KR101731679B1 - Aromatic vinyl-vinyl chloride copolymers and thermoplastic resin composition comprising the same - Google Patents

Abstract

The present invention relates to an aromatic vinyl-vinyl chloride copolymer and a thermoplastic resin composition containing the aromatic vinyl-vinyl chloride copolymer, which are excellent in thermal stability and minimized the generation of HCl which is a corrosive toxic gas generated by processing a vinyl chloride resin at a high temperature. More particularly, Vinyl resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell wrapped around the core and polymerized with an aromatic vinyl monomer. The present invention also relates to an aromatic vinyl-vinyl chloride copolymer.
Also, the present invention includes an aromatic vinyl-vinyl chloride copolymer comprising an acrylonitrile-butadiene-styrene copolymer, a styrene-acrylonitrile copolymer, an aromatic vinyl-vinyl chloride copolymer and a brominated organic flame retardant, Resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell wrapped around the core and polymerized with an aromatic vinyl monomer.

Description

AROMATIC VINYL-VINYL CHLORIDE COMPOUNDS AND THERMOPLASTIC RESIN COMPOSITION COMPRISING THE SAME Technical Field [1] The present invention relates to an aromatic vinyl-

The present invention relates to an aromatic vinyl-vinyl chloride copolymer and a thermoplastic resin composition containing the aromatic vinyl-vinyl chloride copolymer. More particularly, the present invention relates to an aromatic vinyl-vinyl chloride copolymer having a thermoplastic resin To a resin composition.

Generally, acrylonitrile-butadiene-styrene (ABS) resins are widely used in the fields of electrical, electronic products and office equipment due to stiffness and chemical resistance of acrylonitrile, butadiene and styrene processability and mechanical strength. Is widely used as an exterior material.

However, the ABS resin is not resistant to flame by the resin itself, and when the flame is ignited by an external ignition factor, the resin itself decomposes and provides the raw material to expand or sustain the combustion. Recently, as the social interest in fire stability has increased, and the standard has been strengthened, the necessity of flame retardancy of the exterior material of electric and electronic products is increasing more and more.

There is a method of adding a flame retardant agent and a flame retardant adjuvant as a method of imparting flame retardancy to the ABS resin. Examples of the flame retardant agent include halogen-based flame retardants and non-halogen flame retardants such as phosphorus, nitrogen and hydroxyl. A zinc-based compound, and a polysiloxane-based compound.

The halogen-based flame retardant has higher flame retardancy than the non-halogen-based flame retardant and can maintain the mechanical properties of the rubber-modified styrenic resin. Therefore, the halogen-based flame retardant is generally used to impart flame retardancy to ABS resins at present.

On the other hand, polyvinylchloride (hereinafter referred to as PVC) has a limited oxygen index (LOI) value of about 40 to 50%, which is itself a flame retardancy higher than a certain level. In addition, since it is the cheapest resin among resins used for general purpose, there is an advantage that a less expensive material can be supplied even if it is mixed with any resin.

For this reason, there have been many attempts to replace the use of halogen flame retardants by mixing PVC with ABS resin. However, since the C-Cl bond of PVC can not withstand the processing temperature of ABS, it decomposes and generates corrosive toxic gas such as HCl, thereby deteriorating the health of workers and corroding the processing equipment, .

Therefore, it is costly to improve the processing equipment to solve the above problems, and therefore, it is advantageous in terms of cost and efficiency if the resin is improved.

Korean Published Patent No. 2011-0037207 (Published April 13, 2011)

In order to solve the problems of the prior art as described above, the present invention relates to a styrene-vinyl chloride polymer and a thermoplastic resin composition containing the styrene-vinyl chloride polymer, which have minimized the generation of HCl which is a corrosive toxic gas generated by processing a vinyl chloride resin at a high temperature, And to provide the above objects.

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

In order to achieve the above object, the present invention relates to a vinyl chloride resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell wrapped around the core and polymerized with an aromatic vinyl monomer. The present invention also provides an aromatic vinyl-vinyl chloride copolymer.

Further, the present invention relates to (A) an acrylonitrile-butadiene-styrene copolymer; (B) a styrene-acrylonitrile copolymer; (C) an aromatic vinyl-vinyl chloride copolymer; And (D) a brominated organic flame retardant, wherein the aromatic vinyl-vinyl chloride copolymer (C) is a vinyl chloride resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell surrounding the core and polymerized with an aromatic vinyl monomer.

As described above, according to the present invention, there is provided an aromatic vinyl-vinyl chloride copolymer and a thermoplastic resin composition containing the aromatic vinyl-vinyl chloride copolymer excellent in thermal stability and minimizing the generation of HCl which is a corrosive toxic gas generated by processing vinyl chloride resin at a high temperature .

Hereinafter, the present invention will be described in detail.

The aromatic vinyl-vinyl chloride copolymer of the present invention is a vinyl chloride-based resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell wrapped around the core and polymerized with an aromatic vinyl monomer to improve thermal stability and increase flame retardancy.

The thermoplastic resin composition comprising the aromatic vinyl-vinyl chloride copolymer of the present invention has an effect of minimizing the generation of HCl which is a corrosive toxic gas generated by processing at a high temperature and having excellent thermal stability.

In the aromatic vinyl-vinyl chloride copolymer, the pyrolytic vinyl chloride resin is located in the seed, the acrylate-based polymer is surrounded by the core, and the styrene-based polymer constitutes the shell, thereby minimizing thermal decomposition of the vinyl chloride resin And a chlorine element due to thermal decomposition is prevented from being generated at the time of processing at a high temperature, thereby minimizing the deterioration of flame retardancy. The styrene type polymer in a shell is an acrylonitrile-butadiene- Styrene copolymer is improved and the physical properties are improved.

In the aromatic vinyl-vinyl chloride copolymer, the vinyl chloride resin seed may be, for example, 16 to 50% by weight, 27 to 47% by weight, or 35 to 45% by weight, and the flame retardancy is increased in the above range.

Examples of the vinyl chloride resin seeds include copolymers of vinyl chloride homopolymer, vinyl chloride and other monomers copolymerizable with vinyl chloride, olefin compounds such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, acrylonitrile and the like Unsaturated nitriles and vinyl methyl ethyl ether; monomers such as unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; and anhydrides of these fatty acids, which may be used alone or as a mixture of two or more thereof have.

In the aromatic vinyl-vinyl chloride copolymer, the core may be, for example, 24 to 60 wt%, 25 to 45 wt%, or 27 to 37 wt%, and the effect of preventing the chlorine element .

The core is at least one selected from the group consisting of alkyl acrylate monomers, conjugated diene monomers and vinyl cyan monomers.

The alkyl acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate.

The conjugated diene monomer includes 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene.

The vinyl cyan monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile.

In the aromatic vinyl-vinyl chloride copolymer, the shell may be an aromatic vinyl cyan monomer.

The aromatic vinyl cyan monomer is at least one selected from the group consisting of styrene,? -Methylstyrene, o-ethylstyrene, p-ethylstyrene and vinyltoluene.

In the aromatic vinyl-vinyl chloride copolymer, the shell may be, for example, 16 to 50% by weight, 20 to 40% by weight, or 25 to 35% by weight. The balance has an excellent effect.

In the aromatic vinyl-vinyl chloride copolymer, the shell may further include a vinyl cyan monomer. The vinyl cyan monomer is contained in an amount of 28 to 38% by weight or 30 to 35% by weight based on the entire content of the shell, and within the above range, (A) an acrylonitrile-butadiene-styrene copolymer and (B) styrene- It has an excellent affinity with a nitrile copolymer and an excellent balance of physical properties.

The aromatic vinyl-vinyl chloride copolymer may further include divinylbenzene. The content of the aromatic vinyl-vinyl chloride copolymer may be 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total amount of the vinyl chloride- Or 0.1 to 1.0 part by weight. In the above range, there is an effect of maintaining a strong shell by crosslinking while having excellent mechanical properties.

The divinylbenzene is preferably contained in the shell of the aromatic vinyl-vinyl chloride copolymer.

The aromatic vinyl-vinyl chloride copolymer may be prepared by emulsion graft polymerization.

The aromatic vinyl-vinyl chloride copolymer (excluding divinylbenzene) may further contain 0.01 to 5 parts by weight of a crosslinking agent.

The cross-linking agent is preferably included in the core, and in this case, the impact strength at low temperature is improved.

The crosslinking agent may be a (meth) acrylate crosslinking agent.

The (meth) acrylate crosslinking agent is preferably a polyalkylene glycol, diacrylate, polyalkylene glycol dimethacrylate or a mixture thereof.

The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising (A) an acrylonitrile-butadiene-styrene copolymer, (B) a styrene-acrylonitrile copolymer and (C) an aromatic vinyl-vinyl chloride copolymer; And (D) 5 to 30 parts by weight of a brominated organic flame retardant, wherein the aromatic vinyl-vinyl chloride copolymer (C) is a vinyl chloride resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell wrapped around the core and polymerized with an aromatic vinyl monomer.

The thermoplastic resin composition comprises (A) 1 to 40% by weight of an acrylonitrile-butadiene-styrene copolymer, (B) 40 to 80% by weight of a styrene-acrylonitrile copolymer, and (C) (D) 5 to 30 parts by weight of a brominated organic flame retardant based on 100 parts by weight of the base resin.

The acrylonitrile-butadiene-styrene copolymer (A) in the base resin may be, for example, 1 to 40% by weight, 3 to 30% by weight, or 5 to 15% by weight, and a balance of mechanical properties and physical properties It has excellent effect.

The acrylonitrile-butadiene-styrene copolymer (A) can be prepared, for example, by emulsion graft polymerization. Butadiene rubber, acrylonitrile monomer and styrene monomer may be emulsion-graft-polymerized and then aggregated, dehydrated and dried to prepare a powder. 5 to 40% by weight of acrylonitrile and 10 to 45% by weight of styrene are added to a mixed solution of 50 to 70% by weight of butadiene rubber, 0.6 to 2 parts by weight of an emulsifier, 0.2 to 1 part by weight of a molecular weight adjuster and 0.05 to 0.5% (The content of butadiene rubber, acrylonitrile and styrene is expressed in terms of% by weight and the amount of the remaining materials is determined by the total weight of butadiene rubber, acrylonitrile and styrene Based on 100 parts by weight).

The acrylonitrile-butadiene-styrene copolymer (A) has a rubber content of, for example, 50 to 70% by weight or 55 to 65% by weight, and has an excellent impact strength within the above range.

The butadiene rubber preferably has an average particle diameter of 0.1 to 0.5 占 퐉 or 0.2 to 0.4 占 퐉, for example.

The styrene-acrylonitrile copolymer (B) in the base resin may be, for example, 40 to 80% by weight, 50 to 70% by weight or 55 to 65% by weight, and excellent balance of mechanical properties and physical properties within the above range .

The styrene-acrylonitrile copolymer has a weight-average molecular weight of, for example, 50,000 to 300,000 g / mol, 70,000 to 200,000 g / mol or 100,000 to 150,000 g / mol, have.

The styrene-acrylonitrile copolymer has an acrylonitrile content of 20 to 40% by weight or 25 to 35% by weight, and has an excellent affinity with the ABS copolymer and styrene-vinyl chloride copolymer within the above range have.

The acrylonitrile monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The styrene-vinyl chloride copolymer (C) in the base resin may be, for example, 10 to 40% by weight, 20 to 37% by weight or 25 to 35% by weight, and the flame retardancy is improved within the above range.

Wherein the aromatic vinyl-vinyl chloride copolymer is a vinyl chloride resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell surrounding the core and polymerized with an aromatic vinyl monomer.

A vinyl cyan monomer may be further included in the shell of the aromatic vinyl-vinyl chloride copolymer.

The aromatic vinyl-vinyl chloride copolymer includes 16 to 50% by weight of a vinyl chloride resin seed, 24 to 60% by weight of a core and 16 to 50% by weight of a shell.

The brominated organic flame retardant may be used in an amount of 5 to 30 parts by weight, 6 to 25 parts by weight, or 10 to 15 parts by weight based on 100 parts by weight of the base resin. In the range, mechanical strength and fluidity are not significantly deteriorated, There is an effect of having weather resistance.

The brominated organic flame retardant is at least one selected from the group consisting of the following formulas (1), (2) and (3).

[Chemical Formula 1]

(2)

(3)

Examples of the brominated organic flame retardant include hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenylethane, ethylenebis (Tetrabromophthalimide), brominated diepoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, tetrabromobisphenol-A bis (allyl isocyanurate) (Tribromobiphenyl) cyanurate, tetrabromobisphenol-A, or a brominated epoxy oligomer. The term " tris "

The thermoplastic resin composition may further include at least one member selected from the group consisting of a flame retardant, an impact modifier, a lubricant, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a UV blocking agent, a pigment and an inorganic filler.

The present invention provides a molded article comprising the above-mentioned thermoplastic resin composition.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.

Production Example 1

Preparation of aromatic vinyl-vinyl chloride copolymer

Hereinafter, the content of the components used in the reaction is represented by weight% of the vinyl chloride resin, the alkyl acrylate monomer, the conjugated diene monomer, the vinyl cyan monomer and the aromatic vinyl monomer, and the components other than the monomer are represented by the total weight of the seed and the monomer Was expressed in parts by weight based on 100 parts by weight.

60 parts by weight of distilled water, 30 parts by weight of butyl acrylate, 0.3 part by weight of polyethylene glycol diacrylate, 0.3 part by weight of allyl methacrylate, and 0.1 part by weight of cumene hydroperoxide in the presence of 40% by weight of vinyl chloride resin having an average particle size of 0.2 [ 0.5 parts by weight of an oxide and 0.5 parts by weight of sodium lauryl sulfate were continuously added at 75 DEG C to prepare a core having an average particle diameter of 0.3 mu m.

50 parts by weight of distilled water, 20 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.5 part by weight of divinylbenzene, 0.5 part by weight of cumene hydroperoxide and 0.5 part by weight of sodium lauryl sulfate were mixed in the presence of the core prepared above And polymerized at 75 캜 to obtain a crosslinked shell.

The cross-linked shell was aged at 80 ° C under atmospheric pressure, and then aged, dehydrated and washed at 95 ° C, and dried by hot air at 90 ° C for 30 minutes to prepare an aromatic vinyl-chloride copolymer powder.

Production Example 2

Preparation of aromatic vinyl-vinyl chloride copolymer

The procedure of Preparative Example 1 was repeated except that 0.5 part by weight of divinylbenzene was not used in the process of preparing the outer shell of the crosslinked shell in Preparation Example 1.

Example 1

10% by weight of an ABS copolymer having a rubber content of 60% by weight prepared by emulsion graft polymerization with butadiene rubber latex having an average particle diameter of 0.3 占 퐉, styrene having 25% by weight of acrylonitrile and a weight average molecular weight of 120,000 g / Based on 100 parts by weight of a base resin containing 60% by weight of an acrylonitrile copolymer resin (SAN resin) and 30% by weight of an aromatic vinyl-vinyl chloride copolymer produced by Preparation Example 1 based on 100 parts by weight of a basic organic flame retardant, tetrabromobis 15 parts by weight of phenol-A, 4 parts by weight of antimony trisodium benzoate as a flame retardant additive, and 0.1 part by weight of an anti-drip agent were added and homogeneously mixed using a Henschel mixer, followed by preparing a thermoplastic resin composition in the form of a pellet through a twin screw extruder.

Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that tris (tribromobenzyl) cyanurate was used instead of brominated organic flame retardant tetrabromobisphenol-A in Example 1.

Example 3

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the aromatic vinyl-vinyl chloride copolymer of Production Example 2 was used instead of the aromatic vinyl-vinyl chloride copolymer of Production Example 1 in Example 1 above.

Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the aromatic vinyl-vinyl chloride copolymer of Production Example 2 was used instead of the aromatic vinyl-vinyl chloride copolymer of Production Example 1 in Example 2 above.

Comparative Example 1

In the same manner as in Example 1 except that 25% by weight of ABS resin and 75% by weight of SAN resin were used as the base resin in Example 1, and the aromatic vinyl-vinyl chloride copolymer of Production Example 1 was not used, the thermoplastic resin composition .

Comparative Example 2

In the same manner as in Example 1 except that 50 wt% of the SAN resin and 50 wt% of the aromatic vinyl-vinyl chloride copolymer of Production Example 1 were used as the base resin in Example 1 and the brominated organic flame retardant was not used To prepare a thermoplastic resin composition.

Comparative Example 3

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1, except that 10 parts by weight of a PVC resin was used in place of the aromatic vinyl-vinyl chloride copolymer in Comparative Example 1.

Comparative Example 4

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 except that tris (tribromobenzyl) cyanurate was used in place of tetrabromobisphenol-A, which is an organic flame retardant, in Comparative Example 1, and 10 parts by weight of a PVC resin was used .

[Test Example]

The properties of the thermoplastic resin composition samples prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.

* Notched Izod Impact Strength (Kgf · cm / cm): Measured according to ASTM D-256 using 1/8 "thick specimens.

* Flammability: A 1/8 "thick specimen was manufactured by injection molding in accordance with UL-94 Vertical Combustion Evaluation.

     NR: No rating (other than rating)

* Yellowness: The L, a, and b values are measured using a colorimeter (Hunter Lab). Among them, the b value is yellow, and the larger the b value, the greater the yellowing.

division Example Comparative Example One 2 3 4 One 2 3 4 ABS resin 10 10 10 10 25 25 25 SAN resin 60 60 60 60 75 50 75 75 Aromatic vinyl-vinyl chloride copolymer
(Production Example 1) 30 30 50 Aromatic vinyl-vinyl chloride copolymer
(Production Example 2) 30 30 PVC resin 10 10 I
year
My Tetrabromobisphenol-A 15 15 15 15 Tris (tribromo phenyl) cyanurate 10 10 10 Antimony trioxide 4 4 4 4 4 4 4 4 Anti-drop agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Impact strength 17 16 13 11 22 4 6 7 Flammability V-0 V-0 V-0 V-0 NR NR NR NR Yellowness 10 8 22 18 7 35 30 25

As shown in Table 1, Examples 1 to 4 including the aromatic vinyl-vinyl chloride copolymer according to the present invention had a high impact strength, excellent flame retardancy, and no yellow color degradation due to thermal decomposition.

When the vinyl chloride resin according to the present invention is used as a seed and the aromatic vinyl-vinyl chloride copolymer grafted with the core and the shell is applied to the resin composition, there is no decrease in yellow color due to thermal decomposition and flame retardancy It was found that there was no deterioration and toxic gas generation, and the mechanical properties were excellent.

On the other hand, in Comparative Examples 3 and 4, when the PVC resin was added, the impact strength was lowered, the flame retardancy was lowered due to pyrolysis, and the physical properties such as yellowing were increased.

Also, Comparative Example 2 using only an aromatic vinyl-vinyl chloride copolymer without a bromine-based organic flame retardant had a problem that pyrolysis became severe due to the use of a large amount of aromatic vinyl-vinyl chloride copolymer to impart flame retardancy.

Claims (16)

Vinyl chloride resin seeds;
A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And
A shell wrapped around the core and polymerized with an aromatic vinyl monomer;
And an aromatic vinyl-vinyl chloride copolymer.
The method according to claim 1,
Wherein the shell further comprises a vinyl cyan monomer. ≪ RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
Wherein the seed comprises from 16 to 50 wt%, the core comprises from 24 to 60 wt%, and the shell comprises from 16 to 50 wt%.
The method according to claim 1,
Wherein the aromatic vinyl-vinyl chloride copolymer further comprises divinylbenzene in the aromatic vinyl-vinyl chloride copolymer.
5. The method of claim 4,
Wherein the divinylbenzene is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin seed and the sum of monomers.
(A) an acrylonitrile-butadiene-styrene copolymer;
(B) a styrene-acrylonitrile copolymer;
(C) an aromatic vinyl-vinyl chloride copolymer; And
(D) a brominated organic flame retardant;
, Wherein the aromatic vinyl-vinyl chloride copolymer (C) is a vinyl chloride-based resin seed; A core surrounding the seed and polymerized with at least one member selected from the group consisting of an alkyl acrylate monomer, a conjugated diene monomer and a vinyl cyan monomer; And a shell surrounding the core and polymerized with an aromatic vinyl monomer.
The method according to claim 6,
Wherein the shell of the aromatic vinyl-vinyl chloride copolymer (C) further comprises a vinyl cyan monomer.
The method according to claim 6,
(B) from 40 to 80% by weight of a styrene-acrylonitrile copolymer and from 10 to 40% by weight of a styrene-vinyl chloride copolymer (C) in an amount of from 1 to 40% by weight of the acrylonitrile-butadiene- 100 parts by weight of a base resin; And (D) 5 to 30 parts by weight of a brominated organic flame retardant.
The method according to claim 6,
Wherein the acrylonitrile-butadiene-styrene copolymer (A) is emulsion-graft-polymerized.
The method according to claim 6,
The thermoplastic resin composition according to claim 1, wherein the acrylonitrile-butadiene-styrene copolymer (A) has a rubber content of 50 to 70% by weight.
The method according to claim 6,
The styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 50,000 to 300,000 g / mol.
The method according to claim 6,
The styrene-acrylonitrile copolymer (B) has an acrylonitrile content of 20 to 40% by weight.
The method according to claim 6,
Wherein the aromatic vinyl-vinyl chloride copolymer (C) comprises 16 to 50% by weight of the seed, 24 to 60% by weight of the core and 16 to 50% by weight of the shell.
The method according to claim 6,
Wherein the brominated organic flame retardant (D) is at least one selected from the group consisting of the following general formulas (1) and (2).
[Chemical Formula 1]

(2)

The method according to claim 6,
The thermoplastic resin composition may further comprise at least one selected from the group consisting of a flame retardant, an impact modifier, a lubricant, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a UV light stabilizer, a pigment and an inorganic filler And a thermoplastic resin composition.
A molded article produced by including the thermoplastic resin composition according to any one of claims 6 to 15.