KR101066930B1 - Polycarbonate Resin Composition Having Good Flame retardancy And Transparency - Google Patents

Abstract

The polycarbonate resin composition according to the present invention comprises (A) 100 parts by weight of a polycarbonate resin, (B) 1 to 15 parts by weight of an aromatic vinyl polymer, (C) 5 to 20 parts by weight of a phosphate ester compound or a mixture thereof, and (D) 1-12 parts by weight of tris (halogen-substituted phenoxy) -s-triazine. The polycarbonate resin composition has excellent fluidity and impact resistance, but has high flame retardancy and transparency.

Polycarbonate resin, aromatic vinyl polymer, phosphate ester compound, tris (halogen-substituted phenoxy) -s-triazine, melt flowability, transparency, flame retardancy

Description

Polycarbonate Resin Composition Having Good Flame retardancy And Transparency

 Field of invention

The present invention relates to a polycarbonate resin composition excellent in transparency and flame retardancy. More specifically, the present invention by applying an aromatic vinyl polymer, phosphate ester flame retardant and tris (halogen-substituted phenoxy) -s-triazine compound to the polycarbonate resin, while maintaining excellent flame retardancy and transparency, fluidity and impact resistance It is related with the outstanding polycarbonate resin composition.

Background of the Invention

Polycarbonate resins are excellent in transparency, impact resistance, heat resistance and electrical properties, and are easy to exhibit flame retardancy in chemical structure, and thus are applied to large injection molding products such as electrical and electronic products and office equipment. However, as the injection molding material gradually increases in size and thickness, conventional polycarbonate resins having poor melt flowability have a great difficulty in injection molding. In addition, as safety against fire has recently emerged as an important issue, demand for resins capable of satisfying flame retardancy while maintaining transparency of polycarbonate resins has been expanded.

In order to impart flame retardance to the transparent polycarbonate resin as described above, fluorinated polyethylene resins have been conventionally used together with metal salts or halogen flame retardants. However, the use of fluorinated polyethylene-based resins and metal salt-based flame retardants has caused a decrease in transparency, which is one of the advantages of polycarbonate.

In order to overcome such a drop in transparency, various materials were used as antidropping agents instead of fluorinated polyolefin resins. Examples include materials described in US Patent Nos. 3,971,756, 4,028,297, 4,110,299, 4,130,530, 4,303,575, 4,335,038, 4,552,911, 4,916,194, and the like. However, despite these various attempts, a flame-retardant polycarbonate resin composition which is free from dropping, transparent, and high fluidity during combustion is still a problem that needs to be developed.

U.S. Patent No. 6,353,046 describes a flame retardant polycarbonate resin composition containing a combination of perfluoroalkane sulfonate and cyclic siloxane using a flame retardant synergistic effect. However, the composition according to this technique has a disadvantage of high melt viscosity is not suitable for large injection.

As a method of improving the flame retardancy of an aromatic polycarbonate without using a bromine-based flame retardant, JP-A-47-40445 discloses a method of blending an aromatic polycarbonate with an alkali metal salt or an alkaline earth metal salt of perfluoro alkanesulfonic acid, Japanese Laid-Open Patent Publication No. 60-38418 discloses a method of preventing dropping during combustion by combining an organic alkali metal salt or alkaline earth metal salt with polytetrafluoroethylene in an aromatic polycarbonate. However, since the aromatic polycarbonate resin composition according to the prior arts has a small shear rate dependency of melt viscosity, it is easy to cause molding defects such as short shot due to lack of fluidity of the molten resin when molding a thin molded article. there is a problem. In addition, blending polytetrafluoroethylene has a problem that the transparency is greatly lost.

On the other hand, a method of using a branched aromatic polycarbonate having a branched structure in a molecular structure alone or blending an aromatic polycarbonate having no branched structure with it and maintaining transparency to prevent dropping during combustion has been attempted. For example, Japanese Patent Laid-Open No. 7-258532 describes that by mixing an organic alkali metal salt or an organic alkaline earth metal salt with a branched aromatic polycarbonate, it is possible to prevent dropping during combustion without using polytetrafluoroethylene. have. However, the resin composition according to Japanese Patent Laid-Open No. 7-258532 secures flame retardancy, but has a disadvantage in that fluidity and transparency are not sufficient.

In order to solve the problems described above, the present inventors found that high molecular weight aromatic vinyl-based (co) polymer resins, phosphate ester-based flame retardants, and tris (halogen-substituted phenoxy) s-triazine were added to the polycarbonate resin. By discovering that the resin composition which can ensure transparency and high fluidity | liquidity can be obtained, without reducing flame-retardance, mechanical strength, heat resistance, etc. of a resin, this invention was completed.

An object of the present invention is to provide a polycarbonate resin composition excellent in physical properties such as flame retardancy and transparency, mechanical strength, heat resistance, flowability.

Another object of the present invention is to provide a polycarbonate resin composition having high fluidity and impact resistance while maintaining excellent flame retardancy and transparency.

Still another object of the present invention is to provide a polycarbonate resin composition capable of preventing dropping during combustion.

Another object of the present invention is to provide a plastic molded article having excellent flame retardancy and appearance.

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

Summary of the Invention

The present invention provides a polycarbonate resin composition having excellent flowability and impact resistance, and a plastic molded article made of the polycarbonate resin composition, without deteriorating transparency and flame retardancy.

The polycarbonate resin composition according to the present invention comprises (A) 100 parts by weight of polycarbonate resin, (B) 1-15 parts by weight of an aromatic vinyl polymer having a weight average molecular weight of 1.9 × 10 ^{5 to} 4.5 × 10 ⁸ g / mol, ( C) 5 to 20 parts by weight of an oligomeric phosphate ester compound derived from bisphenol A represented by the following formula (1) or a mixture thereof, and (D) 1 to 12 parts by weight of tris (halogen-substituted phenoxy) -s-triazine.

[Formula 1]

In Formula 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 to represent the number of repeating units An integer of 5, the average value of m in the mixture of the oligomeric phosphate ester compound represented by the formula (1) is 0.5 to 2.

In an embodiment of the present invention, the aromatic vinyl polymer (B) is preferably (B ₁ ) branched aromatic vinyl polymer, (B ₂ ) linear aromatic vinyl polymer or a mixture thereof.

In an embodiment of the present invention, the branched aromatic vinyl polymer (B ₁ ) is preferably composed of 100 parts by weight of the aromatic vinyl monomer and 0.001 to 3 parts by weight of the polyfunctional vinyl compound.

In an embodiment of the present invention, the aromatic vinyl monomer is selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, chloro styrene and substituents thereof, wherein the polyfunctional vinyl compound is ethylenedi Methacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, trimethylene propane triacrylate, 1,3-butanediol methacrylate, 1,6-hexanedioldi It is preferably selected from the group consisting of methacrylate, allyl acrylate and mixtures thereof.

In an embodiment of the present invention, the linear aromatic vinyl polymer (B ₂ ) is preferably a weight average molecular weight of 2.5 × 10 ⁵ ~ 8.0 × 10 ⁶ g / mol.

In an embodiment of the present invention, R ₁ of Formula 1 is a phenyl group or a naphthyl group, respectively, or a methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl or t-amyl group is substituted. It is preferable that it is a phenyl group or a naphthyl group.

In an embodiment of the present invention, the tris (halogen-substituted phenoxy) -s-triazine (D) is preferably represented by the following formula (2).

[Formula 2]

In this case, in Formula 2, n is an integer of 1 to 3, respectively, X is fluorine, chlorine or bromine.

In an embodiment of the present invention, it is preferable that the resin composition does not contain a fluorinated polyolefin resin.

In an embodiment of the present invention, the resin composition may further include an additive selected from the group consisting of antioxidants, flame retardants, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, dyes, pigments and mixtures thereof.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Detailed Description of the Invention

(A) polycarbonate resin

The polycarbonate resin (A) according to the present invention can be prepared by reacting diphenols represented by the following general formula (III) with phosgene, halogen formate or carbonic acid diester.

(3)

(In the formula (III), A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C _{5 to} C ₆ cycloalkylidene, -S- or -SO _2- Indicates)

Specific examples of the diphenol of the general formula (III) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxy 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 are preferred, more preferably 2,2-bis- (4-hydroxyphenyl) -propane, 1,1-bis- (4 -Hydroxyphenyl) -cyclohexane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like can be used, most preferably the most aromatic polycarbonate used industrially 2,2-bis- (4-hydroxyphenyl) -propane also called phosphorus bisphenol-A can be used.

Suitable polycarbonates used in the preparation of the polycarbonate resin composition according to the present invention preferably have a weight average molecular weight of 10,000 to 200,000, more preferably 15,000 to 80,000.

As the polycarbonate of the present invention, a branched chain may be used, and preferably 0.05 to 2 mol% of a tri- or more polyfunctional compound, such as trivalent or more, based on the total amount of diphenols used for polymerization. It can manufacture by adding the compound which has the above phenol group. In other embodiments, linear polycarbonates can be used. In another embodiment, a mixture of linear polycarbonates and branched polycarbonates can be used.

Examples of the polycarbonate include homo polycarbonates and copolycarbonates, and may also be used in the form of a blend of copolycarbonates and homo polycarbonates. Examples of copolycarbonates used in the preparation of the resin composition of the present invention include aromatic polyester-carbonate copolymer resins obtained by polymerization in the presence of ester precursors such as bifunctional carboxylic acids, and polyorganosiloxane-carbonate copolymers. Resins can be used.

(B) aromatic vinyl polymer

The aromatic vinyl polymer (B) according to the present invention preferably has a weight average molecular weight of 1.9 × 10 ⁵ g / mol to 4.5 × 10 ⁸ g / mol, more preferably 8.0 × at 4.0 × 10 ⁶ g / mol. 10 ⁷ g / mol is preferred. If the weight average molecular weight is 1.9 × 10 ⁵ g / mol or less, there is a problem in that the effect of preventing dropping during combustion is small, and if the weight average molecular weight is 4.5 × 10 ⁸ g / mol or more, the viscosity of the resin composition is increased to reduce workability.

The aromatic vinyl polymer (B) may be prepared by adding a polyfunctional vinyl compound and / or a polyfunctional initiator to an aromatic vinyl monomer to polymerize it. The polymerization method can be prepared by a general polymerization method such as bulk polymerization, solution polymerization, suspension polymerization. In addition, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, etc. may be optionally added together with the aromatic vinyl monomer, and may be used in the range of 0 to 30% by weight of the total monomers.

As the aromatic vinyl monomer, styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, chloro styrene, and substituents thereof may be used, but are not necessarily limited thereto. These may be used alone or in combination of two or more, preferably styrene.

As the polyfunctional vinyl compound, a (meth) acrylate compound having two or more functional groups may be used. Preferably, ethylene dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, trimethylene propane triacrylate, 1,3-butanediol methacrylate, 1, 6-hexanediol dimethacrylate, allyl acrylate and the like can be used, but are not necessarily limited thereto. The polyfunctional vinyl compound may be used alone or in combination of two or more thereof.

Examples of the multifunctional initiator include 2,2-bis (4,4-di (t-butylperoxy) cyclohexyl) propane, tri (t-butylperoxy) triazine and tri (t-butylperoxy) trimeli Peroxycarbonate compounds such as art or polyether poly-t-butylperoxy carbonate and alkylperoxy-alkylfumarate compounds such as t-butylperoxy methylfumarate and t-butylperoxy ethylfumarate May be used, but is not necessarily limited thereto. The multifunctional initiator may be used alone or in combination of two or more thereof.

In the present invention, the aromatic vinyl polymer (B) may be a branched aromatic vinyl polymer, a linear aromatic vinyl polymer, or a mixture thereof.

In one embodiment the aromatic vinyl polymer (B) is a branched aromatic vinyl polymer. The branched aromatic vinyl polymer may be prepared by adding a polyfunctional vinyl compound to an aromatic vinyl monomer and copolymerizing the same. Preferably, it can be prepared by copolymerizing 0.001 to 3 parts by weight of the polyfunctional vinyl compound in 100 parts by weight of the aromatic vinyl monomer. In another embodiment, the branched aromatic vinyl polymer may be prepared by copolymerizing a polyfunctional vinyl compound and a polyfunctional initiator into an aromatic vinyl monomer. In this case, 0.01 to 0.3 parts by weight of the polyfunctional initiator may be added to 100 parts by weight of the aromatic vinyl monomer and 0.001 to 3 parts by weight of the polyfunctional vinyl compound, followed by copolymerization.

The content of the multifunctional vinyl compound is suitably 0.001 to 3 parts by weight, more preferably 0.003 to 1 part by weight based on 100 parts by weight of the aromatic vinyl monomer. When the total content of the multifunctional vinyl compound is less than 0.001 parts by weight, the chaining effect due to the branched structure does not appear sufficiently, and when it exceeds 3 parts by weight, the molecular weight rapidly increases or the crosslinking reaction proceeds to cause gelation. This deteriorates and contaminates the reactor inner wall, resulting in a problem that the surface of the final product is not smooth.

In addition, the polyfunctional initiator is used in 0.01 to 0.3 parts by weight based on 100 parts by weight of the aromatic vinyl monomer. It has proper fluidity in this range and is advantageous in physical property balance . Preferably it is 0.03-0.2 weight part.

In another embodiment, the aromatic vinyl polymer (B) is a linear aromatic vinyl polymer. The linear aromatic vinyl polymer may be prepared by adding a polyfunctional initiator to the aromatic vinyl monomer and polymerizing the same. Preferably, 0.01 to 0.3 parts by weight of the polyfunctional initiator is polymerized to 100 parts by weight of the aromatic vinyl monomer. In a preferred embodiment, the linear aromatic vinyl polymer has a weight average molecular weight of 2.5 × 10 ⁵ g / mol to 8.0 × 10 ⁶ g / mol, more preferably 4.5 × 10 ⁶ g / at 3.0 × 10 ⁵ g / mol mol is good. When the weight average molecular weight is 2.5 × 10 ⁵ g / mol or more, the effect of preventing dropping during combustion is excellent, and excellent workability can be obtained by appropriately maintaining the viscosity of the resin composition below 8.0 × 10 ⁶ g / mol. .

In another embodiment, the aromatic vinyl polymer (B) is a mixture of a branched aromatic vinyl polymer and a linear aromatic vinyl polymer. Preferably, the mixture may be composed of 1 to 99% by weight of a branched aromatic vinyl polymer and 1 to 99% by weight of a linear aromatic vinyl polymer. In another embodiment, the mixture may consist of 50 to 90% by weight of branched aromatic vinyl polymer and 10 to 50% by weight of linear aromatic vinyl polymer.

In the present invention, the aromatic vinyl polymer (B) may be used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the aromatic vinyl polymer (B) is used in less than 1 part by weight, sufficient flame retardancy may not be obtained. When the aromatic vinyl polymer (B) is used in excess of 15 parts by weight, the balance of physical properties of transparency and fluidity may be degraded, and the flame retardancy may be rather deteriorated. In the specific embodiment, when the aromatic vinyl polymer (B) is branched, it is 2 to 12 parts by weight, preferably 2 to 10 parts by weight, more preferably 2 to 8 parts by weight. In the specific embodiment, when the aromatic vinyl polymer (B) is linear, it is 1 to 10 parts by weight, preferably 1 to 7 parts by weight, more preferably 1 to 5 parts by weight.

(C) bisphenol-A derived oligomeric phosphate ester compound

The oligomeric phosphate ester compound (C) derived from bisphenol-A according to the present invention is a phosphate ester compound represented by the following formula (1) or a mixture thereof.

[Formula 1]

In Formula 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 to 5 representing the number of repeating units And an average value of m in the mixture of the oligomeric phosphate ester compound of Formula 1 above.

R ₁ in Formula 1 may be a phenyl group or a naphthyl group or a phenyl group or a naphthyl group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. Etc., and a phenyl group in which a phenyl group, a naphthyl group or a methyl, ethyl, isopropyl or t-butyl group is substituted is more preferable.

The compound of formula 1 used in the preparation of the polycarbonate resin composition of the present invention is an oligomeric phosphate ester compound derived from bisphenol-A, and is an oligomeric bisphenol-A derived phosphate ester having an average value of m of 0.5 to 2. In the present invention, two or more phosphate ester compounds having different m values may be used in a mixed form. In the polymerization process, two or more phosphate ester compounds having different m values are already mixed, or each separately. It is also possible to mix and use the manufactured thing.

In the present invention, the bisphenol-A derived oligomeric phosphate ester compound (C) is preferably used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the bisphenol-A derived oligomeric phosphoric acid ester compound (C) is used in less than 5 parts by weight, sufficient flame retardancy may not be obtained, and when used in excess of 20 parts by weight, mechanical properties or transparency may be degraded. Preferably, the bisphenol-A derived oligomeric phosphate ester compound (C) may be used in an amount of 10 to 17 parts by weight based on 100 parts by weight of the polycarbonate resin (A).

(D) s-triazine-induced tris (halogen substituted phenoxy) -s-triazine compound

S-triazine-induced tris (halogen substituted phenoxy) -s-triazine compound (D) according to the present invention is a tris (halogen-substituted phenoxy) -s-tri derived from s-triazine represented by the following formula (2) It is a azine compound.

[Formula 2]

In Formula 2, n is an integer of 1 to 3, respectively, and X is a halogen element such as fluorine, chlorine or bromine.

In consideration of transparency and flame retardancy, the compound of Formula 2 used in the resin composition of the present invention is preferably a halogen-substituted phenoxy s-triazine compound in which n is 3 and X is chlorine or bromine, and the content of chlorine or bromine is 50% or more is preferred and may be mixed and used alone, depending on the end use.

In the present invention, the tris (halogen substituted phenoxy) -s-triazine compound (D) may be used in an amount of 1 to 12 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the tris (halogen-substituted phenoxy) -s-triazine compound (D) is used in less than 1 part by weight, sufficient flame retardancy cannot be obtained, and there is a problem in that transparency or fluidity is poor, whereas when used in excess of 12 parts by weight. In addition, yellowing may occur, transparency may be degraded, and flame retardancy may be reduced. Preferably, the tris (halogen substituted phenoxy) -s-triazine compound (D) may be used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A).

In an embodiment of the present invention, the polycarbonate resin composition preferably does not contain a fluorinated polyolefin resin. When the fluorinated polyolefin resin is applied to the polycarbonate resin according to the present invention, a fibrillar network is formed in the resin to reduce the flow viscosity of the resin during combustion and increase the shrinkage rate to prevent the dropping of the resin. However, it is not preferable because there is a problem that the transparency, which is an advantage of the polycarbonate resin, is lowered.

In an embodiment of the present invention, the polycarbonate resin composition may further include an additive according to each use. The additives may include ultraviolet stabilizers, fluorescent brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, antioxidants, heat stabilizers, reinforcing agents, inorganic additives, pigments or dyes, and the like, but are not limited thereto. These can be used individually or in mixture of 2 or more types. The additive may be used in an amount of 0.1 to 60 parts by weight or less, preferably 1 to 40 parts by weight, based on 100 parts by weight of the base resin.

The polycarbonate resin composition according to 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 at the same time and then melt-extruded in an extruder to produce pellets or chips.

Since the thermoplastic resin composition of the present invention has excellent transparency while having high flame retardancy, impact resistance and fluidity, it can be used for molding various products requiring high appearance. For example, electrical and electronic products such as TVs, audios, mobile phones, digital cameras, navigation systems, washing machines, computers, monitors, MP3s, video players, CD players, and washing machines that require excellent transparency, flame retardancy, impact resistance and moldability. It can be widely used in the manufacture of housings and office automation equipment and other large injection molding products.

There is no particular limitation on the method of molding the plastic molded article using the thermoplastic resin composition according to the present invention. For example, an extrusion, injection, or casting molding method may be applied. The molding can be easily carried out by those skilled in the art.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of each component used in the following Examples and Comparative Examples are as follows.

(A) polycarbonate resin

(A1) PANLITE L-1250WP of Teijin, Japan, which is a bicarbonate-type polycarbonate resin having a weight average molecular weight of 25,000 g / mol, was used.

(A2) PANLITE L-1225WX of Teijin, Japan, which is a bicarbonate-type polycarbonate resin having a weight average molecular weight of 22,000 g / mol, was used.

(B) aromatic vinyl polymer

As the branched aromatic vinyl polymer (B1), polystyrene BLENDEX865 manufactured by Chemtura having a weight average molecular weight of 1.9x10 ⁷ g / mol was used.

As the linear aromatic vinyl polymer (B2), a high molecular weight polystyrene HRM-40 of Toyo styrene of Japan having a weight average molecular weight of 4.0 × 10 ⁵ g / mol was used.

(B3) As the linear aromatic vinyl polymer, a polystyrene having a weight average molecular weight of 1.2 × 10 ⁵ g / mol was used.

(C) Phosphoric acid ester compound: CR-741 from Daihachi, Japan, which is a mixture of bisphenol-A derived oligomeric phosphoric acid esters, was used.

(D) Tris (halogen substituted phenoxy) -s-triazine

FLAM-245 from Jingsu Htuading, China, was used as the tris (brominated) phenoxy-s-triazine having n of 3 derived from s-triazine.

(D ') halogen substituted polycarbonate oligomers

BC-58, a tetrabromobisphenol-A polycarbonate oligomer from Great Lakes, USA, was used.

Examples 1-8 and Comparative Examples 1-13

The components were added to the contents as shown in Table 1 and Table 2, antioxidants and heat stabilizers were mixed in a conventional mixer and extruded using a twin screw extruder of L / D = 35, Φ = 45mm, and then the extrudate It was prepared in the form of pellets, and the specimen was prepared using a 10 oz injection machine at an injection temperature of 260 ~ 280 ℃. The specimen was left at 23 ° C., 50% relative humidity for 48 hours, and then measured as follows according to ASTM standards.

Property evaluation method

(1) Yellowness Index (YI): Minolta 3600D CIE Lab. With 2.5t thickness specimen using ASTM D1925. It measured using the color difference meter.

(2) Transparency: Measured by a color computer measuring instrument manufactured by SUGAINSTRUMENT, Japan, and the results are expressed as total light transmittance and HAZE.

Total light transmittance (%) = (sample transmitted light) / (sample irradiation light) x 100

HAZE (%) = (dispersed transmitted light) / (total light transmittance) x 100

(3) IZOD impact strength (kg · cm / cm): Measured based on ASTM D-256 (1/8 ", notched).

(4) Flame retardant: Flame retardancy was measured according to the UL 94 V flame retardant regulations for 2.1 mm thick specimens.

(5) Total combustion time: The total combustion time was measured in accordance with UL 94 flame retardancy for 2.1 mm thick specimens.

(6) Melt Flow Index: According to ASTM D1238, evaluated at 250 ° C. with a 10 kgf load (g / 10 min).

As shown in Table 1 and Table 2, Examples 1 to 8, while having a flame retardancy and excellent transparency of V-0, exhibited a high Izod impact strength and melt flow index exhibited good moldability. In contrast, when no aromatic vinyl polymer (B) or tris (brominated) phenoxy-s-triazinevinyl (D) was applied (Comparative Examples 1, 2, 3, 4, 7, 8 and 10) The flame retardancy was reduced to V-2 or V-1, it was confirmed that the transparency is inferior.

On the other hand, Comparative Examples 4 and 10 in which TBBA PC oligomer (D ') was applied instead of tris (bromine substituted) phenoxy-s-triazinevinyl (D) which is a flame retardant of the present invention are tris (brominated substituted) phenoxy-s- Compared with Examples 1 and 5 to which triazine vinyl (D) was applied, the flame retardancy was remarkably decreased.

In addition, when tris (bromine substituted) phenoxy-s-triazinevinyl (D) was used in a composition outside the scope of the present invention (Comparative Examples 5 and 11), the flow phenomenon of the melt index during the flame retardation evaluation was significantly increased. It was confirmed that it was difficult to secure the flame retardancy of UL94 V-0, and when the aromatic vinyl polymer (B) was used in a composition outside the scope of the present invention (Comparative Example 6), transparency and flame retardancy were also reduced. .

The present invention provides a polycarbonate resin composition having improved flow and impact resistance while maintaining excellent flame retardancy and transparency by applying an aromatic vinyl polymer, a phosphate ester compound, and tris (halogen-substituted) phenoxy-s-triazine to a polycarbonate resin. It has the effect of providing the invention.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

(A) 100 parts by weight of polycarbonate resin; (B) 1 to 15 parts by weight of an aromatic vinyl polymer having a weight average molecular weight of 1.9 × 10 ^{5 to} 4.5 × 10 ⁸ g / mol; (C) 5 to 20 parts by weight of an oligomeric phosphate ester compound derived from bisphenol A represented by the following formula (1) or a mixture thereof; And (D) 1-12 parts by weight of tris (halogen-substituted phenoxy) -s-triazine; A polycarbonate resin composition having excellent transparency and flame retardancy, comprising: [Formula 1]

In Formula 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 to represent the number of repeating units An integer of 5, the average value of m in the mixture of the oligomeric phosphate ester compound represented by the formula (1) is 0.5 to 2. The polycarbonate resin composition according to claim 1, wherein the aromatic vinyl polymer (B) is a (B ₁ ) branched aromatic vinyl polymer, (B ₂ ) linear aromatic vinyl polymer or a mixture thereof. The polycarbonate resin composition according to claim 2, wherein the branched aromatic vinyl polymer (B ₁ ) comprises 100 parts by weight of an aromatic vinyl monomer and 0.001 to 3 parts by weight of a polyfunctional vinyl compound. The method of claim 3, wherein the aromatic vinyl monomer is selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, chloro styrene and substituents thereof; The polyfunctional vinyl-based compound may be ethylene dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, trimethylene propane triacrylate, 1,3-butanediol methacrylate A polycarbonate resin composition, characterized in that it is selected from the group consisting of latex, 1,6-hexanediol dimethacrylate, allyl acrylate, and mixtures thereof. The polycarbonate resin composition according to claim 2, wherein the linear aromatic vinyl polymer (B ₂ ) has a weight average molecular weight of 2.5 × 10 ^{5 to} 8.0 × 10 ⁶ g / mol. According to claim 1, wherein in Formula 1 R ₁ is a phenyl group or a naphthyl group, respectively, or methyl, ethyl, prefill, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl or t-amyl group substituted It is a phenyl group or a naphthyl group, The polycarbonate resin composition characterized by the above-mentioned. The polycarbonate resin composition of claim 1, wherein the tris (halogen-substituted phenoxy) -s-triazine (D) is represented by the following Chemical Formula 2: [Formula 2]

In Formula 2, n is an integer of 1 to 3, respectively, X is fluorine, chlorine or bromine. The polycarbonate resin composition according to claim 1, wherein the resin composition does not contain a fluorinated polyolefin resin. The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of antioxidants, flame retardants, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, dyes, pigments and mixtures thereof. Polycarbonate resin composition. The plastic molded article shape | molded with the resin composition of any one of Claims 1-9.