KR100396404B1 - Thermoplastic Flameproof Resin Composition - Google Patents

Abstract

The resin composition of the present invention is based on 100 parts by weight of the base resin consisting of 40 to 100 parts by weight of acrylonitrile-butadiene-styrene (ABS) resin (A) and 0 to 60 parts by weight of polyphenylene ether resin (B). It is a thermoplastic resin composition which has the outstanding flame retardance as a composition which applied 2-30 weight part of ester compounds (C) and 0.01-20 weight part of copper compounds (D).

Description

Thermoplastic Flameproof Resin Composition

Field of invention

The present invention relates to a thermoplastic flame retardant resin composition. More specifically, the present invention applies a phosphate ester as a flame retardant to a rubber-modified styrene resin, a styrene copolymer and a polyphenylene ether resin blend, and adds a copper compound to further improve the flame retardancy. It is about.

Background of the 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, in application to heat-dissipating products such as personal computers or fax machines, rubber-modified styrene resins have generally been manufactured by applying flame retardant resins due to the disadvantage of being combustible. The most commonly used flame retardant method is to impart flame retardancy by applying a halogen compound and an antimony compound to a rubber-modified styrene resin. However, halogen-containing compounds can damage the mold and have a fatal effect on the human body due to the hydrogen halide gas generated during processing. In addition, 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 compound containing no halogen has been studied, when the phosphorus compound is used alone, the heat resistance of the rubber-modified styrene resin is lowered and the flame retardancy is insufficient. There is a disadvantage in that the application is limited.

In general, rubber-modified styrene-based resins, particularly acrylonitrile-butadiene-styrene copolymer resins (hereinafter referred to as ABS resins) have a disadvantage in that it is difficult to expect a flame retardant effect in a solid phase because there is little char remaining during combustion (Journal of Applied Polymer Science, 1998, vol 68, p1067). Therefore, it is necessary to add a char forming agent to the ABS resin so that the char can be produced smoothly to obtain the desired flame retardancy.

Japanese Patent Application Laid-Open No. 7-48491 discloses that a phosphate ester is applied as a flame retardant to a thermoplastic copolymer resin composed of a rubber polymer and a polymer component containing a monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, or a maleimide monomer. A thermoplastic flame retardant resin composition prepared by adding a phenolic resin in the form of a novolak as a forming agent is disclosed. However, the phenol resin not only lowers the heat resistance of the ABS resin, but also has a disadvantage in that the heat resistance is further lowered because a relatively large amount of phosphate ester and novolak resin must be added to obtain a desired flame retardancy due to the lack of char forming ability. .

Accordingly, the present inventors use a blend of a rubber-modified styrene-based copolymer and a polyphenylene ether resin as a base resin without using a phenol resin to improve compatibility and to improve thermal stability and flame retardancy. A styrene-acrylonitrile copolymer having an acrylonitrile content of 18% by weight was used, and a flame retardant was used to develop a thermoplastic resin having excellent flame retardancy by using a phosphate ester compound, and by adding a styrene-based resin at low load The thermal stability of the excellent and developed a resin composition with improved flowability has already been filed in Korean Patent Application No. 99-28442. However, the above method has a disadvantage in that the char product must be added when it is combusted.

Accordingly, the present inventors have improved the disadvantages of the present invention to develop a resin composition which greatly improves the flame retardancy of the rubber-modified styrene-based resin composition even in a state in which the addition of the char generation material is minimized or the char production material is not added. .

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

Another object of the present invention is to apply a phosphate ester flame retardant to a rubber-modified styrene resin, a styrene copolymer and a polyphenylene ether resin blend, to provide a thermoplastic resin composition excellent in flame retardancy to which a copper compound is added to further improve flame retardancy. It is to.

Still another object of the present invention is to provide a thermoplastic resin composition which greatly improves the flame retardancy of the rubber-modified styrene resin composition even in a state in which the addition of the char generation material is minimized or the char generation material is not added.

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

Thermoplastic resin composition according to the present invention is based on 100 parts by weight of the base resin consisting of 40 to 100 parts by weight of acrylonitrile-butadiene-styrene (ABS) resin (A) and 0 to 60 parts by weight of polyphenylene ether resin (B). To 2 to 30 parts by weight of the phosphate ester compound (C) and 0.01 to 20 parts by weight of the copper compound (D).

Hereinafter, the composition of the resin will be described in detail.

(A) Rubber modified styrene resin (ABS resin)

Rubber-modified styrene resins are polymers in which rubbery polymers are dispersed in a particulate form in a matrix (continuous phase) made of vinyl aromatic polymers, and polymerized by adding an aromatic vinyl monomer and a vinyl monomer copolymerizable therewith to the rubbery polymer. do. Such rubber-modified styrene-based resins can be prepared by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and are generally prepared by mixing and extruding graft copolymer resin and copolymer resin. In the case of the bulk polymerization, the rubber modified styrene resin is produced by only one step reaction without producing the graft copolymer resin and the copolymer resin separately, but in all cases, the rubber content of the final rubber modified styrene resin component is It is preferable that it is 2-30 weight part with respect to.

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

The resin may be applied to the graft resin alone or to the graft copolymer resin and the copolymer resin together, preferably in consideration of their compatibility.

(a ₁ ) Styrene-containing graft copolymer resin

Examples of the rubber used for the graft copolymer resin include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubber and isoprene rubber in which hydrogen is added to the diene rubber. , Chloroprene rubber, acrylic rubber such as butyl polyacrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). Among these, diene rubber is particularly preferable, butadiene rubber is more preferable. The content of the rubber is preferably 10 to 68% by weight in the total components of the graft copolymer resin.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methylstyrene, p-methylstyrene, and the like may be added, of which styrene is most preferred. One or more monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. Preferable monomers include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as methacrylonitrile.

The content of the rubber in the graft copolymer as a whole component is 10 to 68% by weight, 35 to 82% by weight of aromatic vinyl monomers such as styrene and 65 to 18 unsaturated unsaturated monomers in the rubber, except the rubber component Add weight percent to graft copolymerize. Further, in order to impart properties such as workability and heat resistance, monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be added and graft polymerization. The monomer may be added in an amount of 0 to 40 parts by weight based on the entire graft resin.

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

(a ₂ ) Styrene-containing copolymer resin

The copolymer resin is prepared according to the monomer ratio and compatibility of the graft copolymer prepared in the above composition except for rubber, and the components thereof are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methylstyrene, p-methylstyrene, and the like may be added. Of these, styrene is most preferable, and 35 to 82% by weight of all components of the copolymer resin are introduced. One or more monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. As the monomer to be introduced, vinyl cyanide-based compounds such as acrylonitrile and unsaturated nitrile-based compounds such as methacrylonitrile are preferable, and 65 to 18% by weight of the total components of the copolymer are introduced. In addition, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be added to 0 to 40 parts by weight of 100 parts by weight of the copolymer to be copolymerized.

Rubber-modified styrene resin (A) consists of 20 to 90% by weight of the styrene-containing graft copolymer resin (a ₁ ) and 80 to 10% by weight of styrene-containing copolymer resin (a ₂ ).

(B) polyphenylene ether resin

In the present invention, the rubber-reinforced styrenic resin itself is used because it is insufficient in flame retardancy and low in rigidity and heat resistance. Examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-di Propyl-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 ) Copolymer of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5) A copolymer of -triethyl-1,4-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, and more preferably poly (2,6-dimethyl-1,4-phenylene) ether is used. 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 0.2-0.8 in consideration of the thermal stability and workability of a resin composition.

(C) Phosphate Ester Compounds

Phosphate ester that can be used in the present invention has a structure shown in the following formula (1), the phosphate ester compound is applied to 2 to 30 parts by weight based on 100 parts by weight of the resin composition (A) + (B).

Formula 1

In formula (1), R ₁ , R ₂ , R ₃ are each independently hydrogen or an alkyl group of C ₁ -C ₄ , X is C ₆ -C ₂₀ substituted with an aryl group or alkyl group of C ₆ -C ₂₀ Is an aryl group derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S, and N is an integer of 0 to 4.

Examples of the compound corresponding to the formula (1) include triphenylphosphate, tricresylphosphate, trigyrenylphosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4,6- when N is 0 Trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when N is 1, resorcinol bis (diphenyl) phosphate, Lesosinolbis (2,6-dimethylphenyl) phosphate, Lesosinolbis (2,4-dibutylbutylphenyl) phosphate, Hydroquinolbis (2,6-dimethylphenyl) phosphate, Hydroquinolbis (2,4 -Dibutylbutylphenyl) phosphate and the like.

These phosphoric acid ester compounds may be applied alone or in combination with each other.

(D) copper compound

A copper compound is used in 0.01-20 weight part with respect to 100 weight part of said resin compositions (A) + (B).

The copper compound is a monovalent or divalent copper compound and includes oxides, sulfides, chlorides, fluorides, phosphates, nitrates, organic acid salts, and the like. In the case of a solid copper compound, the diameter of 0.01-10 micrometers is the most preferable. Copper oxide (divalent) [Cu (II) O], copper oxide (monovalent) [Cu (I) ₂ O], copper sulfide (divalent) [Cu (II) S], copper sulfide (monovalent) [Cu (I) ₂ S] and the like are typical, and these copper compounds may be applied alone or in each mixture.

The thermoplastic resin of the present invention may be added an antidripping agent, an impact modifier, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye according to each use. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics, sulfates, carbonates, and the like, which may be used within the range of 0 to 30 parts by weight based on 100 parts by weight of the base resin of the present invention.

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

Example

Preparation and specifications of the base resin, flame retardant additive and copper compound used in the Examples and Comparative Examples are as follows.

(A) Rubber modified styrene resin

(a ₁ ) Graft ABS Resin

36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water were added to 50 parts by weight of butadiene rubber latex solids, and 1.0 parts by weight of potassium oleate and 0.4 parts 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, 0.3 parts by weight of sodium pyrophosphate, and maintained at 75 ° C. for 5 hours to complete the reaction to prepare graft ABS latex, 0.4 parts by weight of sulfuric acid was added to the solid content of the resin and coagulated to prepare a graft copolymer resin (g-ABS) powder.

(a ₂ ) Styrene-containing copolymer resin

(a ₂₁ ) Styrene-containing copolymer resin (AN content 25% by weight)

To 75 parts by weight of styrene and 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 part by weight of azobisisobutyronitrile, 0.4 part by weight of tricalcium phosphate, and 0.2 part by weight of mercaptan-based chain transfer agent were added thereto at room temperature to 80 ° C. After raising the temperature for 90 minutes to 180 minutes at this temperature to prepare a copolymer resin (SAN) having an acrylonitrile content of 25% by weight. It is washed with water, dehydrated and dried to prepare a SAN powder. The weight average molecular weight of the synthesized styrene-acrylonitrile copolymer resin is in the range of 160,000 to 200,000.

(a ₂₂ ) Styrene-containing copolymer resin (AN content 40%)

60 parts by weight of styrene and 40 parts by weight of acrylonitrile were added 120 parts by weight of deionized water, 0.15 part by weight of azobisisobutyronitrile, 0.4 part by weight of tricalcium phosphate, and 0.2 part by weight of mercaptan-based chain transfer agent at 80 ° C. After the temperature was raised for 90 minutes and maintained at this temperature for 180 minutes, an acrylonitrile-styrene copolymer having a weight average molecular weight of 100,000 to 160,000 and an acrylonitrile content of 36 to 42% by weight was prepared. It is washed with water, dehydrated and dried to prepare a SAN powder.

(B) polyphenylene ether (PPE) resin

Poly (2,6-dimethyl-phenylether) (trade name P-402) from Asahi Kasei of Japan, in powder form, was used.

(C) phosphate ester compound

Triphenylphosphate (TPP) was used as a material having a melting point of 48 ° C.

(D) copper compound

Copper oxide (bivalent) [Cu (II) O]. Copper oxide (monovalent) [Cu (I) ₂ O], copper sulfide (bivalent) [Cu (II) S], or copper sulfide (monovalent) [Cu (I) ₂ S] was used.

The materials of (A) to (D) were added to the contents shown in the following Tables 1, 2, and 3 to extrude at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder to prepare pellets.

The prepared pellets were dried at 80 ° C. for 3 hours and then injected into a 6 oz injection machine at a molding temperature of 220-280 ° C. and a mold temperature of 40-80 ° C. to prepare a physical specimen. The prepared specimens were measured for flame retardancy by a horizontal combustion evaluation method.

The horizontal combustion evaluation method for flame retardancy is the same condition as the UL94 HB evaluation method, and after the flame is applied for 30 seconds with the burner adjusted to emit blue flame at 45 ° angle, the burning time is measured after the specimen is burned up to 25 mm section. It is to measure the time taken for combustion in the section up to mm. More specifically, the horizontal combustion evaluation is made by removing the flame when the flame reaches the 25 mm point within 30 seconds after applying the flame and measuring the time that the combustion proceeds in the interval from the 25 mm point to the 100 mm point. . In the case of horizontal combustion test, the combustion time until extinguishing was measured in seconds (sec) in case of having self-extinguishing.

The content of char generated during flame retardancy evaluation of the specimen was measured between 350 and 450 ° C. using a thermogravimetric analyzer (TGA). The content of this char is closely related to the flame retardancy, and the higher the content of the char, the higher the flame retardancy is.

Example 1A-1D

A rubber modified styrene resin (A) was prepared by mixing a graft ABS resin (a ₁ ) and a styrene-containing copolymer resin (a ₂₁ ) having an acrylonitrile content of 25% in a weight ratio of 30:70. 10 parts by weight of phosphoric acid ester compound (C) triphenylphosphate (TPP) and 1 part by weight of Cu (I) ₂ O (D) were added to 100 parts by weight of the resin (A), and a small amount of heat was added. The stabilizers were mixed and pellets were prepared using a twin screw extruder having a diameter of 40 mm.

Comparative Example 1

Pellets were prepared in the same manner as in Example 1 except that no Cu (I) ₂ O (D) was added.

Table 1 shows the char content generated during the flame retardancy evaluation of the pellets prepared in Examples 1A-1D and Comparative Example 1.

ABS resin (A) TPP (C) Cu (I) ₂ O (D) Char content (%) Example 1A 100 10 One 12.4 Example 1B 100 10 3 15.8 Example 1C 100 10 5 19.6 Example 1D 100 10 10 26.4 Comparative Example 1 100 10 - 7.2

As shown in Table 1, the Char content of Examples 1A-1D to which 1, 3, 5, and 10 parts by weight of Cu (I) ₂ O was added was compared with that of Comparative Example 1, in which Cu (I) ₂ O was not added at all. It was observed that the flame retardancy of the resin was improved by the addition of Cu (I) ₂ O.

Example 2A-2D

A rubber modified styrene resin (A) was prepared by mixing graft ABS resin (a ₁ ) and styrene-containing copolymer resin (a ₂₁ ) in a weight ratio of 30:70. 10 parts by weight of the phosphate ester compound (C) and 10 parts by weight of Cu (I) ₂ O (D) based on 100 parts by weight of the mixture containing 10 parts by weight of the polyphenylene ether (PPE) resin (B) based on 90 parts by weight of the resin (A). ), 1, 3, 5, 10 parts by weight was added and a small amount of the heat stabilizer was mixed to prepare pellets using a twin screw extruder having a diameter of 40 mm. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

Comparative Example 2

A pellet was prepared in the same manner as in Example 2 except that Cu (I) ₂ O (D) was not added at all. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

Example 3A-3D

A rubber modified styrene resin (A) was prepared by mixing graft ABS resin (a ₁ ) and styrene-containing copolymer resin (a ₂₁ ) in a weight ratio of 30:70. 10 parts by weight of a phosphate ester compound (C) and 10 parts by weight of Cu (I) ₂ O (D) based on 100 parts by weight of the mixture obtained by adding 20 parts by weight of polyphenylene ether (PPE) resin (B) to 80 parts by weight of the resin (A). 1, 3, 5, 10 parts by weight was added, and a small amount of the thermal stabilizer was mixed to prepare pellets using a twin screw extruder having a diameter of 40 mm. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

Comparative Example 3

Pellets were prepared in the same manner as in Example 3 except that Cu (I) ₂ O (D) was not added at all. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

Example 4A-4D

A rubber modified styrene resin (A) was prepared by mixing graft ABS resin (a ₁ ) and styrene-containing copolymer resin (a ₂₁ ) in a weight ratio of 30:70. 10 parts by weight of a phosphate ester compound (C) and 10 parts by weight of Cu (I) ₂ O (D) based on 100 parts by weight of the mixture containing 30 parts by weight of polyphenylene ether (PPE) resin (B) based on 70 parts by weight of the resin (A) 1, 3, 5, 10 parts by weight was added, and a small amount of the thermal stabilizer was mixed to prepare pellets using a twin screw extruder having a diameter of 40 mm. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

Comparative Example 4

Pellets were prepared in the same manner as in Example 4, except that Cu (I) ₂ O (D) was not added at all. Table 2 shows the results of horizontal combustion evaluation of the prepared pellets and the char content generated during the evaluation of flame retardancy.

ABS resin (A) PPE (B) TPP (C) Cu (I) ₂ O (D) Char content (%) Horizontal combustion result (sec) Example 2A 90 10 10 One 15.8 42 Example 2B 3 21.1 44 Example 2C 5 22.7 40 Example 2D 10 27.1 41 Comparative Example 2 90 10 10 - 11.1 84 Example 3A 80 20 10 One 15.2 13 Example 3B 3 20.8 12 Example 3C 5 21.6 8 Example 3D 10 30.0 7 Comparative Example 3 80 20 10 - 14.8 18 Example 4A 70 30 10 One 18.3 6 Example 4B 3 22.3 6 Example 4C 5 24.2 6 Example 4D 10 28.1 5 Comparative Example 4 70 30 10 - 16.4 12

As shown in Table 2, in the examples in which Cu (I) ₂ O 1, 3, 5, or 10 parts by weight was added, the char content evaluated by TGA was greatly increased, and the combustion time was reduced as a result of the horizontal combustion evaluation, resulting in obvious flame retardancy. The effect of the improvement was confirmed.

Example 5A-5C

A rubber modified styrene resin (A) was prepared by mixing a graft ABS resin (a ₁ ) and a styrene-containing copolymer resin (a ₂₂ ) having an acrylonitrile content of 40% in a 30:70 weight ratio. 10 parts by weight of the phosphate ester compound (C) and 10 parts by weight of Cu (II) O, Cu (100) by weight of 100 parts by weight of the mixture containing 10 parts by weight of polyphenylene ether (PPE) resin (B) I) ₂ O or 3 parts by weight of Cu (I) ₂ S (D) were added and a small amount of heat stabilizer was mixed to prepare pellets using a twin screw extruder having a diameter of 40 mm. The content of char generated during flame retardancy evaluation of the prepared pellets is shown in Table 3.

Comparative Example 5

A pellet was prepared in the same manner as in Example 5, except that no copper compound (D) was added. The content of char generated during flame retardancy evaluation of the prepared pellets is shown in Table 3.

ABS resin (A) PPE (B) TPP (C) Copper Compound (D) Char content (%) Kinds content Example 5A 90 10 10 Cu (II) O 3 12.4 Example 5B 90 10 10 Cu (I) ₂ O 3 15.8 Example 5C 90 10 10 Cu (I) ₂ S 3 19.6 Comparative Example 5 90 10 10 - - 7.2

As shown in Table 3, in the case of Examples 5A-5C to which the copper compound was applied, the char content was significantly increased compared to Comparative Example 5, and thus it was found that the resin composition prepared by applying the copper compound was excellent in flame retardancy.

That is, the present invention is a resin composition composed of constituents (A), (C), and (D) or (A), (B), (C), and (D), in particular a copper compound (D) is applied. The resin composition by which the flame retardance was remarkably improved by this can be manufactured.

The present invention provides a thermoplastic resin composition which minimizes the addition of the char-generating material or improves the flame retardancy of the rubber-modified styrene resin composition even in the absence of the char-generating material. And adding a phosphate ester flame retardant and a copper compound to the polyphenylene ether resin blend to provide a thermoplastic resin composition having excellent flame retardancy.

Simple modifications and variations of the present invention can be easily made 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 (7)

(A) (a ₁₎ contains 10 to 68% by weight of the rubber component, and the exception of the rubber component and the content of acrylonitrile from 18 to 65% by weight of styrene-acrylonitrile graft copolymer resin 20 to 90% by weight And (a ₂ ) 100 parts by weight of a rubber-modified styrene-acrylonitrile copolymer resin composed of 80 to 10 wt% of styrene-acrylonitrile copolymer resin having an acrylonitrile content of 18 to 65 wt%; (C) 2 to 30 parts by weight of the aromatic phosphate ester compound; And (D) 0.01 to 20 parts by weight of one or two or more copper compounds of oxides, sulfides, chlorides, fluorides, phosphates, nitrates and organic acid salts as monovalent and divalent copper compounds; Thermoplastic flame retardant resin composition, characterized in that consisting of. The method of claim 1, wherein the thermoplastic flame retardant resin composition further comprises a polyphenylene ether resin (B) of 60 parts by weight or less based on 100 parts by weight of rubber-modified styrene-acrylonitrile copolymer resin (A). Thermoplastic flame retardant resin composition. The thermoplastic flame retardant resin composition according to claim 1, wherein the aromatic phosphate ester (C) is used alone or in combination of two or more compounds represented by the following general formula (1): Formula 1 An alkyl group wherein _{R, R 1, R 2, R} 3 are independently hydrogen or C ₁ -C ₄ from each other, X is an aryl group as a C ₆ -C ₂₀ aryl group or a substituted C ₆ -C ₂₀ alkyl group Derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S, and N is an integer from 0 to 4. The thermoplastic flame retardant resin composition according to claim 3, wherein the aromatic phosphate ester compound (C) is a mixture of at least two kinds of aromatic phosphate ester compounds having different N values. The method of claim 1, wherein the copper compound is copper oxide (bivalent) [Cu (II) O], copper oxide (monovalent) [Cu (I) ₂ O], copper sulfide (bivalent) [Cu (II ) S] and copper sulfide (monovalent) [Cu (I) ₂ S], the diameter of the thermoplastic flame-retardant resin composition, characterized in that 0.01 to 10 ㎛ The antidripping agent of claim 1. A thermoplastic flame retardant resin composition further comprising a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment and / or a dye, and an inorganic additive. delete