KR100475932B1 - Flame Retardant Thermoplastic Resin Composition with Good Impact Strength and Good Heat Resistance - Google Patents

Abstract

Flame-retardant thermoplastic resin composition excellent in impact resistance and heat resistance of the present invention is (A) (a ₁ ) graft polymer and average particles prepared by the graft polymerization method using a small particle size rubber having an average particle size of 0.08-0.18 ㎛ 20-50% by weight of graft ABS resin composed of 40: 60 to 80: 20% by weight of graft polymer prepared by graft polymerization using a medium-size rubber having a size of 0.28-0.38 mu m and (a ₂ ) A thermoplastic acrylonitrile-butadiene-styrene copolymer resin 100 having a weight average molecular weight of 120,000 to 200,000, consisting of 50 to 80% by weight of a SAN resin composed of 60 to 76% by weight of styrene and 40 to 24% by weight of acrylonitrile. Parts by weight; (B) 5 to 30 parts by weight of a halogen flame retardant having a weight average molecular weight in the range of 2,000 to 10,000; (C) 1 to 15 parts by weight of antimony oxide; And (D) 0.05 to 10 parts by weight of the aluminosilicate inorganic compound.

Description

Flame Retardant Thermoplastic Resin Composition with Good Impact Strength and Good Heat Resistance

Field of invention

The present invention relates to a thermoplastic acrylonitrile-butadiene-styrene copolymer (ABS) flame retardant resin composition having excellent impact resistance and heat resistance. More specifically, the present invention relates to an acrylonitrile-butadiene-styrene-based copolymer resin halogen-based flame retardant antimony oxide and aluminosilicate-based inorganic compound, excellent impact resistance and heat resistance resin composition.

Background of the Invention

In general, the thermoplastic acrylonitrile-butadiene-styrene copolymer (ABS) resin has good processability and mechanical strength, and thus is widely used for the manufacture of interior and exterior parts such as electrical / electronic products and office automation equipment. However, the ABS copolymer resin itself is not resistant to combustion, and when the spark is ignited by an external ignition factor, the resin itself acts as an energy to help the combustion to continuously spread the fire.

For this reason, in order to secure stability against fires in electric and electronic products, the United States, Europe, and other countries have legalized to use only flame-retardant resins for the production of molded parts of internal and external parts of electrical and electronic products.

There are various methods for imparting flame retardancy to the ABS copolymer resin, and a commercialized method mainly used is an additional flame retardant method in which a flame retardant and a flame retardant aid are added. For example, an acrylonitrile-butadiene-styrene copolymer resin is prepared by adding an organic compound containing halogen such as bromine and an inorganic compound containing antimony oxide to the resin.

Halogen-containing organic compounds are mainly bromine or chlorine-based compounds, and when added to acrylonitrile-butadiene-styrene copolymer resins, the flame retardancy is excellent, but the overall impact of the resin itself on impact strength, weather stability, heat resistance, processability, etc. This will cause serious degradation in physical properties.

Therefore, in manufacturing a flame retardant resin, while maintaining excellent flame retardancy, a technique for minimizing side effects such as deterioration of physical properties and workability, lowering of weather resistance, in particular impact resistance, heat resistance and thermal stability, is very important. To prevent degradation of the thermal stability of these products, additives, commonly referred to as thermal stabilizers, are added to the flame retardant resin. Commonly used thermal stabilizers in flame retardant acrylonitrile-butadiene-styrene copolymer resins include tinmalate compounds.

Flame-retardant ABS resin is widely used in various applications due to its excellent workability and physical properties, but its use is limited in parts requiring heat resistance, such as lack of heat resistance compared to engineering plastics. Therefore, the development of a flame retardant resin having excellent heat resistance is also a great concern of the flame retardant resin manufacturers.

In order to impart heat resistance to the flame retardant ABS resin, a SAN resin having a high molecular weight, a narrow polymer diversity index (PDI) and a high acrylonitrile content is used as a matrix, and together with a halogen having a high molecular weight One organic compound is used.

However, flame retardant ABS resins having such high heat resistance generally have a problem of significantly lowering the impact resistance of the product and causing cracks during assembly of the molded article, and thus cannot be used in products requiring high impact resistance. Or limited. In particular, in the case where a heat resistant SAN resin is used as the matrix SAN resin, the heat resistant SAN resin has a brittle property, and the phenomenon is further intensified.

In contrast, the present inventors have graft ABS resin in which a graft ABS resin polymerized using a small particle rubbery polymer and a graft ABS resin polymerized using a medium particle rubbery polymer are mixed in a proportion to overcome the above problems. In the acrylonitrile-butadiene-styrene copolymer resin composed of a SAN resin having a high molecular weight and acrylonitrile content, a halogen-based compound having a certain molecular weight range is used as a flame retardant, and an inorganic compound of antimony trioxide and aluminosilicate-based By adding, it is possible to develop a thermoplastic resin composition having good flame retardancy and mechanical properties and having excellent heat resistance.

An object of the present invention is to provide a thermoplastic resin composition having good flame resistance and at the same time excellent heat resistance.

Another object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance.

Still another object of the present invention is to provide a thermoplastic resin composition which is very useful for the manufacture of interior and exterior parts such as various electrical and electronic products and office automation equipment.

The above and other objects of the present invention can be achieved by the present invention described in detail below.

Flame retardant thermoplastic resin composition excellent in impact resistance and heat resistance according to the present invention is (A) acrylonitrile-butadiene-styrene copolymer resin, (B) halogen flame retardant, (C) antimony oxide and (D) aluminosilicate It consists of an inorganic compound, the detailed description of each of these components is as follows.

(A) Acrylonitrile-butadiene-styrene copolymer resin

Acrylonitrile-butadiene-styrene copolymer resin of the present invention (A) is composed of 5 to 40% by weight of acrylonitrile, 5 to 30% by weight of butadiene rubber and 20 to 70% by weight of styrene, (a ₁ ) 20 to 50 weight percent graft ABS resin and (a ₂ ) 50 to 80 weight percent SAN resin.

(a ₁ ) Graft ABS Resin

The graft ABS resin (a ₁ ) used in the present invention is a graft polymer prepared by graft polymerization of small particle rubber having an average particle size of 0.08-0.18 μm, and a medium particle rubber having an average particle size of 0.28-0.38 μm. The graft polymer prepared by graft polymerization is mixed and used in a ratio of 40:60 to 80: 20% by weight based on 100% by weight of the graft ABS resin.

The reason for mixing and using the graft polymers described above is that when the rubbery polymer having a thickness of 0.20 µm or less is used alone, the surface gloss is improved, but the impact resistance is remarkably lowered. This is because the impact resistance is improved, but the surface glossiness is significantly reduced.

Therefore, in order to compensate for these disadvantages and simultaneously obtain the properties of each rubbery polymer, a graft ABS resin using a rubbery polymer composed of small particles having an average particle diameter of about 0.08 to 0.18 μm and a large particle of about 0.28 to 0.38 μm It is preferable to mix and use the graft ABS resin using the rubbery polymer which consists of these.

In the present invention, it is preferable to separately prepare two kinds of ABS resins by graft emulsion polymerization of two kinds of rubbery polymers having different rubber particle sizes, and use them in a compounding process.

If the different rubbery polymers are mixed before the graft polymerization and the ABS resin is subjected to the graft reaction, the impact resistance and glossiness cannot be improved at the same time. This is because the graft reaction is difficult to uniformly occur in each particle due to the difference in surface area per volume of the small rubber and the large rubber.

In addition, the first graft latex was prepared by first presenting a rubbery polymer latex having a small particle diameter in the graft polymerization system and graft polymerizing to an appropriate conversion rate by emulsion polymerization method, and then in the presence of the prepared primary graft latex. The ABS resin produced by completing the secondary graft reaction by adding a large amount of rubbery polymer latex and continuously adding the remaining graft monomer is suitable for the glossiness of the small particle rubber and the impact resistance of the medium particle rubber. Although it is possible to obtain a harmonized ABS resin, a large amount of unplasticized particles are generated during the polymerization process, causing surface defects of the final molded product.

Therefore, in the present invention, two kinds of rubber polymers having different rubber particle sizes are respectively graft-emulsified to separately prepare two kinds of ABS resins, which are mixed and used in the compounding process, thereby improving the appearance quality of the small particle rubber. In addition to physical properties such as impact resistance of the medium and large-sized rubber, the polymerization process is stabilized to minimize coagulaum and unplasticized particles.

The average particle diameter of the small particle size rubber | gum of the rubber which can be used for this invention shall be about 0.05-0.20 micrometer, Especially about 0.08-0.18 micrometer is preferable. Moreover, the average particle diameter of a medium particle size rubber shall be 0.25-0.40 micrometers, and about 0.28-0.38 micrometers is preferable.

The rubbery polymers having different particle sizes are each graft polymerized and used by mixing a small particle size: medium particle size graft polymer in a ratio of 40:60 to 80:20 parts by weight. If the ratio is out of the ratio, the characteristics of the rubbery polymers having the respective particle sizes may not be harmonized, and the surface gloss may be degraded by the small-diameter rubber, or may be broken by the small-diameter rubber.

It is preferable that the graft ratio of each said graft polymer shall be 40-90%. If the graft ratio is lower than this, it is difficult to obtain a white powder having a uniform particle size distribution during solidification and drying, and also fisheye, pinhole or sandsurface as unplasticized particles on the surface of the molded article during extrusion and injection. ), The surface gloss is reduced. In addition, when the graft ratio exceeds 90%, physical properties such as impact strength, fluidity, and surface gloss decrease. The graft ABS resin constitutes 20-50% by weight of the total ABS resin.

(a ₂ ) SAN resin

The SAN resin used in the present invention is composed of 60 to 76% by weight of styrene and 40 to 24% by weight of acrylonitrile, and preferably has a weight average molecular weight in the range of 120,000 to 200,000. If the weight average molecular weight is 120,000 or less, there is a problem that the heat resistance and impact resistance is significantly lowered, and if the weight average molecular weight is more than 200,000, fluidity is lowered, which may cause unmolding, poor GAS generation, etc. during injection molding of a complicated structure.

The SAN resin is well known to those skilled in the art to which the present invention belongs, and may be polymerized by suspension polymerization or bulk polymerization, but the amount of additives added to the polymerization manufacturing process is low and the gel generation is low. It is preferable to use SAN resin manufactured by the bulk polymerization method. When the additive content is high during the polymerization manufacturing process, it is easy to cause appearance defects such as GAS defects in molded parts during injection molding, and when the resin is contained in the SAN resin, it protrudes on the surface of the final molded product. There is a problem of lowering.

(B) Halogenated flame retardants having a weight average molecular weight in the range of 2,000 to 10,000

In the present invention, the halogen-based compound used as a flame retardant is a commercially available product. Examples of the halogen-based compound that can be used include tetra bromobisphenol A and bis (tribromophenoxy) ethane. (tribromophenoxy) ethane), brominated epoxy resin, or brominated epoxy resin terminated with tribromophenol in which the epoxy end is substituted with tribromophenol.

The halogen flame retardant is used 5 to 30 parts by weight based on 100 parts by weight of the base resin (A) of the present invention. When 5 parts by weight or less is added, the flame retardant effect is insufficient, and when 30 parts by weight or more is used, deterioration of workability and mechanical strength occurs, which is not preferable because the balance of physical properties is lost.

In addition, it is preferable to use a halogen flame retardant having a weight average molecular weight of about 2,000 to 10,000. If the weight average molecular weight is 2,000 or less, there is a problem that the heat resistance is significantly lowered. If the weight average molecular weight is 10,000 or more, the fluidity is decreased, which may cause unmolding and poor GAS generation during injection molding of a complicated structure. Degrades.

(C) antimony oxide

In the present invention, antimony oxide is used as a flame retardant adjuvant to synergize with the halogen-based compound used as a flame retardant to impart proper flame retardancy to the thermoplastic acrylonitrile-butadiene-styrene copolymer resin.

The antimony oxide is antimony trioxide or antimony pentoxide.

In the present invention, the flame retardant adjuvant is preferably used 1 to 15 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of acrylonitrile-butadiene-styrene copolymer resin (A). If antimony oxide is used in an amount less than 1 part by weight, sufficient flame retardant effect cannot be obtained, and when used in excess of 15 parts by weight, the balance of physical properties of the resin composition is not good.

(D) Aluminosilicate Inorganic Compound

In the present invention, the aluminosilicate inorganic compound is used as a heat stabilizer, and is composed of aluminum (Al), silicon (Si) and sodium (Na) or calcium (Ca). It said aluminosilicate-based inorganic compound (D) is often referred to as zeolite (zeolite) as a formula said aluminosilicate (Aluminosilicate), aluminum oxide (Al ₂ O ₃₎ and silicon oxide (SiO ₂₎ is a three-dimensional basic skeleton Sodium oxide (Na ₂ O) or calcium oxide (CaO) is added to achieve electronic neutrality. The inorganic compound is composed of 10 to 60% Al ₂ O ₃ , 10 to 60% SiO ₂ and 5 to 30% Na ₂ O or CaO, the average particle size is 0.5 to 5 ㎛.

In the present invention, the aluminosilicate inorganic compound (D) is added in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the acrylonitrile-butadiene-styrene copolymer resin (A) which is the base resin. When the aluminosilicate inorganic compound is added in an amount of 0.05 parts by weight or less, the effect of improving thermal stability is small, and when used in an amount of 10 parts by weight or more, it is not preferable because it impairs the physical properties of the resin.

The aluminosilicate inorganic compound (D) of the present invention may be used alone or in combination with a tinmalate-based compound (E) heat stabilizer described below.

The aluminosilicate inorganic compound (D) is added to improve the thermal stability of the flame retardant acrylonitrile-butadiene-styrene copolymer resin using a halogen compound as a flame retardant. Due to the improved thermal stability, the disintegration of flame retardants due to frictional heat generated by heat or high shear stress applied to the resin during extrusion processing and injection molding is suppressed or the decomposition gas is trapped to minimize discoloration and black streaks of the resin. The effect of suppressing the gas silver is very large.

(E) Tin Maleate Compound

In the present invention, the tinmalate-based compound is used as an auxiliary heat stabilizer, and is typically a tinmalate-based compound. It is synergistic when used in combination with the inorganic thermal stabilizer (D) rather than used alone, and stays in the injection molding machine, especially for a long time, compared to the resin composition using the tinmalate-based and hydrotalcite-based compounds as the thermal stabilizer. Even so, the effect of suppressing discoloration of the resin, black streaks and gas silver is greatly increased.

In the present invention, the tin maleate compound is preferably used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the basic resin (A) of the present invention. When it is used at 0.05 parts by weight or less, the effect of improving the thermal stability is small, and when it is added at 5 parts by weight or more, there is no obvious improvement of the thermal stability, and the physical property balance of the flame retardant resin may be lowered, in particular, the fluidity decrease.

(F) fluorine compound

The fluorine-based compound is used to prevent dropping during combustion of the resin. The fluorine-based compound used in the present invention is polytetrafluoroethylene (PTFE, TEFLON), and the amount is 0.05 to 2 parts by weight based on 100 parts by weight of the base resin (A).

(G) Chlorine Compound

In the present invention, in order to improve the impact strength of the resin, chlorine-based compounds such as chlorinated polyethylene (CPE) may be further added. The preferable addition amount of the said chlorine compound is 1-10 weight part with respect to 100 weight part of base resin (A).

In addition to the above components, the flame retardant thermoplastic resin composition of the present invention may further include inorganic additives, antioxidants, light stabilizers, metal lubricants, waxes, pigments, and / or dyes.

The flame retardant acrylonitrile-butadiene-styrene resin composition of the present invention uses a halogen compound as a flame retardant, adds antimony trioxide as a flame retardant aid, and uses a chlorine compound or a fluorine compound as an anti-dropping agent or impact reinforcing material, aluminum (Al ), An aluminosilicate inorganic compound composed of silicon (Si) and sodium (Na) or calcium (Ca) is added alone or in combination with tinmalate-based compounds, and other antioxidants, metal lubricants and waxes titanium dioxide, benzo After addition of the triazole and hindered amine light stabilizer, the mixture is mixed in a conventional mixer and the mixture is prepared into a resin composition in pellet form through an extruder.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

(A) Acrylonitrile-butadiene-styrene copolymer resin, (B) Halogen-based flame retardant, (C) Antimony oxide, (D) Aluminosilicate inorganic compound used in the following Examples and Comparative Examples, ( E) The specifications of a tin maleate compound, (F) fluorine compound, and (G) chlorine compound are as follows. (A) ABS resin was used by Cheil Industries, Inc., and other additives such as flame retardants were purchased on the market and used as they were without further purification.

(A) Acrylonitrile-butadiene-styrene copolymer resin

(a ₁ ) Acrylonitrile-butadiene-styrene copolymer resin

(a ₁₁ ) ABS resin (PBD CONTENT: 50%) prepared by graft polymerization using a small particle rubber having an average particle diameter of 0.12 μm was used.

(a ₁₂ ) ABS resin (PBD CONTENT: 50%) prepared by graft polymerization using a medium particle rubber having an average particle diameter of 0.32 μm was used.

(a ₂ ) SAN resin

(a ₂₁ ) A SAN resin having a weight average molecular weight of 88,000, an acrylonitrile content of 24% and a styrene content of 76% was used.

(a ₂₂ ) A SAN resin having a weight average molecular weight of 180,000, an acrylonitrile content of 32% and a styrene content of 68% was used.

(B) halogen flame retardant

(B ₁ ) SAYTEX RB 100, a flame retardant of the TBBA system manufactured by ALBEMARLE, USA, having a weight average molecular weight of 550 was used.

(B ₂ ) A brominated epoxy resin ECX-30 manufactured by DIC, Japan having a weight average molecular weight of 3,000 was used.

(C) antimony oxide

Antimony trioxide (manufactured by Ilsung Antimony Co., Ltd., Korea) was used.

(D) Aluminosilicate Inorganic Compound

Zeolite (APS30, manufactured by Aekyung Materials, Korea) was used.

(E) Tin Maleate Compound

TM-600P, a dibutyl tin maleate polymer manufactured by Songwon Industrial Co., Ltd., was used.

(F) fluorine compound

TEFLON 7A-J manufactured by Dupont-Mitsui was used.

(G) Chlorine Compound

DDE's cloned polyethylene (CPE) 3611P was used.

Example 1-3

Each component is added in the amount as shown in Table 3 below, 0.5 parts by weight of Irganox1076, a hindered phenol-based antioxidant manufactured by Korea Songwon Industries, and SONGSTAB Ca-ST, a stearic acid-based metal lubricant, as other antioxidants. 0.5 parts by weight and 1 part by weight of wax were added and mixed uniformly with a mixer, followed by extrusion with a twin screw extruder to prepare pellets.

Comparative Example 1-5

Either (a ₁₁ ) or (a ₁₂ ) was used in the graft ABS resin, and Comparative Example 4 used a low molecular weight SAN resin.

Table 1 shows the components and compositions of Examples and Comparative Examples.

Example Comparative Example One 2 3 One 2 3 4 5 (A) ABS resin Graft ABS resin (a ₁₁ ) 26 13 10 36 36 - - (a ₁₂ ) 10 13 26 - - 36 36 36 SAN resin (a ₂₁ ) - - - - - - 74 - (a ₂₂ ) 74 74 74 74 74 74 - 74 (B) Halogenated Compound (B ₁ ) - - - 23 - 23 - (B ₂ ) 22 23 22 - 23 - 23 23 (C) antimony trioxide 7 6 6 6 6 6 6 6 (D) Aluminosilicate Inorganic Compounds 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Tin Maleate Compound 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

According to the composition shown in Table 1, each component was uniformly mixed by a mixer, and then extruded by a twin screw extruder to prepare pellets. From the prepared pellets, test specimens for physical properties and flame retardancy were prepared by injection molding, and the measurement method for each property item was experimentally evaluated based on the following test analysis criteria.

(1) Measurement of crack initiation energy: 1/8 inch thick, 10cm × 10cm specimens were evaluated by the Gardner Impact method, ASTM D-5420 test method, and the unit was J.

(2) Impact strength measurement: evaluated by 1/4 inch thickness by ASTM D-256 test method, the unit is kgcm / cm.

(3) Fluidity: It was evaluated under the condition of 200 ℃ and 5 kg load by ASTM D-1238 test method, the unit is g / 10min.

(4) Thermal softening point temperature: The temperature was evaluated by the test method of ASTM D1525 under the condition of 50 ℃ / hr at 5 kg load, the unit is ℃.

(5) Flame retardancy measurement: According to the UL-94 flame retardance determination test method, it was determined by testing about 1/10 inch or 1/16 inch thickness.

The physical properties of the resins prepared in Examples 1-3 and Comparative Examples 1-5 are shown in Table 2.

Test Items unit Example Comparative Example One 2 3 One 2 3 4 5 Crack generation energy J 31 31 32 10 9 16 13 20 Notched Izod Impact Strength (1/4 ″, 23 ℃) Kgcm / cm 27 29 30 13 15 20 15 25 Flow index (10㎏, 220 ℃) g / 10min 12 13 14 15 12 15 18 13 Hot softening point temperature (5㎏, 50 ℃ / hr) ℃ 100 99 100 92 100 91 90 100 Flame retardant - V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

As shown in Table 2, ABS graft-polymerized small-size rubbery polymer and ABS resin graft-polymerized a medium-size rubbery polymer are each used alone or composed of a SAN resin having a low molecular weight and low acrylonitrile content. Unlike the comparative example using ABS resin or halogen-based compound having low molecular weight, ABS graft polymerized small particle rubber polymer and ABS resin graft polymerized medium particle rubber polymer are used. It can be seen that the crack generation energy and the thermal softening point temperature of the flame retardant resin are significantly increased in the embodiment using the ABS resin composed of the high SAN resin and the high molecular weight halogen-based compound in combination. Therefore, ABS resin composed of a high molecular weight and high acrylonitrile-containing SAN resin mixed with ABS graft-polymerized small particle rubber polymer and ABS graft-polymerized medium-size rubber polymer has a high molecular weight halogen. By using together a system compound, it turns out that manufacture of the flame-retardant acrylonitrile- butadiene- styrene-type copolymer resin which has the outstanding impact resistance and heat resistance is possible.

The present invention possesses good flame retardancy and mechanical properties, and has excellent impact resistance and heat resistance, and is very useful for the production of interior and exterior parts such as various electrical and electronic products and office automation equipment. It has the effect of providing the copolymer resin composition.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

(A) (a ₁ ) Graft polymer prepared by graft polymerization using small particle rubber having an average particle size of 0.08-0.18 μm and medium particle rubber having an average particle size of 0.28-0.38 μm 20-50% by weight of the graft ABS resin and (a ₂ ) the weight average molecular weight is 120,000-200,000, and the styrene 60- 100 parts by weight of a thermoplastic acrylonitrile-butadiene-styrene copolymer resin composed of 76% by weight and 50-80% by weight of a SAN resin composed of 40 to 24% by weight of acrylonitrile; (B) 5 to 30 parts by weight of a halogen flame retardant having a weight average molecular weight in the range of 2,000 to 10,000; (C) 1 to 15 parts by weight of antimony oxide; And (D) 0.05 to 10 parts by weight of the aluminosilicate inorganic compound; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises 0.05 to 5 parts by weight of the (E) tin maleate compound. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises 0.05 to 2 parts by weight of the (F) fluorine compound. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises 1 to 10 parts by weight of a chlorine compound. The flame retardant thermoplastic resin composition of claim 1, wherein the graft rate of each graft polymer is 40-90%. The method of claim 1, wherein the halogen-based flame retardant (B) is tetra bromobisphenol A, bis (tribromophenoxy) ethane, tribromophenoxy ethane, brominated epoxy resin (brominated epoxy) A flame retardant thermoplastic resin composition characterized in that the resin or the epoxy terminal is a brominated epoxy resin terminated with tribromophenol substituted with tribromophenol. According to claim 1, wherein the aluminosilicate inorganic compound (D) is composed of 10 to 60% Al ₂ O ₃ , 10 to 60% SiO ₂ and 5 to 30% of Na ₂ O or CaO Flame retardant thermoplastic resin composition, characterized in that the average particle size is 0.5 to 5 ㎛ zeolite. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises an inorganic additive, an antioxidant, a light stabilizer, a metal lubricant, a wax, a pigment, and / or a dye.