180A. As the sample, a notched sample having a thickness of 4mm was used.

* Heat distortion temperature (c): the heat distortion temperature of a sample having a thickness of 4mm was measured under a stress of 45MPa according to ISO 75-2.

* Flame retardancy: flame retardancy of injection molded specimens having 127mm x 12.7mm x 1.5mm dimensions was measured according to UL 94 standard (vertical burn test).

* Flame endurance time (seconds): flame according to UL 945V test having the dimensions specified in ASTM D5207 (125 mm (500W)) was applied to injection molded specimens of 100mm x 1mm in size, and the flame application time required until holes or drips were created in the specimens was measured.

* Appearance evaluation: visual evaluation the appearance of injection molded articles under the following conditions: such as an injection molding temperature of 290 ℃ to 300 ℃, an injection molding speed of 50mm/s, a holding pressure of 60 bar, a holding pressure application time of 5 seconds, and a cooling time of 20 seconds. When it was completely molded without gas marks and non-molded portions, it was evaluated as "excellent", and when the appearance quality was deteriorated due to non-molded portions, gas marks, and the like, it was evaluated as "poor".

TABLE 1

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TABLE 2

TABLE 3

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TABLE 4

As shown in tables 1 to 4, it was confirmed that in the case of the poly (arylene ether) resin compositions of the present invention (examples 1 to 15), mechanical properties such as tensile strength, flexural strength and impact strength, heat distortion temperature, heat resistance and flame retardancy were excellent as compared with the compositions of comparative examples 1 to 14. Further, the flame endurance time of the battery was 500 seconds or more, which indicates that flame retardation performance during thermal runaway of the battery is excellent.

Specifically, in the case of comparative example 1 including 3.13 parts by weight of one type of phosphorus-based flame retardant, flame retardancy and flame endurance time were reduced, and in the case of comparative example 2 including 7.5 parts by weight of one type of phosphorus-based flame retardant, all mechanical properties were reduced.

Further, comparative examples 3 and 4, which do not include the mica powder (d), and comparative example 5, which includes two types of phosphorus-based flame retardants in a content lower than the range of the present invention, show poor flame retardancy and flame endurance time.

Further, in the case of comparative example 6 in which the composition ratio of the base resin is outside the range of the present invention, the heat distortion temperature and flame endurance time are deteriorated, and in the case of comparative example 7 in which both types of flame retardants are contained in an excessive amount, the flame endurance time is very short, and the heat distortion temperature is low.

Further, in the case of comparative example 8 in which the content of the mica powder (d) is less than the range of the present invention, the flame endurance time is very short, and the flame retardancy is lowered. On the other hand, in the case of comparative example 9 in which the content of the mica powder (d) exceeded the range of the present invention, the impact strength was lowered.

Further, also in the case of comparative examples 10 and 11 in which the content of barium sulfate (e-1) is outside the range of the present invention, the flame endurance time was shortened, so that thermal runaway could not be prevented when applied to the battery portion of an electric vehicle.

In addition, in the case of comparative example 12 including barium sulfate (e-2), in which the average particle diameter of the barium sulfate (e-2) was outside the range of the present invention, the flame endurance time was shortened.

Further, in the case of comparative example 13 in which the content of glass fiber (c) was less than the range of the present invention, all of mechanical properties, heat distortion temperature, flame retardancy and flame durability time were lowered, and in the case of comparative example 14 in which the content of glass fiber (c) was greater than the range of the present invention, mechanical properties, heat distortion temperature, flame retardancy and flame durability time were excellent, but flowability was lowered, so that the molding processability and appearance of molded articles were poor.

In summary, it was confirmed that the poly (arylene ether) resin composition according to the present invention comprises: a base resin comprising a predetermined content of poly (arylene ether) resin and polystyrene resin, two or more types of organic phosphorus flame retardants having different phosphorus contents, glass fiber, mica powder, and a predetermined content of sulfate of alkaline earth metal having a predetermined average particle diameter, exhibit excellent mechanical properties such as excellent impact strength, tensile strength, and flexural strength, heat resistance, flame retardancy, and excellent flame retardant properties during thermal runaway, thus satisfying the properties required in electronic components such as electric vehicle batteries.

Claims

1. A poly (arylene ether) resin composition comprising:

100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2);

12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents:

10 to 40 parts by weight of glass fiber (c);

0.5 to 5 parts by weight of mica powder (d); and

1 To 4 parts by weight of a sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm.

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

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

4. The poly (arylene ether) resin composition of claim 1, wherein the two or more types of organophosphorus flame retardant (b) having different phosphorus contents comprise an organophosphorus flame retardant (b-1) comprising 5 to 15 wt% phosphorus and an organophosphorus flame retardant (b-2) comprising 20 to 35 wt% phosphorus.

5. The poly (arylene ether) resin composition of claim 4, wherein the weight ratio (b-1:b-2) of the organophosphorus flame retardant (b-1) to the organophosphorus flame retardant (b-2) is 6:4 to 8.5:1.5.

6. The poly (arylene ether) resin composition of claim 4, wherein the organophosphorus flame retardant (b-1) comprising 5 to 15 weight percent phosphorus is selected from one or more of bisphenol a bis (diphenyl phosphate) (BPADP), triphenyl phosphate (TPP), and resorcinol bis (diphenyl phosphate) (RDP).

7. The poly (arylene ether) resin composition of claim 4, wherein the organophosphorus flame retardant (b-2) comprising 20 to 35 weight percent phosphorus is selected from one or more of the following: a dialkylphosphinate represented by the following formula 3, a diphosphinate represented by the formula 4, and a polymer of one or more thereof:

[ 3]

[ 4]

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

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

10. The poly (arylene ether) resin composition of claim 1, wherein, after flame having a size specified in ASTM D5207 (125 mm (500W)) according to UL 94 5v test is applied to an injection molded specimen of 100mm x 1mm made from the poly (arylene ether) resin composition, the flame endurance time taken until holes or drops are generated in the specimen is 500 seconds or more.

11. The poly (arylene ether) resin composition of claim 1, wherein a notched izod impact strength of a notched specimen made from the poly (arylene ether) resin composition and having a thickness of 4mm, measured according to ISO 180A, is 7.7kJ/m ² or greater.

12. The poly (arylene ether) resin composition of claim 1, wherein a specimen made from the poly (arylene ether) resin composition and having a thickness of 4mm has a heat distortion temperature of 120 ℃ or greater, measured at a stress of 1.8MPa according to ISO 75-2.

13. A method of preparing a poly (arylene ether) resin composition, the method comprising:

Kneading and extruding 100 parts by weight of a base resin comprising 75 to 95% by weight of a poly (arylene ether) resin (a-1) and 5 to 25% by weight of a polystyrene resin (a-2), 12 to 17 parts by weight of two or more types of organic phosphorus flame retardants (b) having different phosphorus contents, 10 to 40 parts by weight of glass fiber (c), 0.5 to 5 parts by weight of mica powder (d), and 1 to 4 parts by weight of sulfate (e) of an alkaline earth metal having an average particle diameter of 0.05 to 3 μm,

Wherein the kneading and extrusion are performed using an extruder equipped with 9 or more kneading blocks.

14. A molded article comprising the poly (arylene ether) resin composition of any of claims 1 to 12.