KR20180067291A - Polymer resin composition and molded product of the same - Google Patents

Abstract

The present invention relates to a polymer resin composition, which has excellent flame retardancy and insulation properties and can attain improved mechanical properties, and to a molded product thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer resin composition,

The present invention relates to a polymer resin composition and a molded article thereof. More particularly, the present invention relates to a polymeric resin composition which is excellent in compatibility between components and has improved mechanical properties such as heat resistance and tensile strength and molding processability, and a molded product thereof.

Recently, materials for housing electrical and electronic parts used in home appliances are required to have excellent flame retardancy and excellent insulation properties, for example, a comparative tracking index (CTI) and a glow wire temperature (GWT).

Conventionally, materials such as flame retardant polybutylene terephthalate (PBT) or polyamide (PA) have been mainly used as materials for housing electrical and electronic parts. There was a difficult limit.

In order to solve this problem, research on a method of blending a polyester resin and a polycarbonate resin, which are compatible resins, has continued. Polycarbonate resins have self-extinguishing properties and are excellent in flame retardancy and fire resistance. They are used in various building materials and various appearance fields of electronic products, packaging materials, cases, boxes, interior and exterior materials, and the like.

On the other hand, polyester resins are widely used for reinforced plastics, paints, films, molding resins and the like because of their excellent heat resistance, mechanical strength and elastic strength, and they are also used as textile materials for clothing. There is a limit in that it is difficult to sufficiently realize flame retardancy and insulation properties apart from thermal stability.

Accordingly, development of a polymer resin composition capable of achieving stable mechanical properties while simultaneously realizing excellent flame retardancy and insulation properties is required.

The present invention provides a polymer resin composition having excellent flame retardancy and insulation properties and capable of achieving improved mechanical properties and a molded product thereof.

In this specification, polycarbonate resin; A silicone-polyester copolymer resin containing repeating units represented by the following formulas (1) to (3); And at least two kinds of flame retardants, wherein the content of the silicone-polyester copolymer resin is 5 to 80 parts by weight based on 100 parts by weight of the polycarbonate resin.

[Chemical Formula 1]

(2)

(3)

In the general formulas (1), (2) and (3), Ar ¹ is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, R ¹ is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R ² is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms, Y is -O-, -NH- or -S-, u is an integer of 0 or 1, and R ³ to R ⁶ Is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 18 carbon atoms, and D ¹ and D ² are each independently substituted or unsubstituted L ¹ and L ² are each independently a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, n is an integer of 5 to 200, and p and q is independently an integer of 0 or 1;

The present invention also provides a molded article comprising the polymeric resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION The polymer resin composition and molded articles thereof according to specific embodiments of the present invention will be described in detail below.

According to one embodiment of the invention, a polycarbonate resin; A silicone-polyester copolymer resin containing repeating units represented by the following formulas (1) to (3); And at least two kinds of flame retardants, wherein the content of the silicone-polyester copolymer resin is 5 parts by weight to 80 parts by weight based on 100 parts by weight of the polycarbonate resin.

The present inventors have found that when the above-mentioned specific polymer resin composition is used, two or more kinds of flame retardants are added while mixing a specific silicone-polyester copolymer resin together with a polycarbonate resin, , It is possible to produce a polymer resin composition having improved mechanical properties.

Particularly, the silicone-polyester copolymer resin to be mixed together with the polycarbonate resin in the polymer resin composition contains a silicone-based recurring unit having a polysiloxane bond in the molecular structure unlike the conventionally used polyester resin, Impact strength can be realized, stable flame retardancy and moldability can be ensured with improved insulation characteristics.

The silicone-polyester copolymer resin may be used in an amount of 5 to 80 parts by weight, or 5 to 50 parts by weight, or 15 to 80 parts by weight, or 15 to 80 parts by weight, based on 100 parts by weight of the polycarbonate resin, By weight to 50 parts by weight, so that the flame-retardant property of the polycarbonate resin can be realized, and the mechanical properties, heat resistance and insulation properties of the silicone-polyester copolymer resin can be realized.

In addition, in the polymer resin composition, two or more kinds of flame retardants may be mixed and added for the purpose of improving the flame retardancy, so that the flame retardancy can be improved as compared with the case where only one type of flame retardant is added.

Hereinafter, the polymer resin composition of one embodiment will be described in more detail.

The silicone-polyester copolymer resin

The polymer resin composition of one embodiment may include a silicone-polyester copolymer resin. The silicone-polyester copolymer resin may include repeating units represented by the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

In the above formulas (1), (2) and (3)

Ar ¹ is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms,

R ¹ is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 10 carbon atoms,

R ² is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,

Y is -O-, -NH- or -S-,

u is an integer of 0 or 1,

R ³ to R ⁶ are each independently a substituted or unsubstituted, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms,

D ¹ and D ² are each independently a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,

L ¹ and L ² each independently represent a substituted or unsubstituted arylene group having 6 to 18 carbon atoms,

n is an integer between 5 and 200,

p and q are each independently an integer of 0 or 1;

Unless defined otherwise herein, the following terms may be defined as follows.

The straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms includes, for example, a straight chain alkyl group such as methyl group, ethyl group, n-propyl group and n-butyl group; a branched chain alkyl group such as an isopropyl group and a t-butyl group; And a cyclic alkyl group such as a cyclohexyl group.

Examples of the straight chain, branched chain or cyclic alkylene group having 1 to 10 carbon atoms include linear alkylene groups such as an ethylene group, an n-propylene group and an n-butylene group; A branched chain alkylene group such as a neopentylene group; A cyclohexylene group, a cyclohexylene dimethylene group, and other cyclic alkylene groups.

The aryl group having 6 to 18 carbon atoms is an arylalkyl group and may include, for example, a phenyl group, a naphthyl group, a benzyl group, a methylphenyl group, and the like.

The arylene group having 6 to 18 carbon atoms is a term including an alkylenearylene group and may include, for example, a phenylene group, a naphtylene group, a methylenephenylene group and the like .

The substituents described above may be substituted with any substituent within the range of exhibiting the same or similar effect as the desired effect. As a non-limiting example, the substituents may be substituted with a hydroxyl group, a carboxyl group, a halogen, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms,

The silicone-polyester copolymer resin containing the repeating units represented by the above formulas (1) to (3) has improved inherent physical properties as compared with the conventional poly (cyclohexylene dimethylene terephthalate) resin and has excellent insulation properties such as impact strength, elongation, And a molded resin article having improved physical properties such as moldability and workability.

The silicone-polyester copolymer resin containing the repeating units represented by formulas (1) to (3) can be prepared by esterifying a diol compound with a polysiloxane with a dicarboxylic acid, or by transesterifying a diol compound with a polysiloxane with a dicarboxylic acid ester compound have. Through the esterification reaction or transesterification reaction, a repeating unit of the formula (1) is formed from a dicarboxylic acid or a dicarboxylic acid ester compound, a repeating unit of the formula (2) is formed from a diol compound, and a repeating unit of the formula .

Examples of the dicarboxylic acid for polymerizing the silicone-polyester copolymer resin include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid 2 , 6-NDA) or a mixture thereof may be used. As the dicarboxylic acid ester compound, dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), dimethyl 2,6-naphthalenedicarboxylate dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC) or mixtures thereof. For example, when terephthalic acid is used in an amount of 90 wt% or more based on the total amount of the dicarboxylic acid, or when dimethyl terephthalate is used in an amount of 90 wt% or more based on the total amount of the dicarboxylic acid ester compound, It is possible to provide a resin composition which maintains initial physical properties at an excellent level even in a high humidity environment and exhibits excellent crystallinity at low temperature molding. Accordingly, at least 90% by weight of the repeating unit represented by the formula (1) is a repeating unit derived from terephthalic acid, wherein Ar ^{1 in the} formula ( ¹⁾ is a 1,4-phenylene group.

Examples of the diol compound for polymerizing the silicone-polyester copolymer resin include one selected from the group consisting of cyclohexane dimethanol, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol and neopentyl glycol Or more can be used. For example, when cyclohexanedimethanol is used in an amount of 90 wt% or more based on the total amount of the diol compound, a resin composition having excellent heat resistance, weather resistance, reflectivity and vulcanization resistance and exhibiting excellent crystallinity at low temperature molding can be provided. Accordingly, at least 90% by weight of the repeating units represented by the general formula (2) is a repeating unit derived from cyclohexane dimethanol, wherein R ^{1 in the general} formula (2) is cyclohexylene dimethylene and u is 0.

As the polysiloxane for polymerizing the silicone-polyester copolymer resin, a polysiloxane represented by the following formula (4) can be used.

[Chemical Formula 4]

In the above formula (4), the definition of each symbol is as shown in formula (3).

Specifically, R ³ to R ⁶ in the general formula (3) or (4) independently represent an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; Or an aryl group such as a phenyl group or a naphthyl group. The hydrogen of the alkyl group or the aryl group may be substituted with an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the like.

In Formula 3 or 4, D ¹ and D ² each independently represent an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, and the hydrogen of the alkylene group may have 1 to 5 carbon atoms An alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the like.

In Formula 3 or 4, p and q are each independently an integer of 0 or 1, and when p is 1, L ¹ may be a phenylene group, and when q is 1, L ² may be a phenylene group. The hydrogen of the phenylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the like.

In Formula 3 or 4, n may be represented by various integers ranging from 5 to 200, depending on the molecular weight of the polysiloxane.

The repeating unit represented by the formula (3) derived from the polysiloxane may be contained in the polyester resin in an appropriate amount to provide a resin composition having excellent mechanical properties and improved insulation characteristics. For example, the silicone-polyester copolymer resin may contain 0.1 to 25% by weight, 0.1 to 25% by weight of the repeating unit represented by the formula (3) based on the total weight of the repeating unit represented by the formula (2) By weight or 15% by weight or 0.1% by weight to 10% by weight, to provide a resin composition having improved mechanical properties such as impact strength and elongation, and improved insulation properties such as a comparative tracking index and molding processability.

The repeating unit represented by Formula 3 may be used in an amount of 0.1 to 30 wt%, 0.1 to 25 wt%, 1 wt% to 20 wt%, or 1 wt% to 15 wt% based on the total weight of the silicone- , It is possible to provide a resin composition capable of fully manifesting the effect of improving the impact strength upon introduction of the repeating unit derived from the polysiloxane and stably discharging the resin from the inside of the reactor.

The silicone-polyester copolymer resin containing the repeating units represented by the above formulas (1) to (3) has a high melting point of 200 ° C or more or 250 ° C or more and can exhibit excellent heat resistance. The silicone-polyester copolymer resin is not particularly limited, but it may have a melting point of 350 DEG C or less, for example.

The silicone-polyester copolymer resin containing the repeating units of the formulas (1) to (3) has an intrinsic viscosity of 0.4 dL / g to 1.5 dL / g calculated from the viscosity measured at 35 ° C after dissolving in o- . Thus, a resin composition having appropriate moldability and processability can be provided. As a specific method of measuring the intrinsic viscosity, reference may be made to the contents described in the following Production Examples.

The silicone-polyester copolymer resin comprising the repeating units of Formulas 1 to 3 has a weight average molecular weight of 10,000 g / mol to 100,000 g / mol or 30,000 g / mol to 80,000 g / mol; A number average molecular weight of from 10,000 g / mol to 50,000 g / mol or from 15,000 g / mol to 35,000 g / mol can be provided to exhibit appropriate mechanical properties.

Such a silicone-polyester copolymer resin may be prepared by esterifying a diol compound and a polysiloxane with a dicarboxylic acid, or transesterifying a diol compound and a polysiloxane with a dicarboxylic acid ester compound; And condensation polymerization of the reaction product obtained in the above step.

Specific examples and contents of the diol compound, polysiloxane, dicarboxylic acid and dicarboxylic acid ester compound have been described above, and therefore, detailed description thereof is omitted here.

In the esterification reaction or transesterification step, a diol compound and a polysiloxane are esterified with a dicarboxylic acid in the presence of a catalyst commonly used in the technical field of the present invention, or a diol compound and a polysiloxane are reacted with a dicarboxylic acid ester compound Ester exchange reaction can be carried out.

Nonlimiting examples of such catalysts include titanium-based catalysts. Examples of the titanium-based catalysts include titanium oxide, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra- Isobutyl titanate, and butyl-isopropyl titanate.

Further, in the esterification reaction or transesterification reaction step, a phosphorus stabilizer may be further added at the initial stage of the reaction to effectively suppress the side reactions that may occur during the esterification reaction or the transesterification reaction at a high temperature.

Phosphorus stabilizers which may be used herein include phosphoric acid and phosphorous acid such as phosphoric acid and triethyl phosphate, trimethyl phosphate, triphenyl phosphate, triethylphosphate, Phosphoric acid ester compounds such as triethyl phosphonoacetate can be used.

In the esterification or transesterification step, other additives commonly employed in the technical field of the present invention may be used in addition to the above-mentioned components. The esterification reaction or the transesterification reaction can be carried out under the reaction conditions usually employed in the technical field of the present invention.

In the condensation polymerization step, a reaction product obtained in an esterification reaction or an ester exchange reaction step is intensively polymerized to provide a silicone-polyester copolymer resin having a desired molecular weight. If necessary, a step of forming a pellet by molding a polycondensation reaction product after the polycondensation step and / or a step of solid-phase polymerization by crystallizing the polycondensation reaction product or pellet are further employed to form a silicone-polyester copolymer Resin can be produced.

For the concrete production method of the silicone-polyester copolymer resin containing the repeating units represented by the above formulas (1) to (3), the contents described in the following Production Examples can be referred to. However, the manufacturing method of the silicone-polyester copolymer resin is not limited thereto, and various methods known to those skilled in the art can be employed.

The content of the silicone-polyester resin may be 1 wt% to 35 wt%, or 5 wt% to 30 wt%, or 5 wt% to 25 wt% based on the total weight of the polymeric resin composition.

Polycyclohexylene dimethylene terephthalate resin

The polymer resin composition of one embodiment may further include a polycyclohexylene dimethylene terephthalate resin together with a silicone-polyester copolymer resin. The polycyclohexylidene methylene terephthalate resin has a higher crystallization speed than PBT but is much faster than PET and can be injection molded, has high heat resistance and relatively high price competitiveness, has a high possibility of potential use, , And has a low water absorption rate as compared with the PA-based polymer and is excellent in heat discoloration resistance.

Accordingly, when the polymeric resin composition of the present invention further includes the polycyclohexylenedimethylene terephthalate resin together with the silicone-polyester copolymer resin, the technical effect of further improving the heat resistance and the mechanical strength while maintaining the impact strength Can be implemented.

Specifically, the polymeric resin composition of one embodiment comprises 10 to 500 parts by weight, or 10 to 50 parts by weight of polycyclohexylenedimethylene terephthalate resin, based on 100 parts by weight of the silicone-polyester copolymer resin, Or 300 parts by weight to 500 parts by weight.

The heat distortion temperature of the polycyclohexylenedimethylene terephthalate resin is higher than the heat distortion temperature of the silicone-polyester copolymer resin. This makes it excellent in resistance to deformation due to external forces at high temperatures.

 Specifically, the heat distortion temperature of the polycyclohexylenedimethylene terephthalate resin is 10 ° C to 15 ° C higher than the heat distortion temperature of the silicone-polyester copolymer resin, and the resin composition containing the polycyclohexylenedimethylene terephthalate The heat resistance characteristics of the heat sink can be improved.

The heat distortion temperature can be measured using a heat distortion temperature tester by making test specimens according to ASTM D 648

Examples of the method for producing the PCT resin are not limited. For example, the PCT resin may be obtained by an esterification reaction between a dicarboxylic acid and a diol compound, or by an ester exchange reaction between a dicarboxylic acid ester compound and a diol compound .

The dicarboxylic acid may include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (2,6-NDA), or mixtures thereof. have. As an example, at least 90 parts by weight of the total dicarboxylic acid may be terephthalic acid. The dicarboxylic acid may include dicarboxylic acid other than terephthalic acid in an amount of 10 parts by weight or less based on the total dicarboxylic acid. In particular, when the total dicarboxylic acid is terephthalic acid, a resin composition having excellent weather resistance and vulcanization resistance can be provided.

The dicarboxylic acid ester compound includes dimethyl terephthalic acid, dimethylisophthalate (DMI), dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC), or a mixture thereof. can do. As an example, at least 90 parts by weight of the total dicarboxylic acid ester compound may be dimethyl terephthalic acid. The dicarboxylic acid ester compound may contain other dicarboxylic acid ester compounds in an amount of not more than 10 parts by weight based on the total dicarboxylic acid ester compound. In particular, when the total dicarboxylic acid ester compound is dimethylterephthalic acid, a resin composition having excellent weather resistance and vulcanization resistance can be provided.

The diol compound may include at least one member selected from the group consisting of cyclohexane dimethanol, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and neopentyl glycol. As an example, at least 90 parts by weight of the total diol compound may be cyclohexanedimethanol. And, the diol compound may contain not more than 10 parts by weight of the total diol compound and other diol compounds other than cyclohexanedimethanol. Particularly, even in the case of the diol compound, when the entire diol compound is cyclohexane dimethanol, it is possible to provide a resin composition having more excellent weather resistance and vulcanization resistance.

On the other hand, a PCT resin can be prepared by further adding a phosphorus stabilizer at the beginning of the esterification reaction or transesterification reaction. As a result, it is possible to effectively suppress side reactions that may occur during the esterification reaction or the transesterification reaction at a high temperature.

Phosphorus stabilizers which may be used herein include phosphoric acid and phosphorous acid such as phosphoric acid and triethyl phosphate, trimethyl phosphate, triphenyl phosphate, triethylphosphate, Phosphoric acid ester compounds such as triethyl phosphonoacetate can be used.

The PCT resin may be polymerized in addition to the above-mentioned compounds by using other additives commonly used in the technical field of the present invention. In addition, the PCT resin can be polymerized using such components by a method commonly employed in the art to which the present invention belongs. As a non-limiting example, the PCT resin may be obtained by esterifying a dicarboxylic acid and a diol compound or a transesterification reaction of a dicarboxylic acid ester compound and a diol compound in the presence of the catalyst described above; And polycondensing the reaction product obtained by the reaction. The PCT resin may further include, if necessary, shaping the polycondensation reaction product to form pellets; And / or crystallizing the polycondensation reaction product or pellet to solid-state polymerize.

Preferably, the polycyclohexylenedimethylene terephthalate resin includes a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit represented by the following formula (5). Specifically, a SKYPURA product manufactured by SK Chemicals may be used.

[Chemical Formula 5]

The content of the polycyclohexylenedimethylene terephthalate resin may be 1 wt% to 35 wt%, or 5 wt% to 30 wt%, or 5 wt% to 20 wt% based on the total weight of the polymer resin composition .

Polycarbonate resin

The polycarbonate resin may include a polycarbonate resin having a melt flow index (300 캜, 1.2 kg load) measured by ASTM D1238 of more than 30 g / 10 min. Specific examples of the polycarbonate resin having a melt flow index (300 캜, 1.2 kg load) of more than 30 g / 10 min, or more than 30 g / 10 min and less than 300 g / 10 min measured by the ASTM D1238 include TRIREX 3017PJ .

The Melt mass-Flow Rate (MFR) is a measure of the fluidity of the polymer material. A large MFR means a low viscosity, and a small MFR means a large viscosity. In the case of the same material, it is known that the smaller the MFR, the higher the breaking point of the tensile strength, the elongation, the impact strength, and the environmental stress cracking resistance.

The content of the polycarbonate resin may be 40 wt% to 90 wt%, or 50 wt% to 70 wt%, or 55 wt% to 65 wt% based on the total weight of the polymer resin composition.

The polycarbonate may have a glass transition temperature of 50 ° C to 200 ° C and a weight average molecular weight of 10,000 g / mol to 200,000 g / mol. The glass transition temperature can be confirmed through DSC measurement data. For example, the polycarbonate resin is maintained at 300 DEG C for 5 minutes, slowly cooled to room temperature, and then resampled at a heating rate of 10 DEG C / min to measure Method or the like can be used. If the weight average molecular weight of the polycarbonate resin is less than 10,000 g / mol, mechanical properties such as impact strength and tensile strength may be significantly deteriorated. If the polycarbonate resin is more than 200,000 g / mol, molding workability may decrease due to an increase in melt viscosity . An example of the method of measuring the weight average molecular weight is not particularly limited, but the weight average molecular weight in terms of polystyrene measured by the GPC method can be used.

Specifically, the polycarbonate resin means a polymer containing a carbonate functional group, for example, a linear polycarbonate resin, a branched polycarbonate resin, a copolycarbonate resin, a polyester carbonate resin, or a mixture of two or more thereof Can be used. The polycarbonate resin, the method for producing the polycarbonate resin, and the use of the polycarbonate resin may be used without limitation for the thermoplastic aromatic polycarbonate resin that is commonly used in the field. To give a concrete example, the aromatic polycarbonate resin may be prepared from a divalent phenol, a carbonate precursor and a molecular weight modifier. Examples of the dihydric phenols include, but are not limited to, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis Bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- And the like.

Examples of the carbonate precursor include, but are not limited to, carbon monomers such as carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate and the like as another monomer constituting the aromatic polycarbonate resin .

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the thermoplastic aromatic polycarbonate resin may be used. Examples of molecular weight regulators include phenol based derivatives such as para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumylphenol, para-isooctylphenol, para-isononylphenol Etc.), aliphatic alcohols and the like.

Flame retardant

The polymer resin composition of one embodiment may include two or more flame retardants. Thus, it is possible to realize improved flame retardancy compared with the case where one type of flame retardant is added.

Specifically, the flame retardant may include a brominated polystyrene flame retardant and an antimony trioxide flame retardant.

The brominated polystyrene-based flame retardant may include a brominated polystyrene repeating unit. The brominated polystyrene repeating unit includes a repeating unit in which at least one bromine group is substituted on a benzene ring contained in the polystyrene repeating unit, and more specifically, may be represented by the following formula (6).

[Chemical Formula 6]

In the above formula (6), examples of the position where the bromine group is substituted are not limited to a great degree, and may be substituted at the para position based on the polystyrene repeating unit. The X-Guard FR803 product of Chempia may preferably be used as the brominated polystyrene flame retardant.

The antimony trioxide flame retardant may include antimony trioxide (Sb ₂ O ₃ ) as an internal component. Preferably, X-Guard ATO 910 product of Chempia can be used as the antimony trioxide flame retardant.

More specifically, the polymeric resin composition may contain 20 to 40 parts by weight, or 25 to 38 parts by weight, of an antimony trioxide flame retardant based on 100 parts by weight of a brominated polystyrene-based flame retardant.

On the other hand, the content of the two or more flame retardants may be 8 wt% to 30 wt%, or 8 wt% to 15 wt%, or 11 wt% to 15 wt% based on the total weight of the polymer resin composition.

Polymer resin composition

In the process of preparing the polymeric resin composition, conventional methods and apparatuses used for producing a blend or a mixture of polymeric resins can be used without limitation. For example, polycarbonate resin, silicone-polyester copolymer resin; And a flame retardant in a conventional mixer, a blender or a tumbler, and mixing the mixture through a twin-screw extruder, the polymer resin composition may be provided. In the course of producing the polymer resin composition, it is preferable that each of the resins is used in a sufficiently dried state.

The content of the silicone-polyester copolymer resin is 5 parts by weight to 80 parts by weight, or 5 parts by weight to 50 parts by weight, and 15 parts by weight, relative to 100 parts by weight of the polycarbonate resin, To 80 parts by weight, or 15 parts by weight to 50 parts by weight. As a result, it is possible to realize an excellent impact strength without adding an impact modifier, and it is possible to secure stable flame retardancy and moldability with improved insulation characteristics.

On the other hand, when the content of the silicone-polyester copolymer resin is reduced to less than 5 parts by weight based on 100 parts by weight of the polycarbonate resin, the impact strength may be lowered and the comparative tracking index may not be sufficiently secured.

When the content of the silicone-polyester copolymer resin is increased to more than 80 parts by weight based on 100 parts by weight of the polycarbonate resin, the mechanical strength may be lowered and flame retardancy may not be sufficiently secured.

The content of the flame retardant may be 10 parts by weight to 30 parts by weight, or 15 parts by weight to 25 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the flame retardant is added in an excessively small amount compared to the polycarbonate resin, it is difficult to sufficiently realize the flame retardant property, and when the flame retardant is added in excess to the polycarbonate resin, the mechanical properties and molding processability of the resin composition may be decreased.

Meanwhile, the polymer resin composition may further include a compatibilizing agent including a vinyl-based copolymer grafted with glycidyl (meth) acrylate, a vinyl-based copolymer substituted with a halogen, or a mixture thereof. With the inclusion of the compatibilizing agent, the compatibility between the components of the polymer resin composition can be enhanced and excellent molding processability can be ensured.

As used herein, '(meth) acrylic' is meant to include both acrylic and methacrylic.

Specifically, the glycidyl (meth) acrylate-grafted vinyl-based copolymer is obtained by copolymerizing an unsaturated nitrile-aromatic vinyl-glycidyl (meth) acrylate, an alkene-alkyl (meth) acrylate-glycidyl ) Acrylate copolymers or mixtures thereof.

The alkyl (meth) acrylate may be methyl acrylate, ethyl acrylate, propyl acrylate. Butyl acrylate, n-butyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate may be used.

Specifically, the unsaturated nitrile-aromatic vinyl-glycidyl (meth) acrylate copolymer may have a glass transition temperature of 20 ° C to 200 ° C and a weight average molecular weight of 200 to 300,000. The alkene-alkyl (meth) acrylate-glycidyl (meth) acrylate copolymer may have a glass transition temperature of -150 ° C to 200 ° C and a weight average molecular weight of 200 to 300,000.

An example of the unsaturated nitrile-aromatic vinyl-glycidyl (meth) acrylate copolymer is styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-GMA). Preferably, the styrene-acrylonitrile-glycidyl methacrylate copolymer may be a SAG-005 product of Sunny FC.

An example of the alkene-alkyl (meth) acrylate-glycidyl (meth) acrylate copolymer is ethylene-methyl methacrylate-glycidyl methacrylate copolymer.

On the other hand, the halogen-substituted vinyl-based copolymer may be an aromatic vinyl-unsaturated nitrile copolymer, an aromatic vinyl-diene-aromatic vinyl copolymer, an aromatic vinyl-alkene-alkene-aromatic vinyl copolymer, an aromatic vinyl- Vinyl copolymers, or mixtures of two or more thereof with halogen-substituted compounds.

In particular, examples of the aromatic vinyl-unsaturated nitrile copolymer include a styrene-acrylonitrile copolymer (SAN), and as the halogen-substituted compound of the aromatic vinyl-unsaturated nitrile copolymer, a fluorinated styrene acrylonitrile copolymer . Preferably, the fluorinated styrene acrylonitrile copolymer may be a FS200 product of Nanotech Co., Ltd.

Examples of the aromatic vinyl-diene-aromatic vinyl copolymer include styrene-butadiene-styrene copolymer (SBS), and examples of the aromatic vinyl-alkene-alkene-aromatic vinyl copolymer include styrene- - styrene copolymer (SEPS). Examples of the aromatic vinyl-alkene-diene-aromatic vinyl copolymer include styrene-ethylene-butadiene-styrene copolymer (SEBS).

The content of the compatibilizing agent may be 0.1 to 10 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the total polymer resin composition. If the amount of the compatibilizing agent is less than 0.1 part by weight based on 100 parts by weight of the polymer resin composition, the effect of improving the molding processability by the compatibilizing agent can be reduced, and if the content of the compatibilizing agent is 100 parts by weight If the amount is more than 10 parts by weight, the mechanical properties of the polymer resin composition may be reduced.

More specifically, the polymer resin composition may be a mixture of a vinyl copolymer in which glycidyl (meth) acrylate is grafted as a compatibilizing agent and a vinyl copolymer in which a halogen is substituted. In this case, 10 parts by weight to 40 parts by weight of a halogen-substituted vinyl copolymer may be used relative to 100 parts by weight of vinyl (meth) acrylate-grafted vinyl copolymer.

In addition, the polymer resin composition may further include an antioxidant. The antioxidant suppresses the yellowing of the polymer resin, thereby improving the appearance of the polymer resin composition and the molded article, and inhibiting oxidation or pyrolysis. If the content of the antioxidant is too low, the appearance of the polymer resin composition and the molded article may become poor. On the other hand, when the content of the antioxidant is excessively high, the mechanical properties of the polymer resin composition, particularly, the heat resistance and the like may be lowered.

Examples of the antioxidant include, but are not limited to, hindered phenol antioxidants, phosphorus antioxidants, phosphite antioxidants, thioester antioxidants, and mixtures of two or more thereof. The hindered phenol-based antioxidant may have a weight average molecular weight of 50 to 300,000, and preferably an AO-60 product of ADEKA.

In addition, examples of the phosphorus-based antioxidant are not limited to a great extent. For example, Irgafos 168 product of BASF can be used.

The phosphite antioxidant may include at least one selected from the group consisting of the following chemical formulas (33), (34), and (35).

(33)

In Formula 33, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

(34)

In Formula 34, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and n is an integer of 1 or more, Lt; / RTI >

(35)

In Formula 35, R ₁ , R ₂ , R _3, and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

Meanwhile, the thioester antioxidant may be a compound represented by the following chemical formula (36) or (37).

(36)

(37)

In the above Chemical Formulas 36 and 37, R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In addition, the polymeric resin composition may contain various known additives such as moisture release agents, nucleating agents, organic or inorganic fillers, plasticizers, chain extenders, ultraviolet stabilizers, coloring agents, matting agents, transesterification inhibitors, And may further contain various additives such as a coloring agent, a coupling agent, a deodorant, a flame retardant, a weathering additive, an antistatic agent, a releasing agent, an ion exchanger, a color pigment, an inorganic or organic particle, a lubricant, a light stabilizer,

Dewatering is a reactive compound capable of reacting with a hydroxyl group or a carboxyl group, which is a terminal component of a polymer, as well as the hydrolysis resistance and durability of the polymer resin composition. That is, the moisture release is applied to an ester resin such as polyester, polyamide or polyurethane to end-cap the end of the polymer chain to prevent hydrolysis of the resin composition by water or acid It plays a role. The moisture release may be a carbodiimide compound, for example, a modified poly (carbodiimide), poly (relacododiimide), poly (4,4'-diphenylmethanecarbodiimide), poly -Dimeryl-4,4'-biphenylcarbadodiimide), poly (P-phenylene carbodiimide), poly (m-phenylenecarbodiimide), poly (3,3'- Diphenylmethanecarbodiimide). The moisture release can be used within 5 parts by weight based on 100 parts by weight of the polymer resin composition.

The nucleating agent may be contained in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the polymer resin composition. When the amount is within the above range, heat resistance and injection moldability are improved. The nucleating agent may be a talc / organometallic salt mixture, a sorbic acid metal salt, a phosphate metal salt, a quinacridone, a calcium carboxylate, a montanic metal salt, an amide organic compound, talc and the like, preferably a talc / Lt; / RTI >

Examples of the plasticizer include phthalic acid ester plasticizers such as diaryl phthalate, dioleyl phthalate and dicyclohexyl phthalate; Aliphatic dibasic acid ester plasticizers such as adipic acid di-1-butyl, adipic acid di- eta -oleyl, sebacic acid di-n-butyl, and azelaic acid di-2-ethylhexyl; Phosphoric acid ester plasticizers such as diphenyl-2-phthalate, diphenyloctyl phosphate and the like; Hydroxy-polycarboxylic acid ester plasticizers such as tributyl acylate citrate, tri-2-ethynylhexyl acylate citrate, and tributyl citrate; Fatty acid ester type plasticizers such as meryl maleic acid, and amyl stearic acid; Polyhydric alcohol ester plasticizers such as glycerin triacetate; Epoxy-based plasticizers such as epoxidized soybean oil, epoxidized amami-oil fatty acid butyl ester, and epoxy stearic acid oats.

Examples of the colored pigments include inorganic pigments such as carbon black, titanium oxide, zinc oxide and iron oxide; Organic pigments such as cyanine pigments, phosphorus pigments, quinone pigments, lineron pigments, isoindolinone pigments, and thioindigo pigments.

The lubricant may be at least one selected from the group consisting of a metal stearate lubricant, an amide lubricant, a paraffin lubricant, and an ester lubricant.

The light stabilizer may be a halide-based light stabilizer, and the light absorber may be a benzotriazole-based light absorber or a benzophenone-based light absorber.

The transesterification inhibitor may be a phosphorus compound containing at least a hydroxyl functional group and an alkyl ester functional group, or a hydrazine compound containing a repeating unit represented by the following formula (38).

(38)

As the coupling agent, a compound containing a glycidyl methacrylate repeating unit may be used.

The polymeric resin composition may be molded by various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding and extrusion molding, and post-processing such as a heat molding process using the same, .

The polymeric resin composition may have a tensile strength of 570 kg / cm < 2 > or more as measured by ASTM D638. In addition, the polymer resin composition may have a heat distortion temperature measured by ASTM D648 of 107 ° C or higher. Accordingly, the polymer resin composition can achieve high tensile strength and heat resistance.

On the other hand, the polymer resin composition can be used as a material for components of automobiles, home appliances, and office machines that require excellent flame retardancy and electrical characteristics. Specifically, it relates to plastic parts of automobile related parts, relays, connector parts and household appliances, plastic parts related to refrigerator, plastic parts related to washing machine, air conditioner housing parts, office equipment related parts, Can be used.

According to another embodiment of the present invention, a molded article comprising the polymer resin composition of one embodiment may be provided.

The molded product may be produced by various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding and profile extrusion molding, and post-processing such as thermoforming using the molding method, Can be obtained by molding.

As described above, the molded article can be used as a material for components of automobiles, home appliances, and office machines that require excellent flame retardancy and electrical characteristics. Specifically, it relates to plastic parts of automobile related parts, relays, connector parts and household appliances, plastic parts related to refrigerator, plastic parts related to washing machine, air conditioner housing parts, office equipment related parts, Can be used.

The specific shape and size of the molded article may vary depending on the application, and examples thereof may be, for example, a shape such as a sheet, a container, or a pellet.

The content of the above-mentioned polymer resin composition includes the above-mentioned contents with respect to the above embodiment.

According to the present invention, it is possible to provide a polymer resin composition and a molded product thereof that have excellent flame retardance and insulation properties and can achieve improved mechanical properties.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Preparation Example: Preparation of silicone-PCT copolymer resin &

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 90 g of polydimethylsiloxane of formula A (Mw 2,253 g / mol) Based catalyst (trade name: Hombifast PC, available from Sachtleben, 15% effective Ti in the catalyst) was charged to the reactor.

(A)

Then, the temperature of the reactor was raised to 280 DEG C, and the esterification reaction was carried out at 280 DEG C and normal pressure for 3 hours.

Thereafter, the product obtained by the esterification reaction is subjected to polycondensation reaction at a temperature of 300 ° C. and a pressure of 0.5 to 1 torr for about 150 minutes to obtain a silicone-modified polyolefin having an intrinsic viscosity [η] of 0.7 dL / g and a melting point of 287 ° C., PCT copolymer resin was obtained.

≪ Examples 1 to 5: Preparation of polymeric resin composition >

Example 1

60% by weight of polycarbonate, 25% by weight of silicone-PCT copolymer resin, 12% by weight of brominated polystyrene flame retardant, and 3% by weight of antimony trioxide flame retardant auxiliary by using a twin screw extruder (Φ: 40 mm, L / D = 44) 0.3 parts by weight of a fluorinated styrene acrylonitrile copolymer, 0.2 parts by weight of a phenol-based primary oxidation stabilizer, 0.2 parts by weight of a phosphorus-based secondary oxidation stabilizer, 0.1 part by weight of a styrene acrylonitrile glycidyl methacrylate copolymer 1.5 parts by weight were uniformly kneaded and extruded to prepare pellets.

In Example 1, polycarbonate was TRIREX 3017PJ of domestic Samyang Corp., silicone-PCT copolymer resin was the resin obtained in the above preparation example, the brominated polystyrene type flame retardant was X-Guard FR803 of domestic company Kempia, and antimony trioxide- X-Guard ATO910 of PIASA, fluoro styrene acrylonitrile copolymer FS200 of domestic Nanotech Co., phenolic first oxidation stabilizer AO-60 of ADEKA of Japan, Irgafos 168 of BASF second oxidative stabilizer of phosphorus, styrene acrylonitrile The glycidyl methacrylate copolymer was a SAG-005 product from Sunny FC, China.

Example 2

60% by weight of polycarbonate, 12.5% by weight of silicone-PCT copolymer resin, 12.5% by weight of PCT resin, 12% by weight of brominated polystyrene flame retardant, antimony trioxide flame retardant , 0.3 parts by weight of a fluorinated styrene acrylonitrile copolymer, 0.2 parts by weight of a phenol-based primary oxidation stabilizer, 0.2 parts by weight of a phosphorus-based secondary oxidation stabilizer, 100 parts by weight of a styrene acrylonitrile glycidyl And 1.5 parts by weight of diallyl methacrylate copolymer were uniformly kneaded and extruded to prepare pellets.

In Example 1, polycarbonate was TRIREX 3017PJ of domestic Samyang Corp., silicone-PCT copolymer resin was the resin obtained in the above production example, PCT resin was SKYPURA of SK Chemical Co., Ltd., and brominated polystyrene type flame retardant was X-Guard FR803 , X-Guard ATO910 for domestic antioxidant flame retardant antimony trioxide, FS200 for fluorinated styrene acrylonitrile copolymer for domestic Nanotech, AO-60 for phenolic primary oxidation stabilizer for Japan ADEKA, AO-60 for phosphorus secondary oxidizing stabilizer Irgafos 168, a styrene acrylonitrile glycidyl methacrylate copolymer from BASF, was used as the SAG-005 product of Sunny FC, China.

Example 3

A resin composition consisting of 64% by weight of polycarbonate, 25% by weight of a silicone-PCT copolymer resin, 8% by weight of a brominated polystyrene flame retardant, and 3% by weight of an antimony trioxide flame retardant auxiliary and 1.0% by weight of a styrene acrylonitrile glycidyl methacrylate copolymer Pellets were prepared in the same manner as in Example 1,

Example 4

Except that a resin composition consisting of 60% by weight of polycarbonate, 5% by weight of silicone-PCT copolymer resin, 20% by weight of PCT resin, 12% by weight of brominated polystyrene flame retardant, and 3% by weight of antimony trioxide flame retardant auxiliary was used. . ≪ / RTI >

Example 5

Except that a resin composition consisting of 60% by weight of polycarbonate, 20% by weight of silicone-PCT copolymer resin, 5% by weight of PCT resin, 12% by weight of brominated polystyrene flame retardant, and 3% . ≪ / RTI >

≪ Comparative Examples 1 to 5: Production of polymeric resin composition >

Comparative Example 1

A resin composition comprising 45% by weight of polycarbonate, 40% by weight of PCT resin, 12% by weight of a brominated polystyrene flame retardant, and 3% by weight of an antimony trioxide flame retardant auxiliary, and 1.0 part by weight of a styrene acrylonitrile glycidyl methacrylate copolymer , Pellets were prepared in the same manner as in Example 1.

Comparative Example 2

A resin composition comprising 75% by weight of polycarbonate, 10% by weight of PCT resin, 12% by weight of a brominated polystyrene flame retardant, and 3% by weight of an antimony trioxide flame retardant auxiliary and 1.0 part by weight of a styrene acrylonitrile glycidyl methacrylate copolymer Pellets were prepared in the same manner as in Example 1, except that X-Guard ATO101 of Chempia Co., Ltd. was used as antimony trioxide flame retarding auxiliary.

Comparative Example 3

A resin composition comprising 60% by weight of polycarbonate, 25% by weight of PCT resin, 12% by weight of a brominated polystyrene flame retardant, and 3% by weight of an antimony trioxide flame retardant auxiliary, and 1.0 part by weight of a styrene acrylonitrile glycidyl methacrylate copolymer , Pellets were prepared in the same manner as in Example 1.

Comparative Example 4

A pellet was prepared in the same manner as in Example 2, except that a resin composition consisting of 60% by weight of polycarbonate, 12.5% by weight of a silicone-PCT copolymer resin, 12.5% by weight of a PCT resin and 15% by weight of a brominated polystyrene flame retardant was used.

Comparative Example 5

A pellet was prepared in the same manner as in Example 1, except that a resin composition consisting of 45% by weight of polycarbonate, 40% by weight of silicone-PCT copolymer resin, 12% by weight of a brominated polystyrene type flame retardant, and 3% Respectively.

<Experimental Example> Measurement of physical properties of polymeric resin composition obtained in Examples and Comparative Examples>

The pellets prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 were injected at the injection temperature of 250 DEG C by the use of an injection machine and then the injected specimens were conditioned at 23 ± 2 ° C. and 50 ± 5% , And the physical properties of each of them were measured by the methods described below and in the Examples.

Experimental Example 1: Measurement of tensile strength

In accordance with ASTM D 638, tensile strength was measured using a universal testing machine (Zwick Roell Z010) by making test specimens.

Experimental Example 2: Measurement of tensile elongation

A tensile elongation was measured at a test speed of 50 mm / min using a universal testing machine (Zwick Roell Z010) by making a test specimen according to ASTM D 638.

Experimental Example 3: Measurement of Impact Strength

The impact strength was measured by Izod notched type according to ASTM D256 method at a temperature of 25 ° C, and the thickness of the specimen used was 1/8 ".

Experimental Example 4: Measurement of heat resistance

According to ASTM D 648, test specimens were prepared and the heat distortion temperature was measured using a heat deflection temperature (HDT) tester (HDT Tester, Toyoseiki), and the heat resistance was evaluated.

Experimental Example 5: Measurement of flammability

The flame retardancy was measured at 1/10 "thickness according to UL 94 V Test (Vertical Burning Test).

EXPERIMENTAL EXAMPLE 6: Measurement of Comparative Tracking Index

In accordance with IEC 60112 standard, the comparative tracking index was measured by dropping a standard contaminant onto a specimen and measuring the peak voltage at which no contaminant-induced tracking between the two electrodes occurred.

The results of the experimental examples of the above Examples and Comparative Examples are shown in Table 1 below.

Experimental Example Results of Examples and Comparative Examples division unit Example Comparative Example One 2 3 4 5 One 2 3 4 5 Furtherance Polycarbonate weight% 60 60 64 60 60 45 75 60 60 45 Silicone-PCT copolymer resin 25 12.5 25 5 20 - - - 12.5 40 PCT resin - 12.5 - 20 5 40 10 25 12.5 - Brominated polystyrene flame retardant 12 12 8 12 12 12 12 12 15 12 Antimony trioxide flame retardant preparation 3 3 3 3 3 3 3 3 0 3 The tensile strength 3.2mm kg / cm ² 590 630 600 650 620 550 630 610 580 520 Tensile elongation 3.2mm % 5.0 5.0 5.5 5.0 5.5 7.5 6.5 6.0 4.5 4.5 Impact strength 3.2mm J / m 60 60 75 55 75 30 40 20 35 80 Heat distortion temperature 1.82 MPa ℃ 105 111 105 115 110 100 104 115 105 95 Flammability (UL94) Thickness: 0.8mm - V-0 V-0 V-0 V-0 V-0 V-2 V-0 V-1 V-2 V-1 Comparative tracking index (PLC rating) Thickness: 3mm Solution A - 0 0 0 0 0 0 2 0 One 0

As shown in Table 1, in Examples 1 to 5, a high impact strength of 55 J / m or more could be achieved by mixing a polycarbonate resin with a silicone-PCT copolymer resin. On the other hand, in the case of Comparative Examples 1 to 3 in which the silicone-PCT copolymer resin was not contained at all, it can be confirmed that the impact strength was reduced to 40 J / m or less.

On the other hand, when the excessive amount of the silicone-PCT copolymer resin was mixed with the polycarbonate as in Comparative Example 5, the impact strength was improved to 80 J / m but the tensile strength and heat distortion temperature decreased, The grade was V-1 indicating that the flame retardant properties were deteriorated.

In addition, in the case of Examples 1 to 5, flame retardancy of the flame retardant grade according to the UL 94 V test was excellent as flame retardancy of V-0 due to mixing of the brominated polystyrene flame retardant and antimony trioxide flame retardant aid, In Comparative Example 4 in which only the polystyrene-based flame retardant was used alone, the flame retardance grade of the UL 94 V Test was V-2, and it was confirmed that the flame retardancy was poor.

On the other hand, in the case of Examples 2, 4 and 5, when a general PCT resin is mixed with a silicone-PCT copolymer resin, a high impact strength of 55 J / m or more is maintained, It is confirmed that excellent heat resistance characteristics can be realized.

Claims (15)

Polycarbonate resin;
A silicone-polyester copolymer resin containing repeating units represented by the following formulas (1) to (3); And
And at least two flame retardants,
Wherein the content of the silicone-polyester copolymer resin is 5 parts by weight to 80 parts by weight based on 100 parts by weight of the polycarbonate resin,
[Chemical Formula 1]

(2)

(3)

In the above formulas (1), (2) and (3)
Ar ¹ is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms,
R ¹ is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 10 carbon atoms,
R ² is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,
Y is -O-, -NH- or -S-,
u is an integer of 0 or 1,
R ³ to R ⁶ are each independently a substituted or unsubstituted, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms,
D ¹ and D ² are each independently a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,
L ¹ and L ² each independently represent a substituted or unsubstituted arylene group having 6 to 18 carbon atoms,
n is an integer between 5 and 200,
p and q are each independently an integer of 0 or 1;
The method according to claim 1,
The above-mentioned silicone-polyester copolymer resin is a polymer resin comprising a repeating unit represented by the formula (3) in an amount of 0.1 to 25% by weight based on the total weight of the repeating unit represented by the formula (2) and the repeating unit represented by the formula Composition.
The method according to claim 1,
Wherein the content of the flame retardant is 10 parts by weight to 30 parts by weight based on 100 parts by weight of the polycarbonate resin.
The method according to claim 1,
Wherein the flame retardant comprises a brominated polystyrene flame retardant and an antimony trioxide flame retardant.
5. The method of claim 4,
And 20 to 40 parts by weight of an antimony trioxide flame retardant based on 100 parts by weight of the brominated polystyrene-based flame retardant.
5. The method of claim 4,
Wherein the brominated polystyrene-based flame retardant comprises a repeating unit represented by the following formula (6):
[Chemical Formula 6]

5. The method of claim 4,
Wherein the antimony trioxide flame retardant comprises antimony trioxide (Sb ₂ O ₃ ).
The method according to claim 1,
40% to 90% by weight of a polycarbonate resin;
1% to 35% by weight of a silicone-polyester copolymer resin; And
And 8 to 30% by weight of a flame retardant.
The method according to claim 1,
Wherein the polymeric resin composition further comprises a polycyclohexylene dimethylene terephthalate resin.
10. The method of claim 9,
And 10 to 500 parts by weight of polycyclohexylenedimethylene terephthalate resin based on 100 parts by weight of the silicone-polyester copolymer resin.
10. The method of claim 9,
Wherein the polycyclohexylenedimethylene terephthalate resin has a high thermal deformation temperature as compared with the heat distortion temperature of the silicone-polyester copolymer resin.
The method according to claim 1,
Wherein the polycarbonate resin comprises a polycarbonate resin having a melt flow index (300 DEG C, load of 1.2 kg) measured by ASTM D1238 of 30 g / 10 min or more.
The method according to claim 1,
And at least one compatibilizing agent selected from the group consisting of a vinyl-based copolymer grafted with glycidyl (meth) acrylate and a vinyl-substituted copolymer substituted with halogen.
The method according to claim 1,
A polymeric resin composition for use in parts of automobiles, home appliances and office machines.
A molded product comprising the polymer resin composition of any one of claims 1 to 14.