KR100344895B1 - Thermoplastic Polycarbonate Resin Composition having Flame-retarding properties - Google Patents

Abstract

Polycarbonate-based thermoplastic resin composition of the present invention (A) 45 to 99 parts by weight of a polycarbonate resin; (B) 50 to 95 parts by weight of styrene, α-methylstyrene, halogen or methyl ring-substituted styrene, C _1-8 methacrylic acid alkyl esters, C _1-8 methacrylic acid esters, or mixtures thereof and acryl Ronitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, C _1-8 methacrylic acid esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimides, or mixtures thereof 5 5 to 95 parts by weight of a mixture with -50 parts by weight of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber having a glass transition temperature (T _G ) of -10 ° C. or less, Rubber modified graft grafted to 5 to 95 parts by weight of one or a mixture thereof selected from the group consisting of ethylene-propylene-diene terpolymer (EPDM) and a polyorganosiloxane / polyalkyl (meth) acrylate rubber composite 1 to 50 parts by weight of the polymer resin; And (C) 0.5 to 30 parts by weight of a phosphate ester compound derived from (D) aliphatic dihydric alcohols, relative to 100 parts by weight of a base resin composed of 0 to 50 parts by weight of a vinyl copolymer resin, and (E) other organic phosphate esters. 0.05 to 5 parts by weight of at least one flame retardant and flame retardant aid selected from the group consisting of compounds, halogen-containing organic compounds, cyanate compounds, fluorinated polyolefin resins and metal salts.

Description

Thermoplastic Polycarbonate Resin Composition having Flame-retarding properties

Field of invention

The present invention relates to a polycarbonate-based thermoplastic resin composition having flame retardancy. More specifically, the present invention relates to a polycarbonate-based thermoplastic having a flame retardance composed of a polycarbonate resin, a rubber-modified graft copolymer resin, a vinyl copolymer resin, a phosphate ester compound derived from an aliphatic dihydric alcohol, and other flame retardants and flame retardants. It relates to a resin composition.

Background of the Invention

Polycarbonate resins are excellent in transparency, mechanical strength and heat resistance, and are widely used in applications such as electric, electronic products, and automobile parts. However, since polycarbonate resins have disadvantages of low notch impact strength and poor workability, they are blended with other types of resins to improve them. For example, blends of polycarbonate / styrene containing copolymers are resin mixtures that improve processability while maintaining high notch impact strength. In addition, since the polycarbonate resin composition is generally applied to a large heat dissipating material such as a computer housing or other office equipment, it is essential to maintain flame retardancy and high mechanical strength.

In order to impart flame retardance to such a resin composition, a halogen-based flame retardant and an antimony compound have been conventionally used. U.S. Patent Nos. 4,983,658 and 4,883,835 disclose examples of using halogen containing compounds as flame retardants. However, when halogen-based flame retardants are used, the demand for resins that do not contain halogen-based flame retardants has been rapidly expanded recently due to the problem of human health of gases generated during combustion.

As a technique for imparting flame retardancy without using a halogen flame retardant, the most common at present is to use a phosphate ester flame retardant. U.S. Patent No. 4,692,488 discloses a thermoplastic resin composition consisting of a non-halogen aromatic polycarbonate (PC) resin, a non-halogen SAN (styrene-acrylonitrile) copolymer, a non-halogen phosphorous compound, a tetrafluoroethylene polymer and a small amount of ABS copolymer Is starting. When the phosphorus-based compound and the fluorinated alkane polymer are used to impart flame retardancy to the PC / ABS blend resin composition as described above, it is possible to prevent the dropping of sparks generated during combustion. There is a problem in that a surface crack occurs due to a bleeding out phenomenon that migrates to the surface.

U.S. Patent 5,030,675 discloses flame retardant resin compositions composed of aromatic polycarbonate resins, ABS copolymer resins and polyalkylene terephthalate resins, monomeric phosphoric acid esters and fluorinated polyolefins. In the case of the composition, the stress crack resistance is somewhat improved, but the impact resistance is lowered, and in particular, there is a disadvantage that the thermal stability is sharply lowered during processing at high temperature.

On the other hand, JP-A-59-202,240 uses a phosphate ester oligomer as a flame retardant in polyamide or polycarbonate resin. However, it is not disclosed that the stress crack resistance is improved when the phosphate ester oligomer is used. U.S. Patent No. 5,204,394 discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, a styrene-containing copolymer or a graft copolymer and a phosphate ester oligomer derived from aromatic dihydric alcohols, in which case the phosphorus content of the phosphate ester oligomer This lowers the flame retardancy is low, in particular there is a disadvantage that the fluidity is lowered.

U.S. Patent 5,061,745 discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, an ABS graft copolymer, a copolymer and a monomeric phosphate ester. The composition may cause a surface crack problem by the bleeding phenomenon due to the volatilization of the monomeric phosphate ester, there is a disadvantage that the degradation of heat resistance is severe. U.S. Patent 5,672,645 discloses PC / ABS resin compositions comprising aromatic polycarbonate resins, vinyl copolymers, graft copolymers, mixtures of monomeric and oligomeric phosphate esters and fluorinated polyolefins. Although the patent uses resorcinol or hydroquinone derivatives as oligomeric phosphate esters, these resorcinol or hydroquinone derived oligomeric phosphorus flame retardants have the advantages of less bleeding and improved heat resistance than monomeric phosphate esters. There is a disadvantage that the fluidity of the resin composition is lowered.

In order to solve the above problems, the present inventors use phosphate ester compounds derived from aliphatic dihydric alcohols as flame retardants, and have excellent flame resistance and heat resistance, and have excellent mechanical properties and bleeding to which the flame retardant moves to the surface of the injection molded product. (Bleeding out) To develop a polycarbonate-based resin composition does not occur.

An object of the present invention is to provide a polycarbonate-based resin composition having excellent flame retardancy that does not lower heat resistance by using a phosphate ester compound derived from aliphatic dihydric alcohols as a flame retardant.

Another object of the present invention is to provide a polycarbonate resin composition having excellent heat resistance and mechanical properties by using a fluorinated polyolefin or the like together with a phosphate ester compound as a flame retardant.

Still another object of the present invention is to provide a polycarbonate-based resin composition suitable for thin molding in which stress cracking due to bleeding does not occur by using a phosphate ester compound derived from aliphatic dihydric alcohols, a fluorinated polyolefin, and the like.

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

The polycarbonate thermoplastic resin composition of the present invention is a phosphate ester compound derived from (A) polycarbonate resin, (B) rubber modified graft copolymer resin, (C) vinyl copolymer resin, and (D) aliphatic dihydric alcohols. And (E) other flame retardants and flame retardant aids, the details of each of which are as follows.

(A) polycarbonate resin

The polycarbonate resin of the present invention is prepared by reacting diphenols represented by the following general formula (1) with phosgene, halogen formate, or carbonic acid diester as an aromatic polycarbonate which does not contain halogen:

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

Examples of the diphenols represented by the formula (1) 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, etc. are mentioned. Among them, 2,2'-bis- (4-hydroxyphenyl) -propane, 2,2'-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1'-bis- (4-hydroxyphenyl) -cyclohexane and the like. Bisphenols are preferable, and 2,2'-bis- (4-hydroxyphenyl) -propane also called bisphenol-A is more preferable.

The polycarbonate resin (A) of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000. The branched polycarbonate resin may be used, and preferably, may be prepared by adding a compound having 0.05 to 2 mol% of a trivalent or more phenol group based on the total amount of diphenols used in the polymerization. The polycarbonate (PC) used in the preparation of the resin composition of the present invention may be used in the form of a homopolymer, a copolymer, or a mixture thereof. In addition, the polycarbonate resin (A) may be used in part or in whole by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of a bifunctional carboxylic acid which is an ester precursor.

The polycarbonate resin (A) together with the rubber modified graft copolymer (B) and / or vinyl copolymer (C) constitutes a base resin. It is used in the range of 45-99 weight part in base resin.

(B) rubber modified graft copolymer resin

The rubber-modified graft copolymer resin used in the present invention is styrene, α-methylstyrene, halogen or methyl ring-substituted styrene, C _1-8 methacrylic acid alkyl esters, C _1-8 methacrylic acid esters, or 50-95 parts by weight of a mixture thereof, acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, C _1-8 methacrylic acid esters, maleic anhydride, C _1-4 alkyl, or phenyl N-substituted maleimide, or 5 to 95 parts by weight of a mixture with 5 to 50 parts by weight of a mixture thereof Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber having a glass transition temperature (T _G ) of -10 ° C. or less Or acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), and polyorganosiloxane / polyalkyl (meth) acrylate rubber composites A graft copolymer in which 5 to 95 parts by weight of the compound. The C _1-8 methacrylic acid alkyl esters are monohydryl alcohols containing 1 to 8 carbon atoms as esters of methacrylic acid. Preferred examples include methacrylic acid methyl ester, methacrylic acid ethyl ester, or methacrylic acid propyl ester, most preferably methacrylic acid methyl ester.

The graft copolymer resin may be prepared by a conventional polymerization method, but is preferably one synthesized by emulsion polymerization and bulk polymerization. Acrylonitrile / butadiene / styrene (ABS) resins in which acrylonitrile and styrene are grafted to butadiene rubber are widely used.

The rubber modified graft copolymer is used in the range of 1 to 50 parts by weight of the total base resin. When preparing the graft copolymer, the average size of the rubber particles is suitably in the range of 0.05 to 4 μm in consideration of impact strength and appearance.

(C) vinyl copolymer resin

Vinyl copolymers used in the present invention are styrene, α-methylstyrene, ring-substituted styrene, C _1-8 methacrylic acid alkyl esters, C _1-8 methacrylic acid esters, or mixtures thereof 50-95 Parts by weight with acrylonitrile, 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 these The vinyl copolymer obtained by copolymerizing 5-50 weight part of mixtures of these, or a mixture of these copolymers. This vinyl copolymer resin is used in 0-50 weight part of all the base resin.

Vinyl-based copolymers may be produced as by-products in the preparation of rubber-modified graft copolymers (B), especially when grafting excess vinyl-based monomers to small amounts of rubbery polymers. The content of the vinyl copolymer (C) used in the preparation of the resin composition of the present invention does not include by-products generated during the production of the graft copolymer (B). That is, the copolymer (C) used for manufacture of the resin composition of this invention is a thermoplastic resin and does not contain rubber | gum.

As a preferable specific example of the said vinyl copolymer (C), it is manufactured by emulsion polymerization, suspension polymerization, solution polymerization, or block polymerization using methacrylic acid methyl ester and / or acrylic acid methyl ester.

Other specific examples of the vinyl copolymer (C) include monomer mixtures of styrene and acrylonitrile and optionally methacrylic acid methyl ester, monomer mixtures of α-methylstyrene and acrylonitrile and optionally methacrylic acid methyl ester, or Styrene and α-methylstyrene and acrylonitrile and optionally from a monomer mixture of methacrylic acid methylester. 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 (M _w ) of 15,000 to 200,000.

Another specific example of the vinyl copolymer (C) is a copolymer of styrene and maleic anhydride, which may be prepared using a continuous bulk polymerization method and a solution polymerization method. In this case, the component composition ratio of styrene and maleic anhydride can be varied in a wide range, and the content of maleic anhydride is preferably 5 to 25 parts by weight. The styrene / maleic anhydride copolymer may be used in a wide range of 60,000 to 200,000 weight average molecular weight, and it is preferable to use an intrinsic viscosity of 0.3 to 0.9.

As the styrene monomer used in the preparation of the vinyl copolymer (C) of the present invention, other substituted styrene monomers such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and α-methylstyrene may be used.

The vinyl-based copolymers (C) described above can also be used alone or in mixture of two or more thereof.

(D) phosphate ester compounds derived from aliphatic dihydric alcohols

The phosphate ester compound used in the present invention is a phosphate ester compound alone or a mixture thereof represented by the following formula (2):

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each a C _6-20 aryl group or an alkyl substituted C _6-20 aryl group, and R ₃ is a derivative of C _1-5 aliphatic dihydric alcohols. , n is an integer of 0 to 5, and the average n value of the mixture is 0.1 to 5.0).

Preferred examples of R ₁ , R ₂ , R ₄ , and R ₅ are phenyl groups or phenyl groups substituted with alkyl groups such as t-butyl, isopropyl, isobutyl, isoamyl, t-amyl and the like. Preferred examples of the C _1-5 aliphatic dihydric alcohol of R ₃ are ethylene glycol, propylene glycol, butylene glycol, 1-methyl 1,2-ethanediol, 1-ethyl 1,2-ethanediol, 2-methyl 1 Linear or chain aliphatic dihydric alcohols such as, 3-propane diol, 2-methyl 1,4-butanediol and 2-ethyl 1,3 propane diol.

The preparation method of the phosphoric acid ester compound (D) is not particularly limited, and in general, a phenyl group or an alkyl-substituted phenyl group including phosphorus oxychloride (POCl ₃ ) and aliphatic dihydric alcohols and one hydroxy group such as phenol and cresol It can be prepared by reacting. The phosphate ester compound (D) is used as a flame retardant in the thermoplastic resin composition of the present invention, it is preferable to use 0.5 to 30 parts by weight based on 100 parts by weight of the base resin.

(E) other flame retardants and flame retardants

The thermoplastic resin composition of the present invention is at least one selected from the group consisting of other organic phosphate ester compounds, halogen-containing organic compounds, cyanurate compounds, fluorinated polyolefin resins, and metal salts in addition to the above phosphate ester compounds (D) for improving flame retardancy. Flame retardants and flame retardants may be added.

Other organic phosphate ester compounds include one or two selected from phosphate ester monomers such as triphenylphosphate and tricresylphosphate and condensed phosphate ester compounds derived from aromatic dihydric alcohols such as resorcinol, hydroquinone and bisphenol-A. There is a mixture of the above.

Fluorinated polyolefin resins are conventionally available resins as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer or ethylene / Tetrafluoroethylene copolymers. These may be used independently of each other, or a mixture of two or more different types may be used. Most preferably polytetrafluoroethylene having a particle size of 0.05-1,000 μm and specific gravity 2.0-2.3 g / cm ² . The usage-amount of fluorinated polyolefin resin is 0.05-5 weight part with respect to 100 weight part of base resins.

The fluorinated polyolefin resin may be prepared using a known polymerization method, for example, sodium at a pressure of 7 to 71 kg / cm ² and a temperature of 0 to 200 ℃, preferably at a temperature of 20 to 100 ℃ It can be prepared in an aqueous medium containing a free radical forming catalyst such as potassium or ammonium peroxydisulfate. When the fluorinated polyolefin resin is mixed with the other constituent resins of the present invention and extruded, the fluorinated polyolefin resin forms a fibrillar network in the resin to lower the flow viscosity of the resin during combustion and increase the shrinkage rate so that the resin is dropped. Prevent the phenomenon. The resin may be used in an emulsion state or a powder state. However, in the case of using the fluorinated polyolefin resin in the emulsion state, the dispersibility in the entire resin composition is good, but there is a disadvantage that the manufacturing process is complicated. Therefore, even if it is powder state, if it can disperse | distribute suitably in whole resin composition and can form a fibrous network, it is preferable to use it in powder state.

Metal salts are conventionally used, and any suitable one for polycarbonate may be used, and preferred examples thereof include sodium trichlorobenzenesulfonate, diphenylsulfon potassium salt, alkane sulfonate or sodium ammonium hexafluoride. The usage-amount of a metal salt is 0.01-1 weight part with respect to 100 weight part of base resins.

In addition, the thermoplastic resin composition of the present invention is mixed in a conventional mixer after adding a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a reinforcing agent, an inorganic additive, a pigment and / or a dye according to each use. This mixture is prepared into a resin composition in pellet form through an extruder. At this time, the inorganic additives added may include asbestos, glass fibers, talc and ceramics, which may be used in the range of 0 to 60 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the base resin.

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

(A) polycarbonate resin

A bicarbonate-type polycarbonate having a melt flow index (250 ° C., 10 kg load) measured by ASTM D1238 of 20 g / 10 min was used.

(B) rubber modified graft copolymer resin

Butadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the whole monomer, 1.0 parts by weight of potassium oleate, cumene hydroperoxide, which was an additive necessary for a mixture of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water. 0.4 parts by weight, 0.3 parts by weight of mercaptan-based chain transfer agent was added to the reaction while maintaining at 75 ℃ for 5 hours to prepare a g-ABS latex. 1% sulfuric acid solution was added to the resultant polymer latex to coagulate and dried to prepare a graft ABS copolymer resin in powder form.

(C) vinyl copolymer resin

A SAN copolymer resin was prepared by suspension polymerization by adding 0.2 parts by weight of azobisisobutyronitrile and 0.5 parts by weight of tricalcium phosphate, which are necessary additives to a mixture of 70 parts by weight of styrene, 30 parts by weight of acrylonitrile, and 120 parts by weight of deionized water. . The copolymer was washed with water, dehydrated and dried to obtain a SAN copolymer resin in powder form.

(D) phosphate ester compound

(d ₁ ) Ethylene glycol bis (diphenylphosphate) having an average n value of 1.4 was used as a phosphate ester compound derived from aliphatic dihydric alcohols.

(d ₂ ) Resorcinol bis (diphenylphosphate) having an average n value of 1.3 was used as a phosphate ester compound derived from aromatic dihydric alcohols.

(E) fluorinated polyolefin resin

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

Table 1 shows the composition and measured physical properties of each component used in Examples 1, 2 and Comparative Examples. Examples and Comparative Examples are resin compositions each used by mixing a phosphate ester compound derived from aliphatic dihydric alcohols and a phosphate ester compound derived from aromatic dihydric alcohols as a flame retardant.

As shown in Table 1, each component was mixed, antioxidant and heat stabilizer were added, and then mixed in a conventional mixer and extruded using a twin screw extruder of L / D 35 and Φ 45 mm. Mixed extrusion was prepared in a resin composition in the form of pellets, and specimens for physical property measurement and flame retardancy evaluation were prepared at an injection temperature of 250 ° C. These specimens were measured for 48 hours at 23 ° C. and 50% relative humidity, and then measured for physical properties according to ASTM standards.

Izod impact strength was evaluated using 3.2 mm thick, V-notched specimens in accordance with ASTM D256, and the heat deflection temperature was measured at 18.6 kgf load in accordance with ASTM D648. The flame retardancy was evaluated using 1.2 mm thick specimens in accordance with UL94. The total combustion time is the sum of both primary and secondary combustion times when five specimens were evaluated. The melt flow index was evaluated according to ASTM D1238, and the measurement conditions were evaluated at 250 ° C and 10 kg load. In addition, the bleeding was evaluated by observing the surface of the injection molding by visually injecting a container of 200x200x100 mm, thickness 3mm using a 40-ounce injection machine.

Example 1 Example 2 Comparative example ingredient (A) polycarbonate 75 80 75 (B) g-ABS 13 20 13 (C) SAN 12 - 12 (D) (d ₁ ) ethylene glycol bis (diphenyl phosphate) 13 12 - (d ₂ ) resorcinol bis (diphenyl phosphate) - - 13 (E) Fluorinated Polyolefin (7AJ) 0.2 0.2 0.2 Properties Izod impact strength (kgfcm / cm) 35 42 33 Heat deflection temperature (℃) 80 83 81 Flame retardant (UL Class) V-0 V-0 V-1 Total combustion time (sec) 41 40 68 Melt Flow Index (g / 10min) 58 52 49 Bleeding none none none

As shown in Examples 1 and 2 of Table 1 and the comparative example, when using a phosphate ester compound derived from an aliphatic dihydric alcohol as a flame retardant, the flame retardancy was superior to the phosphate ester compound derived from an aromatic dihydric alcohol. In particular, it can be seen that the fluidity is excellent, but the bleeding phenomenon does not occur.

The present invention uses a phosphate ester compound derived from an aliphatic dihydric alcohol as a flame retardant, and has excellent physical properties including flame retardancy and impact strength, and has excellent workability without bleeding. It has the effect of providing a polycarbonate-based thermoplastic resin composition useful for producing an injection product.

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 (8)

(A) 45-99 weight part of polycarbonate resins, (B) styrene, (alpha) -methylstyrene, halogen or methyl ring-substituted styrene, C1-8 methacrylic acid alkylesters, C1-8 methacrylic acid esters, or 50-95 parts by weight of a mixture thereof, acrylonitrile, methacrylonitrile, C1-8 methacrylic acid alkyl esters, C1-8 methacrylic acid esters, maleic anhydride, C1-4 alkyl or phenyl N-substituted malees 5 to 95 parts by weight of a mixture of 5 to 50 parts by weight of the mead or a mixture thereof, butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / having a glass transition temperature (TG) of -10 ° C. or less. 5 to 95 parts by weight of one or a mixture thereof selected from the group consisting of butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), and polyorganosiloxane / polyalkyl (meth) acrylate rubber composite Rapeuteu in which rubber-modified graft copolymer resin and 1 to 50 parts by weight of (C) vinyl-based copolymer resin based on 100 parts by weight of resin comprising 0 to 50 parts by weight; (D) 0.5 to 30 parts by weight of an oligomeric phosphate ester compound derived from aliphatic dihydric alcohols; And (E) 0.05 to 5 parts by weight of at least one flame retardant and flame retardant aid selected from the group consisting of other organic phosphate ester compounds, halogen-containing organic compounds, cyanurate compounds, fluorinated polyolefin resins and metal salts; Polycarbonate-based thermoplastic resin composition having a flame retardance, characterized in that consisting of. The polycarbonate-based thermoplastic resin composition of claim 1, wherein the oligomeric phosphate ester compound (D) is represented by the following general formula (2): Formula (2) Wherein R 1, R 2, R 4 and R 5 are each a C 6-20 aryl group or an alkyl substituted C 6-20 aryl group, R 3 is a derivative of C 1-5 aliphatic dihydric alcohols, n is an integer of 1 to 5 And the mean n value of the mixture is 1.0 to 5.0. The flame retardant polycarbonate-based thermoplastic resin composition according to claim 2, wherein R ₁ , R ₂ , R ₄ , and R ₅ are each a phenyl group or a phenyl group substituted with a methyl group or a hydroxy group. The compound of claim 2, wherein R ₃ is ethylene glycol, propylene glycol, butylene glycol, 1-methyl1,2-ethanediol, 1-ethyl1,2-ethanediol, 2-methyl1,3-propanediol, A polycarbonate-based thermoplastic resin composition having flame retardancy, characterized in that it is one or two or more mixtures selected from the group consisting of 2-methyl1,4-butanediol and 2-ethyl1,3-propanediol. The polycarbonate-based thermoplastic resin composition having flame retardancy according to claim 2, wherein the average value of n is 1.0 to 3.0. The polycarbonate-based thermoplastic resin composition having flame retardancy according to claim 1, wherein the content of the phosphate ester compound (D) is used in an amount of 10 to 25 parts by weight based on 100 parts by weight of the base resin. The flame retardant of claim 1, wherein the resin composition further comprises an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment and / or a dye, a lubricant, a mold release agent, a filler, a nucleating agent, or an antistatic agent. Polycarbonate-based thermoplastic resin composition. The molded article manufactured from the resin composition of Claim 1.