KR101847249B1 - Flame retardant thermoplastic resin composition and article comprising the same - Google Patents

Abstract

상기 화학식 1에서, A는 탄소수 1 내지 20의 탄화수소기, 또는 수산화기, 알콕시기, 아릴옥시기 및 카르복시기 중 1종 이상을 포함하는 관능기로 치환된 탄소수 1 내지 20의 탄화수소기이고, R₁, R₂, R₃ 및 R₄는 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 5의 탄화수소기이며, a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이고, n은 0 또는 1이다.The thermoplastic resin composition of the present invention comprises a polycarbonate resin; Rubber-modified vinyl-based graft copolymer; Fluorinated olefinic resins; And a phosphorus-based flame retardant including a phosphorus-based compound represented by the following general formula (1) and a phosphoric acid ester-based compound other than the phosphorus-based compound, wherein the weight ratio of the phosphorus-containing compound to the phosphoric ester-based compound is 1: 5 to 1:20 . The thermoplastic resin composition is excellent in flame retardancy, impact resistance, heat resistance, physical properties and the like.
[Chemical Formula 1]

Wherein A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms substituted with a functional group containing at least one of a hydroxyl group, an alkoxy group, an aryloxy group and a carboxyl group, R ₁ and R _2, R ₃ and R ₄ are each independently a hydrocarbon group or a halogen atom having 1 to 5, a, b, c and d are each independently an integer of 0 to 4, n is 0 or 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a flame retardant thermoplastic resin composition and a molded article including the flame retardant thermoplastic resin composition,

The present invention relates to a flame retardant thermoplastic resin composition and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition excellent in flame retardance, impact resistance, physical properties and the like, and a molded article comprising the same.

Polycarbonate resin is an engineering plastic excellent in mechanical strength, heat resistance and transparency. The polycarbonate resin is used in various fields such as office automation equipment, electric / electronic parts, and building materials. Particularly, when a rubber-modified aromatic vinyl copolymer resin such as an acrylonitrile-butadiene-styrene copolymer (ABS) is mixed with the above polycarbonate resin, the polycarbonate resin is excellent in workability and heat resistance, Chemical properties and the like can be improved. As described above, the blend (resin composition) of the polycarbonate resin and the rubber-modified aromatic vinyl copolymer resin can obtain excellent physical properties as compared with the rubber-modified aromatic vinyl copolymer resin, and the cost is lower than that of the polycarbonate resin So that it can be used for various purposes.

Such a thermoplastic resin composition comprising a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin can be applied to an injection molded article which dissipates heat much, such as an internal or external material of an electric / electronic product or the like. In order to use the thermoplastic resin composition for such use, excellent flame retardancy, heat resistance and mechanical strength are required. In order to impart flame retardancy and the like to the thermoplastic resin composition, a phosphorus-based flame retardant is widely used instead of a halogen-based flame retardant having a human health hazard. As the phosphorus flame retardant, a monomeric phosphoric acid ester compound, an oligomeric phosphoric acid ester compound and the like are used.

However, when the monomeric phosphoric acid ester compound is used as the flame retardant agent, a juicing phenomenon may occur in which the flame retardant agent moves to the surface of the molded article during molding. When the oligomeric phosphoric acid ester compound is used, And a larger amount should be added in order to obtain an equivalent flame retardancy. However, when an excessive amount of a flame retardant is used, the mechanical strength and heat resistance of the thermoplastic resin composition may be lowered.

Accordingly, development of a flame retardant thermoplastic resin composition which is excellent in flame retardance, impact resistance, heat resistance, appearance characteristics, physical properties balance thereof, and the like has been demanded without the problems of human health and juicing.

The background art of the present invention is disclosed in U.S. Patent No. 5,061,745.

It is an object of the present invention to provide a thermoplastic resin composition excellent in flame retardance, impact resistance, physical properties and the like, and a molded article comprising the same.

Another object of the present invention is to provide a flame-retardant thermoplastic resin composition which is environment-friendly, excellent in heat resistance, appearance and the like without using a halogen-based flame retardant, and a molded article containing the same.

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

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition is a polycarbonate resin; Rubber-modified vinyl-based graft copolymer; Fluorinated olefinic resins; And a phosphorus-based flame retardant including a phosphorus-based compound represented by the following general formula (1) and a phosphoric acid ester-based compound other than the phosphorus-based compound, wherein the weight ratio of the phosphorus-containing compound to the phosphoric ester-based compound is 1: 5 to 1:20 Features:

[Chemical Formula 1]

Wherein A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms substituted with a functional group containing at least one of a hydroxyl group, an alkoxy group, an aryloxy group and a carboxyl group, R ₁ and R _2, R ₃ and R ₄ are each independently a hydrocarbon group or a halogen atom having 1 to 5, a, b, c and d are each independently an integer of 0 to 4, n is 0 or 1.

In an embodiment, the thermoplastic resin composition comprises 100 parts by weight of the polycarbonate resin, 1 to 40 parts by weight of the rubber-modified vinyl-based graft copolymer, 0.1 to 5 parts by weight of the fluorinated olefin resin, and 1 to 30 parts by weight of the phosphorus- Section.

In an embodiment, the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubber-like polymer.

In an embodiment, the phosphorus compound may have an asymmetric structure.

In an embodiment, the phosphorus compound may be one having a gemini structure.

In an embodiment, the phosphorus compound may include at least one of the compounds represented by the following general formulas (1a), (1b), (1c) and (1d).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In an embodiment, the phosphoric acid ester compound may be represented by the following formula (2):

(2)

In Formula 2, R ₅ and R ₉ are each independently an aryl group of hydrogen, C6-C20 aryl group, or a C1-C10 with C6-C20 alkyl group is substituted for, R ₆ and R ₈ are each independently is a hydrogen atom, a hydroxy group, C6-C20 aryl group or aryloxy group, or an aryl group, or an aryloxy C1-C10 with C6-C20 alkyl group is substituted, the R ₇ is a C6-C20 aryl group or a C1-C10 C20 arylene group in which the alkyl group is substituted, and the average value of m is 0 to 3. [

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured by the UL-94 vertical test method.

In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of 1/8 "thick specimen measured according to ASTM D256 of 25 to 70 kgf · cm / cm.

In an embodiment, the thermoplastic resin composition may have a heat distortion temperature (HDT) of 80 to 110 ° C measured according to ASTM D648.

Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.

An object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition which is excellent in flame retardance, impact resistance, heat resistance, appearance, balance of physical properties and the like, and does not use a halogen flame retardant.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a rubber-modified vinyl-based graft copolymer; (C) a fluorinated olefin-based resin; And (D) a phosphorus-based flame retardant comprising (Dl) a phosphorus compound and (D2) a phosphate ester compound other than the phosphorus compound.

(A) Polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, conventional thermoplastic polycarbonate resins can be used without limitation. For example, an aromatic polycarbonate resin prepared by reacting at least one diphenol (aromatic dihydroxy compound) with a carbonate precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Specific examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, mixtures thereof, and the like, but are not limited thereto. Examples of the above diphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1- -Hydroxyphenyl) cyclohexane, and specifically 2,2-bis (4-hydroxyphenyl) propane, also referred to as bisphenol-A, can be used.

The polycarbonate resin may be used in the form of a branched chain. For example, 0.05 to 2 mol% of a trifunctional or more polyfunctional compound, for example, trivalent or more, And further adding a compound having a phenol group. The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof. The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.

In embodiments, the weight average molecular weight (Mw) of the polycarbonate resin may be 10,000 to 50,000 g / mol, such as 15,000 to 40,000 g / mol. Within the above range, the thermoplastic resin composition can have excellent processability, impact resistance, flame retardancy, heat resistance and the like.

(B) a rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention can improve the impact resistance, fluidity, and the like of the thermoplastic resin composition, and can be obtained by copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer Can be used.

In the specific examples, the rubber-modified vinyl-based graft copolymer can be polymerized by adding an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer to the rubbery polymer, and the polymerization can be carried out by emulsion polymerization, Polymerization, and the like.

In the specific examples, the rubbery polymer includes a diene rubber such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubber in which hydrogen is added to the diene rubber, isoprene rubber, polybutylacrylic acid And an ethylene-propylene-diene monomer terpolymer (EPDM). For example, a diene rubber can be used, and specifically, a butadiene rubber can be used. The content of the rubbery polymer may be 5 to 65% by weight, for example, 10 to 60% by weight, specifically 20 to 50% by weight, based on 100% by weight of the total rubber-modified vinyl-based graft copolymer. The average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 탆, for example, 0.15 to 4 탆, specifically 0.25 to 3.5 탆. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery copolymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- But are not limited to, styrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. Specifically, styrene or the like can be used. The content of the aromatic vinyl monomer may be 15 to 94% by weight, for example, 20 to 80% by weight, specifically 30 to 60% by weight, based on 100% by weight of the entire rubber-modified vinyl-based graft copolymer. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile, (meth) acrylic acid and alkyl esters thereof, maleic anhydride , And N-substituted maleimide. These may be used alone or in combination of two or more. Specifically, methyl methacrylate, acrylonitrile, a combination of these, and the like can be used. The content of the monomer copolymerizable with the aromatic vinyl monomer may be 1 to 50% by weight, for example, 5 to 45% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the entire rubber modified vinyl-based graft copolymer . In the above range, the impact resistance, fluidity, appearance and the like of the thermoplastic resin composition can be excellent.

In a specific example, non-limiting examples of the rubber-modified vinyl-based graft copolymer include a styrene monomer which is an aromatic vinyl compound and a copolymer in which methyl methacrylate is grafted as a monomer copolymerizable therewith (g -MBS), a copolymer obtained by grafting an aromatic vinyl compound styrene monomer and an acrylonitrile monomer, which is a vinyl cyanide compound, to a butadiene rubber-like polymer, and the like (g-ABS). When the g-MBS is used, the appearance characteristics such as transparency of the thermoplastic resin composition can be further improved.

In an embodiment, the rubber-modified vinyl-based graft copolymer may be contained in an amount of 1 to 40 parts by weight, for example, 10 to 30 parts by weight, based on 100 parts by weight of the polycarbonate resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

(C) Fluorinated olefin resin

The fluorinated olefin based resin according to one embodiment of the present invention is capable of reducing the melt viscosity of the thermoplastic resin composition during burning and preventing the dropping phenomenon. Examples of the fluorinated olefin based resin include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene Ethylene / vinylidene fluoride copolymers, tetrafluoroethylene / hexafluoropropylene copolymers, ethylene / tetrafluoroethylene copolymers, combinations thereof, and the like, but are not limited thereto. For example, polytetrafluoroethylene (trade name: Teflon) having a particle size of 0.05 to 1,000 μm and a specific gravity of 1.2 to 2.3 g / cm ³ can be used.

In embodiments, the fluorinated olefinic resin may be prepared using known polymerization methods and may be prepared in an aqueous medium containing, for example, a free radical-forming catalyst such as sodium, potassium, ammonium peroxydisulfate, have.

In an embodiment, the fluorinated olefin-based resin may be used in an emulsion state or a powder state. The fluorinated olefin-based resin in the emulsion state is excellent in dispersibility, but the production process is complicated. Therefore, it is preferable to use the fluorinated olefin-based resin in powder form so long as it can be appropriately dispersed in the whole resin composition even in the powder state.

In an embodiment, the fluorinated olefin resin may be contained in an amount of 0.1 to 5 parts by weight, for example, 0.5 to 3 parts by weight, based on 100 parts by weight of the polycarbonate resin. The flame retardancy and the like of the thermoplastic resin composition may be excellent in the above range.

(D) Phosphorous flame retardant

(D1) Phosphorus compound

The phosphorus compound according to one embodiment of the present invention is used together with a phosphate ester compound to improve the flame retardance, impact resistance, physical properties and balance of the thermoplastic resin composition even at a low content, .

[Chemical Formula 1]

Wherein A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms substituted with a functional group containing at least one of a hydroxyl group, an alkoxy group, an aryloxy group and a carboxyl group, R ₁ and R ₂ , R ₃ and R ₄ are each independently a halogen atom such as a chlorine atom (Cl), a fluorine atom (F) or a bromine atom (Br) or a hydrocarbon group having 1 to 5 carbon atoms, and a, b, Each independently an integer of 0 to 4, and n is 0 or 1.

In an embodiment, the phosphorus compound may have an asymmetric structure and / or a gemini structure (both symmetrical structure).

In an embodiment, the phosphorus compound may include at least one of the compounds represented by the following general formulas (1a), (1b), (1c) and (1d).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

(D2) phosphate ester compound

As phosphate ester compounds according to one embodiment of the present invention, phosphate compounds, phosphonate compounds and the like other than the phosphorus compounds may be used singly or in combination of two or more. For example, the phosphate compound may be represented by the following formula (2).

(2)

In Formula 2, R ₅ and R ₉ are each independently a hydrogen atom, C6-C20 (C 6 -C 20) aryl group, or an aryl group of C1-C10 with C6-C20 alkyl group is substituted for a, R _6, and R ₈ are each independently a group of a hydrogen atom, a hydroxy group, C6-C20 aryl or aryloxy group, or an aryl group, or an aryloxy C1-C10 with C6-C20 alkyl group is substituted for, R ₇ is a C6-C20 Arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, for example, those derived from an aromatic dialcohol such as resorcinol, hydroquinone, bisphenol-A, or bisphenol-S (a portion excluding an alcohol) M is a number average degree of polymerization, and the average value of m is 0 to 3.

In an embodiment, non-limiting examples of the phosphoric ester compound include diaryl phosphates such as diphenyl phosphate, diphenyl phenyl phosphonate, triphenyl phosphate, tricresyl phosphate, triazylenyl phosphate, tri (2, (2,4-ditertiary butylphenyl) phosphate, tri (2,6-dimethylphenyl) phosphate, bisphenol-A bis (2,4-ditertiary butylphenyl) phosphate], resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis Hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], and hydroquinone bis [bis (2,4-ditertiary butylphenyl) phosphate]. The aromatic phosphoric acid compounds may be used alone or in the form of a mixture of two or more thereof.

The phosphorus flame retardant (D) of the present invention is obtained by mixing the phosphorus compound (D1) and the phosphoric acid ester compound (D2) in a weight ratio (D1: D2) of 1: 5 to 1:20, As shown in FIG. When the weight ratio of the phosphorus compound and the phosphoric acid ester compound is less than 1: 5, the flame retardancy of the thermoplastic resin composition may fall below V-1 on the basis of the UL94 test. When the weight ratio is more than 1:20, Heat resistance, mechanical properties, and the like may be lowered.

In an embodiment, the phosphorus flame retardant may be included in an amount of 1 to 30 parts by weight, for example, 5 to 20 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the flame retardancy, impact resistance, heat resistance, and physical properties of the thermoplastic resin composition can be excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further contain conventional additives as required. Examples of the additives include, but are not limited to, inorganic fillers, antioxidants, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, the content thereof may be 0.01 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention is excellent in flame retardance, impact resistance, heat resistance, appearance, physical properties and balance, and is environmentally friendly because it does not use a halogen-based flame retardant. A 1.5 mm thick specimen may have a flame retardancy greater than V-0.

In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of a 1/8 "thick specimen measured according to ASTM D256 of 25 to 70 kgf · cm / cm, for example, 30 to 60 kgf · cm / cm have.

In a specific example, the thermoplastic resin composition may have a heat distortion temperature (HDT) measured according to ASTM D648 of 80 to 110 ° C, for example, 90 to 110 ° C.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, after mixing the above components and other additives as necessary, they may be melt-extruded in an extruder to produce pellets. The produced pellets can be produced into various molded articles (products) through molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in flame retardancy even at a thin thickness, and is excellent in heat resistance, impact resistance, fluidity, balance of physical properties, etc., and therefore is useful as an automobile part, a part of an electric and electronic product,

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example

The specifications of each component used in the following examples and comparative examples are as follows:

(A) Polycarbonate resin

Bisphenol-A type polycarbonate resin (manufacturer: Samsung SDI, weight average molecular weight: 25,000 g / mol) was used.

(B) a rubber-modified vinyl-based graft copolymer

(B1) g-MBS (manufacturer: Kureha, product name: EXL-2602) was used.

(B2) g-ABS prepared by graft-copolymerizing 42 wt% of styrene and 18 wt% of acrylonitrile was used in 40 wt% of polybutadiene rubber (average particle diameter: 300 nm).

(C) Fluorinated olefin resin

Polytetrafluoroethylene (manufacturer: Dupont, product name: 7AJ) was used.

(D) Phosphorous flame retardant

(D1) A phosphorus compound represented by the following formula (1a) (manufacturer: Sanko, product name: HCA-HQ) was used.

[Formula 1a]

(D2) A phosphorus compound represented by the following formula (1d) (manufacturer: Albemarle, product name: XP-7866) was used.

≪ RTI ID = 0.0 &

Bisphenol-A bis (diphenylphosphate) (manufacturer: Yoke chemical) was used as the phosphoric acid ester compound (D3).

Resinocinol bis [bis (2,6-dimethylphenyl) phosphate] (manufacturer: DAIHACHI, product name: PX-200) was used as the (D4) phosphate ester compound.

Example  1 to 3 and Comparative Example  1 to 5

The components were mixed in a tumbler mixer for 10 minutes and then added to a twin screw type extruder having an L / D of 44 and a diameter of 45 mm according to the composition and content of the following Table 1, And then melted and extruded at 250 rpm to prepare pellets. The prepared pellets were dried at 80 ° C. for 5 hours or more and then injection molded at 250 ° C. using an injection machine (LG Cable, product name: LGH-140N) to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Evaluation of flame retardancy: UL9-4 The flame retardancy and burning time (unit: second) of a specimen having a thickness of 1.5 mm were measured by a vertical test method.

(2) Notch Izod impact strength (unit: kgf cm / cm): Based on the evaluation method described in ASTM D256, the notched Izod impact strength of a 1/8 "thick Izod sample was measured.

(3) Evaluation of heat resistance: According to ASTM D648, the heat distortion temperature (HDT, unit: 占 폚) was measured under a load of 1.8 MPa and a heating rate of 120 占 폚 / hr.

(4) Appearance evaluation: The surface of the specimen having a size of 10 cm x 10 cm was visually observed, and sensory evaluation was performed as follows.

?: Appearance good (without gas generation),?: Appearance deterioration due to gas generation partially around the gate,?: Degradation of appearance due to generation of gas as a whole of the specimen

Example Comparative Example One 2 3 One 2 3 4 (A) (parts by weight) 100 100 100 100 100 100 100 (B1) (parts by weight) 22.5 - 22.5 22.5 - 22.5 22.5 (B2) (parts by weight) - 22.5 - - 22.5 - - (C) (parts by weight) 1.4 1.4 1.4 1.4 1.4 1.4 1.4 (D1) (parts by weight) 1.4 1.4 - - - 12 12 (D2) (parts by weight) - - 1.4 - - - 1.4 (D3) (parts by weight) 10 10 10 12 12 1.4 - (D4) (parts by weight) - - 1.4 1.4 - - 1.5 mm V Flame retardancy V-0 V-0 V-0 V-1 V-1 V-0 V-0 Burning time (seconds) 25 25 22 49 53 20 18 Notch Izod impact strength (kgf · cm / cm) 40.4 50.0 45.2 13.6 15.2 12.3 13.4 Heat deformation temperature (캜) 108 108 108 101 100 102 103 Appearance evaluation ○ ○ ○ ○ ○ × △

From the above results, it can be seen that the flame retardant thermoplastic resin composition according to the present invention is superior in flame retardancy, impact resistance, heat resistance, appearance, and physical properties.

On the other hand, in the case of Comparative Example 1 and Comparative Example 2 in which phosphoric acid ester compound alone was used without using a phosphorus compound and phosphoric acid ester compound in the same amount of phosphorus flame retardant, flame retardancy and impact resistance were both lowered, In Comparative Example 3 in which an excess amount of the compound was used, it was found that a large amount of gas was generated during injection molding to be deposited in the appearance of the injection specimen and the impact resistance was lowered. In Comparative Example 4 using only the phosphorus compound, It is evident that a large amount of gas is generated and deposited on the outer surface of the injection specimen, and the impact resistance and the like are lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

Polycarbonate resin;
Rubber-modified vinyl-based graft copolymer;
Fluorinated olefinic resins; And
A phosphorus-containing flame retardant comprising a phosphorus compound represented by the following formula (1) and a phosphate ester compound other than the phosphorus compound,
Wherein the weight ratio of the phosphorus compound and the phosphate ester compound is 1: 5 to 1:20.
[Chemical Formula 1]

Wherein A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms substituted with a functional group containing at least one of a hydroxyl group, an alkoxy group, an aryloxy group and a carboxyl group, R ₁ and R _2, R ₃ and R ₄ are each independently a hydrocarbon group or a halogen atom having 1 to 5, a, b, c and d are each independently an integer of 0 to 4, n is 0 or 1.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 100 parts by weight of the polycarbonate resin, 1 to 40 parts by weight of the rubber-modified vinyl-based graft copolymer, 0.1 to 5 parts by weight of the fluorinated olefin resin, 30 parts by weight of a thermoplastic resin composition.
The thermoplastic resin composition according to claim 1, wherein the rubber-modified vinyl-based graft copolymer is a copolymer obtained by graft-polymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubbery polymer.
The thermoplastic resin composition according to claim 1, wherein the phosphorus compound has an asymmetric structure.
The thermoplastic resin composition according to claim 1, wherein the phosphorus compound has a gemini structure.
The phosphorous compound according to claim 1, wherein the phosphorus compound comprises at least one compound selected from the group consisting of a compound represented by the following formula (1a), a compound represented by the following formula (1b), a compound represented by the following formula (1c) and a compound represented by the following formula By weight of the thermoplastic resin composition.
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

The thermoplastic resin composition according to claim 1, wherein the phosphoric acid ester compound is represented by the following formula (2)
(2)

In Formula 2, R ₅ and R ₉ are each independently an aryl group of hydrogen, C6-C20 aryl group, or a C1-C10 with C6-C20 alkyl group is substituted for, R ₆ and R ₈ are each independently is a hydrogen atom, a hydroxy group, C6-C20 aryl group or aryloxy group, or an aryl group, or an aryloxy C1-C10 with C6-C20 alkyl group is substituted, the R ₇ is a C6-C20 aryl group or a C1-C10 C20 arylene group in which the alkyl group is substituted, and the average value of m is 0 to 3. [
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured by a UL-94 vertical test method.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notch Izod impact strength of 1/8 "thick specimen measured according to ASTM D256 of 25 to 70 kgf · cm / cm.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a heat distortion temperature (HDT) of 80 to 110 ° C as measured according to ASTM D648.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 10.