KR100302416B1 - Flameproof thermoplastic resin composition - Google Patents

Abstract

The flame-retardant thermoplastic resin composition of the present invention is (A) (a ₁ ) 20 to 100 weight of styrene-containing graft copolymer resin having a acrylonitrile content of 18 to 50 weight except the rubber part and (a ₂ ) acryl 40 to 95 parts by weight of a rubber-modified styrene resin composed of 0 to 80 weights of a styrene-containing copolymer resin having a nitrile content of 18 to 50 weight; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 2 to 40 parts by weight of a styrene-containing copolymer or styrene-containing graft copolymer resin having an acrylonitrile content of 5 to 18 parts by weight based on 100 parts by weight of the above (A) + (B); (D) 2-30 weight part of phosphazene compounds with respect to 100 weight part of said (A) + (B); And (E) 0-20 weight part of aromatic phosphate ester compounds with respect to 100 weight part of said (A) + (B).

Description

Flame retardant thermoplastic resin composition

(Field of invention)

The present invention relates to a thermoplastic resin composition having flame retardancy. More specifically, the present invention relates to a thermoplastic resin composition using a rubber-modified styrene resin and a polyphenylene ether resin as a base resin, using phosphazene as an essential component as a flame retardant, and optionally having a flame retardancy to which a phosphate ester compound is applied. will be.

(Background of invention)

Rubber modified styrene resins have been widely applied to various applications such as electrical appliances and office equipment because of their good processability, excellent physical properties, particularly impact strength and good appearance. However, since rubber modified styrene resin is combustible, when applied to heat-dissipating products such as personal computers or fax machines, the flame retardancy should be reinforced. Typically, flame retardants are added to impart flame retardancy, and these additive type flame retardants bring about a reduction in mechanical or thermal properties as well as impart flame retardancy, so it is important to minimize them.

The most widely known flame retardant method is to impart flame retardant properties by applying a halogen-based compound and an antimony-based compound together to the rubber-modified styrene resin. As the halogen-based compound, polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds, chlorinated polyethylene and the like are mainly used. Antimony trioxide and antimony pentoxide are mainly used as an antimony compound.

The method of applying the halogen and antimony compound together to impart flame retardancy is easy to secure flame retardancy and hardly deteriorates the physical properties.However, the hydrogen halide gas generated during processing may damage the mold. The generation of these gases is likely to have a fatal effect on the human body. In particular, polybrominated diphenyl ethers, which are mainly halogen-based flame retardants, have a high possibility of generating very toxic gases such as dioxins and furans during combustion.

Although a method of imparting flame retardancy to a resin composition by adding a compound containing phosphorus or nitrogen as a halogen-free flame retardant has been studied, the phosphorus compound alone has a disadvantage in that it lowers the heat resistance of the rubber-modified styrene-based resin and lacks flame retardancy. Its application is limited.

In general, rubber-modified styrene resins, particularly acrylonitrile-butadiene-styrene copolymer (ABS) resins, are hardly expected to have a flame retardant effect in a solid phase because almost all parts are decomposed and vaporized during combustion. (Polymer Degradation and Stability, 1995, vol 47, p217; and Journal of Applied Polymer Science, 1998, vol 68, p1067). Therefore, a high flame retardance can be obtained by adding a char forming agent so that the char can be produced smoothly. Char forming agent forms a three-dimensional carbon chain bond on the surface of the rubber molecule during combustion to effectively form the char to block the entry of oxygen from the outside and prevent the release of fuel from the inside.

Japanese Patent Application Laid-Open No. 7-48491 discloses a thermoplastic flame retardant resin in which a phosphate ester is applied as a flame retardant to a thermoplastic copolymer resin of a rubbery polymer and an aromatic vinyl monomer, and a phenolic resin in the form of a novolak is added as a char forming agent. However, phenolic resin has a problem of lowering the heat resistance of rubber modified styrene resin (ABS), and in order to obtain a desired flame retardancy, a relatively large amount of phosphate ester and novolak phenolic resin should be added. There are disadvantages.

The present inventors blended polyphenylene ether resin with rubber-modified styrene resin to use as a base resin to solve the problems of existing flame retardant thermoplastic resins, and a styrene-acrylonitrile copolymer having an acrylonitrile content of 5 to 18 weight. The resin is used as a compatibilizer to prevent the mechanical properties of the resin composition from deteriorating, and an aromatic phosphate ester compound and a phenol resin are applied to develop a thermoplastic resin composition having excellent flame retardancy without containing halogen, and has already been applied for a patent application No. 98-36004 ( 2 September 1998).

In addition, the present inventors found that the phenol resin introduced as the char forming agent of ABS resin lowers the heat stability and weather resistance of the ABS resin, and provides compatibility between the ABS resin and the polyphenylene ether resin without using the phenol resin. By using a SAN copolymer resin having a controlled acrylonitrile content as a compatibilizer and applying phosphazene as a flame retardant to rubber-modified styrene resins, a resin composition having excellent heat resistance and flame retardancy was developed.

An object of the present invention is to provide a thermoplastic resin composition excellent in heat resistance and flame retardancy.

Another object of the present invention is to provide a flame retardant thermoplastic resin composition containing no halogen compound that generates environmental pollution during processing or combustion of the resin.

Still another object of the present invention is to provide a flame retardant thermoplastic resin composition capable of imparting compatibility to ABS resins and polyphenylene ether resins by using a SAN copolymer having a controlled acrylonitrile content as a kind of compatibilizer.

Another object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance and flame retardancy by using phosphazene as a flame retardant and optionally applying an aromatic phosphate ester compound.

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

The resin composition of the present invention comprises a rubber-modified styrene resin (A), a polyphenylene ether resin (B), in which a styrene-containing graft copolymer resin (a ₁ ) and optionally a styrene-containing copolymer resin (a ₂ ) are mixed; It consists of styrene-acrylonitrile copolymer or styrene containing graft copolymer resin (C), phosphazene compound (D), and aromatic phosphate ester compound (E) whose content of acrylonitrile is 5-18 weight.

40-95 weight part of rubber modified styrene resins (A), 5-60 weight part of polyphenylene ether resins (B), and styrene containing resin (C) with respect to 100 weight part of said (A) + (B). Is 2 to 40 parts by weight, 2 to 30 parts by weight of the phosphazene compound (D), and 0 to 20 parts by weight of the aromatic phosphate ester compound (E). The rubber-modified styrene-based resin (A) is a styrene-containing graft copolymer resin (a ₁ ) having an acrylonitrile content of 18 to 50 wt. is SAN copolymer resin (a ₂₎ it consists of 0~80 wt.

In the present invention, a rubber modified styrene resin (A) and a polyphenylene ether resin (B) constitute a basic resin, and optionally, rubber may be applied, but the SAN having an acrylonitrile content of 5 to 18 parts by weight except for rubber is used. Copolymer resin or graft copolymer resin (C) is used as a compatibilizer for the resins (A) and (B), and the phosphazene compound (D) and the aromatic phosphate ester compound (E) are added as a flame retardant.

Hereinafter, each component of the resin composition of the present invention will be described in detail.

(A) Rubber modified styrene resin

Rubber modified styrene resin refers to a polymer in which a rubber polymer is dispersed in the form of particles in a matrix (continuous phase) made of an aromatic vinyl polymer, and can be copolymerized with an aromatic vinyl monomer and a vinyl polymer in the presence of a rubber polymer. Prepared by addition of monomer and polymerization.

Such rubber-modified styrenic resins can be prepared by known polymerization methods such as emulsion polymerization, suspension polymerization or bulk polymerization, and are usually produced by mixing and extruding styrene-containing graft copolymer resin and styrene-containing copolymer resin. In the case of bulk polymerization, the rubber-modified styrene resin is produced by only one step reaction without producing the styrene-containing graft copolymer resin and the styrene-containing copolymer resin separately, but in any case, the rubber content of the final rubber-modified styrene resin component is It is suitable that it is 5-30 weight.

Examples of such resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymers (AES) resins, and the like. There is this.

The above resin may be applied to the styrene-containing graft copolymer resin alone or styrene-containing graft copolymer resin and styrene-containing copolymer resin together, preferably in consideration of their compatibility. The present invention uses a mixture of a styrene-containing graft copolymer resin (a ₁₎ 20~100 jungryangwa styrene-containing copolymer resin (a ₂₎ 0~80 jungryangreul.

(a ₁ ) Styrene-containing graft copolymer resin

Examples of the rubber used for the production of the styrene-containing graft copolymer resin include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); Saturated rubber hydrogenated to the diene rubber; Acrylic rubbers such as isoprene rubber and butyl polyacrylate; Although ethylene-propylene-diene monomer terpolymer (EPDM) etc. can be enumerated, diene rubber is preferable, and butadiene rubber is more preferable.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methyl styrene, p-methyl styrene, and the like may be used. Of these, styrene is most preferable, and a monomer copolymerizable with the aromatic vinyl monomer may be used. Apply by introducing one or more. As a monomer which can be introduced, a vinyl cyanide compound such as acrylonitrile or methacrylonitrile is preferable.

In the styrene-containing graft copolymer resin as described above, the rubber is contained in an amount of 10 to 60 parts by weight, and the amount of the aromatic vinyl monomer such as styrene is 50 to 82 parts by weight in the components of the monomers except the rubber. It is preferable that the quantity of a monomer is 18-50 weight part.

In addition, in order to impart properties such as workability, heat resistance, and the like, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be added to graft polymerization. The amount added is in the range of 0 to 40 parts by weight based on the styrene-containing graft copolymer resin.

In preparing the styrene-containing graft copolymer, in consideration of impact strength and appearance, the average size of the rubber particles is preferably in the range of 0.1 to 4 μm.

(a ₂ ) Styrene-containing copolymer resin

Styrene-containing copolymer resin is prepared according to the monomer ratio and compatibility among the components of the styrene-containing graft copolymer resin prepared in the above composition except rubber, the components are as follows. The styrene-containing copolymer resin is a resin obtained by copolymerizing an aromatic vinyl monomer and one or more monomers copolymerizable therewith. The styrene-containing copolymer resin (a ₂ ) preferably used in the present invention includes a SAN copolymer having an acrylonitrile content of 18 to 50 weight.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methyl styrene, p-methyl styrene, etc. may be used. Among them, styrene is most preferable, and the weight ratio of the aromatic vinyl monomer in the components of the copolymer resin is 50 to 82 parts by weight. Corresponding. One or more monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. As the monomer to be introduced, a vinyl cyanide compound such as acrylonitrile or methacrylonitrile is preferable, and 18 to 50 parts by weight of the components of the entire copolymer is introduced. Furthermore, 0-40 weight part of monomers, such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide, can also be added and copolymerized here.

The rubber-modified styrene resin (A) in the present invention, except for the rubber component, has 20 to 100 weights of styrene-containing graft copolymer resin (a ₁ ) having an acrylonitrile content of 18 to 50 weights and an acrylonitrile content of 18 to 50 weight. a styrene-containing copolymer resin is 50 parts by weight of (a ₂₎ consists of 0~80 wt. The rubber modified styrene resin (A) forms a base resin together with the polyphenylene ether resin (B) described below, and the rubber modified styrene resin (A) constitutes 40 to 95 parts by weight in 100 parts by weight of the base resin. , Polyphenylene ether resin (B) constitutes 5 to 60 parts by weight.

(B) polyphenylene ether resin

The rubber-modified styrene resin alone is used as a base resin by adding polyphenylene ether resin because it is insufficient in flame retardancy and degrades rigidity and heat resistance. Such compounds include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4 -Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl- 6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly ( Copolymer of 2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5-triethyl-1 And copolymers of 4-phenylene) ether. Preferably a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl- 1,4-phenylene) ether is used, of which poly (2,6-dimethyl-1,4-phenylene) ether is most preferred.

Although the polymerization degree of polyphenylene ether is not specifically limited, It is preferable that the intrinsic viscosity measured in 25 degreeC chloroform solvent is 0.1-0.8 in consideration of the thermal stability and workability of a resin composition.

(C) styrene-containing copolymer resin or styrene-containing graft copolymer resin having an acrylonitrile content of 5-18 weight

The resin is a polymer added to improve the compatibility between the rubber-modified styrene resin (A) and the polyphenylene ether resin (B) used as the base resin. The components of the resin (C) used in the present invention is 0 to 60 parts by weight of rubber, styrene is 82 to 95 parts by weight, except for the rubber portion, acrylonitrile is 5 to 18 parts by weight. The polymerization method of the copolymer may be prepared by applying emulsification, suspension, bulk polymerization and the like and a suitable weight average molecular weight is 50,000 to 300,000. Further monomers copolymerizable with the styrene-acrylonitrile include methacrylate, maleic anhydride, phenylmaleimide, and the like, and styrene may be replaced with α-methylstyrene to improve heat resistance. The styrene-acrylonitrile copolymer or graft copolymer resin is added to improve the compatibility of the blend of the rubber-modified styrene resin (A) and the polyphenylene ether resin (B), and the addition amount thereof is ( It can be applied in the range of 2 to 40 parts by weight based on 100 parts by weight of the sum of A) and (B). The resin composition to which the copolymer resin (C) is not added cannot improve the compatibility of the blend of the rubber-modified styrene-based resin (A) and the polyphenylene ether resin (B), and thus the mechanical strength is sharply lowered so that the actual Not applicable to the product.

(D) phosphazene compounds

In the present invention, a phosphazene compound represented by the following general formula (1) is used:

or

In formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ are independently compounds containing no halogen, preferably amines and phenol, p-aminophenol, ethyl alcohol, Alcohols such as propyl alcohol; And R ₇ and R ₈ independently of each other are derivatives from alcohols such as phenol, methylphenol, xylenol, methyl alcohol, and n has a value of 2 to 10.

The phosphazene compound having the formula (1) is used as a main flame retardant, it can be applied singly or mixed, 2 to 30 parts by weight based on 100 parts by weight of the base resin.

(E) Aromatic Phosphate Ester Compounds

In the present invention, an aromatic phosphate ester compound represented by the following general formula (2) is used:

In formula (2), R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group of C _1-4 , and X is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S N has a value of 0-4. As the compound corresponding to the formula (2), when n value is 0, triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, gyrenyl thiphenyl phosphate, tri (2,6-dimethylphenyl) phosphate, and tri ( 2,4,6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when n is 1, resorcinol Bis (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dibutylbutylphenyl) phosphate, hydroquinolbis (2,6-diethylphenyl) phosphate, hydroquinolbis (2,4-diter Sheryl butylphenyl) phosphate etc. are typical examples.

In the present invention, a phosphate ester compound represented by the following general formula (3) having a phloroglucinol as a skeleton may also be used:

In formula (3), R ₁₂ , R ₁₃ and R ₁₄ are hydrogen or an alkyl group of C _1-4 . Examples of the compound represented by formula (3) include 1,3,5-tri (diphenylphosphate) fluoroglucinol, 1,3,5-tri (dicresylphosphate) fluoroglucinol, 1,3 , 5-tri (designinylphosphate) fluoroglucinol and the like.

Phosphate ester compounds having the above formulas (2) and (3) may be applied singly or mixed, and it is not preferable to apply a compound having a molecular weight of 1,500 or more in the structure because of its low flame retardancy effect and limited melting point. Although not present, it is preferable to apply a phosphate ester having a melting point of 90 ° C or higher.

In the present invention, the aromatic phosphate ester compound to be applied as a flame retardant is superior to the phosphazene compound, so it is applied in consideration of the balance of physical properties, and used in the range of 0 to 20 parts by weight based on 100 parts by weight of the base resin. desirable.

The resin composition of the present invention may be added dropping inhibitors, impact modifiers, processing aids, heat stabilizers, antioxidants, light stabilizers and the like, organic or inorganic pigments, dyes, sulfates, asbestos, glass fibers, talc, Inorganic fillers such as silica and ceramics may also be added. These are used in the amount of 0-50 weight part with respect to 100 weight part of base resin of this invention.

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

Rubber modified styrene resin having an acrylonitrile content of 18 to 80 parts by weight, except for the rubber portion (A) used in the resin compositions of the following Examples and Comparative Examples, (B) polyphenylene ether resin, (C) acrylic The production and specifications of the styrene-acrylonitrile copolymer having a ronitrile content of 5 to 18 weight, the (D) phosphazene compound, and the (E) phosphate ester compound are as follows.

(A) Rubber modified styrene resin

To a styrene-containing graft copolymer resin (a ₁₎ was prepared by mixing 40 jungryangwa styrene-containing copolymer resin (a ₂₎ 60 jungryangreul manufactured.

(a ₁ ) Styrene-containing graft copolymer resin (ABS)

36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water are added to 50 parts by weight of butadiene rubber latex, 1.0 part by weight of potassium oleate, 0.4 part by weight of cumene hydroperoxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of sodium pyrophosphate were maintained at 75 ° C. for 5 hours, and the reaction was completed to prepare a graft ABS latex. Styrene-containing graft copolymer resin (g-ABS) powder was prepared by adding and solidifying 0.4 parts by weight of sulfuric acid to the solid content of.

(a ₂ ) Styrene-containing copolymer resin (AN content 25 weight)

To 75 parts by weight of styrene and 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of mercaptan-based chain transfer agent were added. The copolymer resin (SAN) having an acrylonitrile content of 25 weight was prepared by increasing the temperature to 80 ° C. and maintaining the temperature at 80 ° C. for 180 minutes. It was washed with water, dehydrated and dried to prepare a SAN powder. The weight average molecular weight of the synthesized styrene-acrylonitrile copolymer resin was in the range of 160,000 to 200,000.

(B) polyphenylene ether resin

Poly (2,6-dimethyl-1,4-phenylene) ether of Asahi Kasei Co., Ltd., Japan, was used, and the particle size was in the form of a powder having an average particle diameter of several μm. The trade name is P-402.

(C) Styrene-containing copolymer resin (AN content 13 weight)

120 parts by weight of deionized water, 87 parts by weight of styrene and 13 parts by weight of acrylonitrile, 0.1 part by weight of azobisisobutyronitrile, 1,1'-di (tertiarybutylperoxy) -3,3 ', 5-trimethyl 0.2 part by weight of cyclohexane, 0.4 part by weight of tricalcium phosphate, and 0.3 part by weight of mercaptan-based chain transfer agent were added. The temperature was raised from room temperature to 80 ° C. for 90 minutes, then maintained at this temperature for 240 minutes, and then elevated to 100 ° C. and 240 minutes. Was maintained to prepare a copolymer resin (SAN) having an acrylonitrile content of 13 weight. It was washed with water, dehydrated and dried to prepare a SAN powder. The weight average molecular weight of the synthesized styrene-acrylonitrile copolymer resin was in the range of 100,000 to 140,000.

(D) phosphazene compounds

As the phenoxy phosphazene oligomer, a compound having a phosphorus content of 13 and represented by the following formula was used:

N has an average value of 3-4.

(E) Aromatic Phosphate Ester Compounds

(e ₁ ) triphenyl phosphate

Triphenyl phosphate having a melting point of 48 ° C. was used.

(e ₂ ) tri (2,6-dimethylphenyl) phosphate

Tri (2,6-dimethylphenyl) phosphate having a melting point of 137 ° C was used.

Each of the components was prepared in the resin compositions of Examples 1 to 5 and Comparative Example 1 in the composition shown in Table 1.

ingredient Example Comparative Example 1 One 2 3 4 5 (A) 75 75 75 75 75 75 (B) 25 25 25 25 25 25 (C) 15 15 15 15 15 - (D) 20 15 15 10 10 20 (E) (e ₁ ) - 5 - 10 - - (e ₂ ) - - 5 - 10 -

(Unit: parts by weight)

The resin compositions of Examples 1 to 5 and Comparative Example 1 were added in the amounts shown in Table 1, and extruded at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder to prepare pellets. The prepared pellets were dried for 3 hours at a temperature of 80 ° C., and then injected in a 60 oz injection machine under conditions of a molding temperature of 220 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a physical specimen and a flame retardant specimen.

The prepared specimens were measured for Izod impact strength with 1/8 'notched specimens in accordance with ASTM D-256. The higher the value is, the better it should be maintained at 10 or higher, and the flow chart (MI) is determined according to ASTM D-1238. Measured at 10 ℃ load, ℃, the higher the flow rate is better workability. Heat resistance (VST) was measured at 5 kg load in accordance with ASTM D-1525, the results are shown in Table 2.

ingredient Example Comparative Example 1 One 2 3 4 5 Izod impact strength (kgfcm / cm) 20 21 19 18 19 7 Flowchart (MI) (g / 10min) 20 25 22 30 26 18 Heat resistance degree (℃) 92 87 91 83 90 94 Flame Retardant (1/10 ') V-1 V-1 V-1 V-1 V-1 V-1

In order to apply flame-retardant resin for commercial use, the softening temperature must be over 80 ℃. In Examples 1 to 5 of the present invention, the components (D) and (E) were applied as the flame retardant, so that they were excellent in impact strength, heat resistance and flame retardancy. Considering the heat resistance and the flow chart, it is preferable to use in combination with a common phosphate.

In the case of Comparative Example 1, the component (C) was excluded, and the compatibility between ABS and PPE was lowered, and the impact strength was lowered to 7.

The thermoplastic resin composition of the present invention improves compatibility by adding a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18 weight to a blend of a rubber-modified styrene resin and a polyphenylene ether resin, thereby improving impact strength. It is excellent in, and by applying a phosphazene compound as a main flame retardant, and optionally by applying an aromatic phosphate ester compound has the effect of the invention excellent in flame retardancy and heat resistance.

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₎ except the rubber part containing wife acrylonitrile content of 18 to 50 parts by weight of styrene-containing graft copolymer resin is 20 to 100 jungryangwa (a ₂₎ the content of acrylonitrile of 18-50 weight styrene 40 to 95 parts by weight of a rubber-modified styrene resin composed of 0 to 80 weight of a copolymer resin; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 100 parts by weight of the (A) + (B), the rubber part may be selectively applied up to 60 parts by weight and the styrene-containing copolymer resin having an acrylonitrile content of 5-18 weight except for the rubber part or 2 to 40 parts by weight of graft copolymer resin; (D) 2-30 weight part of phosphazene compounds with respect to 100 weight part of said (A) + (B); And (E) 0-20 weight part of aromatic phosphate ester compounds with respect to 100 weight part of said (A) + (B); A thermoplastic resin composition having flame retardance, characterized in that consisting of. The polyphenylene ether resin (B) according to claim 1, wherein the polyphenylene ether resin (B) is poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether , Poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6- Copolymer of dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether And a copolymer of poly (2,3,5-triethyl-1,4-phenylene) ether. The method of claim 1, wherein the styrene-containing copolymer resin (C) is a copolymerizable monomer is further copolymerized, the copolymerizable monomer is selected from the group consisting of methacrylate, maleic anhydride and phenylmaleimide. Thermoplastic resin composition having flame retardancy. The thermoplastic resin composition according to claim 1, wherein the phosphazene compound (D) is represented by the following general formula (1): Formula 1 or In formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ are independently compounds containing no halogen, preferably amines and phenol, p-aminophenol, ethyl alcohol, Derivatives of alcohols such as propyl alcohol; And R ₇ and R ₈ are independently of each other derivatives of alcohols such as phenol, methylphenol, xylenol, methyl alcohol, and n value is a number of 2 to 10. The thermoplastic resin composition according to claim 1, wherein the aromatic phosphate ester compound (E) is a compound represented by the following general formula (2), a compound represented by the following general formula (3), or a mixture thereof. : Formula 2 Formula 3 In formula (2), R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group of C _1-4 , and X is derived from a dialcohol such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S will a, n value is a number of 0 to 4, being R _12, R ₁₃ and R ₁₄ is hydrogen or C _1~4 alkyl group in the formula (3). The thermoplastic resin composition according to claim 1, wherein the aromatic phosphate ester (E) has a melting point of 90 ° C or higher. The flame retardant according to any one of claims 1 to 7, further comprising a drip inhibitor, an impact modifier, a processing aid, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a dye, and / or an inorganic additive. Thermoplastic resin composition. Molded article processed with the resin composition of any one of Claims 1-8.