Resin composition and molded article

Abstract

The present invention relates to a resin composition, which contains 25 to 50 parts by weight of a phosphorus-based flame retardant composition relative to 100 parts by weight of a graft copolymer containing a rubber polymer and a base resin containing a styrene-based copolymer, and the phosphorus-based flame retardant composition is M n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5) and 30 to 70% by weight of ammonium polyphosphate, and a molded article molded from the same.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0139933, filed on October 27, 2020, and all contents disclosed in the documents of that Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a resin composition, and more particularly to a flame-retardant resin composition which does not contain a char-forming agent and is capable of forming its own char, and a molded article made from the same. [Background technology]

[0003] Acrylonitrile-butadiene-styrene (ABS) copolymer is produced by graft copolymerizing styrene and acrylonitrile onto butadiene rubber polymer. Compared to existing high-impact polystyrene (HIPS), ABS copolymer has superior impact resistance, chemical resistance, heat stability, colorability, fatigue resistance, rigidity and processability, and is used in interior and exterior materials for automobiles, office equipment, parts for various electric and electronic products, toys, etc.

[0004] On the other hand, resins used in fields where there is a risk of fire must meet the flame retardant standards required for the field. However, since ABS copolymers do not exhibit flame retardancy by themselves, a method has been proposed in which a flame retardant is mixed with the ABS copolymer to meet the flame retardant standards and ensure safety against fire.

[0005] Here, as the flame retardant, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, hydroxide-based flame retardants, etc. can be used, among which halogen-based flame retardants have the advantage of high flame retardancy efficiency and maintaining the mechanical properties of the resin, but they decompose during processing to generate halogen gas, which is not only very harmful to the human body but also has a problem of adversely affecting the environment. Therefore, recently, there has been an increasing need for halogen-free flame retardant resins that do not contain halogens.

[0006] Therefore, methods have been proposed that utilize non-halogen flame retardants, such as phosphorus-based flame retardants, nitrogen-based flame retardants, and hydroxide-based flame retardants, particularly phosphorus-based flame retardants, rather than halogen-based flame retardants, which impart flame retardancy through a gas-phase reaction with phosphate and a solid-phase reaction to form char, such as CPO(N).

[0007] However, resins having a carbon backbone such as polycarbonate resins can easily form char with phosphorus-based flame retardants, making it easy to apply the phosphorus-based flame retardants, but ABS copolymers cannot form char with phosphorus-based flame retardants by themselves, so they require the addition of a charring agent. However, charring agents are expensive materials, which reduces price competitiveness and ultimately reduces productivity. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent No. 10-1411825B1 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been devised to solve the problems of the conventional art, and aims to provide a resin composition that can simultaneously ensure flame retardancy and thermal stability without adding a char-forming agent by applying a phosphorus-based flame retardant composition capable of self-char formation as a flame retardant in a flame-retardant resin composition containing a graft copolymer such as an ABS copolymer.

[0010] Another object of the present invention is to provide a molded article made from the resin composition. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention provides a flame retardant composition comprising 25 to 50 parts by weight of a phosphorus-based flame retardant composition based on 100 parts by weight of a graft copolymer containing a rubber polymer and a base resin containing a styrene-based copolymer, and the phosphorus-based flame retardant composition is M n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) and 30% to 70% by weight of ammonium polyphosphate.

[0012] The present invention also provides a molded article made from the resin composition. Effect of the Invention

[0013] The resin composition according to the present invention is capable of forming its own char from the phosphorus-based flame retardant composition, and has the effect of being excellent in flame retardancy and thermal stability without containing a char-forming agent. [Brief description of the drawings]

[0014] [Figure 1] 1 is a photograph of aluminum diethylphosphinate particles, in which Mn+(diethylphosphinate)-n is aluminum (Al), according to an embodiment of the present invention, taken with a scanning electron microscope. [Diagram 2] 1 is a photograph of ammonium polyphosphate particles according to an embodiment of the present invention taken with a scanning electron microscope. [Diagram 3] 3 is a photograph of the surface of the resin composition according to Example 2 of the present invention after combustion, taken with a scanning electron microscope. [Figure 4] 1 is a graph illustrating trends in flame retardancy depending on the content of phosphorus-based flame retardant compositions according to Examples 1 to 3 of the present invention and Comparative Example 1. [Diagram 5] 1 is a graph illustrating trends in flame retardancy depending on the composition of phosphorus-based flame retardant compositions according to Example 2 of the present invention and Comparative Examples 2 to 5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In the following, the present invention will be described in more detail in order to facilitate understanding of the present invention.

[0016] The terms and words used in the description of the present invention and the claims should not be interpreted in a limited manner to their ordinary or dictionary meanings, but should be interpreted in a manner that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0017] In the present invention, the term "monomer unit" may refer to a component, structure, or substance itself derived from a monomer, and as a specific example, may refer to a repeating unit formed in a polymer by an input monomer participating in a polymerization reaction during polymerization of a polymer.

[0018] As used herein, the term "composition" is inclusive of mixtures of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0019] The present invention provides a resin composition, specifically a flame-retardant resin composition.

[0020] According to one embodiment of the present invention, the resin composition contains 25 to 50 parts by weight of a phosphorus-based flame retardant composition with respect to 100 parts by weight of a base resin containing a graft copolymer containing a rubber polymer and a styrene-based copolymer, and the phosphorus-based flame retardant composition is M n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) The composition may contain 30% to 70% by weight of ammonium polyphosphate and 30% to 70% by weight of ammonium polyphosphate.

[0021] According to an embodiment of the present invention, the graft copolymer may be a resin for imparting basic physical properties to the resin composition as a part of a base resin of the resin composition.

[0022] According to an embodiment of the present invention, the graft copolymer may include a rubber polymer, an aromatic vinyl monomer unit, and a vinylcyan monomer unit. As a specific example, the rubber polymer may be a conjugated diene polymer, and the conjugated diene polymer may be prepared by polymerization of a conjugated diene monomer and may include a conjugated diene monomer unit. As a more specific example, the conjugated diene polymer may be prepared by emulsion polymerization of a conjugated diene monomer, and in this case, it is easy to control the average particle size of the conjugated diene polymer, and a conjugated diene polymer suitable for the desired mechanical properties may be used.

[0023] According to an embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit of the conjugated diene polymer may be at least one 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 thereof may be 1,3-butadiene.

[0024] According to one embodiment of the present invention, the graft copolymer may be a rubber polymer grafted with an aromatic vinyl monomer unit and a vinylcyan monomer unit. Thus, the graft copolymer may include the rubber polymer, and the aromatic vinyl monomer unit and the vinylcyan monomer unit grafted to the rubber polymer, and may include both the aromatic vinyl monomer unit and the vinylcyan monomer unit that are not grafted to the rubber polymer in the portion where the graft layer of the graft copolymer is formed, depending on the conditions of the graft polymerization. In this case, the graft polymerization may be carried out by emulsion polymerization or bulk polymerization.

[0025] 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 at least one 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 thereof may be styrene.

[0026] According to an embodiment of the present invention, the vinylcyan-based monomer for forming the vinylcyan-based monomer unit of the graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and a specific example thereof may be acrylonitrile.

[0027] According to one embodiment of the present invention, the graft copolymer may contain 40% by weight to 90% by weight of a rubber polymer, 5% by weight to 50% by weight of an aromatic vinyl monomer unit, and 1% by weight to 30% by weight of a vinylcyan monomer unit. As a specific example, the graft copolymer may contain 50% by weight to 80% by weight or 50% by weight to 70% by weight of a rubber polymer, 10% by weight to 40% by weight or 10% by weight to 30% by weight of an aromatic vinyl monomer unit, and 1% by weight to 20% by weight or 5% by weight to 15% by weight of a vinylcyan monomer unit. Within this range, it is possible to ensure the mechanical properties of the resin composition.

[0028] According to one embodiment of the present invention, the styrene-based copolymer may be a matrix resin as part of a base resin of a resin composition.

[0029] According to an embodiment of the present invention, the styrene-based copolymer may include an aromatic vinyl-based monomer unit and a vinylcyan-based monomer unit. For example, the styrene-based copolymer may be prepared by emulsion polymerization or bulk polymerization of an aromatic vinyl-based monomer and a vinylcyan-based monomer.

[0030] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the styrene-based copolymer may be at least one 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 thereof may be styrene.

[0031] According to an embodiment of the present invention, the vinylcyan-based monomer for forming the vinylcyan-based monomer unit of the styrene-based copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and a specific example thereof may be acrylonitrile.

[0032] According to one embodiment of the present invention, the styrene-based copolymer may contain 10% by weight to 90% by weight of aromatic vinyl-based monomer units and 10% by weight to 90% by weight of vinylcyan-based monomer units. Specifically, the styrene-based copolymer may contain 20% by weight to 80% by weight or 30% by weight to 70% by weight of aromatic vinyl-based monomer units and 20% by weight to 80% by weight or 30% by weight to 70% by weight of vinylcyan-based monomer units. Within this range, the graft copolymer has excellent dispersibility and excellent mechanical properties and balance of physical properties.

[0033] According to one embodiment of the present invention, the base resin may contain 10% to 50% by weight of graft copolymer and 50% to 90% by weight of styrene copolymer, and as a specific example, it may contain 10% to 40% by weight or 20% to 40% by weight of graft copolymer and 60% to 90% by weight or 60% to 80% by weight of styrene copolymer, and within this range, the mechanical properties of the base resin are excellent. In addition, the graft copolymer and the styrene copolymer each contain an aromatic vinyl monomer unit and a vinylcyan monomer unit, and when the types of the aromatic vinyl monomer unit and the vinylcyan monomer unit forming each copolymer are the same, they are mixed and dispersed as the same components in the extrusion process of the resin composition, so that in fact, in the resin composition and the molded product molded therefrom, the rubber polymer may be present in a form dispersed in the matrix formed by the aromatic vinyl monomer unit and the vinylcyan monomer unit. Therefore, the content of each of the graft copolymer and styrene copolymer in the base resin can be determined from the total content of aromatic vinyl monomer units and vinylcyan monomer units in the base resin and the content of the rubber polymer.

[0034] As described above, unlike the graft copolymer and styrene-based copolymer according to the present invention, resins having carbon backbones such as polycarbonate resins are easy to form char with phosphorus-based flame retardants, and there is no difficulty in applying the phosphorus-based flame retardants, but the graft copolymer according to the present invention cannot form char with the phosphorus-based flame retardant by itself, and a charring agent must be added. However, there is a problem that the addition of the charring agent reduces the thermal stability of the graft copolymer, and in particular, the charring agent is an expensive material, which reduces price competitiveness and ultimately reduces productivity.

[0035] Meanwhile, the base resin according to the present invention is characterized in that it does not require a char former, particularly a carbon-based char former, and therefore the base resin may further contain, in addition to the graft copolymer and the styrene-based copolymer, an additional resin component for imparting other properties as necessary, but in this case, the additional resin component does not correspond to a carbon-based char former.

[0036] According to one embodiment of the present invention, the phosphorus-based flame retardant composition may be used to impart flame retardancy to a resin that is unable to form char directly with a phosphorus-based flame retardant, such as the base resin, by enabling the base resin to form char by itself without containing a char former, particularly a carbon-based char former.

[0037] According to one embodiment of the present invention, the phosphorus-based flame retardant composition is n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5) and ammonium polyphosphate. n+ (Diethylphosphinate) - n(M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) is a kind of phosphorus-based flame retardant, and the ammonium polyphosphate is a kind of flame retardant enhancer or flame retardant assistant, and it is known that each of them can be used. However, since it was impossible to form char between the graft copolymer and / or styrene-based copolymer and the phosphorus-based flame retardant, it was essentially necessary to include a carbon-based char former such as a polyester resin capable of forming char with the phosphorus-based flame retardant, as described above, in order to apply the present invention to a base resin containing a graft copolymer, particularly an ABS copolymer. In addition, even if the carbon-based char former and the phosphorus-based flame retardant are simultaneously included, char is not sufficiently formed depending on the type of the carbon-based char former and the phosphorus-based flame retardant, and a problem occurs in which flame retardancy is not ensured. Therefore, a method of using a flame retardant enhancer or flame retardant assistant has been proposed, but even in such a case, if the appropriate combination relationship between the char former, the phosphorus-based flame retardant, and the flame retardant enhancer is not fully effective, char cannot be easily formed, and flame retardancy cannot be ensured.

[0038] Meanwhile, when the phosphorus-based flame retardant composition according to the present invention is contained in a predetermined amount in a resin composition while satisfying a predetermined composition relative to a base resin, it can form a char by itself when exposed to a flame or fire, thereby imparting flame retardancy to the resin composition. That is, the resin composition of the present invention including the phosphorus-based flame retardant composition according to the present invention can form a char when exposed to a flame or fire without including a char-forming agent. As a specific example, the resin composition can form a char when exposed to a flame or fire by reacting the polyphosphate derived from the ammonium polyphosphate of the phosphorus-based flame retardant composition with the M n+ (Diethylphosphinate) - n Metal ions derived from n+ ) can form metallosupramolecular.

[0039] As a more specific example, when M is aluminum (Al), a metallosupramolecular can be formed by a reaction such as Scheme 1 below, and the metallosupramolecular formed at this time can be char.

[0040] [ka]

[0041] Here, in order to form a metallo-supermolecule by the reaction as in Scheme 1, M n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) and ammonium polyphosphate. According to one embodiment of the present invention, the phosphorus-based flame retardant composition is n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) 30% by weight to 70% by weight of ammonium polyphosphate and 30% by weight to 70% by weight of ammonium polyphosphate. n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) The resin composition may contain 40% by weight to 60% by weight or 45% by weight to 55% by weight of ammonium polyphosphate, and within this range, there is an effect of ensuring maximum flame retardancy through spontaneous char formation when the resin composition is exposed to flame or fire.

[0042] In addition, even if a metallo-supermolecule is formed by a reaction such as reaction formula 1, if the absolute amount of the metallo-supermolecule is not sufficiently secured, even if char is formed, it cannot cover the entire base resin, and flame retardancy cannot be secured, so it is important to secure the absolute amount of the phosphorus-based flame retardant composition itself. Therefore, the resin composition according to the present invention may contain 25 parts by weight to 50 parts by weight, 25% by weight to 45 parts by weight, or 28 parts by weight to 40 parts by weight of the phosphorus-based flame retardant composition relative to 100 parts by weight of the base resin, and within this range, it is effective to prevent the deterioration of the mechanical properties of the resin composition and to secure maximum flame retardancy.

[0043] According to one embodiment of the present invention, the M n+ (Diethylphosphinate) - n (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5) is a phosphorus-based flame retardant and can contain a metal ion having an oxidation number of 2 to 5. Here, if the metal ion is monovalent, the reaction as shown in Reaction Scheme 1 above will not be induced when the resin composition is exposed to a flame or fire, so the metal ion must be a metal ion having an oxidation number of at least 2.

[0044] According to one embodiment of the present invention, M may be a metal having an oxidation number of 2 to 5, and a specific example thereof may be a white metal having an oxidation number of 2 to 5, and a more specific example thereof may be one or more selected from the group consisting of zinc (Zn), tin (Sn), calcium (Ca), magnesium (Mg), aluminum (Al), scandium (Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb), and tantalum (Ta).

[0045] According to an embodiment of the present invention, the higher the oxidation number of the metal, the more the reaction between the metal ion and ammonium polyphosphate as shown in Reaction Scheme 1 can be induced, and the easier it is to form self-char. Thus, M may be a metal having an oxidation number of 3 to 5, and as a specific example, M may be a white metal having an oxidation number of 3 to 5, and as a more specific example, M may be at least one selected from the group consisting of tin (Sn), aluminum (Al), scandium (Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb), and tantalum (Ta).

[0046] According to one embodiment of the present invention, the resin composition may have a flame retardancy grade of V-1 or higher according to the UL-94 V Test by including the base resin and the phosphorus-based flame retardant composition. Here, in the flame retardancy test according to the UL-94 V Test, since the test piece is directly exposed to flame, even if the resin composition has the same composition, the thinner the test piece, the more difficult it is to ensure flame retardancy, and the thicker the test piece, the more likely it is that the flame retardancy will increase. Therefore, in order for the resin composition to have sufficient flame retardancy, it is necessary for the flame retardancy to be high even at a thin thickness. According to one embodiment of the present invention, the resin composition may have a flame retardancy grade of V-1 or higher according to the UL-94 V Test at a thickness of 1.5 mm. Here, V-1 or higher means V-0 and V-1 grades.

[0047] According to an embodiment of the present invention, the resin composition may have a flame retardant grade of V-0 according to UL-94 V Test at thicknesses of 2.0 mm, 2.5 mm, and 3.0 mm.

[0048] The present invention also provides a molded article made from the resin composition.

[0049] According to one embodiment of the present invention, the molded article may be extrusion or injection molded from the resin composition, and may be applied to products that require both mechanical properties and flame retardancy, and specific examples thereof include interior and exterior materials for automobiles, office equipment, and parts for various electric and electronic products.

[0050] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to exemplary embodiments thereof, so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[0051] Examples and Comparative Examples The following components were mixed together with an activator and a stabilizer in the amounts shown in Tables 1 and 2 to prepare a resin composition.

[0052] (1) Base resin: ABS resin (LG Chemical, product name DP270) as a graft copolymer and SAN resin (LG Chemical, product name 90HR) as a styrene-based copolymer were mixed in the amounts shown in the table. (2-1)M n+ (Diethylphosphinate) - n : Aluminum diethylphosphinate (Al DEP), Clariant, product name OP1240 (2-2)M n+ (Diethylphosphinate) - n Zinc diethylphosphinate (Zn DEP), Clariant, product name OP950 (3) Ammonium polyphosphate (APP): manufactured by LS Chem, product name APP

[0053] Experimental Example The resin compositions prepared in the examples and comparative examples were extruded at 220°C using a twin-screw extruder to prepare pellets, and then test pieces were extruded at 210°C. The flame retardancy and heat distortion temperature were measured by the following method, and the results are shown in Table 1 below.

[0054] In addition, among the phosphorus-based flame retardant composition blended into the resin composition, aluminum diethylphosphinate particles were photographed by a scanning electron microscope and shown in FIG. 1, and ammonium polyphosphate particles were photographed by a scanning electron microscope and shown in FIG. 2. The surface of the resin composition of Example 2 after combustion was photographed by a scanning electron microscope and shown in FIG. 3. The surface of the resin composition of Example 2 after combustion was subjected to elemental analysis using EDS (Energy Dispersive X-ray Spectroscopy), and the results are shown in Table 2 below.

[0055] *Flame retardancy (UL-94 V Test, Vertical Burning Test): Test pieces with thicknesses of 1.5mm, 2.0mm, 2.5mm and 3.0mm were graded as V-0, V-1 and V-2 according to the standard measurement UL-94. The tendency of flame retardancy according to the content and composition of phosphorus-based flame retardant composition is shown diagrammatically in Figure 4 and Figure 5.

[0056] *Heat Deflection Temperature (℃): For a 5 inch x 1 / 2 inch x 1 / 4 inch test piece, a load of 1.82 MPa was applied to the center, and the oil bath heating rate was set to 2℃ / min. According to ASTM D648, the temperature at which the test piece deformed by 0.01 inch was measured.

[0057] [Table 1]

[0058] [Table 2]

[0059] As shown in Table 1, the resin composition according to the present invention is capable of forming its own char with only the composition of the phosphorus-based flame retardant composition containing the phosphorus-based flame retardant without containing a carbon-based char former for the base resin containing the graft copolymer and the styrene-based copolymer (see Figs. 1 to 3), and it was confirmed that even with a thickness of 1.5 mm, a flame retardant grade of V-1 or higher, i.e., V-1 and V-0, according to the UL-94 V Test can be ensured. In particular, it was confirmed that the thicker the resin composition test piece is, at 2.0 mm, 2.5 mm, and 3.0 mm, the easier it is to ensure flame retardancy, and V-0 can be ensured in all of the examples. Such flame retardancy is due to the fact that when the resin composition according to the present invention is exposed to a flame or fire, the polyphosphate derived from ammonium polyphosphate and M n+ (Diethylphosphinate) - n Metal ions derived from n+ ) can be considered to be expressed by forming a metallosupramolecular (see FIG. 3 and Table 2).

[0060] In addition, M contained in the phosphorus-based flame retardant composition n+ (Diethylphosphinate) - n It was confirmed that as the content of M increases, the heat distortion temperature of the resin composition increases and the thermal stability improves. This is because in a resin composition containing a graft copolymer, i.e., ABS resin, which is a thermoplastic resin, the thermal stability is a property determined by the graft copolymer ABS resin of the base resin and the styrene copolymer SAN resin, and the M content increases with the heat applied to the resin composition during the extrusion process. n+ (Diethylphosphinate) - n Metal ion M n+ This is believed to be due to the fact that the graft copolymer reacts with the polymer to improve the thermal properties.

[0061] On the other hand, in the case of Comparative Example 1, in which the composition of the phosphorus-based flame retardant composition was met but the content was insufficient, the formation of autogenous char was insufficient, and flame retardancy could not be secured at a thickness of 1.5 mm. Even when the thickness of the test piece was increased, it was only possible to secure a maximum V-1 at a thickness of 3.0 mm (see FIG. 4).

[0062] In addition, even in the cases of Comparative Examples 2 to 5 in which the composition of the phosphorus-based flame retardant composition deviates from the composition limited by the present invention, when the resin composition is exposed to a flame or fire, the M n+ (Diethylphosphinate) - n It was confirmed that the ratio of ammonium polyphosphate to form a metallo-supermolecule could not be secured, the formation of self-char was insufficient, and flame retardancy could not be secured at a thickness of 1.5 mm, but that flame retardancy could be secured at a thickness of at least 2.0 mm (see Figure 5).

[0063] From these results, it was confirmed that the resin composition according to the present invention is capable of forming its own char from the phosphorus-based flame retardant composition, does not contain a char-forming agent, and has excellent flame retardancy and thermal stability.

Claims

1. the composition comprises 25 to 50 parts by weight of a phosphorus-based flame retardant composition relative to 100 parts by weight of a base resin comprising 10 to 50% by weight of a graft copolymer including a rubber polymer and 50 to 90% by weight of a styrene-based copolymer, The phosphorus-based flame retardant composition is ｎ＋ (Diethyl phosphinate) － ｎ (M is a metal having an oxidation number from 2 to 5, and n is an integer selected from 2 to 5) 30% to 70% by weight and 30% to 70% by weight of ammonium polyphosphate; Contains no carbon-based char formers When exposed to flame or fire, polyphosphates derived from ammonium polyphosphate and M ｎ＋ (Diethyl phosphinate) － ｎ Metal ions derived from ｎ＋ ) forms a metallosupramolecular; A resin composition having a thickness of 1.5 mm and a flame retardant grade of V-1 or higher according to UL-94 V Test.

2. The resin composition according to claim 1 , wherein the graft copolymer comprises a rubber polymer, an aromatic vinyl monomer unit, and a vinylcyan monomer unit.

3. The resin composition according to claim 1 or 2, wherein the styrene-based copolymer contains an aromatic vinyl-based monomer unit and a vinylcyan-based monomer unit.

4. The resin composition according to any one of claims 1 to 3, comprising 28 to 40 parts by weight of a phosphorus-based flame retardant composition per 100 parts by weight of the base resin.

5. The phosphorus-based flame retardant composition is ｎ＋ (Diethyl phosphinate) － ｎ (M is a metal having an oxidation number of 2 to 5, and n is an integer selected from 2 to 5.) 40% to 60% by weight of the resin composition according to any one of claims 1 to 4, and 40% to 60% by weight of ammonium polyphosphate.

6. The resin composition according to any one of claims 1 to 5, wherein M is at least one selected from the group consisting of zinc (Zn), tin (Sn), calcium (Ca), magnesium (Mg), aluminum (Al), scandium (Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb) and tantalum (Ta).

7. The resin composition according to any one of claims 1 to 6, wherein M is at least one selected from the group consisting of tin (Sn), aluminum (Al), scandium (Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb) and tantalum (Ta).

8. A molded article molded from the resin composition according to any one of claims 1 to 7.

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