KR100583172B1 - Flame Retardant Polycarbonate-Containing Resin Composition with Improved Thermal Stability - Google Patents

Abstract

The flame retardant polycarbonate resin composition according to the present invention is a rubber-modified styrene graft obtained by (A) 45 to 95 parts by weight of a polycarbonate resin, (B) agglomerated with acid, washed with ethyl alcohol and deionized water and dried. 1-50 weight part of copolymers, 0-50 weight part of (C) styrene-type copolymers, 1-30 weight part of (D) phosphate ester compounds, (A) + (B) + (C) + (D) It is characterized by consisting of 0.05-5 weight part of (E) fluorinated polyolefin resin with respect to 100 weight part. The flame retardant polycarbonate-based resin composition according to the present invention may be molded and used in molded articles such as electrical appliances and office equipment.

Polycarbonate resin, rubber modified styrene graft copolymer, PC / ABS resin blend, thermal stability, flame retardant.

Description

Flame Retardant Polycarbonate-Containing Resin Composition with Improved Thermal Stability}

Field of invention

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a flame-retardant polycarbonate-based resin composition having excellent thermal stability and appearance characteristics by using a rubber-modified styrene graft copolymer that has been specifically post-treated.

Background of the Invention

Polycarbonate-based resins are excellent in transparency, mechanical strength and heat resistance, and are widely used for electric, electronic products, and automotive parts. However, since the polycarbonate-based resin has a problem of low processability and notched impact strength, it is used in combination with other kinds of resins to improve this. For example, when the polycarbonate resin and the conventional rubber-modified styrenic graft copolymer are blended, the blended resin maintains high impact strength while improving processability.

However, when a conventional rubber-modified styrenic graft copolymer is prepared, an additive is added or a specific compound is produced. Such additives or the resulting compound thermally decompose the polycarbonate resin. That is, the blended resin of the polycarbonate resin and the conventional rubber-modified styrene graft copolymer is a thermal decomposition of the polycarbonate resin due to the above-described additives or the resulting compound when injected at high temperature and high speed, Problems such as discoloration occur on the surface.

In addition, since the polycarbonate-based blend resin is usually molded into a large heat dissipating product such as a computer housing or an office device, it should not only maintain high mechanical strength but also have flame retardancy. In order to impart flame retardancy to such a resin, a halogen-based compound and an antimony compound were conventionally used as a flame retardant. However, when using a halogen-based compound, when the final molded product is burned, there is a problem that a gas harmful to the human body is generated.

Therefore, a technique for imparting flame retardancy without using a halogen-based compound has been developed. A common technique currently developed is to use a monomeric or oligomeric phosphate ester compound as a flame retardant. However, since the phosphate ester compound is also thermally decomposed by the above-described additives or produced compounds, it is produced when a blend of a polycarbonate resin mixed with a phosphate ester compound and a conventional rubber-modified styrene graft copolymer is injected. Problems such as discoloration of the surface of the molded article much more.

Therefore, in order to solve the problems of the prior art, the present inventors have blended a rubber-modified styrene-based graft copolymer that has been specially treated to a composition containing a polycarbonate-based resin, a phosphate ester-based compound, or the like, to thereby It is to develop a flame-retardant polycarbonate-based resin composition improved stability and improved the appearance properties of the injected product without thermal decomposition during injection.

An object of the present invention is to provide a flame retardant polycarbonate-based resin composition with improved thermal stability.

Another object of the present invention is to provide a flame retardant polycarbonate-based resin composition having improved thermal appearance of the injected product without pyrolysis during injection.

Another object of the present invention is to provide a flame retardant polycarbonate-based resin composition excellent in workability and impact strength.

Another object of the present invention is to provide a polycarbonate-based resin composition excellent in flame retardancy, transparency, mechanical strength, and heat resistance.

Still another object of the present invention is to provide a molded article having improved thermal stability by molding a polycarbonate-based resin composition.

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

Summary of the Invention

The flame retardant polycarbonate resin composition according to the present invention is a rubber-modified styrene graft obtained by (A) 45 to 95 parts by weight of a polycarbonate resin, (B) agglomerated with acid, washed with ethyl alcohol and deionized water and dried. 1-50 weight part of copolymers, 0-50 weight part of (C) styrene-type copolymers, 1-30 weight part of (D) phosphate ester compounds, (A) + (B) + (C) + (D) It is characterized by consisting of 0.05-5 weight part of (E) fluorinated polyolefin resin with respect to 100 weight part.

The flame retardant polycarbonate-based resin composition according to the present invention may be molded and used in molded articles such as electrical appliances and office equipment.

Detailed Description of the Invention

Since each component of the flame retardant thermoplastic resin composition according to the present invention does not use a halogen compound as described above, it is an environmentally friendly resin composition. Hereinafter, each component is explained in full detail.

(A) polycarbonate resin

The polycarbonate resin (A) used in the present invention is excellent in transparency, mechanical strength, and heat resistance as a thermoplastic resin, and is used in the range of 45 to 95 parts by weight. Then, the weight average molecular weight (M _w ) of the polycarbonate-based resin (A) is 10,000 to 200,000, preferably 15,000 to 80,000.

Polycarbonate-based resin (A) used in the preparation of the resin composition of the present invention may be used both homopolymers, copolymers, or blends thereof. The polycarbonate resin (A) can also be used in part or in whole by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

The polycarbonate according to the present invention is prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate or diester carbonate.

[Formula 1]

Wherein A is a single bond, alkylene of C _1-5 , alkylidene of C _2-5 , cycloalkylidene of C _5-6 , S or SO ₂ .

Examples of the diphenols represented by the above formula include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, and 2,4-bis- (4- Hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl)-propane, 2,2 -Bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols such as hydroxyphenyl) -cyclohexane are preferred, and 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, is most industrially preferred.

The polycarbonate may be a branched chain, preferably 0.05 to 2 mol% of a tri- or more polyfunctional compound, for example a compound having a trivalent or more phenol group, based on the total amount of diphenols used for the polymerization. It can be prepared by adding.

(B) Rubber Modified Styrene Graft Copolymer

The rubber-modified styrenic graft copolymer according to the present invention is particularly post-treated, and the graft copolymer is aggregated with an acid, washed with ethyl alcohol and deionized water, and dried to use the resin composition. In contrast to the conventional post-treatment method in which the graft copolymer is aggregated with an acid and washed with a deionized water by adjusting the pH with a base, the graft copolymer using the post-treatment method according to the present invention is applied to the resin composition. When used, the thermal stability of the resin composition is improved, and furthermore, the thermal properties of the injected product are improved without the appearance of pyrolysis during the injection. This is because when the rubber-modified styrenic graft copolymer is specifically post-treated as in the present invention, additives or compounds which can thermally decompose the polycarbonate resin are removed. Furthermore, when the additive or the produced compound is removed, there is an effect of preventing thermal decomposition of the phosphate ester compound described later, so that the appearance characteristics of the resin composition according to the present invention are further improved.

In the post-treatment method of the rubber-modified styrenic graft copolymer according to the present invention, the graft copolymer latex is precipitated with 0.2-2% aqueous acid solution, preferably 0.3-1.8% sulfuric acid aqueous solution, followed by ethyl alcohol 1 After washing twice with deionized water twice and drying, 1-50 parts by weight of the rubber-modified styrenic graft copolymer resin thus treated is used in the entire base resin.

The rubber-modified styrenic graft copolymer before post-treatment according to the present invention comprises (b ₁ ) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C _1-8 methacrylic acid alkyl ester, C _1-8 alkyl acrylate 50 to 95% by weight of compounds such as esters or mixtures thereof and acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkylesters, C _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or (B ₂ ) Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acryl, such as a compound such as phenyl N-substituted maleimide or a mixture of 50 to 5% by weight thereof. Rubbers such as nitrile / butadiene rubbers, isoprene rubbers, terpolymers of ethylene-propylene-diene (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites or mixtures thereof 95-5 It is a copolymer obtained by graft-polymerizing to weight%.

C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters according to the present invention are esters obtained from monohydryl alcohols containing 1-8 carbon atoms as esters of methacrylic acid or acrylic acid, respectively. to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester.

Preferred examples of the rubber-modified styrene-based graft copolymers include graft copolymers of styrene, acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in the form of a mixture of butadiene rubber, acrylic rubber, or styrene / butadiene rubber. Can be. Of these, ABS graft copolymers are more preferred.

In the preparation of the graft copolymer, the particle diameter of the rubber particles is suitably in the range of 0.05 to 4 μm in order to improve the impact strength and the surface properties of the molded product, and the method of preparing the graft copolymer is preferably a method of emulsion polymerization.

Since the rubber-modified styrenic graft copolymer according to the present invention is blended with a polycarbonate resin, the problem of low workability and impact strength when the polycarbonate resin is used alone is solved.

(C) Styrene Copolymer

Vinyl-based copolymers used in the preparation of the resin composition of the present invention are (c ₁ ) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C _1-8 methacrylic acid alkyl esters, C _1-8 acrylic acid alkyl esters 40 to 95% by weight of a compound or a mixture thereof and (c ₂ ) acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, C _1-8 acrylic acid alkyl esters, maleic anhydride, C Styrene-type copolymer obtained by copolymerizing 60-5 weight% of compounds, such as _1-4 alkyl or phenyl nucleosubstituted maleimide, and mixtures thereof.

The C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1-8 carbon atoms as esters of methacrylic acid or acrylic acid, respectively. For example, methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester and the like.

Styrene-based copolymer (C) can be produced as a by-product in the preparation of graft copolymer (B), and especially in the case of grafting excess monomer mixture to a small amount of rubbery polymer or used as a molecular weight modifier. It is more likely to occur when the chain transfer agent is used in excess. The content of the styrenic copolymer (C) according to the present invention is not shown including the by-product of the graft copolymer (B).

Preferred vinyl copolymers (C) are monomer mixtures of styrene and acrylonitrile and optionally methacrylic acid methyl ester, monomer mixtures or styrene of α-methylstyrene and acrylonitrile and optionally methacrylic acid methyl ester, α- And those prepared from monomer mixtures of methyl styrene and acrylonitrile and optionally methacrylic acid methyl ester. The styrene / acrylonitrile copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and it is preferable to use a weight average molecular weight (Mw) of 15,000 to 200,000.

Other preferred vinyl copolymers (C) include those prepared from a monomer mixture of methacrylic acid methyl ester monomers and optionally acrylic acid methyl esters. The methacrylic acid methyl ester polymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and it is preferable to use a weight average molecular weight of 20,000 to 250,000.

Another preferred vinyl copolymer is a copolymer of styrene and maleic anhydride, which can be prepared using a continuous bulk polymerization method and a solution polymerization method. The composition ratio of the two monomer components can be varied in a wide range, it is preferable that the content of maleic anhydride is 5 to 60% by weight. The molecular weight of the styrene / maleic anhydride copolymer may also be used in a wide range, but it is preferable to use those having a weight average molecular weight of 20,000 to 200,000 and intrinsic viscosity of 0.3 to 0.9.

The styrene monomers used in the preparation of the styrenic copolymer (C) used in the preparation of the resin composition of the present invention are substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and α-methylstyrene. It can be used instead of the monomer, the styrene-based copolymer is used alone or in the form of a mixture of two or more thereof, it is used in the range of 0 to 50 parts by weight of the total base resin.

(D) Phosphoric Acid Ester Compound

Phosphoric acid ester compound used as a flame retardant in the present invention is represented by the following formula (2), Japanese Patent Laid-Open No. 59-202,240 discloses a method for producing such a compound.

[Formula 2]

In Formula 2, R ₁ , R ₂ , R ₄ , and R ₅ are each a C ₆ -C ₂₀ aryl group or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₃ is a C ₆ -C ₃₀ aryl group or Alkyl-substituted C ₆ -C ₃₀ aryl group, n is the number average degree of polymerization, the average value is 0 to 3.

Preferred R ₁ , R ₂ , R ₄ , and R ₅ are a phenyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, isopropyl, or t-butyl, and a double phenyl group or methyl, ethyl, isopropyl or t-butyl group More preferred are substituted phenyl groups. And R ₃ is a compound such as resorcinol, hydroquinone, bisphenol-A or a mixture thereof.

Phosphoric acid ester compounds are oligomeric phosphoric acid ester compounds derived from C ₆ -C ₃₀ aryl or alkyl substituted C ₆ -C ₃₀ aryl groups. Preferred C ₆ -C ₃₀ aryl or alkyl substituted C ₆ -C ₃₀ aryl groups are resorcinol, hydroquinone, biphenol or bisphenol-A. Moreover, the aryl derived oligomeric phosphate ester whose average value of n is 0-3 is preferable. In the present invention, a phosphate ester compound having n values of 0, 1, 2 and 3 may be used alone or in a mixed form, each of which is already mixed when manufactured in a polymerization process, or separately prepared. It is also preferable to use a mixture of phosphate ester compounds having different n values.

  Among the phosphate esters used in the present invention, as phosphate esters having a value of 0, one or two of tri (alkylphenyl) phosphate, di (alkylphenyl) monophenylphosphate, diphenylmono (alkylphenyl) phosphate or triphenylphosphate It is preferable to use the above mixture.

(E) fluorinated polyolefin resin

The fluorinated polyolefin resin (E) used in the preparation of the flame retardant thermoplastic resin composition of the present invention may be prepared using a known polymerization method, for example, a pressure of 7 to 71 kg / cm 2 and a temperature of 0 to 200 ° C. It may be prepared in an aqueous medium containing a free radical forming catalyst such as sodium, potassium or ammonium peroxydisulfate, preferably at a temperature of 20 to 100 ° C.

Specific examples of the fluorinated polyolefin resin (E) include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and Ethylene / tetrafluoroethylene copolymer etc. are mentioned. These may be used independently from each other, and two or more different types may be used together.

The fluorinated polyolefin resin of the present invention is most preferably polytetrafluoroethylene having a particle size of 0.05 to 1,000 mu m and specific gravity of 1.2 to 2.3 g / cm 3.

When the fluorinated polyolefin resin is mixed and extruded together with the other component resins of the present invention, a fibrillar network is formed in the resin to lower the flow viscosity of the resin during combustion and increase the shrinkage rate to increase the shrinkage. It will act to prevent.

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin resin in an emulsion state is used, the dispersibility in the entire resin composition is good, but the manufacturing process is complicated. Therefore, even if it is powder state, if it can disperse | distribute suitably in the whole resin composition and can form a fibrous network, it is preferable to use it in powder state.

The content of the fluorinated polyolefin resin used in the production of the resin composition of the present invention is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of (A) + (B) + (C) + (D).

The flame retardant polycarbonate resin composition of the present invention has a flame retardant such as other organic phosphate ester compounds, halogen-containing organic compounds, cyanurate compounds, metal salts, etc., in addition to the phosphate ester-based compound (D) to improve flame retardancy and other physical properties. And flame retardant aids may further be used. The organic phosphate ester compound includes monomeric phosphate ester compounds such as triphenylphosphate, tricresylphosphate and the like and condensed phosphate esters derived from dihydric alcohols such as resorcinol, hydroquinone and bisphenol-A. The metal salt may be used as a flame retardant aid, and there are commonly known sulfonic acid metal salts and sulfone sulfonic acid metal salts.

The flame retardant thermoplastic resin composition of the present invention may include general additives such as flame retardant aids, lubricants, plasticizers, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additive pigments or dyes, depending on their respective uses, in addition to the above components. . The inorganic additive to be added may be used in the range of 0 to 60 parts by weight, preferably 0.3 to 40 parts by weight based on 100 parts by weight of (A) + (B) + (C) + (D).

The resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form. Molding the resin composition according to the present invention to produce a molded article can be easily carried out by those skilled in the art.

The composition of the present invention can be used for molding a variety of products, and is particularly suitable for the production of housings of electrical and electronic products, such as computer housings that require flame retardancy and high impact resistance while being injected at high temperatures. According to the molded article, the thermal stability is improved and there is no discoloration.

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) polycarbonate resin, (B) rubber modified styrene graft copolymer, (C) styrene copolymer, (D) phosphate ester compound, (E) used in the following Examples and Comparative Examples The specification of fluorinated polyolefin resin is as follows.

(A) polycarbonate resin

A polycarbonate of bisphenol-A type having a weight average molecular weight (M _w ) of 25,000 g / mol was used.

(B) Rubber modified vinyl graft copolymer

Butadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of monomers, 1.0 parts by weight of potassium rosinate as an emulsifier and cumene hydrochloride as an initiator in a mixture of 29 parts by weight of styrene, 13 parts by weight of acrylonitrile and 150 parts by weight of deionized water. 0.4 parts by weight of peroxide and 0.3 parts by weight of mercaptan-based chain transfer agent were added, and reacted while maintaining at 75 ° C. for 5 hours to prepare an ABS graft latex.

(C) Styrene Copolymer

0.2 part by weight of azobisisobutyronitrile (AIBN), 0.3 part by weight of mercaptan-based chain transfer agent and 0.5 part by weight of tricalcium phosphate, which are necessary additives for the mixture of 71 parts by weight of styrene, 29 parts by weight of acrylonitrile and 120 parts by weight of deionized water. Suspension polymerization was added to prepare a SAN copolymer resin. The copolymer was washed with water, dehydrated and dried to obtain a SAN copolymer resin in powder form.

(D) Phosphoric Acid Ester Compound

3.4 wt% of n in Formula 2 is 0, 85.4 wt% of n is 1, and 11.1 wt% of n is 2 or more, and the average n value is 1.0, R ₁ Bisphenol-A derived oligomeric phosphate ester (d ₁ ) in which R ₂ , R ₄ and R ₅ are each a phenyl group, and triphenylphosphate (d ₂ ) having a value of n in Formula 2 above 0 were used.

(E) fluorinated polyolefin resin

Teflon (trade name) 7AJ of Dupont, USA was used.

Examples 1 to 3

After coagulation by adding 1% sulfuric acid solution to the above-described ABS graft latex, washed once with ethyl alcohol, twice with deionized water and dried to prepare a powder. Each component and stabilizer of the composition shown in Table 1 were added, mixed in a conventional mixer, and extruded using a twin screw extruder having L / D = 35 and Φ = 45 mm, and then an extrudate was prepared in pellet form. The prepared pellets were dried for at least 5 hours in a hot air dryer at 80 ℃ before injection. At an injection temperature of 310 ° C. using a 10 oz injection machine, the body was formed into a cylindrical shape with a length of 11 cm, a radius of 3 cm, and a distal end with a conical shape.

The thermal stability of the resin composition was evaluated by the level of occurrence of discoloration appearing on the surface of the molded article at the time of injection molding. At this time, 20 or more specimens were repeatedly molded to evaluate the occurrence of discoloration.

Comparative Examples 1 to 3

In Comparative Examples 1 to 3, 1% sulfuric acid solution was added to the ABS graft latex and coagulated. The pH was adjusted to 4 with NaOH aqueous solution, and then washed twice with deionized water and dried to prepare a powder. Were carried out in the same manner as in Examples 1 to 3, except that each component of the composition shown in Table 1 was used.

Table 1 shows the compositions and extent of discoloration of Examples 1 to 3 and Comparative Examples 1 to 3.

Example Comparative Example One 2 3 One 2 3 (A) polycarbonate resin 73 73 73 73 73 73 (B) styrenic graft copolymer 14 14 14 14 14 14 (C) Styrene Copolymer 13 13 13 13 13 13 (D) Phosphoric Acid Ester Compound (d ₁ ) 17 12 2 17 12 2 (d ₂ ) - 4 12 - 4 12 (E) fluorinated polyolefin resin 0.4 0.4 0.4 0.4 0.4 0.4 Discoloration occurrence level ◎ ○ ○ △ × ×

In the discoloration incidence level of Table 1, ◎ is very excellent in appearance, there is no discoloration, ○ is excellent in appearance and almost no discoloration, △ is poor appearance and discoloration occurs partially in most specimens, X indicates that the appearance is so poor that discoloration is apparent in all specimens.

From the results of Table 1, it can be seen that Examples 1 to 3 are very excellent in thermal stability because there is almost no discoloration as compared with the corresponding Comparative Examples 1 to 3. Therefore, it can be seen that the resin composition according to the present invention and its molded article have excellent thermal stability and appearance characteristics.

The present invention provides a polycarbonate-based resin composition having improved thermal stability, improved thermal appearance during injection, improved appearance characteristics, excellent processability and impact strength, and excellent flame retardancy, transparency, mechanical strength, and heat resistance. Has the effect of providing.                     

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 (5)

(A) 45 to 95 parts by weight of a polycarbonate resin; (B) (b ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, C _1-8 methacrylic acid alkyl ester, C _1-8 acrylic acid alkyl ester, or mixtures thereof and acryl 50-5% by weight of nitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, C _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimides, or mixtures thereof (B ₂ ) a terpolymer of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, and ethylene-propylene-diene EPDM), a polyorganosiloxane / polyalkyl (meth) acrylate rubber composite, or a copolymer obtained by graft polymerization in 95 to 5% by weight of a mixture thereof is aggregated with an acid, washed with ethyl alcohol and deionized water and dried. Ha 1 to 50 parts by weight of the rubber-modified styrene graft copolymer obtained; (C) 40-95% by weight of (c ₁ ) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C _1-8 methacrylic acid alkyl esters, C _1-8 acrylic acid alkyl esters, or mixtures thereof, and (c ₂₎ acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl ester, C _{1- 8} alkyl acrylate, maleic anhydride, C _1-4 alkyl or phenyl N- substituted maleimide, or mixtures thereof 60 0 to 50 parts by weight of a styrenic copolymer composed of-5% by weight; (D) 1 to 30 parts by weight of a phosphate ester compound; And (E) 0.05 to 5 parts by weight of the fluorinated polyolefin resin based on 100 parts by weight of the base resin (A) + (B) + (C) + (D); Flame-retardant polycarbonate-based resin composition comprising. The flame-retardant polycarbonate-based resin composition according to claim 1, wherein the polycarbonate-based resin (A) contains an ester precursor containing an aromatic polyester-carbonate. The flame retardant polycarbonate-based resin composition according to claim 1, wherein the phosphate ester compound (D) is a compound represented by Formula 2 or a mixture thereof: [Formula 2]

In Formula 2, R ₁ , R ₂ , R ₄ , and R ₅ are each a C ₆ -C ₂₀ aryl group or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₃ is a C ₆ -C ₃₀ aryl group or Alkyl-substituted C ₆ -C ₃₀ aryl group, n is the number average degree of polymerization, the average value is 0 to 3. The flame retardant polycarbonate resin composition according to claim 1, wherein the fluorinated polyolefin resin (E) has an average particle size of 0.05 to 1000 µm and a density of 1.2 to 2.3 g / cm 3. The molded article formed by the resin composition of any one of the said Claims 1-5.