KR100359903B1 - Thermoplastic Flameproof Resin Composition - Google Patents

Abstract

The present invention comprises (A) 20 to 90 parts by weight of (a ₁ ) styrene-containing graft copolymer resin, (a ₂ ) 0 to 80 parts by weight of styrene-containing copolymer resin and (a ₃ ) 5 to 40 parts by weight of styrene resin. 40 to 95 parts by weight of rubber modified styrene resin; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 2 to 30 parts by weight of a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B); (D) 5 to 30 parts by weight of the aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B); And (E) 0.5 to 5 parts by weight of a styrene-rubber block copolymer based on 100 parts by weight of the base resin (A) + (B).

Description

Thermoplastic Flameproof Resin Composition

Field of invention

The present invention relates to a thermoplastic flame retardant resin composition. More specifically, the present invention uses a styrene copolymer as a compatibilizer and applies a phosphate ester as a flame retardant to a rubber-modified styrene resin and a polyphenylene ether resin blend, and to improve the thermal stability and fluidity The present invention relates to a thermoplastic resin composition to which styrene-rubber block copolymer is added so as to have an excellent impact resistance.

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, since the rubber-modified styrene resin is combustible, when applied to a product that emits heat such as a personal computer or a fax machine, the flame retardancy should be reinforced.

The most widely known flame retardant method is to impart flame retardant properties by applying a halogen-based compound and an antimony-based compound in combination to the rubber-modified styrene resin. However, halogen-containing compounds can damage the mold and have a fatal effect on the human body due to 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, and thus, attention has been focused on flame-retardant methods that do not apply halogen-based compounds.

Although a method of imparting flame retardancy to a resin composition by adding a compound such as phosphorus or nitrogen as a halogen-free flame retardant has been studied, the phosphorus compound alone lowers the heat resistance of rubber-modified styrene resins and is poor in flame retardancy. There are disadvantages and there is a limit to their application.

In general, rubber-modified styrene-based resins, particularly acrylonitrile-butadiene-styrene copolymer resins (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, by adding an additional char forming agent so that the char can be produced smoothly to obtain the desired flame retardancy. Here, the 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 ingress of oxygen from the outside and prevent the release of fuel from the inside.

Japanese Patent Application Laid-open No. Hei 7-48491 discloses a thermoplastic flame retardant resin in which a phosphate ester is applied as a flame retardant to a thermoplastic copolymer resin such as a rubbery polymer and an aromatic vinyl monomer, and a novolak-type phenol resin is added as a char forming agent. . However, phenolic resin not only lowers the heat resistance of ABS resin, but also lacks char forming ability, so that relatively high amount of phosphate ester and novolak resin should be added to obtain desired flame retardancy. It has a further disadvantage.

Therefore, the present inventors blended polyphenylene ether-based resin with rubber-modified styrene-based resin and used it as a base resin to solve the problems of existing flame-retardant thermoplastic resins, and styrene-acryl having 5 to 18% by weight of acrylonitrile. By using a ronitrile copolymer resin as a compatibilizer and applying an aromatic phosphate ester compound as a flame retardant, to prevent the mechanical properties of the resin composition to deteriorate and to develop a thermoplastic resin composition excellent in flame retardancy, Patent Application Nos. 99-28442, 99 No. 28443 and No. 99-28444 (both applications filed on July 14, 1999), and the addition of a styrene-based resin to the resin composition that has excellent thermal stability and improved flowability has already been filed. -57030 (filed Dec. 13, 1999).

Therefore, the present inventors have come to develop a resin composition in which the impact resistance is significantly improved by adding a styrene-rubber block copolymer to the resin composition of the present invention.

An object of the present invention is to provide a thermoplastic resin composition excellent in mechanical properties, thermal stability and flame retardancy.

Another object of the present invention is to provide a thermoplastic resin composition having improved thermal stability, flame retardancy and fluidity by using a rubber-modified styrene resin to which styrene resin is added.

Another object of the present invention is to add a styrene-rubber block copolymer to improve impact resistance and at the same time provide a thermoplastic resin composition having excellent thermal stability, flame retardancy and fluidity.

It is another object of the present invention to provide a thermoplastic resin composition having compatibility with rubber modified styrene resin and polyphenylene ether resin by using styrene-acrylonitrile copolymer resin having controlled acrylonitrile content as a kind of compatibilizer. It is to.

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

Summary of the Invention

The thermoplastic resin composition of the present invention comprises (A) 40 to 95 parts by weight of rubber-modified styrene resin, (B) 5 to 60 parts by weight of polyphenylene ether resin, (C) the base resin (A) + (B) 100 2 to 30 parts by weight of styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight, and (D) an aromatic phosphate ester based on 100 parts by weight of the base resin (A) + (B). It consists of 5-30 weight part of system compounds, and 0.5-5 weight part of styrene-rubber block copolymers with respect to 100 weight part of said base resins (A) + (B).

In addition, the (A) rubber-modified styrene resin is (a ₁ ) 20 to 90 parts by weight of styrene-containing graft copolymer resin, (a ₂ ) 0 to 80 parts by weight of styrene-containing copolymer resin and (a ₃ ) styrene-based resin It consists of 5-40 weight part.

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

(A) Rubber modified styrene resin (ABS resin)

Rubber-modified resin refers to a polymer in which a rubbery polymer is dispersed in a particle form in a matrix (continuous phase) made of an aromatic vinylic polymer, and an aromatic vinyl monomer and a vinylic monomer copolymerizable therewith in the presence of a rubbery polymer It is prepared by addition and polymerization.

Such rubber-modified styrene resins can be prepared by known polymerization methods such as emulsion polymerization, suspension polymerization, and 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 5 to 30% by weight based on the entire base resin.

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

Examples of the above resin may be applied in combination with styrene-containing graft copolymer resin and styrene resin, or may be applied in combination with styrene-containing graft copolymer resin, styrene-containing copolymer resin and styrene resin, It is preferable to mix | blend in consideration of each compatibility.

In the present invention, (a ₁₎ styrene-containing graft copolymer resin is made 20 to 90 parts by weight, (a ₂₎ Styrene-containing copolymer resin and 0 to 80 parts by weight of (a ₃₎ a styrene-based resin 5 to 40 parts by weight.

(a ₁ ) Styrene-containing graft copolymer resin

Examples of the rubber used for the styrene-containing graft copolymer resin (a ₁ ) include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); Saturated rubber added with hydrogen to the diene rubber; Acrylic rubbers such as isoprene rubber, chloroprene rubber and butyl polyacrylate; And ethylene-propylene-diene monomer terpolymers (EPDM) and the like, particularly diene rubbers are preferred, and more preferably butadiene rubbers are suitable.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methyl styrene, p-methyl styrene, and the like may be used. Among them, styrene is most preferable, and a monomer copolymerizable with the aromatic vinyl monomer is 1 Apply more than one species. Preferable monomers include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as methacrylonitrile.

The weight ratio of rubber in the styrene-containing graft copolymer resin (a ₁ ) is 10 to 60% by weight, and the component of the monomer grafted to the rubber is 50 to 82 weight of an aromatic vinyl monomer such as styrene. % And unsaturated nitrile monomers such as vinyl cyanide or methacrylonitrile such as acrylonitrile are added in an amount of 18 to 50% by weight and graft copolymerized.

In addition, graft polymerization may be optionally performed by adding monomers such as acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like to impart properties such as workability and heat resistance. The amount added is 40% by weight or less based on the graft resin as a whole.

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

(a ₂ ) Styrene-containing copolymer resin

The styrene-containing copolymer resin (a ₂ ) is a resin prepared according to the monomer ratio and compatibility of the components of the graft copolymer prepared in the above composition except rubber, the components are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methyl styrene, p-methyl styrene and the like may be added, of which styrene is most preferred, and the weight ratio of the aromatic vinyl monomer in the components of the entire copolymer resin is 50 to 82% by weight. Corresponds to One or more monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. As a monomer which can be introduced, a vinyl cyanide compound such as acrylonitrile and an unsaturated nitrile compound such as methacrylonitrile are preferable, and 18 to 50% by weight of the components of the entire copolymer is introduced. Optionally, monomers such as acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like may be added and copolymerized at 40 wt% or less.

(a ₃ ) Styrene-based resin

The styrene-based resin (a ₃ ) may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof, and will be described as an example of the bulk polymerization among these polymerization methods.

Butadiene type rubbers, isoprene type rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers and the like selected from the group consisting of aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid and methacrylic acid 80 to 100 parts by weight of one or more monomers selected from the group is added, and bulk polymerization is carried out using one or more initiators selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide and cumene hydroperoxide. The said resin can be manufactured.

As the styrene resin, a resin lacking a rubber component, a resin containing a rubber component, or a mixture thereof may be used.

(B) polyphenylene ether resin

The polyphenylene ether resin is used because it is a rubber-modified styrene resin, the flame retardancy is insufficient and the rigidity and heat resistance is lowered, and in the present invention is used to form a base resin together with the rubber-modified styrene resin. 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- Copolymers of 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, more preferably poly (2,6-dimethyl-1,4-phenylene) ether.

Although the polymerization degree of polyphenylene ether is not specifically limited, It is preferable that the intrinsic viscosity measured in the chloroform solvent at 25 degreeC is 0.2-0.8 in consideration of the thermal stability and workability of a resin composition.

(C) Styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5-18 wt%

The styrene-acrylonitrile copolymer resin (C) is a polymer added to improve the compatibility of the rubber-modified styrene resin (A) and the polyphenylene ether resin (B) used as the base resin. Among the components of (C) used in the present invention, the content of styrene except for the rubber part is 82 to 95% by weight, and the content of acrylonitrile is 5 to 18% by weight. The polymerization method of the styrene-acrylonitrile copolymer may be prepared by applying emulsification, suspension, bulk polymerization and the like, and a suitable weight average molecular weight is 50,000 to 200,000.

Further monomers copolymerizable with the styrene-acrylonitrile include methacrylate or phenylmaleimide, and styrene may be replaced with α-methyl styrene to improve heat resistance.

The amount of the styrene-acrylonitrile copolymer added may be applied in the range of 2 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B).

When the styrene-acrylonitrile copolymer is not added, the compatibility of the blend of the rubber modified styrene resin and the polyphenylene ether resin cannot be improved, and thus the mechanical strength is drastically lowered, making it difficult to apply the actual product.

(D) Aromatic Phosphate Ester Compounds

An aromatic phosphate ester compound (D) which can be used in the present invention is a compound having the following structural formula (1):

(Formula 1)

In the above structural formula (1) of R _1, R ₂ and R ₃ are independently hydrogen or an alkyl group of C ₁ ~C ₄ to each other, X is a C ₆ ~C ₂₀ aryl group or a substituted C ₆ ~C ₂₀ alkyl group As an aryl group, it is derived from dialcohols, such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S, and the value of N is 0-4.

When N is 0, the compound corresponding to Structural Formula (1) is triphenyl phosphate, tricresyl phosphate, trigyrenyl phosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4,6-tri Methylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when N is 1, resorcinolbis (diphenyl) phosphate, res Sosinolbis (2,6-dimethylphenyl) phosphate, Resorcinolbis (2,4-dibutylbutylphenyl) phosphate, Hydroquinolbis (2,6-dimethylphenyl) phosphate, Hydroquinolbis (2,4- Dietary butylphenyl) phosphate and the like. In addition, the aromatic phosphate ester compound (D) may be applied to each independently or in a mixture.

The aromatic phosphate ester compound (D) constitutes 5 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B).

(E) Styrene-Rubber Block Copolymer

The styrene-rubber block copolymer (E) is added to significantly improve the impact resistance of the entire resin composition, and refers to a triblock type copolymer obtained by block copolymerizing styrene at both ends of the rubber.

Examples of the rubber that can be introduced into the copolymer include butadiene rubbers, isoprene rubbers, or alkyl acrylate rubbers depending on the monomers used, and the most commonly used monomers are butadiene. It is also possible to use hydrogen by adding hydrogen to a part of the rubber. The weight ratio of the rubber in the copolymer (E) is 10 to 70% by weight. The proportion of preferred rubbers is 28 to 32% by weight. In addition, the styrene-rubber block copolymers (E) may be applied independently or in mixtures.

The styrene-rubber block copolymer (E) may be applied in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the base resin (A) + (B).

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

(A) rubber modified styrene resin, (B) polyphenylene ether resin, and (C) acrylonitrile content used for the resin compositions of Examples 1-5 and Comparative Examples 1-3 below The production and specifications of the styrene-acrylonitrile copolymer resin, (D) aromatic phosphate ester compound, and (E) styrene-rubber block copolymer (%) by weight are as follows.

(A) Rubber modified styrene resin

Rubber-modified styrene resin (A) is a styrene-containing graft copolymer resin (a ₁ ), styrene-containing copolymer resin (a ₂ ) and styrene-based resin (a ₃ ) prepared in the following Table 1 It was prepared by mixing.

(a ₁ ) Styrene-containing graft copolymer resin

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, After adding 0.2 part by weight of mercaptan-based chain transfer agent, 0.4 part by weight of glucose, 0.01 part by weight of iron sulfate hydrate, and 0.3 part by weight of sodium pyrophosphate salt, the mixture was maintained at 75 ° C. for 5 hours to complete the reaction to prepare graft ABS latex. To the solid content of the resin, sulfuric acid was added to 0.4 part by weight and coagulated to prepare a graft copolymer resin (g-ABS) powder.

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

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, and the mixture was cooled to room temperature to 80 ° C. The copolymer resin (SAN) having an acrylonitrile content of 25% by weight was prepared by raising the temperature for 90 minutes and maintaining the temperature 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-containing copolymer resin was about 160,000 to 200,000.

(a ₃ ) Styrene-based resin

(a ₃₁ ) Polystyrene (GPPS)

Cheil Industries Co., Ltd. GPPS [brand name HF-2680] was used.

(a ₃₂ ) Rubber reinforced styrene resin (HIPS)

Cheil Industries Co., Ltd., a rubber-reinforced styrene resin (trade name HG-1760S) was used.

(B) polyphenylene ether resin (PPE resin)

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

(C) Styrene-acrylonitrile copolymer resin (AN content 13% SAN)

Styrene 87 parts by weight and 13 parts by weight of acrylonitrile 120 parts by weight of deionized water, 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 0.2 part by weight of mercaptan-based chain transfer agent were heated at room temperature to 80 ° C. for 90 minutes, maintained at this temperature for 150 minutes, and then heated to 95 ° C., and then heated for 120 minutes. To prepare a copolymer resin (SAN) having an acrylonitrile content of 13%. 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 about 100,000 to 140,000.

(D) Aromatic Phosphate Ester Compounds

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

(E) Styrene-Rubber Block Copolymer

(e ₁ ) Styrene-butadiene-styrene block copolymer

A styrene-butadiene-styrene block copolymer (SBS) (trade name ASAPRENE420 P (product of ASAHI CHEMICAL Co.)) having a rubber content of 28 to 32 parts by weight was used.

(e ₂ ) Styrene-ethylenebutadiene-styrene block copolymer

A styrene-ethylenebutadiene-styrene block copolymer (SEBS) (trade name TUFTEC H1041 (manufactured by ASAHI CHEMICAL Co., Ltd.)) having an ethylene butadiene rubber content of 30 parts by weight was used.

The resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared according to the compositions shown in Table 1 below.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Ingredients (parts by weight) (A) (a ₁ ) 20 20 20 20 20 20 20 20 (a ₂ ) 32 32 32 32 32 32 32 32 (a ₃ ) (a ₃₁ ) 20 20 20 - 10 20 - 10 (a ₃₂ ) - - - 20 10 - 20 10 (B) 28 28 28 28 28 28 28 28 (C) 9 9 9 9 9 9 9 9 (D) 15 15 15 15 15 15 15 15 (E) (e ₁ ) 1.5 - 0.7 - - - - - (a ₂ ) - 1.5 0.8 1.5 1.5 - - -

The materials of (A) to (E) indicated above were added to the contents as 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 at 80 ° C. for 3 hours and then injected into a 6 Oz injection molding 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. The fabricated specimens were flame retardant according to UL 94 VB flame retardancy regulations, Izod impact strength (1/8 "notch, kgf · cm / cm) was measured according to ASTM D-256, and 1 kg according to ASTM D-1525. The softening temperature of the picket was measured, and the Melt Flow Index (g / 10min) was measured at 10 ° C and 10 kg by ASTM D-1238, and 50% at a load of 3 kg according to ASTM D1709-98. Falling Dart Impact (FDI) was measured as the breaking height, and the results of the measurement of the physical properties are shown in Table 2 below.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Properties Flame retardant (1/12 '', UL 94 VB) V-1 V-1 V-1 V-1 V-1 V-1 V-1 V-1 Izod impact strength (1/8 '' notch, kgfcm / cm) (ASTM D-256) 28 28 28 30 29 25 27 26 VST (ASTM D-1525) 96 96 96 95 95 96 95 95 Melt Flow Index (g / 10min) (ASTM D-1238) 35 35 35 32 33 35 32 33 Falling Dart Impact (FDI) (ASTM D1709-98) 95 95 95 100 98 30 40 35

As can be seen in Table 2, by applying the styrene resin (a ₃ ) it was possible to obtain a resin composition excellent in fluidity, heat resistance and flame retardancy overall. However, compared to Examples 1 to 5 to which the styrene-rubber block copolymer (E) was applied, Comparative Examples 1 to 3, in which the component (E) was not added, still had excellent Izod impact strength while falling Dart Impact (FDI) was observed. It was measured quite low. In particular, as in the case of Comparative Example 1, the use of GPPS (a ₃₁ ) as a styrene-based resin was measured to have a relatively low FDI (Falling Dart Impact) compared to the case of Comparative Example 2 applying HIPS (a ₃₂ ). On the other hand, when the styrene-rubber block copolymer (E) is added to the composition as in Examples 1 to 5, it can be seen that not only the Izod impact strength but also the FDI is remarkably improved. In other words, when the styrene-butadiene-styrene block copolymer (SBS: e ₁ ) and the styrene-ethylenebutadiene-styrene block copolymer (SEBS: e ₂ ) are used alone or in combination, the impact resistance of the resin composition is significantly improved. It became. That is, the impact resistance deteriorated by the application of the styrene-rubber block copolymer (E) was improved, and at the same time, the heat resistance, the fluidity, and the flame retardancy, which were excellent properties obtained by applying the styrene resin (a ₃ ), were made to the same level. It can be seen that it is maintained.

The thermoplastic resin composition of the present invention improves compatibility by adding a styrene-acrylonitrile copolymer having an acrylonitrile content of 5 to 18% by weight to the rubber-modified styrene resin and the polyphenylene ether resin. By applying an ester compound to improve the flame retardancy, by incorporating the styrene resin in the rubber-modified styrenic resin essentially improves fluidity, heat resistance and flame retardancy, and particularly by applying a styrene-rubber block copolymer significantly impact resistance Has the effect of providing an improved thermoplastic flame retardant 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 (10)

(A) (a ₁₎ and the rubber part of the styrene-containing graft copolymer resin the content of acrylonitrile 18-50% by weight, 20 to 90 parts by weight Except for, (a ₂₎ is an acrylonitrile content of 18-50% by weight 40 to 95 parts by weight of a rubber-modified styrene resin comprising 0 to 80 parts by weight of phosphorus styrene-containing copolymer resin and 5 to 40 parts by weight of (a ₃ ) styrene resin; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 2 to 30 parts by weight of a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B); (D) 5 to 30 parts by weight of the aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B); And (E) 0.5 to 5 parts by weight of styrene-rubber block copolymer based on 100 parts by weight of the base resin (A) + (B); A thermoplastic resin composition, characterized in that consisting of. The thermoplastic resin composition according to claim 1, wherein the content of rubber in the components of the styrene-containing graft copolymer resin (a ₁ ) is 10 to 60 wt% based on the graft copolymer resin. According to claim 1, The styrene-containing graft copolymer resin (a ₁ ) is a monomer selected from acrylic acid, methacrylic acid, maleic anhydride and N- substituted maleimide 40 wt% or less with respect to the styrene-containing graft copolymer resin The styrene-containing copolymer resin (a ₂ ) is prepared by adding a monomer selected from acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide to 40% by weight or less with respect to the styrene-containing copolymer resin. Thermoplastic resin composition characterized in that it is prepared. The thermoplastic resin composition according to claim 1, wherein the styrene resin (a ₃ ) is a resin lacking a rubber component, a resin containing a rubber component, or a mixture thereof. The thermoplastic resin composition according to claim 1, wherein the styrene-acrylonitrile copolymer resin (C) is further copolymerized with methacrylate or phenylmaleimide. The thermoplastic resin composition according to claim 1, wherein the aromatic phosphate ester compound (D) has the following formula: Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group of C _{1 to} C ₄ ; X is a C ₆ -C ₂₀ aryl group substituted with a C ₆ -C ₂₀ aryl group or an alkyl group and is derived from a dialcohol of resorcinol, hydroquinol, bisphenol-A, or bisphenol-S; And the value N ranges from 0 to 4. 7. The thermoplastic resin composition according to claim 6, wherein the aromatic phosphate ester compound (D) is a mixture of at least two or more phosphate ester compounds having different values of N. The thermoplastic resin composition according to claim 1, wherein the styrene-rubber block copolymer (E) is a block copolymer of styrene at both ends of butadiene rubber or ethylenebutadiene rubber. The thermoplastic resin composition of claim 1, further comprising an dripping inhibitor, an impact modifier, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye. delete