Flame-retardant resin composition and method for producing the same

Abstract

The present invention relates to a flame-retardant resin composition in which excellent flame retardancy is ensured by including a specific compound as a phosphorus-based flame retardant in the resin composition, and to a method for producing the same.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2023-0045524 filed on April 6, 2023, and all the contents disclosed in the literature of the Korean Patent Application are incorporated herein by reference in their entirety.

[0002] The present invention relates to a flame-retardant resin composition containing a flame retardant and a method for producing the same.

Background Art

[0003] Generally, styrenic resins include acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, and the like. As an example, in the case of the acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin, due to the rigidity and chemical resistance of acrylonitrile, and the processability and mechanical strength of butadiene and styrene, it is widely used as an exterior material for electrical / electronic products and office equipment. However, the ABS resin itself has the characteristic of being easily combustible and has little resistance to fire. Therefore, the ABS resin used in electrical / electronic products and office equipment needs to meet the flame-retardant standard in order to ensure the stability of electrical / electronic products against fire.

[0004] Regarding regulations on flame retardancy, in accordance with the UL (Underwriters Laboratories) standard, in order to manufacture a resin composition having flame retardancy suitable for the UL standard, particularly a thermoplastic resin composition, mainly, a method of kneading a halogen-based flame retardant into a thermoplastic resin has been adopted. Thus, the method of applying a halogen-based flame retardant to impart flame retardancy to a thermoplastic resin has the merit of excellent flame retardancy and little reduction in the physical properties of the final product. However, during processing, hydrogen halide gas may be generated, which may damage the mold. Due to the presence of halogen compounds, at the time of disposal, both dioxins having strong carcinogenicity and hydrogen bromide gas are discharged from the incinerator, which has a problem of adversely affecting the environment and the human body.

[0005] Therefore, among the flame retardants used in flame-retardant resin compositions, many flame retardants that do not use halogens are called non-halogen flame retardants, and the most widely used non-halogen flame retardants are phosphorus-based flame retardants containing phosphorus. However, phosphorus-based flame retardants have the disadvantage that, depending on the type of styrene resin, they cannot generate char due to the principle of the phosphorus-based flame retardant system, making it difficult to fully exhibit flame retardancy. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] China Patent Publication No. 103772882 A [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention was derived to solve the problems of the above-mentioned prior art, and aims to provide a flame-retardant resin composition and a method for producing the same, in which excellent flame retardancy is ensured by including a specific compound as a phosphorus-based flame retardant in the resin composition. [Means for solving the problem]

[0008] (1) The present invention provides a flame-retardant resin composition comprising a graft copolymer containing a conjugated diene polymer, aromatic vinyl monomer units and vinyl cyanide monomer units, a matrix copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a polyester resin, and a polymeric phosphorus-based flame retardant, wherein the content of the polyester resin is less than the content of the polymeric phosphorus-based flame retardant, and the polymeric phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 1. [ka] Here, R1 to R3 are each either hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each allylene groups having 6 to 20 carbon atoms, and n is a natural number.

[0009] (2) The present invention provides a flame-retardant resin composition in which the content of the graft copolymer is greater than the content of the matrix copolymer, as described in (1) above.

[0010] (3) The present invention provides a flame-retardant resin composition in which, with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant, the graft copolymer is contained in an amount of 38% to 47% by weight and the matrix copolymer is contained in an amount of 22% to 33% by weight.

[0011] (4) The present invention provides a flame-retardant resin composition in which, in any one of (1) to (3) above, the polyester resin is contained in an amount of 18% to 40% by weight and the polymer-type phosphorus-based flame retardant is contained in an amount of 18% to 40% by weight with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin and the polymer-type phosphorus-based flame retardant.

[0012] (5) The present invention provides a flame-retardant resin composition in which, in any one of (1) to (4) above, the polyester resin is polyethylene terephthalate resin.

[0013] (6) The present invention provides a flame-retardant resin composition in which, in any one of (1) to (5) above, the polyester resin is contained in an amount of 18% to 40% by weight, the polymer-type phosphorus-based flame retardant is contained in an amount of 18% to 40% by weight, and the graft copolymer content is greater than the matrix copolymer content.

[0014] (7) In any one of the above (1) to (6), the present invention provides a flame-retardant resin composition in which the polymer-type phosphorus-based flame retardant has one or more structural units represented by the following Chemical Formula 2.

Chem.

[0015] (8) In any one of the above (1) to (7), the present invention provides a flame-retardant resin composition in which in Chemical Formula 2, n is 1 or more and 1000 or less.

[0016] (9) In any one of the above (1) to (8), the present invention is a flame-retardant resin composition in which the weight-average molecular weight of the polymer-type phosphorus-based flame retardant is 5000 g / mol or more.

[0017] (10) The present invention includes a step of mixing and extruding a graft copolymer containing a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyanide-based monomer unit, a matrix copolymer containing an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit, a polyester-based resin, and a polymer-type phosphorus-based flame retardant. The content of the polyester-based resin is smaller than the content of the polymer-type phosphorus-based flame retardant, and the polymer-type phosphorus-based flame retardant has one or more structural units represented by the following Chemical Formula 1, and provides a method for producing a flame-retardant resin composition.

Chem.

Advantages of the Invention

[0018] According to the present invention, a flame-retardant resin composition with excellent flame retardancy can be provided.

Modes for Carrying Out the Invention

[0019] Hereinafter, in order to facilitate the understanding of the present invention, the present invention will be described in more detail.

[0020] In the description of the present invention and the claims, terms and words used should not be construed as being limited to their ordinary or dictionary meanings. The inventors should interpret them in accordance with the principle that they can appropriately define the concept of terms in order to explain their invention in the best way, and should interpret them in meanings and concepts consistent with the technical idea of the present invention.

[0021] The terms used in this specification are merely used to illustrate exemplary embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly has a different meaning.

[0022] In the present invention, the term "monomer unit" can indicate a component, structure, or the substance itself originating from a monomer. As a specific example, when a polymer is polymerized, the monomer introduced participates in the polymerization reaction and can mean the repeating unit formed within the polymer.

[0023] In the present invention, the "weight average molecular weight" is generally measured by gel permeation chromatography (GPC). For example, after dissolving the sample to be measured in a THF (tetrahydrofuran) solution, it can be measured as a relative value to a standard sample (PS, standard polystyrene) by gel permeation chromatography (GPC).

[0024] The term "composition" used in the present invention includes not only reaction products and decomposition products formed from the materials of the composition, but also mixtures of materials containing the composition.

[0025] <Flame-retardant resin composition> The present invention provides a resin composition, specifically, a flame-retardant resin composition.

[0026] The flame-retardant resin composition according to one embodiment of the present invention comprises a graft copolymer containing a conjugated diene polymer, aromatic vinyl monomer units and vinyl cyanide monomer units, a matrix copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a polyester resin, and a polymeric phosphorus-based flame retardant, wherein the content of the polyester resin is less than the content of the polymeric phosphorus-based flame retardant, and the polymeric phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 1.

[0027] [ka]

[0028] Here, R1 and R3 are either hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are allylene groups having 6 to 20 carbon atoms, and n is a natural number. In this specification, alkyl groups may be linear or branched, and allylene groups have two bonding positions to an aromatic ring group, i.e., they are divalent groups.

[0029] According to one embodiment of the present invention, R1 to R3 in the chemical formula 1 are each hydrogen or one alkyl group having 1 to 10 carbon atoms, and A1 and A2 may each be allylene groups having 6 to 15 carbon atoms. As a more specific example, R1 and R3 in the chemical formula 1 are each hydrogen or one alkyl group having 1 to 5 carbon atoms, and A1 and A2 may each be allylene groups having 6 to 10 carbon atoms.

[0030] 1. Graft copolymer 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 that imparts basic physical properties to the flame-retardant resin composition.

[0031] According to one embodiment of the present invention, the graft copolymer may include a conjugated diene polymer, aromatic vinyl monomer units, and vinyl cyanide monomer units. Specifically, the conjugated diene polymer may be produced by polymerization of a conjugated diene monomer and may contain conjugated diene monomer units. More specifically, the conjugated diene polymer may be produced by emulsion polymerization of a conjugated diene monomer. In this case, the average particle size of the conjugated diene polymer can be easily adjusted, and a conjugated diene polymer suitable for the desired mechanical properties can be used.

[0032] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit of the conjugated diene polymer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and a more specific example may be 1,3-butadiene.

[0033] According to one embodiment of the present invention, the graft copolymer may be obtained by graft polymerization of aromatic vinyl monomer units and vinyl cyanide monomer units onto a conjugated diene polymer. Therefore, the graft copolymer may contain the conjugated diene polymer and aromatic vinyl monomer units and vinyl cyanide monomer units grafted onto the conjugated diene polymer, and depending on the graft polymerization conditions, the portion of the graft copolymer where the graft layer is formed may contain both vinyl monomer units and vinyl cyanide monomer units that are not grafted onto the conjugated diene polymer. Here, the graft polymerization can be carried out by emulsion polymerization or bulk polymerization.

[0034] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the graft copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and a specific example may be styrene.

[0035] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer units of the graft copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and a specific example may be acrylonitrile.

[0036] According to one embodiment of the present invention, the graft copolymer may contain 40% to 90% by weight of a conjugated diene polymer, 5% to 50% by weight of aromatic vinyl monomer units, and 1% to 30% by weight of vinyl cyanide monomer units. Specifically, it may contain 50% to 80% or 70% by weight of a conjugated diene polymer; 10% to 40% or 30% by weight of aromatic vinyl monomer units; and 1% to 5% to 20% or 15% by weight of vinyl cyanide monomer units. Within this range, the mechanical properties of the resin composition can be ensured.

[0037] According to one embodiment of the present invention, the impact strength of the flame-retardant resin composition can be improved by having a greater content of the graft copolymer than the content of the matrix copolymer in the flame-retardant resin composition.

[0038] According to one embodiment of the present invention, the flame-retardant resin composition may contain 38% to 47% by weight of the graft copolymer relative to the content of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus-based flame retardant. Specifically, the flame-retardant resin composition may contain 38% or more, 39% or more, or 40% or more by weight of the graft copolymer, as well as 47% or less by weight, 46% or less by weight, or 45% or less by weight, relative to the content of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus-based flame retardant. Within this range, the impact strength of the flame-retardant resin composition can be improved, and excellent flame retardancy can be ensured.

[0039] 2. Matrix copolymer According to one embodiment of the present invention, the matrix copolymer may be a resin that provides basic physical properties to the flame-retardant resin composition as part of the flame-retardant resin composition.

[0040] According to one embodiment of the present invention, the matrix copolymer may contain aromatic vinyl monomer units and vinyl cyanide monomer units, and as a specific example, it may be produced by emulsion polymerization or bulk polymerization of aromatic vinyl monomers and vinyl cyanide monomers.

[0041] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the matrix copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and a specific example may be styrene.

[0042] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer units of the matrix copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and a specific example may be acrylonitrile.

[0043] According to one embodiment of the present invention, the matrix copolymer may contain 10% to 90% by weight of aromatic vinyl monomer units and 10% to 90% by weight of vinyl cyanide monomer units. Specifically, it may contain 20% or more, 30% or more, 80% or less by weight, or 70% or less by weight of aromatic vinyl monomer units. Within this range, the graft copolymer exhibits excellent dispersibility and has the effect of having excellent mechanical properties and balance of physical properties.

[0044] The graft copolymer and matrix copolymer each contain aromatic vinyl monomer units and vinyl cyanide monomer units, respectively. When the types of aromatic vinyl monomer units and vinyl cyanide monomer units forming each copolymer are the same, they are mixed and dispersed with the same components during the extrusion process of the resin composition. Therefore, in the flame-retardant resin composition and the molded articles formed therefrom, the conjugated diene polymer can exist in a dispersed form within the matrix formed by the aromatic vinyl monomer units and vinyl cyanide monomer units. Accordingly, the respective contents of the graft copolymer and matrix copolymer in the flame-retardant resin composition can be determined from the total contents of aromatic vinyl monomer units and vinyl cyanide monomer units and the contents of the conjugated diene polymer in the flame-retardant resin composition.

[0045] According to one embodiment of the present invention, the impact strength of the flame-retardant resin composition can be improved by having a smaller content of the matrix copolymer in the flame-retardant resin composition than the content of the graft copolymer.

[0046] According to one embodiment of the present invention, the flame-retardant resin composition may contain 25% to 30% by weight of the matrix copolymer relative to the content of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus-based flame retardant. Specifically, the flame-retardant resin composition may contain 22% or more by weight, 23% or more by weight, 24% or more by weight, or 25% or more by weight of the matrix copolymer, and may contain 33% or less by weight, 32% or less by weight, 31% or less by weight, or 30% or less by weight, relative to the content of the graft copolymer, the matrix copolymer, the polyethylene terephthalate resin, and the polymeric phosphorus-based flame retardant. Within this range, the impact strength of the flame-retardant resin composition can be improved, and excellent flame retardancy can be ensured.

[0047] 3. Polyester resin According to one embodiment of the present invention, the polyester resin can play a role in forming char when heat is applied to the flame-retardant resin composition.

[0048] According to one embodiment of the present invention, the polyester resin may be polyethylene terephthalate resin or polybutylene terephthalate resin, and more specifically, polyethylene terephthalate resin.

[0049] According to one embodiment of the present invention, the intrinsic viscosity of the polyester resin can have a value of 0.6 to 1.1.

[0050] According to one embodiment of the present invention, the flame-retardant resin composition may contain 18% to 40% by weight of the polyethylene terephthalate resin relative to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant. Specifically, the flame-retardant resin composition may contain 18% or more by weight, 19% or more by weight, or 20% or more by weight of the polyester resin, and 40% or less by weight, 39% or less by weight, 38% or less by weight, or 37% or less by weight, relative to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant. When the above ranges are met, the flame-retardant resin composition can be given excellent flame retardancy without deterioration of other physical properties.

[0051] According to one embodiment of the present invention, the content of the polyester resin can be less than the content of the polymer-type phosphorus-based flame retardant. In this case, the flame retardant resin composition can be given better flame retardancy.

[0052] 4. High molecular weight phosphorus-based flame retardants According to one embodiment of the present invention, the polymeric phosphorus-based flame retardant is for providing flame retardancy to the flame retardant resin composition, and as described above, may have one or more structural units represented by the chemical formula 1.

[0053] More specifically, according to one embodiment of the present invention, the polymeric phosphorus-based flame retardant may have one or more structural units represented by the following chemical formula 2.

[0054] [ka]

[0055] According to one embodiment of the present invention, the weight-average molecular weight of the polymer-type phosphorus-based flame retardant may be 5000 g / mol or more. Specifically, the weight-average molecular weight of the polymer-type phosphorus-based flame retardant may be 5000 g / mol or more, or 7000 g / mol or more and 10000 g / mol or more.

[0056] On the other hand, if the polymeric phosphorus-based flame retardant has one or more structural units represented by chemical formula 2, then n in chemical formula 2 may be between 1 and 1000. Specifically, n in chemical formula 2 may be between 16 and 18, 20 and 22 or 24, or between 950, 900 or 850, 800 or 750. When the above range is satisfied, it is possible to provide excellent flame retardancy without degrading other physical properties of the flame retardant resin composition.

[0057] According to one embodiment of the present invention, the flame-retardant resin composition may contain 18% to 40% by weight of the polymeric phosphorus-based flame retardant relative to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant. Specifically, the flame-retardant resin composition may contain 18% or more, 19% or more by weight, or 20% or more by weight of the polymeric phosphorus-based flame retardant, and 40% or less by weight, 39% or less by weight, 38% or less by weight, or 37% or less by weight, relative to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant. When the above range is satisfied, the flame-retardant resin composition can be given excellent flame retardancy without deterioration of other physical properties.

[0058] 5. Other additives According to one embodiment of the present invention, the flame-retardant resin composition may further contain additives. The additive may be one or more selected from the group consisting of flame retardant enhancers, lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, mold release agents, pigments, antistatic agents, conductivity enhancers, electromagnetic shielding agents, magnetic enhancers, mineral fillers, crosslinking agents, antibacterial agents, processing aids, metal deactivators, smoke suppressants, friction and wear resistant agents, compatibilizers, anti-dripping agents, and coupling agents. The additive may be used without limitation as long as it is used in the art of the present invention, and an ordinary person of the art can select the additives included in the present invention according to the purpose.

[0059] According to one embodiment of the present invention, the flame retardant additive may be ethylene methyl acrylate (EMA).

[0060] The flame retardant additive may be present in amounts of 2 to 7 parts by weight per 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin. Specifically, the flame retardant additive may be present in amounts of 2 to 2.5 parts by weight, or 3 parts by weight, and 7 to 6 parts by weight, or 5 parts by weight, per 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyethylene terephthalate resin. When the above ranges are met, the flame retardant resin composition can be given excellent flame retardancy without deterioration of other physical properties.

[0061] The remaining additives other than the flame retardant aid may be present in amounts of 0.5 parts by weight or more and 2 parts by weight or less, based on the total content 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 can be not impaired.

[0062] <Method for producing flame-retardant resin composition> The present invention provides a method for producing the aforementioned flame-retardant resin composition.

[0063] A method for producing a flame-retardant resin composition according to one embodiment of the present invention comprises the steps of mixing a graft copolymer containing a conjugated diene polymer, aromatic vinyl monomer units and vinyl cyanide monomer units, a matrix copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a polyester resin, and a polymeric phosphorus-based flame retardant, and extruding the mixture, wherein the content of the polyester resin is less than the content of the polymeric phosphorus-based flame retardant, and the polymeric phosphorus-based flame retardant has one or more structural units represented by the chemical formula 1.

[0064] According to one embodiment of the present invention, the polymeric phosphorus-based flame retardant may have one or more structural units represented by the chemical formula 2.

[0065] According to one embodiment of the present invention, the flame-retardant resin composition may contain 38% to 47% by weight of the graft copolymer with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant.

[0066] According to one embodiment of the present invention, the flame-retardant resin composition may contain 25% to 30% by weight of the matrix copolymer with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant.

[0067] According to one embodiment of the present invention, the flame-retardant resin composition may contain 18% to 40% by weight of the polyester resin with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymeric phosphorus-based flame retardant.

[0068] According to one embodiment of the present invention, the flame-retardant resin composition may contain 18% to 40% by weight of the polymer-type phosphorus-based flame retardant with respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymer-type phosphorus-based flame retardant.

[0069] <Molded articles made from flame-retardant resin compositions> Furthermore, the present invention provides a molded article formed from the flame-retardant resin composition.

[0070] According to one embodiment of the present invention, the molded article may be extruded and injection molded from the flame-retardant resin composition and is applicable to a group of products requiring flame retardancy. Specific examples include automotive interior and exterior materials, office equipment, and components for various electrical and electronic products.

[0071] Hereinafter, embodiments of the present invention will be described in detail so that they can be easily implemented by a person with ordinary skill in the art to which the present invention pertains. However, the present invention can be realized in various different forms and is not limited to the embodiments described herein.

[0072] Examples and Comparative Examples In both the examples and comparative examples, the following components were commonly blended in the parts by weight listed in Tables 1 and 3 below.

[0073] (A) Graft copolymer: ABS resin (manufactured by LG Chem, product name: DP270). (B) Matrix copolymer: SAN resin (manufactured by LG Chem, product name: 90HR). (C) Polyester resin: Either (C-1) or (C-2), where (C-1) is PET resin (manufactured by Hubis, IV=0.6~0.7) and (C-2) is PETG resin (manufactured by SK Chemical, product name: SKYGREEN K2012). (D) High-molecular-weight phosphorus-based flame retardant: Manufactured by Nofia, product name: HM1100. (E) Flame retardant: Ethylene methyl acrylate (EMA). (F) Other additives: N,N-ethylene-bis-stearamide (compatibilizer) and polytetrafluoroethylene (delay agent)

[0074] [Table 1]

[0075] [Table 2]

[0076] [Table 3]

[0077] Experimental example *Flame retardancy (UL-94 V Test, Vertical Burning Test): Test specimens were manufactured by injecting the flame retardant resin compositions produced in the above examples and comparative examples to conform to UL standards (125 mm x 12.5 mm). The primary and secondary burning times and glowing time were recorded on 2.0 mm thick test specimens, and the results are shown in Tables 4 to 6 below.

[0078] The UL-94 judgment method, based on the primary and secondary burning times and glowing time, was as follows: If the primary and secondary burning times were each within 10 seconds, the total burning time of all five test specimens was within 50 seconds, and no ignition of the lower cotton was observed, it was evaluated as V-0; if the primary and secondary burning times were each within 30 seconds, the total burning time of all five test specimens was within 250 seconds, and no ignition of the lower cotton was observed, it was evaluated as V-1; and if the burning time was the same as V-1 but ignition of the lower cotton was observed, it was judged as NR.

[0079] *Impact Strength (Notched Izod Impact Strength, kgf·cm / cm): The notched Izod impact strength was measured at 23°C for 1 / 4 inch thick specimens in accordance with ASTM D256. The results are shown in Tables 4 and 6 below.

[0080] *Thermal distortion temperature (HDT, °C): The results measured using test specimens in accordance with ASTM D648 are shown in Tables 4 to 6 below.

[0081] *Tensile strength (TS, Kgf / cm²) 2 The results of measurements performed using test specimens in accordance with ASTM D638 are shown in Tables 4 to 6 below.

[0082] [Table 4]

[0083] [Table 5]

[0084] [Table 6]

[0085] As shown in Tables 4 to 6 above, Examples 1 to 14 had comparable levels of tensile strength and heat distortion temperature, and excellent flame retardancy was confirmed to be achieved compared to Comparative Example 1, in which the polyester resin content and polymeric phosphorus-based flame retardant content were the same, and Comparative Examples 2 and 3, in which the polyester resin content was greater than the polymeric phosphorus-based flame retardant content.

[0086] On the other hand, the flame retardancy evaluation of Comparative Example 4 must be performed in comparison with Examples 9 and 10. This is because the flame retardancy of the resin composition can be improved as the content of polyester resin and polymer-type phosphorus-based flame retardant in the resin composition increases, and an accurate evaluation of flame retardancy can be performed when comparing resin compositions with the same content of polyester resin and polymer-type phosphorus-based flame retardant. Therefore, when comparing Comparative Example 4 with Examples 9 and 10, it was confirmed that Comparative Example 4, which has a higher content of polyester resin and polymer-type phosphorus-based flame retardant, showed a decrease in flame retardancy compared to Examples 9 and 10.

[0087] Although the composition of the polyester resin and the polymeric phosphorus-based flame retardant were the same, when comparing the ratio of graft copolymer to matrix copolymer in other embodiments 1 to 4, it was confirmed that Examples 3 and 4, in which the graft copolymer content was greater than the matrix copolymer content, exhibited superior impact strength compared to Example 1, in which the graft copolymer content was smaller than the matrix copolymer content, and Example 2, in which the graft copolymer content and matrix copolymer content were the same.

[0088] Comparing Examples 3, 4, and 7, in which the graft copolymer content is greater than the matrix copolymer content and the polyester resin and polymeric phosphorus-based flame retardant content are the same, it was confirmed that Examples 3 and 4, which contain appropriate amounts of polyester resin and polymeric phosphorus-based flame retardant relative to the total content of graft copolymer, matrix copolymer polyethylene terephthalate resin, and polymeric phosphorus-based flame retardant, exhibit superior impact strength compared to Example 7, in which the polyethylene terephthalate resin content is less than 18% by weight and the polymeric phosphorus-based flame retardant content exceeds 40% by weight.

Claims

1. Graft copolymers comprising conjugated diene polymers, aromatic vinyl monomer units and vinyl cyanide monomer units, A matrix copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, Polyester resin and It contains a polymeric phosphorus-based flame retardant, The content of the polyester resin is less than the content of the polymer-type phosphorus-based flame retardant. The polymer-type phosphorus-based flame retardant is a flame-retardant resin composition having one or more structural units represented by the following chemical formula 1. 【Chemistry 1】 Here, R １ ~R ３ Each of these is either hydrogen or an alkyl group having 1 to 30 carbon atoms, and A １ and A ２ These are allylene groups with 6 to 20 carbon atoms, and n is a natural number.

2. The flame-retardant resin composition according to claim 1, wherein the content of the graft copolymer is greater than the content of the matrix copolymer.

3. With respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymer-type phosphorus-based flame retardant, The graft copolymer contains 38% by weight or more and 47% by weight or less, The flame-retardant resin composition according to claim 2, comprising 22% by weight or more and 33% by weight or less of the matrix copolymer.

4. With respect to the total content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymer-type phosphorus-based flame retardant, The aforementioned polyester resin contains 18% by weight or more and 40% by weight or less, The flame-retardant resin composition according to claim 1, comprising 18% by weight or more and 40% by weight or less of the polymer-type phosphorus-based flame retardant.

5. The flame-retardant resin composition according to claim 4, wherein the polyester resin is polyethylene terephthalate resin.

6. With respect to the content of the graft copolymer, the matrix copolymer, the polyester resin, and the polymer-type phosphorus-based flame retardant, The aforementioned polyester resin contains 18% by weight or more and 40% by weight or less, The above polymer-type phosphorus-based flame retardant contains 18% by weight or more and 40% by weight or less, The flame-retardant resin composition according to claim 1, wherein the content of the graft copolymer is greater than the content of the matrix copolymer.

7. The flame-retardant resin composition according to claim 1, wherein the polymer-type phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 2. 【Chemistry 2】

8. The flame-retardant resin composition according to claim 7, wherein in the chemical formula 2, n is 1 or more and 1000 or less.

9. The flame-retardant resin composition according to claim 1, wherein the weight-average molecular weight of the polymer-type phosphorus-based flame retardant is 5000 g / mol or more.

10. The process includes the steps of mixing a graft copolymer containing a conjugated diene polymer, aromatic vinyl monomer units and vinyl cyanide monomer units, a matrix copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a polyester resin, and a polymeric phosphorus-based flame retardant, and then extruding the mixture. The content of the polyester resin is less than the content of the polymer-type phosphorus-based flame retardant. A method for producing a flame-retardant resin composition having one or more structural units represented by the following chemical formula 1, wherein the polymer-type phosphorus-based flame retardant is... 【Transformation 3】 Here, R １ ~R ３ Each of these is either hydrogen or an alkyl group having 1 to 30 carbon atoms. A １ and A ２ These are allylene groups with 6 to 20 carbon atoms, n is a natural number.

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