Flame-retardant resin composition and preparation method thereof

Abstract

The present invention relates to a flame-retardant resin composition and a method for preparing the same, the flame-retardant resin composition comprising a specific compound as a phosphorus-based flame retardant in the resin composition and thus obtaining excellent flame retardancy.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0045524 filed on April 6, 2023, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present invention relates to a flame retardant resin composition containing a flame retardant and a preparation method thereof. Background Art

[0004] Generally, styrene-based resins include acrylonitrile-butadiene-styrene copolymers and styrene-acrylonitrile copolymers. For example, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin is widely used as an exterior material for electrical / electronic products, office equipment, etc. due to the stiffness and chemical resistance of acrylonitrile and the processing properties and mechanical strength of butadiene and styrene. However, ABS resin itself is easily flammable and has almost no fire resistance. Therefore, ABS resin used in electrical / electronic products, office equipment, etc. needs to meet flame retardant standards to ensure fire resistance.

[0005] Regulations regarding flame retardancy are based on Underwriters Laboratories (UL) standards. When preparing resin compositions, particularly thermoplastic resin compositions, with flame retardancy that meets UL standards, halogen-based flame retardants are typically mixed into thermoplastic resins. As described above, when halogen-based flame retardants are used to provide flame retardancy to thermoplastic resins, excellent flame retardancy is exhibited, and a final product with virtually no performance degradation is obtained. However, during processing, hydrogen halide gas is generated, potentially damaging the mold. Furthermore, when discarded, the presence of halogen compounds causes highly carcinogenic dioxins and hydrogen bromide gas to be discharged from waste incinerators, adversely affecting the environment and the human body.

[0006] Therefore, among the flame retardants used in flame-retardant resin compositions, flame retardants known as non-halogen flame retardants are primarily used as flame retardants that do not use halogens. The most widely used non-halogen flame retardants are phosphorus-based flame retardants containing phosphorus. However, in some types of styrene-based resins, phosphorus-based flame retardants cannot generate char, as is the case with phosphorus-based flame retardant systems, and therefore rarely exhibit sufficient flame retardancy.

[0007] [Related technical literature]

[0008] [Patent Document]

[0009] (Patent Document 1) Chinese Patent Publication No. 113772882A Summary of the Invention

[0010] Technical issues

[0011] The present invention aims to overcome the limitations of the prior art. Therefore, one aspect of the present invention provides a flame retardant resin composition comprising a specific compound as a phosphorus flame retardant in the resin composition to obtain excellent flame retardancy, and a method for preparing the flame retardant resin composition.

[0012] Technical Solution

[0013] (1) According to one aspect of the present invention, there is provided a flame retardant resin composition comprising: a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a polyester resin; and a polymeric phosphorus flame retardant, wherein the polyester resin is present in an amount smaller than that of the polymeric phosphorus flame retardant, and the polymeric phosphorus flame retardant has at least one structural unit represented by the following formula 1.

[0014] [Formula 1]

[0015]

[0016] In this case, R1 to R3 are each hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an arylene group having 6 to 20 carbon atoms, and n is a natural number.

[0017] (2) The present invention provides the flame retardant resin composition according to (1) above, wherein the graft copolymer is present in a larger amount than the matrix copolymer.

[0018] (3) The present invention provides a flame retardant resin composition according to (1) or (2) above, wherein the content of the graft copolymer is 38 wt% to 47 wt%, and the content of the matrix copolymer is 22 wt% to 33 wt%, relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant.

[0019] (4) The present invention provides a flame retardant resin composition according to any one of (1) to (3) above, wherein the content of the polyester resin is 18 wt% to 40 wt% and the content of the polymeric phosphorus flame retardant is 18 wt% to 40 wt% relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant.

[0020] (5) The present invention provides the flame-retardant resin composition according to any one of (1) to (4) above, wherein the polyester resin is a polyethylene terephthalate resin.

[0021] (6) The present invention provides a flame retardant resin composition according to any one of (1) to (5) above, wherein, relative to the amounts of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant, the content of the polyester resin is 18 wt% to 40 wt%, the content of the polymeric phosphorus flame retardant is 18 wt% to 40 wt%, and the graft copolymer is present in a larger amount than the matrix copolymer.

[0022] (7) The present invention provides the flame-retardant resin composition according to any one of (1) to (6) above, wherein the polymeric phosphorus-based flame retardant has at least one structural unit represented by the following formula 2.

[0023] [Formula 2]

[0024]

[0025] (8) The present invention provides the flame retardant resin composition according to (1) to (7) above, wherein, in the above formula 2, n is in the range of 1 to 1000.

[0026] (9) The present invention provides the flame-retardant resin composition according to (1) to (8) above, wherein the polymeric phosphorus-based flame retardant has a weight average molecular weight of 5000 g / mol or more.

[0027] (10) According to another aspect of the present invention, there is provided a method for preparing a flame retardant resin composition, which comprises mixing and extruding a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a polyester resin; and a polymeric phosphorus flame retardant, wherein the polyester resin is present in an amount less than that of the polymeric phosphorus flame retardant, and the polymeric phosphorus flame retardant has at least one structural unit represented by the following formula 1.

[0028] [Formula 1]

[0029]

[0030] In this case, R1 to R3 are each hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an arylene group having 6 to 20 carbon atoms, and n is a natural number.

[0031] Beneficial effects

[0032] According to the present invention, a flame retardant resin composition having excellent flame retardancy can be provided. DETAILED DESCRIPTION

[0033] Hereinafter, the present invention will be described in detail to help understanding of the present invention.

[0034] It should be understood that the words or terms used in the description and claims of the present invention should not be interpreted as limited to having the meanings defined in commonly used dictionaries. It should also be understood that based on the principle that the inventor can appropriately define the meaning of words or terms to best explain the present invention, words or terms should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology and the technical concept of the present invention.

[0035] The terms used in this specification are for the purpose of describing particular example embodiments only and are not intended to be limiting of the invention. Unless the context clearly indicates otherwise, singular forms are intended to include plural forms as well.

[0036] As used herein, the term "monomer unit" may refer to a component, structure, or material itself generated by each monomer, and specifically, may refer to a repeating unit constituted in a polymer when a monomer to be added participates in a polymerization reaction when polymerizing the polymer.

[0037] In this specification, "weight average molecular weight" is generally measured by gel permeation chromatography (GPC). For example, the sample to be measured can be dissolved in a solution of tetrahydrofuran (THF) and then measured by gel permeation chromatography as a relative value to a standard sample (PS, standard polystyrene).

[0038] As used herein, the term "composition" encompasses reaction products and decomposition products formed from materials of the composition, as well as mixtures comprising the materials of the composition.

[0039] <Flame Retardant Resin Composition>

[0040] The present invention provides a resin composition, in particular, a flame retardant resin composition.

[0041] A flame retardant resin composition according to one embodiment of the present invention includes: a graft copolymer including a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; a matrix copolymer including an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a polyester resin; and a polymeric phosphorus-based flame retardant, wherein the polyester resin is present in an amount smaller than that of the polymeric phosphorus-based flame retardant, and the polymeric phosphorus-based flame retardant has at least one structural unit represented by the following Formula 1.

[0042] [Formula 1]

[0043]

[0044] In this case, R1 and R3 are each hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an arylene group having 6 to 20 carbon atoms, and n is a natural number. Here, the alkyl group may be linear or branched, and the arylene group refers to an aromatic ring group having two bonding positions, that is, a divalent group.

[0045] According to one embodiment of the present invention, R1 and R3 in the above formula 1 may each be hydrogen or an alkyl group having 1 to 10 carbon atoms, A1 and A2 may each be an arylene group having 6 to 15 carbon atoms, and as a more specific example, R1 and R3 in the above formula 1 may each be hydrogen or an alkyl group having 1 to 5 carbon atoms, and A1 and A2 may each be an arylene group having 6 to 10 carbon atoms.

[0046] 1. Graft copolymer

[0047] According to one embodiment of the present invention, the graft copolymer may be a part of the flame retardant resin composition, and may be a resin for imparting basic physical properties to the flame retardant resin composition.

[0048] According to one embodiment of the present invention, the graft copolymer may comprise a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit. As a specific example, the conjugated diene polymer may be prepared by polymerization of a conjugated diene monomer to comprise the conjugated diene monomer unit, and as a more specific example, the conjugated diene polymer may be prepared by emulsion polymerization of a conjugated diene monomer, making it easy to control the average particle size of the conjugated diene polymer in this case, and therefore a conjugated diene polymer suitable for desired mechanical properties may be used.

[0049] According to one embodiment of the present invention, the conjugated diene monomer used to form the conjugated diene monomer unit of the conjugated diene polymer can be at least one selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene, more specifically, it can be 1,3-butadiene.

[0050] According to one embodiment of the present invention, the graft copolymer can be produced by graft polymerization of aromatic vinyl monomer units and vinyl cyanide monomer units on a conjugated diene polymer. Therefore, the graft copolymer can include a conjugated diene polymer, and aromatic vinyl monomer units and vinyl cyanide monomer units grafted onto the conjugated diene polymer, and can also include vinyl monomer units and vinyl cyanide monomer units not grafted onto the conjugated diene polymer in the portion of the graft layer that forms the graft copolymer according to the graft polymerization conditions. In this case, the graft polymerization can be carried out by emulsion polymerization or bulk polymerization.

[0051] According to one embodiment of the present invention, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit of the graft copolymer can be at least one selected from styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene, and as a specific example, it can be styrene.

[0052] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit of the graft copolymer may be at least one selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0053] According to one embodiment of the present invention, the graft copolymer may contain a conjugated diene polymer in an amount of 40 wt % to 90 wt %, an aromatic vinyl monomer unit in an amount of 5 wt % to 50 wt % and a vinyl cyanide monomer unit in an amount of 1 wt % to 30 wt %, and as a specific example, it may contain a conjugated diene polymer in an amount of 50 wt %, 80 wt % or 70 wt % or less, an aromatic vinyl monomer unit in an amount of 10 wt %, 40 wt % or 30 wt % or less, and a vinyl cyanide monomer unit in an amount of 1 wt %, 5 wt % or more, 20 wt % or 15 wt % or less, and within this range, the mechanical properties of the resin composition can be ensured.

[0054] According to one embodiment of the present invention, in the flame retardant resin composition, the amount of the graft copolymer is greater than that of the matrix copolymer, and thus the flame retardant resin composition may have improved impact strength.

[0055] According to one embodiment of the present invention, the flame retardant resin composition may include the graft copolymer in an amount of 38% to 47% by weight relative to the amount of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus flame retardant. Specifically, the flame retardant resin composition may include the graft copolymer in an amount of 38% by weight or more, 39% by weight or more, or 40% by weight or more, and in an amount of 47% by weight or less, 46% by weight or less, or 45% by weight or less relative to the amount of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus flame retardant. Within this range, the flame retardant resin composition may have improved impact strength and obtain excellent flame retardancy.

[0056] 2. Matrix copolymer

[0057] According to one embodiment of the present invention, the matrix copolymer may be a part of the flame retardant resin composition, and may be a resin for imparting basic physical properties to the flame retardant resin composition.

[0058] According to one embodiment of the present invention, the matrix copolymer may include aromatic vinyl-based monomer units and vinyl cyanide-based monomer units, and as a specific example, may be prepared by emulsion polymerization or bulk polymerization of aromatic vinyl-based monomers and vinyl cyanide-based monomers.

[0059] According to one embodiment of the present invention, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit of the matrix copolymer can be at least one selected from styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene, and as a specific example, it can be styrene.

[0060] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit of the matrix copolymer may be at least one selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0061] According to one embodiment of the present invention, the matrix copolymer may contain aromatic vinyl monomer units in an amount of 10 wt % to 90 wt % and vinyl cyanide monomers in an amount of 10 wt % to 90 wt %, and as a specific example, may contain aromatic vinyl monomer units in an amount of 20 wt % or more, 30 wt % or more, 80 wt % or less, or 70 wt % or less, and within this range, the graft copolymer has excellent dispersibility and therefore has an excellent balance of mechanical properties and physical properties.

[0062] The graft copolymer and the matrix copolymer each contain an aromatic vinyl monomer unit and a vinyl cyanide monomer unit. When the aromatic vinyl monomer unit and the vinyl cyanide monomer unit forming each copolymer are of the same type, these units are mixed and dispersed as the same component during the extrusion process of the resin composition. Therefore, in the actual flame-retardant resin composition and the molded article formed therefrom, the conjugated diene polymer can be present in a dispersed form in the matrix formed by the aromatic vinyl monomer unit and the vinyl cyanide monomer unit. Therefore, the amount of each of the graft copolymer and the matrix copolymer in the flame-retardant resin composition can be determined by the total amount of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit and the amount of the conjugated diene polymer in the flame-retardant resin composition.

[0063] According to one embodiment of the present invention, in the flame retardant resin composition, the amount of the matrix copolymer is smaller than that of the graft copolymer, and thus the flame retardant resin composition may have improved impact strength.

[0064] According to one embodiment of the present invention, relative to the amount of graft copolymer, matrix copolymer, polyethylene terephthalate resin and polymerized phosphorus flame retardant, the flame retardant resin composition can include the matrix copolymer in an amount of 25% by weight to 30% by weight. Specifically, relative to the amount of graft copolymer, matrix copolymer, polyethylene terephthalate resin and polymerized phosphorus flame retardant, the flame retardant resin composition can include 22% by weight or more, 23% by weight or more, 24% by weight or more or 25% by weight, and 33% by weight or less, 32% by weight or less, 31% by weight or less or 30% by weight of the matrix copolymer. Within this range, the flame retardant resin composition can have improved impact strength and obtain excellent flame retardancy.

[0065] 3. Polyester resin

[0066] According to one embodiment of the present invention, the polyester-based resin may be used to form char when heat is applied to the flame retardant resin composition.

[0067] According to one embodiment of the present invention, the polyester-based resin may be a polyethylene terephthalate resin or a polybutylene terephthalate resin, and as a more specific example, may be a polyethylene terephthalate resin.

[0068] According to one embodiment of the present invention, the polyester-based resin may have an intrinsic viscosity value of 0.6 to 1.1.

[0069] According to one embodiment of the present invention, the flame retardant resin composition may include polyethylene terephthalate resin in an amount of 18% to 40% by weight relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymerized phosphorus flame retardant. Specifically, the flame retardant resin composition may include more than 18% by weight, more than 19% by weight or more than 20% by weight, and less than 40% by weight, less than 39% by weight, less than 38% by weight or less than 37% by weight of the polyester resin relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymerized phosphorus flame retardant. When the above range is met, excellent flame retardancy can be provided to the flame retardant resin composition without reducing other physical properties.

[0070] According to one embodiment of the present invention, the polyester-based resin may be present in an amount smaller than that of the polymeric phosphorus-based flame retardant. In this case, more excellent flame retardancy may be provided to the flame retardant resin composition.

[0071] 4. Polyphosphorus flame retardants

[0072] According to one embodiment of the present invention, the polymeric phosphorus-based flame retardant is used to provide flame retardancy to the flame retardant resin composition, and may have at least one structural unit represented by Formula 1 as described above.

[0073] More specifically, according to one embodiment of the present invention, the polymeric phosphorus-based flame retardant may have at least one structural unit represented by Formula 2 below.

[0074] [Formula 2]

[0075]

[0076] According to one embodiment of the present invention, the polymeric phosphorus flame retardant may have a weight average molecular weight of 5000 g / mol or more. Specifically, the polymeric phosphorus flame retardant may have a weight average molecular weight of 5,000 g / mol or more, 7,000 g / mol or more, and 10,000 g / mol or more.

[0077] Meanwhile, when the polymeric phosphorus-based flame retardant has at least one structural unit represented by Formula 2, n in the above Formula 2 may be in the range of 1 to 1000. As a specific example, n in the above Formula 2 may be 16 or more, 18 or more, 20 or more, 22 or more, or 24 or more, and may also be 950 or less, 900 or less, 850 or less, 800 or less, or 750 or less. When the above range is met, excellent flame retardancy can be provided without degrading other physical properties of the flame retardant resin composition.

[0078] According to one embodiment of the present invention, the flame retardant resin composition may include the polymeric phosphorus flame retardant in an amount of 18% to 40% by weight relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus flame retardant. Specifically, the flame retardant resin composition may include the polymeric phosphorus flame retardant in an amount of 18% by weight or more, 19% by weight or more, or 20% by weight or more, and in an amount of 39% by weight or less, 38% by weight or less, or 37% by weight or less relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus flame retardant. When the above range is met, the flame retardant resin composition can be provided with excellent flame retardancy without compromising other physical properties.

[0079] 5. Other additives

[0080] According to one embodiment of the present invention, flame retardant resin composition may further include additives.Additives may be selected from at least one of flame retardant auxiliary agents, lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, release agents, pigments, antistatic agents, conductivity imparting agents, electromagnetic wave shielding agents, magnetic imparting agents, mineral fillers, crosslinking agents, antibacterial agents, processing aids, metal passivators, inhibitors, anti-friction and anti-wear agents, compatibilizers, anti-drip agents and coupling agents.Above-mentioned additives can be used without restriction, as long as additives are used in this area, and those skilled in the art can select the additives included in the present invention to adapt to purpose.

[0081] According to one embodiment of the present invention, the flame retardant auxiliary agent in the additive may be ethylene methyl acrylate (EMA).

[0082] The flame retardant auxiliary agent may be included in an amount of 2 to 7 parts by weight relative to 100 parts by weight of the total amount of the graft copolymer, the matrix copolymer, and the polyester resin. Specifically, the flame retardant auxiliary agent may be included in an amount of 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more, and 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the total amount of the graft copolymer, the matrix copolymer, and the polyethylene terephthalate resin. When the above range is met, excellent flame retardancy can be provided to the flame retardant resin composition without reducing other physical properties.

[0083] In addition to the flame retardant auxiliary agent, other additives may be included in an amount of 0.5 to 2 parts by weight relative to 100 parts by weight of the total amount of the graft copolymer, the matrix copolymer, and the polyester resin. When the above range is met, the physical properties of the flame retardant resin composition may not be reduced.

[0084] <Method for Preparing Flame-Retardant Resin Composition>

[0085] The present invention provides a method for preparing a flame retardant resin composition.

[0086] A method for preparing a flame retardant resin composition according to one embodiment of the present invention includes mixing and extruding: a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a polyester resin; and a polymeric phosphorus flame retardant, wherein the polyester resin is present in a smaller amount than the polymeric phosphorus flame retardant, and the polymeric phosphorus flame retardant has at least one structural unit represented by Formula 1 above.

[0087] According to one embodiment of the present invention, the polymeric phosphorus-based flame retardant may have at least one structural unit represented by Formula 2 above.

[0088] According to one embodiment of the present invention, the flame retardant resin composition may include the graft copolymer in an amount of 38 to 47 wt % relative to the total amount of the graft copolymer, the matrix copolymer, the polyester-based resin and the polymeric phosphorus-based flame retardant.

[0089] According to one embodiment of the present invention, the flame retardant resin composition may include the matrix copolymer in an amount of 25 to 30 wt % relative to the total amount of the graft copolymer, the matrix copolymer, the polyester-based resin and the polymeric phosphorus-based flame retardant.

[0090] According to one embodiment of the present invention, the flame retardant resin composition may include the polyester-based resin in an amount of 18 to 40 wt % relative to the total amount of the graft copolymer, the matrix copolymer, the polyester-based resin, and the polymeric phosphorus-based flame retardant.

[0091] According to one embodiment of the present invention, the flame retardant resin composition may include the polymeric phosphorus-based flame retardant in an amount of 18 to 40 wt % relative to the total amount of the graft copolymer, the matrix copolymer, the polyester-based resin, and the polymeric phosphorus-based flame retardant.

[0092] <Molded article formed from the flame retardant resin composition>

[0093] Furthermore, the present invention provides a molded article formed from the flame retardant resin composition.

[0094] According to one embodiment of the present invention, a molded article can be extruded and injection molded from the flame retardant resin composition and can be applied to a product group requiring flame retardancy, specific examples of which can be interior and exterior materials for vehicles, office equipment, and parts for various electrical / electronic products.

[0095] Hereinafter, embodiments of the present invention will be described in detail in a manner that can be easily performed by those skilled in the art. However, the present invention can be embodied in many different forms and is not limited to the embodiments set forth in this specification.

[0096] Examples and Comparative Examples

[0097] In Examples and Comparative Examples, the following components were generally mixed in parts by weight as shown in Tables 1 to 3 below.

[0098] (A) Graft copolymer: ABS resin (DP270 from LG Chemical).

[0099] (B) Matrix copolymer: SAN resin (90HR from LG Chem).

[0100] (C) Polyester resin: (C-1) or (C-2), (C-1) is a PET resin (Hubis, IV = 0.6 to 0.7), (C-2) is a PETG resin (SKYGREEN K2012 from SK Chemicals).

[0101] (D) Polyphosphorus flame retardant: HM1100 from Nofia

[0102] (E) Flame retardant additive: ethylene methyl acrylate (EMA).

[0103] (F) Other additives: N,N-ethylene-bisstearamide (compatibilizer) and polytetrafluoroethylene (anti-drip agent)

[0104] [Table 1]

[0105]

[0106] [Table 2]

[0107]

[0108] [Table 3]

[0109]

[0110] Experimental example

[0111] Flame retardancy (UL-94V test, vertical burning test): A test specimen according to the UL standard (125 mm × 12.5 mm) was prepared by injecting the flame retardant resin composition prepared in the above Examples and Comparative Examples to obtain a test specimen having a thickness of 2.0 mm. The results determined by recording the first burning time and the second burning time and the luminous time are shown in Tables 4 to 6 below.

[0112] In the method of judging UL-94 based on the first burning time and the second burning time and the luminous time, when the first burning time and the second burning time are each within 10 seconds, the total burning time of all five samples is within 50 seconds, and ignition on the lower cotton does not occur, the case is evaluated as V-0; when the first burning time and the second burning time are each within 30 seconds, the total burning time of all five samples is within 250 seconds, and ignition on the lower cotton does not occur, the case is evaluated as V-1; and when the burning time is the same as V-1, but ignition on the lower cotton occurs, the case is evaluated as NR.

[0113] Impact strength: (Izod notched impact strength, kgf·cm / cm): The results of Izod notched impact strength measurements of 1 / 4 inch thick specimens at 23° C. in accordance with ASTM D256 are shown in Tables 4 to 6 below.

[0114] Heat Deflection Temperature (HDT, °C): The measurement results using the test specimens according to ASTM D648 are shown in Tables 4 to 6 below.

[0115] Tensile strength (TS, Kgf / cm 2 ): The measurement results using the test specimens according to ASTM D638 are shown in Tables 4 to 6 below.

[0116] [Table 4]

[0117]

[0118] [Table 5]

[0119]

[0120] [Table 6]

[0121]

[0122] As shown in Tables 4 to 6 above, compared with Comparative Example 1 in which the polyester resin is present in the same amount as the polymeric phosphorus-based flame retardant, and Comparative Examples 2 and 3 in which the polyester resin is present in an amount greater than the polymeric phosphorus-based flame retardant, Examples 1 to 14 were determined to have comparable tensile strength and heat deflection temperature and to obtain excellent flame retardancy.

[0123] At the same time, the flame retardancy evaluation of Comparative Example 4 should be compared with Examples 9 and 10. This is because the greater the amount of polyester resin and polymeric phosphorus flame retardant in the resin composition, the better the flame retardancy of the resin composition. Therefore, in the evaluation of the flame retardancy of the resin composition, accurate flame retardancy evaluation can only be performed when comparing resin compositions containing the same amount of polyester resin and polymeric phosphorus flame retardant. Therefore, when comparing Comparative Example 4 with Examples 9 and 10, it was determined that Comparative Example 4, in which the polyester resin was present in an amount greater than the polymeric phosphorus flame retardant, had reduced flame retardancy compared to Examples 9 and 10.

[0124] When comparing Examples 1 to 4, which have the same composition of the polyester resin and the polymeric phosphorus-based flame retardant but different ratios of the graft copolymer and the matrix copolymer, it was confirmed that Examples 3 and 4, in which the graft copolymer was present in an amount greater than the matrix copolymer, had superior impact strength than Example 1, in which the graft copolymer was present in an amount less than the matrix copolymer, and Example 2, in which the graft copolymer was present in the same amount as the matrix copolymer.

[0125] When comparing Examples 3, 4, and 7, in which the graft copolymer is present in an amount greater than that of the matrix copolymer and the polyester resin and the polymeric phosphorus-based flame retardant are present in the same amount, it is confirmed that Examples 3 and 4, which contain appropriate amounts of the polyester resin and the polymeric phosphorus-based flame retardant, have superior impact strength compared to Example 7, which contains less than 18% by weight of the polyethylene terephthalate resin and more than 40% by weight of the polymeric phosphorus-based flame retardant, relative to the total amount of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus-based flame retardant.

Claims

1. A flame retardant resin composition comprising: A graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; A matrix copolymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units; Polyester resin; and Polyphosphate flame retardants, in, The polyester resin is present in an amount smaller than that of the polymeric phosphorus flame retardant, and The polymeric phosphorus-based flame retardant has at least one structural unit represented by the following formula 1: [Formula 1] wherein in Formula 1, R1 to R3 are each hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an arylene group having 6 to 20 carbon atoms, n is a natural number.

2. The flame retardant resin composition according to claim 1, wherein The graft copolymer is present in a greater amount than the matrix copolymer.

3. The flame retardant resin composition according to claim 2, wherein Relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant, The content of the graft copolymer is 38 wt% to 47 wt%, The content of the matrix copolymer is 22 wt% to 33 wt%.

4. The flame retardant resin composition according to claim 1, wherein Relative to the total amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant, The content of the polyester resin is 18% to 40% by weight. The content of the polymeric phosphorus flame retardant is 18 wt % to 40 wt %.

5. The flame retardant resin composition according to claim 4, wherein The polyester resin is polyethylene terephthalate resin. The flame retardant resin composition according to claim 1, wherein Relative to the amount of the graft copolymer, the matrix copolymer, the polyester resin and the polymeric phosphorus flame retardant, The content of the polyester resin is 18% to 40% by weight. The content of the polymeric phosphorus flame retardant is 18% to 40% by weight. The graft copolymer is present in a greater amount than the matrix copolymer.

7. The flame retardant resin composition according to claim 1, wherein The polymeric phosphorus flame retardant has at least one structural unit represented by the following formula 2: [Formula 2] 8. The flame retardant resin composition according to claim 7, wherein In the above-mentioned Formula 2, n is in the range of 1 to 1000.

9. The flame retardant resin composition according to claim 1, wherein The polymeric phosphorus flame retardant has a weight average molecular weight of 5000 g / mol or more.

10. A method for preparing a flame retardant resin composition, the method comprising: Mixing and extruding a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; and a polyester resin; and polymeric phosphorus flame retardants, wherein the polyester resin is present in an amount less than that of the polymeric phosphorus flame retardant, and The polymeric phosphorus-based flame retardant has at least one structural unit represented by the following formula 1: [Formula 1] wherein in Formula 1, R1 to R3 are each hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an arylene group having 6 to 20 carbon atoms, n is a natural number.

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