KR100348424B1 - Thermoplastic composition with flame retardancy - Google Patents

Abstract

The thermoplastic resin composition having flame retardancy of the present invention comprises 50 to 100 parts by weight of a rubber-modified styrene base resin (A) consisting of 20 to 100% by weight of a styrene-containing graft copolymer resin and 0 to 80% by weight of a styrene-containing copolymer resin, It consists of 5-30 weight part of phenol resins (B), 3-30 weight part of hindered phenolic PPE resins (C), 5-30 weight part of aromatic phosphate esters (D), and 0.1-5 weight part of red (E). The thermoplastic resin composition may further include 0.01 to 2.0 parts by weight of fluororesin (F). The resin composition of the present invention may be added plasticizers, heat stabilizers, antioxidants, light stabilizers, compatibilizers, etc. as needed, organic or inorganic pigment dyes and inorganic fillers such as talc, silica, mica, glass fibers, etc. Can be.

Description

Thermoplastic resin composition having flame retardancy

Field of invention

The present invention relates to a thermoplastic resin composition having flame retardancy. More specifically, the present invention relates to a flame-retardant resin composition having excellent self-extinguishing properties consisting of rubber modified styrene resin, phenol resin, hindered phenolic polyphenylene ether (PPE) resin, aromatic phosphate ester, red and optionally fluorine resin .

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 rubber-modified styrene resins are combustible, when applied to heat-dissipating products such as personal computers or fax machines, flame retardancy is required.

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, a brominated substituted epoxy compound, 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, not only can damage the mold due to the hydrogen halide gas generated during processing, The generation of such gas at the time of combustion 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 difurans during combustion. .

According to U.S. Patent Nos. 4,692,488 and 5,204,394, an aromatic phosphate ester compound is applied to a blend of polycarbonate and acrylonitrile-styrene-butadiene resin, and polytetrafluoroethylene is added to provide a composition having a flame retardancy of UL94 V-0. It is starting. However, the composition of the US patent has a disadvantage in that it is difficult to achieve flame retardancy of V-0 or V-1 when the polycarbonate is used in an amount of 60 parts by weight or less due to the nature of the aromatic phosphate ester itself.

In addition, Japanese Patent Laid-Open No. 7-48491 discloses a thermoplastic flame-retardant resin containing no halogen by adding a novolak-type phenol resin and a phosphate ester flame retardant to a thermoplastic copolymer resin of a rubbery polymer and an aromatic vinyl monomer. have. However, the inventors of the present invention actually evaluated the flame retardancy of UL94 V-1 or V-0, and in order to ensure flame retardancy, a large amount of phenol resin and phosphate ester flame retardant should be added. As a result, the heat resistance is sharply lowered, and thus it is difficult to commercialize it because it has a very difficult disadvantage to secure practical heat resistance. Practical heat resistance refers to heat resistance applied to electrical and electronic devices. In general, the monitor housing of a computer should maintain at least 85 ° C at a load of 5 kg according to ASTM D-1525.

Accordingly, the present inventors have developed a thermoplastic resin composition having excellent flame retardancy and heat resistance properties consisting of a phenolic resin, a hindered phenolic PPE resin, an aromatic phosphate ester, and a red styrene resin in a rubber-modified styrenic resin to solve problems of the conventional flame retardant thermoplastic resin composition. It was early.

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 provide a thermoplastic resin composition having excellent heat resistance.

Still another object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties and processability.

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

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 thermoplastic resin composition having flame retardancy according to the present invention comprises a rubber-modified styrene base resin (A), a phenol resin (B), and a hinine-containing graft copolymer resin (a ₁ ) and a styrene-containing copolymer resin (a ₂ ). It consists of a phenolic PPE resin (C), aromatic phosphate ester (D), and red (E), and may further include a fluororesin (F).

In general, rubber-modified styrene-based resins, such as ABS, decompose and vaporize almost all parts when burned, so that char is not produced. Therefore, flame retardancy is very difficult when halogen-free materials are not added in the gas phase. There is this. Therefore, a high flame retardancy can be obtained by adding a char forming agent so that the char can be produced smoothly. By forming a 3D carbon chain bond to the surface of the rubber molecule by the char forming agent, the char is effectively formed to block the ingress of oxygen from the outside, and the internal rotor prevents the release of fuel.

Japanese Patent Application Laid-Open No. 7-48491 adds only phenolic resin as a char forming agent. Since the char forming effect is smaller than the added amount, it should be added in an excess amount of 30 parts by weight or more, and sufficient flame retardance should be added by adding a large amount of phosphate ester compound. Can be secured. However, when a large amount of phenol resin or phosphate ester compound is added, it is difficult to adapt practically since heat resistance and mechanical properties are lowered.

In the present invention, by adding a polyphenylene ether resin with a phenol resin as a char forming agent, the char is effectively formed and the flame retardancy can be remarkably improved even when a small amount of phenol resin and phosphate ester compound are applied. That is, in the present invention, by using phenol resin and polyphenylene ether resin together as a char forming agent, the phenol resin is formed in a low temperature region of 300 to 450 ° C., and the polyphenylene ether resin is in a high temperature region of 300 to 500 ° C. Char is strengthened on the char film that has already been formed, and synergy with phenol resin promotes the generation of char so that char is effectively formed on the combustion surface.

In the present invention, the flame retardant is used in combination with a phosphate ester compound and red to effectively impart flame retardancy to the resin composition. Phosphoric acid ester compound has the performance of imparting plasticity and reddish silver has the same shape as inorganic material, so it shows ideal synergistic effect when mixed. Phosphate ester compounds not only impart flame retardancy, but also because of the rise in temperature during forced combustion, the phosphate ester having plasticity may move to the surface and play a secondary role in char formation because the flowability is higher than that of the basic resin. In addition, since the fluidity is very small, flame retardancy is imparted in its own kneaded state, so even when a small amount is added, it has an ideal commercial effect.

In the present invention, synergistic effect of char formation can be obtained by adding a phenol resin and a polyphenylene ether resin together as a char forming agent to the rubber-modified styrenic resin. It was possible to produce a thermoplastic resin composition having not only a flame retardant property of UL94 V-0 but also maintaining a heat resistance of 85 ° C. or more by making an amazing flame retardant phase-effect wave.

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

(A) Rubber modified styrene base resin

The rubber-modified styrenic base resin means a styrene-containing graft copolymer resin such as ABS, and the styrene-containing graft copolymer resin may contain a styrene-containing copolymer resin such as SAN.

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 a vinyl aromatic polymer, and an aromatic vinyl monomer and a vinyl monomer copolymerizable with the aromatic polymer in the presence of a rubber polymer. It is prepared by adding and polymerizing.

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 mixed extrusion of a styrene-containing graft copolymer resin and a styrene-containing copolymer resin. . In the case of bulk polymerization, the rubber-modified styrene resin is produced by the one-step reaction process without separately preparing the styrene-containing graft copolymer resin and the styrene-containing copolymer resin, but in any case, the rubber content of the final rubber-modified styrene resin component is 5-30 weight part with respect to the whole base resin is suitable.

Examples of such resins are acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymers (AES) resins Etc.

Examples of the above resin may be a styrene-containing graft copolymer resin alone or a styrene-containing graft copolymer resin and a styrene-containing copolymer resin may be applied together, preferably in consideration of their compatibility.

(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, chloroprene rubber, and butyl polyacrylate; And ethylene-propylene-diene monomer terpolymer (EPDM) and the like, but diene rubber is preferred, and more preferably butadiene rubber is suitable.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methyl styrene, p-methyl styrene, and the like may be added, of which styrene is most preferable, and a monomer copolymerizable with the aromatic vinyl monomer may be added thereto. Apply at least one of them. Preferable monomers include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as methacrylonitrile.

In the styrene-containing graft copolymer resin, 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 30 to 70 parts by weight in the components of the monomer grafted to the rubber. It is preferable that the quantity of a nitrile-type monomer is 10-30 weight part.

In addition, graft polymerization may be performed by adding monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide to impart properties such as workability and heat resistance. The amount added is in the range of 0 to 20 parts by weight based on the styrene-containing graft copolymer resin.

In preparing the styrene-containing 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 styrene-containing copolymer resin is prepared according to the monomer ratio and compatibility of the styrene-containing graft copolymer resin 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-methyl styrene, p-methyl styrene, and the like may be added. Of these, styrene is most preferred, and the weight ratio of the aromatic vinyl monomer in the components of the copolymer resin is 60 to 95 weight. Corresponds to wealth. 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 and an unsaturated nitrile compound such as methacrylonitrile are preferable, and 40 to 5 parts by weight of the components of the entire copolymer are introduced. Moreover, acryl can also copolymerize 0-40 weight part of monomers, such as methacrylic acid, maleic anhydride, and N-substituted maleimide, here.

The rubber-modified styrene base resin (A) is composed of 20 to 100 wt% of styrene-containing graft copolymer resin (a ₁ ) and 0 to 80 wt% of styrene-containing copolymer resin (a ₂ ). The rubber modified styrene base resin is used in an amount of 50 to 100 parts by weight.

(B) phenolic resin

Phenolic resins are classified into resol type phenol resins and novolac type phenol resins, and both of them may be used in the present invention. In addition, the phenol resin may be classified into a thermosetting resin and a thermoplastic resin, all of which may be used. In the present invention, a novolak phenol resin is more preferably used than the resol phenol resin.

The phenol formaldehyde novolak resin, tertiary butyl phenol formaldehyde novolak resin, paraoctyl phenol formaldehyde novolak resin, paracyano phenol formaldehyde novolak resin, etc. may be used as the novolak phenol value, Copolymers may also be used. The novolak-based phenol resin is preferably about 300 to 10,000 average molecular weight.

The phenol resin is applied 5 to 30 parts by weight, preferably 7 to 20 parts by weight. When the phenol resin is used in less than 5 parts by weight, it is difficult to impart flame retardancy, and when applied to 30 parts by weight or more, the mechanical and thermal properties are lowered.

(C) Hindered phenolic polyphenylene ether (PPE) resin

The polyphenylene ether resin is obtained by applying a hindered phenol as a monomer, 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-5-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. 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 degree of polymerization of the polyphenylene ether is not particularly limited, it is preferable that the intrinsic viscosity measured in a chloroform solvent at 25 ° C. is 0.2 to 0.8 in consideration of thermal stability and workability of the resin composition. These polyphenylene ethers may be used alone or in combination of two or more thereof in an appropriate ratio.

The polyphenylene ether resin is used in an amount of 3 to 30 parts by weight.

(D) phosphate ester compound

As the phosphate ester which can be used in the present invention, a compound represented by the structure of the following formula (I) may be used:

Structural Formula I

R ₁ , R ₂ and R ₃ in Formula I are independently hydrogen or alkyl or phenyl having 1 to 6 carbon atoms and may be the same or different. Phosphoric acid esters corresponding to Structural Formula I include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, trigylenyl phosphate and the like.

In the present invention, a phosphate ester compound represented by the following structural formula (II) may also be used:

Structural Formula II

R ₄ , R ₅ and R ₆ in Formula II are hydrogen or alkyl or phenyl having 1 to 6 carbon atoms, X is aryl or alkylaryl having 6 to 20 carbon atoms, and N is greater than or equal to 1. Examples of the compound corresponding to Structural Formula II include resorcinol bis [diphenyl phosphate], resorcinol bis [dicresyl phosphate], resorcinol bis [dizyrenyl phosphate], hydrokinol bis [diphenyl phosphate], Hydrokinolbis [dicresylphosphate], hydrokinolbis [dizyrenylphosphate], biphenylbis [diphenylphosphate], biphenylbis [dicresylphosphate], biphenylbis [dizyrenylphosphate], and the like. It may be used and mixtures thereof may be used.

In the present invention, a phosphate ester compound represented by the following structural formula III having phloroglucinol as a skeleton may also be used:

Structural Formula III

R ₇ , R ₈ and R ₉ in Formula III are hydrogen or alkyl or phenyl having 1 to 6 carbon atoms. Examples of the compound represented by the above formula III include 1,3,5-tri (phenyl sulfate) fluoroglucinol, 1,3,5-tri (cresylphosphate) fluoroglucinol, 1,3,5- Tri (xylenylphosphate) fluoroglucinol and the like.

Although the same phosphate ester may be applied singly or mixed with the above structural formula, it is not preferable to apply a compound having a molecular weight of 1,500 or more in the structure because the effect of imparting flame retardancy is small. Preferably, the phosphate ester whose melting | fusing point is 80 degreeC or more is applied.

In this invention, it is preferable to use the phosphate ester compound applied as a flame retardant in the range of 5-30 weight part.

(E)

The enemy may be used without limitation as long as it exists in particulate form. For safety, it is preferable to coat the surface with resin, mineral oil, aluminum compound or titanium compound and use it in the form of masterbatch.

The additive is added to the resin composition in an amount of 0.1 to 5 parts by weight, and when it exceeds 5 parts by weight, the color control of the resin becomes very difficult because the natural color of the resin turns black red.

(F) Fluoropolymer

Fluororesin is polytetrafluoroethylene, polyvinylidene fluoride, copolymer of tetrafluoroethylene and vinylidene fluoride, copolymer of tetrafluoroethylene and fluoroalkyl vinyl ether, and tetrafluoroethylene and hexafluoro Copolymers of ropropylene, of which polytetrafluoroethylene can be preferably used. These may be used independently from each other, or a mixture of two or more different from each other may be used.

Fluorine resins form a fibrillar network in the resin when extruded by mixing with the resin to reduce the flow viscosity and increase the shrinkage rate of the resin during combustion, thereby preventing the molten resin from dripping down. do. The amount of fluorine resin that can be preferably used in the present invention is 0.01 to 2.0 parts by weight.

The resin composition of the present invention may be added plasticizers, heat stabilizers, antioxidants, light stabilizers, matching agents, etc., if necessary, organic or inorganic pigments, dyes and inorganic fillers such as talc, silica, mica, glass fibers, etc. Can be.

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) base resin, (B) phenol resin, (C) polyphenylene ether resin, (D) phosphate ester compound, (E) used in the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 below ) And / or (F) fluorine resin production and specifications are as follows.

(A) basic resin

(a ₁ ) Styrene-containing graft copolymer resin

35 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, 0.3 parts by weight of sodium pyrophosphate and the reaction was completed at 75 ° C. for 5 hours to prepare graft ABS latex, and the conversion of resin Styrene-containing graft copolymer resin (g-ABS) powder was prepared by solidifying 0.4 parts by weight of solids.

(a ₂ ) Copolymer Resin

To 75 parts by weight of styrene and 25 parts by weight of acrylonitrile was added 120 parts by weight of deionized water, 0.2 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, and at room temperature for 90 minutes. The copolymer resin (SAN) was prepared by raising 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.

(B) phenolic resin

Phenol Novolac structure of PSM 4324 Grade in Gunei, Japan was used.

(C) polyphenylene ether resin

Poly (2,6-dimethyl-1,4-phenyl) ether of Asahi Kasei Co., Ltd., Japan, was used, and the powder name is P-401.

(D) phosphate ester compound

(d ₁ ) tri (2,6-dimethylphenyl) phosphate

Daihachi (trade name: PX-130) from Japan was used.

(d ₂ ) triphenyl phosphate

Triphenyl phosphate (trade name: TPP) from Daihachi, Japan, was used.

(E)

An enemy of Rinka, Japan (trade name: FR-120) was used.

(F) fluorine resin

Fluorine resin (trade name: Teflon 7AJ) from Mitsui Dupont, Japan, was used.

Each of the components to prepare a resin composition of Example 1-2 and Comparative Example 1-6 in the composition shown in Table 1.

TABLE 1

In Example 1-2, phenol resin and polyphenylene ether were added as a char forming agent to a resin having a composition ratio of graft copolymer resin (g-ABS) and copolymer resin (SAN) of 40/60. , 6-dimethylphenyl) phosphate and red were applied, and only fluororesin Example 2 was added.

In Comparative Example 1-6, the basic resin was the same as Example 1-2, but only one of the phenol resin and the polyphenylene ether resin was used as the char forming agent, and only the phosphate ester compound was used as the flame retardant. Hindered phenolic antioxidant or phosphite antioxidant, which is a stabilizer usually added to Examples 1 and Comparative Examples 1-6, was added in an amount of 1 part by weight or less and processed in a range of 200 to 290 ° C. in a twin screw extruder. After injection, the physical properties were evaluated.

TABLE 2

Note) *: Measured at 5kg load according to ASTM D-1525.

**: Measured according to UL94 Flame Retardant Standard.

As can be seen from Table 2, Example 1-2 prepared according to the present invention had a relatively high non-cat softening temperature and had good flame retardant properties of V-0. Example 2 was able to obtain flame retardant properties satisfying UL94 5V as the resin composition in which the fluororesin was added to the resin composition of Example 1.

Comparative Example 1 prepared in the same composition as in Examples 1 and 2 except for the addition of the phosphate ester compound by addition of the amount, but showed a flame retardancy of UL94 V-1, but compared to V-0 of Example The flame retardancy was shown to be reduced. Comparative Examples 2 and 3 did not show satisfactory UL94 flame retardancy as a resin composition in which only one of phenol resin and polyphenylene ether was added as a char forming agent and only tri (2,6-dimethylphenyl) phosphate was applied. Comparative Example 4 was prepared by the same adjustment as Comparative Example 2, except that triphenyl phosphate was applied as a flame retardant, but did not satisfy the UL94 flame retardant specification and had a non-cat softening temperature of 70 ° C. or lower, which lowered the heat resistance, thereby making it practical. It is difficult. Comparative Example 5 was applied to increase the amount of triphenyl phosphate applied as a flame retardant in Comparative Example 4, the flame retardancy increased to V, but the heat resistance was very low to 60 ℃ was less practical.

In the present invention, a phenolic resin and a polyphenylene ether resin are applied together as a char forming agent to a rubber-modified styrene resin, and a flame retardant of UL94 V-0 can be obtained only when the phosphate ester and the phosphorus are applied together as a flame retardant. It can be seen that there is no degradation.

The thermoplastic resin composition of the present invention is applied to a phenolic resin and a polyphenylene ether resin as a char forming agent to a rubber-modified styrene-based underbody resin. By applying the synergistic effect of imparting flame retardancy, the flame retardancy is significantly improved, and heat resistance also has the effect of excellent invention. Even if no halogen compound is added to the rubber-modified styrenic copolymer resin, not only flame retardancy and heat resistance but also workability and mechanical properties have very good effects of the invention. In addition, the present invention does not contain a conventional halogen flame retardant that generates toxic gases during processing or combustion of the resin, thereby not causing any environmental pollution problems, and providing a thermoplastic resin composition having better mechanical strength and processability. .

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 (7)

(A) 50-100 weight part of rubber modified styrene base resins; (B) 5-30 weight part of phenol resins; (C) 3 to 30 parts by weight of a polyphenylene ether resin having a hindered phenol structure; (D) 5-30 weight part of aromatic phosphate esters whose melting | fusing point is 90 degreeC or more; And (E) 0.1-5 weight part of droplets; Wherein the aromatic phosphate ester is a compound represented by the following structural formula (I): Structural Formula I Wherein R ₁ , R ₂ and R ₃ in formula I are independently of each other hydrogen or alkyl or phenyl having 1 to 6 carbon atoms and may be the same or different; The thermoplastic resin composition of claim 1, wherein the phenol resin is a novolac phenol resin. The phenol formaldehyde novolak resin, tertiary butyl phenol formaldehyde novolak resin, paraoctyl phenol formaldehyde novolak resin, paracyano phenol formaldehyde novolak resin and these Flame-retardant thermoplastic resin composition, characterized in that selected from the group consisting of copolymers The method of claim 1, wherein the polyphenylene ether resin 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-phenyl Ethylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1 Copolymer of, 4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether and poly A thermoplastic resin composition having flame retardancy, characterized in that it is selected from the group consisting of copolymers with (2,3,5-triethyl-1,4-phenylene) ether. The compound according to any one of claims 1 to 4, further comprising 0.01 to 2.0 parts by weight of a fluororesin, wherein the fluororesin is polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene and vinylidene fluoride. And a copolymer of tetrafluoroethylene and fluoroalkyl vinyl ether, and a thermoplastic resin composition having flame retardancy, characterized in that it is selected from the group consisting of tetrafluoroethylene and hexafluoropropylene copolymer. The flame retardant thermoplastic resin composition of claim 1, further comprising a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment, a dye, and / or an inorganic additive. According to claim 1, wherein the rubber-modified styrenic base resin is composed of 20 to 100% by weight of styrene-containing graft copolymer resin (a ₁ ) and 0 to 80% by weight of styrene-containing copolymer resin (a ₂ ) Thermoplastic resin composition having a flame retardancy characterized in that.