KR101632571B1 - Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof - Google Patents

Abstract

The present invention relates to a halogen-free flame-retardant polyester resin composition excellent in mechanical properties and a molded article thereof, and more particularly, to a polyester-based resin composition containing a phosphonate / phosphinate flame retardant, a nitrogen- The flame retardancy, the mechanical properties, the heat resistance, the surface quality, the workability and the like of the halogen-free flame retardant polyester resin composition of the present invention can be improved by adding the polysiloxane-polycarbonate copolymer And moldability, surface characteristics, and the like, and is capable of realizing high flame retardancy at various thicknesses, and a molded article thereof.

Description

HALOGEN-FREE FLAME RETARDANT POLYESTER RESIN COMPOSITION WITH GOOD MECHANICAL PROPERTIES AND MOLDED ARTICLE THEREOF FIELD OF THE INVENTION [0001] The present invention relates to a non-

The present invention relates to a halogen-free flame-retardant polyester resin composition excellent in mechanical properties and a molded article thereof, and more particularly, to a polyester-based resin composition containing a phosphonate / phosphinate flame retardant, a nitrogen- The flame retardancy, the mechanical properties, the heat resistance, the surface quality, the workability and the like of the halogen-free flame retardant polyester resin composition of the present invention can be improved by adding the polysiloxane-polycarbonate copolymer And moldability, surface characteristics, and the like, and is capable of realizing high flame retardancy at various thicknesses, and a molded article thereof.

In general, polyester resins are excellent in mechanical / electrical properties and physical / chemical properties and are applied to a wide range of fields such as automobiles, electric / electronic devices and office equipment. Particularly, polyethylene terephthalate (PET) resin is widely used as a composite material in various fields such as automobiles, electric / electronic parts, and the like, because it has excellent economy, heat resistance, chemical resistance, electrical characteristics, mechanical strength and molding processability .

When an inorganic filler such as glass fiber, talc, mica, or layered silicate is added to a polyester resin, the mechanical properties such as tensile strength and flexural strength and heat resistance are greatly improved and can be applied to various applications. However, many applications require mechanical properties and heat resistance as well as flame retardance, and various methods for imparting flame retardancy to polyester resins have been developed.

The polyester resin has a good flame-retardant property, and therefore flame retardancy has been imparted by a method in which an organic halogen flame retardant or an auxiliary flame retardant is separately added in a field requiring flame retardancy. However, in recent years, there have been various regulations regarding the use of halogen-based flame retardants in the environment. For example, in some European countries, polybrominated biphenyl (PBB) And polybrominated diphenylether (PBDE) as a flame retardant. In addition, there has been an attempt to strictly restrict the use of harmful heavy metals, a part of a brominated flame retardant, antimony compounds, etc., due to environmental safety evaluation in automobiles and electric / electronic parts.

Accordingly, various studies have been conducted using non-halogen flame retardants such as phosphinate, melamine cyanurate and melamine phosphonate, and flame retardant adjuvants, and a conventional polyester resin composition market which adds flame retardancy by using a halogen flame retardant Based flame retardant and a flame-retardant adjuvant depending on the characteristics of the final product.

However, the performance level achieved by the non-halogen flame retardant polyester composition is far less than the excellent flame retardancy, mechanical properties, and heat resistance in the thin film implemented by the polyester composition developed using the halogen flame retardant agent, The development of a flame-retardant system that can completely replace the properties and mechanical properties of various materials has not been developed. In addition, there is a considerable shortage in molding stability and productivity which must be exhibited in a mass production system after development, and therefore, there is a great difficulty in replacing the conventional halogen-based flame retardant polyester resin composition.

Therefore, it is still necessary to utilize the existing halogen-based flame retardant system for the production of molded articles suitable for use in important parts requiring long-term use in a high-temperature environment, use in a place where fire is likely to occur, A polyester resin composition is continuously used.

In addition, among the various applications in which the flame retardant polyester composition is used, one of applications that shows its characteristics is the fuser housing of an OA such as a printer. In the case of a fuser housing which generates high temperature heat in the printer to fix the toner on the paper, it is necessary to emit a temperature of 180 to 200 ° C or higher within 15 seconds and to repeat it at least 10,000 times, . In addition, due to the weight reduction and miniaturization of the product, the structure of the molded article is very minute and complicated, and the resin composition for molding must have a high level of flow property and processability, and at the same time, it is left in a high temperature and a high temperature for a long time, It is essential to maintain long-term heat resistance and flame retardancy. In order to simultaneously realize such high heat resistance and mechanical properties, flame retardancy and processability, a polyester resin composition using a conventional halogen-based flame retardant is still used for a fixing device housing of an OA device.

Korean Patent Laid-Open No. 10-2007-0003786 discloses that polybutadiene terephthalate is melamine cyanurate as a nitrogen-based flame retardant, zinc-diethylphosphinate is used as an additional flame retardant, and 30% Discloses a non-halogen flame retardant polyester composition prepared. In this patent, excellent flame retardancy of UL94 standard V-0 grade was achieved at a thickness of 0.8 mm by using a nitrogen flame retardant and a phosphinate flame retardant in an amount of about 12%, respectively. However, the halogen flame retardant There is a problem that the mechanical properties are lowered as compared with the polyester composition using the polyester. In fact, according to the results presented in this patent application, the impact strength is reduced by about 50%, and even after tensile strength retention after high temperature is reduced by 20% in one week, the stability in a high temperature environment is poor . Accordingly, the composition according to the present patent application is superior in environmental friendliness to the conventional halogen-based flame retardant polyester composition, but it may be difficult to apply the composition in practice.

Korean Patent Laid-Open No. 10-2010-0118374 discloses a non-halogen flame retardant polyester resin composition comprising a phosphate-based flame retardant, an aluminum phosphinate and a nitrogen-based flame retardant, and adding a layered silicate to the polyester resin have. The composition disclosed in this patent shows the same level of mechanical properties as polyester compositions using conventional halogen-based flame retardants in terms of tensile strength and impact strength. However, in terms of flame retardance, it is inferior to conventional compositions using halogen flame retardants.

Korean Patent Laid-Open No. 10-2010-0071471 also discloses a non-halogen flame retardant polyester composition having improved mechanical properties. This patent discloses a non-halogen flame retardant composition comprising polyphenylene ether resin and glass fiber added to polybutylene terephthalate to produce a phosphinate flame retardant, a diaryl phosphate flame retardant, a char, and the like. Although this composition shows excellent flame retardancy, it is required to add up to 60% of glass fiber in order to impart mechanical properties equivalent to those of conventional halogen-based polyester materials. The increase in the amount of such glass fibers is good for the appearance and flow properties .

In other words, when the flame retardancy of the conventional non-halogen flame retardant polyester composition as described above is increased, mechanical properties and heat resistance are lowered. In order to reinforce this, an excessive amount of an inorganic material such as glass fiber increases the specific gravity, There arises a problem of degradation of appearance characteristics.

Thus, while realizing excellent flame retardancy at various thicknesses, the same level of mechanical properties as the conventional halogen-based flame retardant polyester composition can be secured without increasing the amount of inorganic substances, and harmful halogen- The development of a non-halogen flame-retardant polyester resin composition which does not contain a halogen-free flame retardant is desired.

The present invention has been made to solve the problems of the prior art as described above and it is an object of the present invention to provide a halogen-free flame-retardant polyester resin excellent in flame retardancy, mechanical properties, heat resistance, dimensional stability, surface quality and processability, To provide a composition and a molded article thereof.

In order to achieve the above object, the present invention provides a polyester resin composition comprising (A) 38 to 74% by weight of a polyester resin, (B) 2 to 9% by weight of a phosphonate-based flame retardant; (C) 5 to 9% by weight of a phosphinate-based flame retardant; (D) 1 to 4% by weight of a nitrogen-based flame retardant; And (E) 15 to 40% by weight of an inorganic filler.

According to a preferred embodiment of the present invention, the non-halogen flame retardant polyester resin composition further comprises (F) 3 to 5% by weight of the polysiloxane-polycarbonate copolymer based on the total weight of the composition.

According to another aspect of the present invention, there is provided a molded article characterized by being produced by processing the non-halogenated flame retardant polyester resin composition.

The polyester resin composition of the present invention can realize a high flame retardancy at various thicknesses without containing a halogen-based substance, and at the same time, it can be used as a halogen-based flame retardant polyester material which has been conventionally used for various purposes, Quality, processability, moldability and the like can be excellently maintained. Accordingly, the molded article produced from the polyester resin composition of the present invention can be applied to various applications such as automobiles, electric / electronic parts, office equipment, etc., in which conventional halogen-based flame retardant polyester resin compositions are variously applied. A housing of a fixing device which is a main component in an OA device, and the like.

Hereinafter, the polyester resin composition of the present invention will be described in detail by constituent elements.

(A) a polyester resin

The polyester resin contained in the composition of the present invention is a resin which is generally excellent in mechanical / electrical properties and physical / chemical properties as a main component of the composition of the present invention.

As the polyester resin, a resin selected from a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin and a mixture thereof may be used, but is not limited thereto. Preferably, a polyethylene terephthalate (PET) resin which is excellent in heat resistance, chemical resistance, electrical properties, mechanical strength and molding processability and is economically advantageous is used.

In terms of processability and mechanical properties, the intrinsic viscosity (IV) of the polyester resin at 25 캜 is preferably from 0.45 to 1 dl / g, more preferably from 0.5 to 0.8 dl / g.

The polyester resin is contained in an amount of 38 to 74% by weight, more preferably 40 to 65% by weight based on the total weight of the composition of the present invention. When the content is less than 38% by weight, the amount of the polyester resin relative to the flame retardant and the inorganic filler is relatively decreased, so that the processing efficiency at the time of injection and extrusion is lowered, and the probability of appearance defect of the molded article is increased due to the protrusion of the inorganic filler. On the other hand, if the content exceeds 74% by weight, the solidification rate is delayed, the productivity decreases, the dimensional instability due to the post-warpage becomes relatively large, and an excessive amount of flame retardant is added to achieve effective flame retardant properties.

According to one embodiment of the present invention, the polyester resin may be one prepared by condensation polymerization of at least one aromatic, aliphatic or alicyclic dicarboxylic acid with at least one aliphatic or alicyclic glycol. Preferably, the aromatic dicarboxylic acid is composed of 6 to 20 carbon atoms, the aliphatic or alicyclic dicarboxylic acid is composed of 3 to 20 carbon atoms, and the aliphatic or alicyclic glycol is 2 to 20 carbon atoms.

The polyester resin can be synthesized using a dicarboxylic acid compound and a glycol compound as described above. The production of a polyester resin using a dicarboxylic acid compound and a glycol compound is usually carried out in two stages of an esterification reaction and a polycondensation reaction, and the production process thereof is already well known in the art. Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, 4-, 1,5-, 2,3-, 2,6- or 2,7-) naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-dibenzyldicar And the like may be used, but the present invention is not limited thereto. Preferably, terephthalic acid, isophthalic acid or a mixture thereof is used. Examples of the glycol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-, 1,3- or 1,4-) cyclohexanedimethanol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like, It is not. Preferably, ethylene glycol, cyclohexanedimethanol or a mixture thereof is used.

(B) Phosphonate system Flame retardant

The phosphonate-based flame retardant contained in the composition of the present invention is a component that imparts flame retardancy to the composition and at the same time helps increase surface characteristics, processability, and mechanical properties.

In the present invention, various conventional phosphonate-based flame retardants may be used. Preferably, a flame retardant copolymerized with a polycarbonate having a crosslinked polyphosphonate structure which is reactive by introducing a phosphoric acid ester bond into the molecule It is suitable for realizing excellent flame retardancy and mechanical properties. Specifically, a flame retardant having a repeating unit structure represented by the following general formula (1) can be preferably used.

[Chemical Formula 1]

In the flame retardant of Formula 1, the phosphorus content is preferably 6.5% by weight and the weight average molecular weight is 45,000 to 500,000.

The phosphonate-based flame retardant is contained in an amount of 2 to 9 wt%, more preferably 2 to 4 wt%, based on the total weight of the composition. When the content is less than 2% by weight, it is difficult to effectively impart flame retardancy at various thicknesses (for example, 0.8 mm or 1.6 mm). When the content exceeds 9% by weight, the flame retardancy is increased, It is difficult to produce a non-halogen environment-friendly flame retardant polyester composition having excellent strength.

 (C) Phosphinate system Flame retardant

In the present invention, by using a phosphinate-based flame retardant together with the phosphonate-based flame retardant as the non-halogen-based flame retardant, the halogen-based gas is not generated during processing or molding and combustion, The deterioration of the physical properties can be minimized.

As the phosphinate-based flame retardant, a monophosphinate or a phosphinite flame retardant may preferably be used alone or in combination. According to one preferred embodiment of the present invention, the monophosphinate and the diphosphinate flame retardant represented by the following general formulas (2) and (3) can be used alone or in combination.

(2)

(3)

Wherein R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ represents a linear or branched alkylene (preferably C ₁ -C ₁₀ alkyl Arylene) (preferably, C ₆ Arylene), alkyl-substituted arylene (preferably C ₆ -C ₁₀ alkyl substituted with one or more C ₁ -C ₁₀ alkyl) (Preferably C ₁ -C ₁₀ alkylene substituted with one or more C ₆ aryl), M is a metal such as calcium, magnesium, zinc or aluminum, m is 2 Or 3, n is 1 to 3, and X is 1 or 2.

The phosphinate-based flame retardant is contained in an amount of 5 to 9% by weight, more preferably 6 to 8% by weight based on the total weight of the composition. When the content is less than 5% by weight, it is difficult to effectively impart flame retardancy at various thicknesses (e.g., 0.8 mm or 1.6 mm). When the content exceeds 9% by weight, mechanical properties such as heat distortion temperature and tensile strength Which is not only disadvantageous from the viewpoint of cost, but also causes a great disadvantage in workability in injection and molding at the time of extrusion and injection, and the surface characteristics of the molded article may also be deteriorated.

(D) Nitrogen series Flame retardant

As the nitrogen-based flame retardant in the present invention, a nitrogen-phosphorus-containing flame retardant may be preferably used. Specifically selected from melamine, melamine cyanurate, triphenyl isocyanurate, melamine polyphosphonate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkylamine phosphate, piperidine acid polyphosphate, and mixtures thereof A nitrogen-phosphorus flame retardant may be used. It is also possible to add one or more of various nitrogen-based flame retardants and / or intumescent additives (for example, polyhydric compounds such as dipentaerythritol, starch, dextrin, etc.) It can also be used.

The nitrogen-based flame retardant is contained in an amount of 1 to 4% by weight, more preferably 1 to 3% by weight based on the total weight of the composition. If the content is less than 1% by weight, the synergistic effect with the phosphonate / phosphinate flame retardant is small and it is difficult to realize the flame retardancy of the composition. When the content is more than 3% by weight, Gas may be generated and the quality of the surface of the molded article may deteriorate.

(E) Weapons filler

The inorganic filler contained in the composition of the present invention is a component that contributes mechanical strength, heat resistance and dimensional stability to a molded article and contributes to improvement of processability and moldability.

As the inorganic filler, inorganic fillers conventionally used in the flame retardant resin composition can be used without any particular limitation. For example, at least one selected from the group consisting of glass fiber, carbon fiber, glass bead, glass flake, clay, kaolin, talc, mica, calcium carbonate and barium sulfate can be used, . As the glass fiber, the use of a chopped strand of a short fiber length, for example, chopped glass having a diameter of 8 to 18 탆 and a length of 2 to 7 mm, is preferred because the processability and mechanical properties . A coupling agent may be additionally added to improve adhesion to the resin.

The inorganic filler is contained in an amount of 15 to 40% by weight, more preferably 20 to 40% by weight based on the total weight of the composition. If the content is less than 15% by weight, the effect of improving the mechanical strength and heat resistance is insignificant. If the content exceeds 40% by weight, the workability is deteriorated and the inorganic filler is projected to the outer surface of the molded article,

(F) Polysiloxane - Polycarbonate Copolymer

The composition of the present invention may preferably further comprise a polysiloxane-polycarbonate copolymer.

The polysiloxane-polycarbonate copolymer that can be included in the composition of the present invention may preferably have the structure shown in the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (4) and (5), R ₁ may independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group, and R ₂ may independently represent a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms , R ₃ may independently represent an alkylene group having 2 to 8 carbon atoms, and R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is optionally substituted with alkyl, cycloalkyl, alkenyl, alkoxy, halogen atom, , 1 represents an integer of 1 to 20, m represents an integer of 0 to 10, and n represents an integer of 2 to 1000.

The polysiloxane-polycarbonate copolymer may have an aromatic, aliphatic or aromatic and aliphatic structure, and may contain halogen, oxygen, nitrogen, and / or sulfur.

Polysiloxane-polycarbonate copolymers that may be included in the composition of the present invention may also preferably comprise hydroxy-terminated siloxane, and the content thereof is preferably 0.5 to 20% by weight based on the total weight of the copolymer. Polysiloxane-polycarbonate copolymers that may be included in the compositions of the present invention may also preferably have a viscosity average molecular weight in the range of from 15,000 to 200,000.

When the polysiloxane-polycarbonate copolymer is contained in the composition of the present invention, the content thereof is preferably 3 to 5% by weight based on the total weight of the composition. If the content is less than 3% by weight, the effect of improving the mechanical properties, workability, and surface properties of the polysiloxane-polycarbonate copolymer is insignificant. When the content exceeds 5% by weight, the flame retardant content And the mechanical properties such as the heat distortion temperature and the tensile strength are deteriorated, which is not preferable.

Any other optional ingredient

In addition to the above-described components, the composition of the present invention may additionally include additives that can be generally used in a flame retardant polyester resin composition that does not contain a halogen material, without departing from the object of the present invention. Those skilled in the art will readily be able to select according to various purposes.

In one embodiment, a lubricant, an antioxidant, a light stabilizer, a hydrolysis stabilizer, a releasing agent, a pigment, an antistatic agent, a conductivity imparting agent, a magnetic agent, a crosslinking agent, an antibacterial agent, a processing aid, Or two or more kinds thereof may be mixed and added to the composition. The total amount of these additives to be added is usually 0.2 to 5 parts by weight based on 100 parts by weight of the composition before addition, but is not limited thereto.

There is no particular limitation on the method for producing the polyester resin composition of the present invention by using each of the components as described above, and the resin composition can be produced using a general resin composition manufacturing method known in the art. For example, the compositions of the present invention can be obtained by mixing and uniformly dispersing each component in a mixer.

According to another aspect of the present invention, there is provided a molded article characterized by being produced by processing the non-halogenated flame retardant polyester resin composition of the present invention. The method of producing the polyester resin composition of the present invention by processing it is not particularly limited and may be molded and manufactured by using a general resin composition processing method known in the art. According to one embodiment, the polyester resin composition of the present invention is extruded through a twin-screw melt-kneading extruder at a temperature of 240 to 280 ° C by a commonly used blending method to prepare a molding pellet (in this case, it is more preferable to perform the vacuum degassing at the vent portion). The pellet thus produced is then hot-air dried at 100 to 120 DEG C for 4 hours or more, and then molded into an injection molding machine to produce a final molded product.

The polyester resin composition according to the present invention and the molded article produced therefrom have effective flame retardancy at various thicknesses without containing a halogen material, and have high heat resistance and mechanical properties, and have effective processability and appearance characteristics , Molded products for various purposes, and interior / exterior parts, and can be particularly useful for a housing of a printer fixing machine.

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Example  1 to 5 and Comparative Example  1 to 12

The components used in this embodiment and the comparative examples are as follows.

(A) Polyester resin: polyethylene terephthalate (intrinsic viscosity: 0.80 dl / g (25 DEG C, in phenol / tetrachloroethane 50/50 solution))

(B) Phosphonate flame retardant: Crosslinked polyphosphonate of formula (1) (phosphorus content: 6.5 wt%, weight average molecular weight: about 46000)

(C) phosphinate-based flame retardant: aluminum diethyl polyphosphinate (phosphorus content: 23%)

(D) Nitrogen-based flame retardant: melamine polyphosphonate (phosphorus content: 12% by weight)

(E) Inorganic filler: glass fiberglass (length: about 3mm)

(F) Polysiloxane-polycarbonate copolymer (siloxane content: 10% by weight) of formula (4)

(G) Halogen flame retardant: bromine polystyrene flame retardant (bromine content: 66% by weight)

(H) antimony flame retardant aid: sodium antimonate (antimony content: 25% by weight)

The raw materials of the components and contents shown in the following Table 1 (Examples 1 to 5) and Table 2 (Comparative Examples 1 to 12) were mixed by a Henschel mixer and uniformly dispersed. Then, L / D = 40 and f = Extruded at a temperature of 240 to 280 DEG C by a biaxial melt-kneading extruder to prepare pellets, hot-air drying at 100 to 120 DEG C for 4 hours, and injection molding at 240 to 280 DEG C to prepare a polyester resin composition specimen Respectively. All ingredients except the inorganic filler were added to the main feeder with total mixing, and the inorganic filler was side fed through the middle point of the extruder.

The physical properties of each specimen thus prepared were measured by the following methods. The results are shown in Table 3 (Examples 1 to 5) and Table 4 (Comparative Examples 1 to 12).

(1) Tensile strength: Evaluated according to ASTM D638.

(2) Flexural strength: Evaluated according to ASTM D790.

(3) Impact strength: Evaluation was made according to ASTM D256 (1/8 inch thickness, Notch Izod).

(4) Heat deformation temperature (HDT): It was evaluated according to ASTM D648 at a load of 18.6 kgf / cm ² .

(5) Flammability: Measured according to the UL94 test method prescribed by Underwriter's Laboratory Inc. of the United States. This is a method of evaluating the flame retardancy from the durability and durability of the flame after the flame of the burner is applied to the specimen of a certain size maintained vertically for 10 seconds. The surface of the label, which is located about 300 mm below the lower end of the specimen, is dripped from the specimen by the drip, It is determined through the ignition by water, the flammability class is divided as follows.

(6) Bromine content: A filter for bromine was attached to the tube, and a constant voltage of 50 kilovolts was applied for a predetermined period of time, followed by quantitative analysis using the XRF method. The atmosphere was airborne and SEA 1000A ID 2445 was used as the measuring instrument.

(7) Surface properties of external appearance: A specimen having a thickness of 3 mm was injection molded to observe the end of the thin film molded article having insufficient flowability, and visually judged whether or not the glass fiber protruded on the surface (depending on the state of the surface observed with the naked eye Relatively [◎ - Excellent, ○ - Good, X - poor].

(8) Molding processability: The ease and extinction of continuous extrusion due to the swell and the strength of the strand generated in the extruder die during the extrusion of the composition under the same conditions were evaluated by the number of breaks of the strand. (Relatively [◎ - continuous extrusion possible, ○ - comparatively continuous processable, X-continuous processability].

[Table 1]

[Table 2]

[Table 3]

[Table 4]

As can be seen from Tables 3 and 4, the non-halogen polyester resin compositions of Examples 1 to 5 according to the present invention exhibited excellent flame retardancy at various thicknesses in comparison with Comparative Examples 1 to 5 in which flame retardants of different compositions were added , Mechanical properties (heat distortion temperature, tensile strength, flexural strength, impact strength), surface characteristics and workability were also good.

Claims (11)

Based on the total weight of the composition
(A) 38 to 56% by weight of a polyester resin;
(B) 2 to 9% by weight of a phosphonate-based flame retardant;
(C) 5 to 9% by weight of a phosphinate-based flame retardant;
(D) 1 to 4% by weight of a nitrogen-based flame retardant;
(E) 30 to 40% by weight of an inorganic filler; And
(F) 3 to 5% by weight of a polysiloxane-polycarbonate copolymer having a structure represented by the following formula (4) or (5);
Halogenated flame retardant polyester resin composition comprising:
[Chemical Formula 4]

[Chemical Formula 5]

In the above, R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, or aryl, R ₂ is independently represent a hydrocarbon group or hydroxy group of a carbon number of 1 to 13, R ₃ are independently C2 And R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted with alkyl, cycloalkyl, alkenyl, alkoxy, halogen atom or nitro, l is 1 to 20, m is 0 to 10, and n represents an integer of 2 to 1000. The non-halogenated flame retardant polyester resin composition according to claim 1, wherein the polyester resin component (A) is selected from the group consisting of a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin and a mixture thereof . The non-halogenated flame retardant polyester resin composition according to claim 1, wherein the polyester resin component (A) has an intrinsic viscosity (IV) at 25 캜 of 0.45 to 1 dl / g. The non-halogen flame retardant polyester resin composition according to claim 1, wherein the phosphonate flame retardant component (B) has a repeating unit structure represented by the following formula (1):
[Chemical Formula 1]

The non-halogen flame retardant composition according to claim 1, wherein the phosphinate-based flame retardant component (C) is a monophosphinate represented by the following formula (2), a diphosphinate represented by the following formula Polyester resin composition:
(2)

(3)

Wherein R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ represents a linear or branched C ₁ -C ₁₀ alkylene, C ₆ arylene, It represents a C ₁ -C ₁₀ alkylene substituted with a C ₆ arylene group, or one or more C ₆ aryl substituted with at least one C ₁ -C ₁₀ alkyl, M is a calcium, magnesium, zinc or aluminum, m represents 2, or 3, n is an integer of 1 to 3, and X is 1 or 2. The method according to claim 1, wherein the nitrogen-based flame retardant component (D) is selected from the group consisting of melamine, melamine cyanurate, triphenylisocyanurate, melamine polyphosphonate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkylamine phosphate, Peridinic acid polyphosphate and mixtures thereof. ≪ RTI ID = 0.0 > 5. < / RTI > The composition according to claim 1, wherein the inorganic filler component (E) is at least one selected from the group consisting of glass fiber, carbon fiber, glass bead, glass flake, clay, kaolin, talc, mica, calcium carbonate and barium sulfate. Halogenated softened polyester resin composition. delete delete A molded article characterized by being produced by processing the non-halogenated flame retardant polyester resin composition according to any one of claims 1 to 7. 11. A molded article according to claim 10, which is used in a housing of a printer fixing machine.