Flame-retardant resin composition and method for producing the same

Abstract

The present invention improves impact strength and flame retardancy by applying a first flame retardant additive containing EMA (ethylene methylacrylate copolymer) and / or a second flame retardant additive containing silane-coated ammonium polyphosphate (SAPP) as flame retardant additives to a flame retardant resin composition to which a reactive phosphorus-based flame retardant is applied.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2023-0045525 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, styrene resins include acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, etc. 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 property of being easily combustible and has almost no 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 UL (Underwriters Laboratories) standards, in order to produce a resin composition having flame retardancy suitable for UL standards, particularly a thermoplastic resin composition, mainly a method of kneading a halogen-based flame retardant with 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 almost no reduction in the physical properties of the final product. However, during processing, there is a possibility that hydrogen halide gas is generated and damages the mold, and due to the presence of halogen compounds, dioxins having strong carcinogenicity are discharged together from the incinerator during disposal, which has a problem of adversely affecting the environment and the human body.

[0005] Therefore, flame retardants that do not use halogens, known as non-halogen flame retardants, are widely used, 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] Korean Registered Patent Publication No. 10-2145797 B1 [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 impact strength and flame retardancy are simultaneously improved by applying a reactive phosphorus-based flame retardant and EMA (Ethylene methylacrylate) and / or an ammonium phosphate-based compound as a flame retardant aid to the flame-retardant 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, a polymeric phosphorus-based flame retardant, and a first flame retardant aid containing an alkyl methyl acrylate copolymer.

[0009] (2) The present invention provides a flame-retardant resin composition in which the polymeric phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 1, as described in (1) above. [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.

[0010] (3) The present invention provides a flame-retardant resin composition in which the polymeric phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 2, in accordance with (1) or (2) above. [ka]

[0011] (4) The present invention provides a flame-retardant resin composition in which, in the chemical formula 2, n is 1 or more and 1000 or less, as described in (3) above.

[0012] (5) The present invention provides a flame-retardant resin composition in which, in any one of (1) to (4) above, the first flame-retardant additive is contained in an amount of 0.1 parts by weight or more and 7 parts by weight or less, based on the total content of the graft copolymer, the matrix copolymer, and the polyester resin of 100 parts by weight.

[0013] (6) The present invention provides a flame-retardant resin composition further comprising a second flame-retardant additive, wherein, in any one of (1) to (5) above, ammonium polyphosphate and / or its derivatives are coated and crosslinked with one selected from the group consisting of silane, siloxane, melamine, and melamine resin.

[0014] (7) The present invention provides a flame-retardant resin composition in which, in any one of (1) to (6) above, the second flame-retardant additive is the ammonium polyphosphate or a derivative thereof coated and cross-linked with silane.

[0015] (8) The present invention provides a flame-retardant resin composition comprising 1 to 3 parts by weight of the second flame-retardant aid with respect to 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin in any one of the above (1) to (7).

[0016] (9) The present invention provides 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 in any one of the above (1) to (8).

[0017] (10) The present invention provides a flame-retardant resin composition comprising 18 to 40% by weight of the polyester resin and 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 in any one of the above (1) to (9).

[0018] (11) The present invention provides a method for producing a flame-retardant resin composition, which 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 resin, a polymer-type phosphorus-based flame retardant, and a first flame-retardant aid containing an (alkyl) methyl acrylate copolymer, wherein the polymer-type phosphorus-based flame retardant has one or more structural units represented by the chemical formula 1.

Advantages of the Invention

[0019] According to the present invention, it is possible to provide a flame-retardant resin composition in which excellent impact strength and flame retardancy are simultaneously ensured.

Brief Description of the Drawings

[0020] [Figure 1] It is a diagram showing the FT-IR spectra measured for the flame-retardant resin composition of Example 1 and the flame-retardant resin composition of the Comparative Example.

Modes for Carrying Out the Invention

[0021] Hereinafter, in order to facilitate the understanding of the present invention, the present invention will be described in more detail.

[0022] In the description and claims of the present invention, 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 meaning and concept consistent with the technical idea of the present invention in accordance with the principle that they can appropriately define the concept of terms in order to explain their invention in the best way.

[0023] 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.

[0024] In the present invention, the term "monomeric unit" can indicate a component, structure, or the substance itself resulting 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.

[0025] 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).

[0026] 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 including the composition.

[0027] <Flame-retardant resin composition> The present invention provides a resin composition, specifically, a flame-retardant resin composition.

[0028] 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, a polymeric phosphorus-based flame retardant, and a first flame-retardant aid containing an ethylene methyl acrylate copolymer, wherein the polymeric phosphorus-based flame retardant has one or more structural units represented by the following chemical formula 1.

[0029] [ka]

[0030] Here, R1 to R3 are each either hydrogen or an alkyl group having 1 to 30 carbon atoms, A1 and A2 are each an allylene group having 6 to 20 carbon atoms, and n is a natural number. In this specification, alkyl groups may be linear or branched, and an allylene group means a group with two bonding positions to an aromatic ring group, i.e., a divalent group.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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 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 38% or more, 39% or more, or 40% or more, and 47% or less, 46% or less, or 45% or less by weight of the graft copolymer relative to the total content of the graft copolymer, the matrix copolymer, the polyester 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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 polyester 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 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 polyester 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] According to one embodiment of the present invention, the flame-retardant resin composition may contain 18% to 40% by weight of the polyester 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 may contain 40% or less by weight, 39% or less by weight, 38% or less by weight, or 37% or less by weight, relative to the 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] [ka]

[0057] 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.

[0058] 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 16 or more, 18 or more, 20 or more, 22 or more, or 24 or more, or 950 or less, 900 or less, 850 or less, 800 or less, or 750 or less. 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.

[0059] 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.

[0060] 5. First Flame Retardant According to one embodiment of the present invention, the first flame retardant additive may be an (alkyl)methyl acrylate copolymer. As a specific example, according to one embodiment of the present invention, the first flame retardant additive may be one selected from the group consisting of ethylene methyl acrylate copolymer, propylene methyl acrylate copolymer and butylene methyl acrylate copolymer, and as a more specific example, it may be an ethylene methyl acrylate copolymer.

[0061] According to one embodiment of the present invention, the first flame retardant additive may contain 18 wt% to 35 wt% of methyl acrylate comonomer.

[0062] According to one embodiment of the present invention, the first flame retardant is an ethylene methyl acrylate (EMA) copolymer. In this case, a trans-estreification reaction occurs between the first flame retardant and the polymeric phosphorus-based flame retardant. This increases the amount of carbides during combustion of the flame retardant resin composition, thereby improving the flame retardancy of the flame retardant resin composition.

[0063] According to one embodiment of the present invention, the first flame retardant additive may be present in an amount of 0.1 parts by weight or more and 7 parts by weight or less based on 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin. Specifically, the first flame retardant additive may be present in an amount of 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more, and 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin. When the above range is satisfied, the flame retardant resin composition can be given excellent flame retardancy without deterioration of other physical properties.

[0064] 6. Second Flame Retardant Agent According to one embodiment of the present invention, the flame-retardant resin composition may further include a second flame-retardant additive comprising an ammonium polyphosphate and / or derivative coated and crosslinked with one selected from the group consisting of silane, siloxane, melamine, and melamine resin.

[0065] As a more specific example, the second flame retardant additive may be coated with silane and cross-linked. In this case, when the flame retardant resin composition is burned, the silane groups form inorganic substances during the combustion process, acting as an additional source of phosphorus, thereby improving flame retardant stability.

[0066] According to one embodiment of the present invention, the second flame retardant additive may be present in an amount of 0.1 parts by weight or more and 4 parts by weight or less per 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin. Specifically, the second flame retardant additive may be present in an amount of 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more, and 4 parts by weight or less, 3.5 parts by weight or less, or 3 parts by weight or less per 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin. When the above range is satisfied, the flame retardant resin composition can be given excellent flame retardancy without deterioration of other physical properties.

[0067] 7. 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 lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, mold release agents, pigments, antistatic agents, conductivity imparters, electromagnetic shielding agents, magnetic imparters, mineral fillers, crosslinking agents, antibacterial agents, processing aids, metal deactivators, fume suppressants, friction and wear resistant agents, compatibilizers, anti-dripping agents, and coupling agents. The additives can be used without limitation as long as they are 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.

[0068] According to one embodiment of the present invention, the additive may be present in an amount 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 satisfied, the physical properties of the flame-retardant resin composition can be not impaired.

[0069] <Method for producing flame-retardant resin composition> The present invention provides a method for producing the aforementioned flame-retardant resin composition.

[0070] 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, a polymeric phosphorus-based flame retardant, and a first flame retardant aid, and extruding the mixture, wherein the polymeric phosphorus-based flame retardant has one or more structural units represented by the chemical formula 1.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] According to one embodiment of the present invention, the first flame retardant additive may be present in an amount of 0.1 parts by weight or more and 7 parts by weight or less based on the total content of the graft copolymer, the matrix copolymer, and the polyester resin, which is 100 parts by weight.

[0077] A method for producing a flame-retardant resin composition according to one embodiment of the present invention may involve further mixing the graft copolymer, the matrix copolymer, the polyester resin, the polymeric phosphorus-based flame retardant, and the first flame retardant additive with the second flame retardant additive. In this case, the second flame retardant additive may be present in an amount of 0.1 parts by weight or more and 4 parts by weight or less, based on the total content of the graft copolymer, the matrix copolymer, and the polyester resin (100 parts by weight).

[0078] <Molded articles made from flame-retardant resin compositions> Furthermore, the present invention provides a molded article formed from the flame-retardant resin composition.

[0079] 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.

[0080] 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.

[0081] Examples and Comparative Examples In both the examples and comparative examples, the following components were blended in the parts by weight listed in Tables 1 and 2 below.

[0082] (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: PET resin (manufactured by Hubis, IV = 0.6~0.7) (D-1) High molecular weight phosphorus-based flame retardant: Manufactured by Nofia, product name: HM1100 (weight-average molecular weight 12,000 g / mol). (D-2) Phosphorus-based flame retardant: Manufactured by Nofia, product name: OL1001 (weight-average molecular weight 1000 g / mol). (E) First flame retardant additive: Ethylene methyl acrylate copolymer (EMA, manufactured by SK Geocentric, methyl acrylate copolymer content 29 wt%). (F-1) Second flame retardant: Silane-coated ammonium polyphosphate (SAPP, manufactured by Budenheim, product name: FR CROS 486). (F-2) Third flame retardant additive: Melamine-coated ammonium polyphosphate (MAPP, manufactured by Bundeheim, FR CROS C30). (E) Other additives: N,N-ethylene-bis-stearamide (compatibilizer) and polytetrafluoroethylene (de-loading agent)

[0083] Experimental example *Flame retardancy (UL-94 V Test, Vertical Burning Test): Test specimens were manufactured by injection molding the flame retardant resin compositions produced in the above examples and comparative examples according 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 1 and 2 below.

[0084] 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.

[0085] *Impact Strength (Notched Izod Impact Strength, kgf·cm / cm): The notched Izod impact strength was measured at 23°C for a 1 / 4 inch thick specimen in accordance with ASTM D256. The results are shown in Tables 1 and 2 below.

[0086] *Heat distortion temperature (HDT, °C): The results of measuring the manufactured test specimens in accordance with ASTM D648 are shown in Tables 1 and 2 below.

[0087] *Tensile strength (TS, Kgf / cm²) 2 ) and tensile elongation (TE, %): The results of measurements taken on the manufactured test specimens in accordance with ASTM D638 are shown in Tables 1 and 2 below.

[0088] *Toughness (kgf / ms): The results of measuring the manufactured test specimens in accordance with ASTM E1820 are shown in Tables 1 and 2 below.

[0089] *Bending strength (FS, Kgf / cm) 2 ) and flexural modulus (%): The manufactured test specimens were measured according to the ASTM D790 standard at a bending speed of 1.3 mm / min. The results are shown in Tables 1 and 2 below.

[0090] [Table 1]

[0091] [Table 2]

[0092] As shown in Table 1 above, Examples 1 to 8 possessed comparable levels of melt flow index, heat distortion temperature, tensile strength, tensile elongation, toughness, flexural strength, and flexural modulus compared to Comparative Examples 1 to 3, and it was confirmed that excellent impact strength and excellent flame retardancy were simultaneously ensured.

[0093] Figure 1 shows the FT-IR spectra measured for the flame-retardant resin composition of Example 1 and the flame-retardant resin composition of the Comparative Example. Referring to Figure 1, it can be confirmed that the FT-IR spectrum of the flame-retardant resin composition of Example 1 shows significantly greater asymmetric stretching of COC and symmetric stretching of C=O compared to the flame-retardant resin composition of Comparative Example 1. In other words, it can be confirmed that the transesterification reaction was carried out in the flame-retardant resin composition of Example 1, which further contains ethylene methyl acrylate as the first flame retardant additive, compared to the flame-retardant resin composition of Comparative Example 1. As a result, it can be confirmed that the impact strength and flame retardancy of the flame-retardant resin composition of Example 1 are improved compared to the impact strength and flame retardancy of the flame-retardant resin composition of Comparative Example 1.

[0094] In Comparative Example 2, where the content of the second flame retardant additive exceeded 3 parts by weight per 100 parts by weight of the graft copolymer, matrix copolymer, and polyethylene terephthalate resin, it was confirmed that the impact strength, tensile elongation, and toughness were reduced compared to Examples 6 and 7.

[0095] In Comparative Example 3, where the content of the first flame retardant additive exceeded 5 parts by weight per 100 parts by weight of the graft copolymer, matrix copolymer, and polyethylene terephthalate resin, it was confirmed that the flame retardancy was lower compared to Example 3.

[0096] In Comparative Example 4, which uses a low-molecular-weight phosphorus-based flame retardant instead of a high-molecular-weight phosphorus-based flame retardant, it was confirmed that the processability was significantly inferior to that of the Examples, making extrusion molding for physical property measurement impossible.

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 High molecular weight phosphorus-based flame retardants, A flame-retardant resin composition comprising a first flame retardant additive containing an alkyl methyl acrylate copolymer.

2. 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 1. 【Chemistry 1】 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.

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

4. The flame-retardant resin composition according to claim 3, wherein in the chemical formula 2, n is 1 or more and 1000 or less.

5. With respect to 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin, The flame-retardant resin composition according to claim 1, comprising 0.1 parts by weight or more and 7 parts by weight or less of the first flame-retardant additive.

6. The flame-retardant resin composition according to claim 1, further comprising a second flame-retardant additive, which includes an ammonium polyphosphate and / or derivative thereof coated and crosslinked with one selected from the group consisting of silane, siloxane, melamine, and melamine resin.

7. The flame-retardant resin composition according to claim 6, wherein the second flame-retardant additive is the ammonium polyphosphate or its derivative coated and cross-linked with silane.

8. With respect to 100 parts by weight of the total content of the graft copolymer, the matrix copolymer, and the polyester resin, The flame-retardant resin composition according to claim 6, comprising 1 to 3 parts by weight of the second flame-retardant additive.

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. 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.

11. 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, a polymeric phosphorus-based flame retardant, and a first flame retardant aid containing an alkyl methyl acrylate copolymer, and then extruding the mixture. 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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