KR20130132004A - 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 with excellent mechanical properties and a molded article using the same, more specifically: a polyester resin composition which contains a polyester based resin composition, a phosphonate/phosphinate flame retardant, a nitrogen based flame retardant, and inorganic filler in specific contents, additionally contains a polysiloxane-polycarbonate copolymer, does not contain halogen, has similar flame retardant properties, mechanical properties, thermal resistance, surface quality, processing ability, moldability, and surface properties compare to a halogen based flame retardant polyester resin composition, and is capable of expressing high flame retardant properties in various thicknesses; and a molded article using the same.

Description

Non-halogen flame-retardant polyester resin composition and molded article thereof having excellent mechanical properties {HALOGEN-FREE FLAME RETARDANT POLYESTER RESIN COMPOSITION WITH GOOD MECHANICAL PROPERTIES AND MOLDED ARTICLE THEREOF}

The present invention relates to a non-halogen flame-retardant polyester resin composition and a molded article thereof having excellent mechanical properties, and more particularly to a phosphonate / phosphinate-based flame retardant, a nitrogen-based flame retardant and an inorganic filler in a polyester-based resin composition. By including a specific content, preferably further comprising a polysiloxane-polycarbonate copolymer, equivalent flame retardancy, mechanical properties, heat resistance, surface quality, processability compared to halogen-based flame retardant polyester resin composition without containing halogen And it relates to a polyester resin composition and a molded article thereof that exhibits moldability, surface properties and the like, and can implement high flame retardancy at various thicknesses.

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, electrical / electronic devices, and office equipment. In particular, polyethylene terephthalate (PET) resin is widely used as a composite material in various fields such as automobiles, electrical / electronic parts, etc. due to its excellent economy, heat resistance, chemical resistance, electrical properties, mechanical strength, and molding processability, and its usage is also increasing. .

When inorganic fillers such as glass fibers, talc, mica, and layered silicates are added to the polyester resin, mechanical properties such as tensile strength and flexural strength and heat resistance are greatly improved, and thus they can be applied to more various applications. However, many applications require flame retardancy together with mechanical properties and heat resistance, and various methods for imparting flame retardance to polyester resins have been developed.

Since polyester resins are well burned, flame retardancy has been imparted by a method of separately adding an organic halogen flame retardant or auxiliary flame retardant in a field requiring flame retardancy. However, in recent years, various environmental regulations have been imposed on the use of halogen-based flame retardants. For example, some European countries are concerned about the occurrence of dioxins in fires and incinerations, resulting in polybrominated biphenyls (PBBs). And the use of flame retardants such as polybrominated diphenylether (PBDE) has been proposed. In addition, due to environmental safety evaluations in automobiles and electrical / electronic parts, there have been attempts to strictly limit the use of harmful heavy metals, some bromine-based flame retardants, and antimony compounds.

Therefore, various studies using non-halogen-based flame retardants and flame retardant aids such as phosphinate, melamine cyanurate, and melamine phosphonate have been conducted, and there is a market for existing polyester resin compositions that add flame retardancy using halogen flame retardants. Depending on the properties of the final product is a situation that is being replaced finely by a composition using a non-halogen-based flame retardant and a flame retardant aid.

However, compared to the excellent flame retardant properties, mechanical properties and heat resistance of the thin film formed by the polyester composition developed by using a halogen-based flame retardant, it is true that the performance level of the non-halogen flame retarded polyester composition is still insufficient. There is no development of a flame retardant system that can completely replace the characteristics and mechanical properties. In addition, there is a significant difficulty in replacing the existing halogen-based flame retardant polyester resin composition due to the significant lack of continuous molding stability and productivity that must be expressed in a mass production system made after development.

Therefore, existing halogen-based flame retardant systems are still used to manufacture molded products suitable for use in critical parts that require long-term use in high-temperature environments, fire-prone locations, or flame retardant properties and excellent mechanical properties. One polyester resin composition is continuously used.

In addition, one of the various applications in which the flame-retardant polyester composition is used is well exhibited in its properties, such as a fuser housing of an OA machine such as a printer. In the case of a fuser housing that generates high temperature heat in the printer to fix the toner on the paper, the flame retardance and the high temperature stability are excellent because the temperature of 180 to 200 ° C or more must be released within 15 seconds and repeated at least 10,000 times. Is required. In addition, as the weight and size of the product are reduced, the structure of the molded article is very fine and complicated, and the molding resin composition must have a high level of flow characteristics and processability, and at the same time, it is high in a use environment in which it is repeatedly driven after being left for a long time at high temperature and high temperature. Maintaining long-term heat resistance and flame resistance is essential. In order to realize such high heat resistance and mechanical properties as well as flame retardancy and processability, polyester resin compositions using conventional halogen-based flame retardants are still used in the fuser housing of the OA device.

Korean Patent Publication No. 10-2007-0003786 uses melamine cyanurate as a nitrogen-based flame retardant in polybutadiene terephthalate, zinc-diethylphosphinate as an additional flame retardant, and 30% glass fiber is added A non-halogen flame-retardant polyester composition prepared is disclosed. In this patent, the flame retardant of the V94 grade of UL94 standard is realized at 0.8 mm thickness using nitrogen-based flame retardant and phosphinate-based flame retardant in the amount of about 12%, but the halogen flame retardant in the content range of added flame retardant There is a problem that the mechanical properties are lowered compared to the polyester composition using. In fact, according to the results presented in this patent, the impact strength is about 50% lowered, and the tensile strength retention after the high temperature is left 20% in one week even after high temperature stability, resulting in poor stability in the high temperature environment when the final product is implemented. It can be seen. Therefore, the composition according to the present disclosure is excellent in environmental friendliness compared to the conventional halogen-based flame retardant polyester composition, but it is judged to be difficult to apply in practice.

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

Republic of Korea Patent Publication No. 10-2010-0071471 also discloses a non-halogen flame-retardant polyester composition with improved mechanical properties. This publication discloses a non-halogen flame retardant composition in which a polybutylene terephthalate is added a phosphinate flame retardant, a diaryl phosphate flame retardant, a polyphenylene ether-based resin for producing char, and glass fibers. Although the composition shows excellent flame retardancy, up to 60% glass fiber must be added to give mechanical properties equivalent to those of conventional halogen-based polyester materials, and the increase in glass fiber is poor for the appearance and flow characteristics of the molding. Has no effect.

In short, when the flame retardancy of the conventional non-halogen flame-retardant polyester composition as described above is increased, there is a problem that the mechanical properties and heat resistance are lowered.In order to reinforce this, an excessive addition of inorganic materials such as glass fiber increases specific gravity, decreases fluidity, and The problem of deterioration in appearance characteristics occurs.

Thus, while achieving excellent flame retardancy at various thicknesses, it ensures the same mechanical properties as conventional halogen-based flame retardant polyester composition without increasing the inorganic material, and does not generate harmful halogen-based material during processing or in the use environment of the final molded product The development of a non-halogen flame-retardant polyester resin composition is required.

The present invention is to solve the problems of the prior art as described above, non-halogen flame-retardant polyester resin excellent in mechanical properties, heat resistance, dimensional stability, surface quality and workability as well as flame-retardant, halogen-free harmful substances are not generated It is a technical subject to provide a composition and its molded article.

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

According to a preferred embodiment of the present invention, the non-halogen flame-retardant polyester resin composition further comprises 3 to 5% by weight of (F) 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, which is produced by processing the non-halogen flame-retardant polyester resin composition.

The polyester resin composition of the present invention realizes high flame retardancy at various thicknesses without containing a halogen-based material, and at the same level as the halogen-based flame retarded polyester material that has been used for various purposes, mechanical properties, heat resistance, and surface It is possible to maintain excellent quality, processability and moldability. Therefore, the molded article manufactured from the polyester resin composition of the present invention can be applied to various applications such as automobiles, electrical / electronic parts, office equipment, etc., in which the conventional halogen-based flame retardant polyester resin composition is variously applied, and in particular, printers, etc. It can be usefully used for the housing of the fixing unit, which is a main component in the OA apparatus.

Hereinafter, the polyester resin composition of the present invention will be described in detail for each component.

(A) a polyester resin

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

The polyester resin may be selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and mixtures thereof, but is not limited thereto. Preferably, polyethylene terephthalate (PET) resin is used which is excellent in heat resistance, chemical resistance, electrical properties, mechanical strength and molding processability and is advantageous in terms of economy.

In view of workability and mechanical properties, the intrinsic viscosity (IV) at 25 ° C. of the polyester resin is preferably 0.45 to 1 dl / g, more preferably 0.5 to 0.8 dl / g.

The polyester resin is included 38 to 74% by weight, more preferably 40 to 65% by weight relative to the total weight of the composition of the present invention. If 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 reduced, thereby reducing the processing efficiency during injection and extrusion, and the probability of appearance defects of the molded article is increased due to the protrusion of the inorganic filler. On the contrary, if the content exceeds 74% by weight, the solidification rate is lowered, the productivity is decreased, the dimensional instability due to post deformation is relatively large, and the problem of adding an excessive flame retardant to implement an effective flame retardant property occurs.

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

Polyester resin can be synthesize | combined using the dicarboxylic acid compound and glycol compound as mentioned above. The preparation of polyester resins using dicarboxylic acid compounds and glycol compounds is usually carried out in two stages: ester reactions and polycondensation reactions, the preparation of which 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, sebacic acid, (1, 4-, 1,5-, 2,3-, 2,6- or 2,7-) naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-dibenzyldicar Acids and the like can be used, but are not necessarily limited thereto. Preferably, terephthalic acid, isophthalic acid or mixtures thereof are used. Examples of glycol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, ( 1,2-, 1,3- or 1,4-) cyclohexanedimethanol, neopentylglycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like may be used, but are not limited thereto. It doesn't happen. Preferably, ethylene glycol, cyclohexanedimethanol or mixtures thereof are used.

(B) Phosphonate Flame retardant

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

In the present invention, various conventional phosphonate-based flame retardants can be used, and preferably, a flame retardant copolymerized with polycarbonate has a crosslinked polyphosphonate structure reactive by introducing a phosphate ester bond into the molecule. It is suitable to realize excellent flame retardancy and mechanical properties. Specifically, a flame retardant having a repeating unit structure as shown in the following formula (1) can be preferably used.

[Formula 1]

In the above formula (1) flame retardant, preferably, the phosphorus content is 6.5% by weight, the weight average molecular weight is 45000-50000.

The phosphonate-based flame retardant is included in an amount of 2 to 9 wt%, more preferably 2 to 4 wt%, based on the total weight of the composition. If the content is less than 2% by weight, it is difficult to effectively impart flame retardance at various thicknesses (for example, 0.8 mm or 1.6 mm). If the content is more than 9% by weight, the flame retardancy is increased, but the thermal deformation temperature is severely lowered, so that mechanical It is difficult to produce a non-halogen, environmentally friendly flame retardant polyester composition with excellent strength.

 (C) Phosphinate system Flame retardant

In the present invention, by using a phosphinate-based flame retardant in combination with the phosphonate-based flame retardant as a non-halogen-based flame retardant, it is eco-friendly by generating a halogen-based gas during processing, molding and combustion, mechanical and thermal through a combination of flame retardants The degradation of physical properties can be minimized.

As the phosphinate flame retardant, monophosphinate or diphosphinate flame retardant may be preferably used alone or in combination. According to one preferred embodiment of the present invention, monophosphinates and diphosphinate flame retardants represented by the following Chemical Formulas 2 and 3 may 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) Ethylene), arylene (preferably C ₆₎ Arylene), alkyl-substituted arylene (preferably, C ₆ substituted with one or more C ₁ -C ₁₀ alkyl Arylene) or aryl-substituted alkylene (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 included in an amount of 5 to 9 wt%, more preferably 6 to 8 wt%, based on the total weight of the composition. If the content is less than 5% by weight, flame retardancy at various thicknesses (e.g., 0.8mm or 1.6mm) is difficult to be effectively imparted. If the content is more than 9% by weight, mechanical properties such as heat deformation temperature and tensile strength due to the increase in the flame retardant content are increased. In addition to the disadvantages in terms of cost, as well as in the extrusion and injection during injection and molding may result in a large disadvantage in processability, and also the surface properties of the molded article may be deteriorated.

(D) nitrogen system 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 Nitrogen-phosphorus containing flame retardants can be used. In addition, one or two or more of various nitrogen-based flame retardants and / or intumescent additives (for example, polyhydric compounds such as dipentaerythritol, starch, dextrin, inorganic acids, etc.) Can also be used.

The nitrogen-based flame retardant is included in an amount of 1 to 4 wt%, more preferably 1 to 3 wt%, based on the total weight of the composition. If the content is less than 1% by weight, the synergistic effect of the composition with the phosphonate / phosphinate flame retardant is low, making it difficult to realize the flame retardancy of the composition. If the content is more than 3% by weight, it may cause a great disadvantage in processability, Gas may occur to cause deterioration of the surface of the molded article.

(E) Weapons filler

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

As an inorganic filler, the inorganic filler normally used for a flame-retardant resin composition can be used without a restriction | limiting in particular. For example, one or more selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, clay, kaolin, talc, mica, calcium carbonate and barium sulfate can be used, and preferably glass fibers can be used. . As glass fibers, conventional chopped strands such as glass fibers chopped to a diameter of 8 to 18 μm and a length of 2 to 7 mm are used. It is preferable in terms of. A coupling agent may be additionally introduced to improve adhesion to the resin.

The inorganic filler is included 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 is more than 40% by weight, the workability is lowered, and the inorganic filler protrudes into the appearance of the molded article, thereby deteriorating the surface properties.

(F) Polysiloxane - Polycarbonate Copolymer

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

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

[Chemical Formula 4]

[Chemical Formula 5]

In Chemical 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 hydroxyl group having 1 to 13 carbon atoms, and , R ₃ may independently represent an alkylene group having 2 to 8 carbon atoms, R ₄ is an aromatic hydrocarbon group having 6 to 30 carbon atoms unsubstituted or substituted with alkyl, cycloalkyl, alkenyl, alkoxy, halogen atom, or nitro 1 may represent 1 to 20, m may represent 0 to 10, and n may represent an integer of 2 to 1000.

The polysiloxane-polycarbonate copolymer may have an aromatic, aliphatic, or a structure having both aromatic and aliphatic at the same time, and may include halogen, oxygen, nitrogen, and / or sulfur.

The polysiloxane-polycarbonate copolymers that can be included in the composition of the present invention may also preferably comprise hydroxy-terminated siloxanes, the content of which is preferably at the level of 0.5 to 20% by weight of the total weight of the copolymer. The polysiloxane-polycarbonate copolymers that may be included in the composition of the present invention may also have a viscosity average molecular weight, preferably in the range of 15,000 to 200,000.

When the polysiloxane-polycarbonate copolymer is included in the composition of the present invention, the content is preferably used in 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, processability and surface properties by the polysiloxane-polycarbonate copolymer is insignificant. If the content is more than 5% by weight, the flame retardant content is effectively prevented from drip properties generated during the flame retardant test. It is not preferable to cause an increase of, resulting in lowering of mechanical properties such as heat deformation temperature and tensile strength.

Any other additional ingredients

In addition to the components described above, the composition of the present invention may additionally include additives generally usable in flame retardant polyester resin compositions containing no halogen material within a range not departing from the object, and the type and content of specific additives It will be readily apparent to those skilled in the art for a variety of purposes.

In one embodiment, lubricants, antioxidants, light stabilizers, hydrolytic stabilizers, mold release agents, pigments, antistatic agents, conductive agents, magnetic imparting agents, crosslinking agents, antimicrobial agents, processing aids, anti-friction agents, anti-wear agents and coupling agents alone Or two or more kinds can be mixed and added to a composition. The total amount of these additives is usually included in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the composition before addition, but is not necessarily limited thereto.

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

According to another aspect of the present invention, there is provided a molded article which is produced by processing the non-halogen flame-retardant polyester resin composition of the present invention. The method of processing the polyester resin composition of the present invention to produce a molded article is not particularly limited, and may be molded and manufactured 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 into a twin screw melt kneading extruder at a temperature of 240 ~ 280 ℃ by a commonly used blending method to produce a pellet (molding pellets of the extruder at this time) It is more preferable to carry out vacuum defoaming at the (vent) site), and then, the final molded product can be manufactured by hot air drying at 100 to 120 ° C. for 4 hours or more, and then molding with an injection molding machine.

The polyester resin composition and the molded article prepared therefrom according to the present invention have effective flame retardant properties at various thicknesses without containing a halogen material, and together with this, realize high heat resistance and mechanical properties and have effective processability and appearance characteristics. It may be used as molded products and internal / exterior parts for various uses, and may be particularly useful for a housing of a printer fixing unit.

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 the present Example and the comparative example are specifically as follows.

(A) Polyester resin: polyethylene terephthalate (intrinsic viscosity: 0.80 dl / g (at 25 ° C., 50/50 solution of phenol / tetrachloroethane))

(B) phosphonate flame retardant: crosslinked polyphosphonate of formula (phosphorus content: 6.5% by weight, weight average molecular weight: about 46000)

(C) Phosphate flame retardant: aluminum diethyl polyphosphinate (phosphorus content: 23%)

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

(E) Inorganic filler: chopped glass fiber (length: about 3mm)

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

(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)

Raw materials of the ingredients and contents shown in Table 1 (Examples 1 to 5) and Table 2 (Comparative Examples 1 to 12) were uniformly dispersed by mixing with a Henschel mixer, and then L / D = 40 and f = 25mm. Extruded in a twin-screw melt kneading extruder at a temperature of 240 ~ 280 ℃ prepared in pellet form, hot-air dried at 100 ~ 120 ℃ for 4 hours, injection molding at a temperature of 240 ~ 280 ℃ to prepare a specimen of the polyester resin composition It was. All components except the inorganic filler were introduced in a total mixing state with the main feeder, and the inorganic filler was side fed through the middle point of the extruder.

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

(1) Tensile strength: It evaluated based on ASTMD638.

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

(3) Impact strength: It evaluated based on ASTMD256 (1/8 inch thickness, Notched Izod).

(4) Heat deflection temperature (HDT): Based on ASTM D648, it was evaluated with a load of 18.6 kgf / cm ² .

(5) Flame retardancy: Measured according to the UL94 test method defined by Underwriter's Laboratory Inc. of the United States. This is a method of evaluating the flame retardancy from the residual flame time or drip property after the flame of the burner is flamed for 10 seconds on a constant size specimen. Afterflaming time is the length of time that the specimen continues flame burning after the ignition source is far away, and the surface of the drip is dripping from the specimen about 300 mm below the lower end of the specimen. Determined by complexation by water, the flame retardancy is divided into:

(6) Bromine content: A bromine filter was attached to the tube, a fixed voltage of 50 kilovolts was applied for a predetermined time, and then quantitatively analyzed using the XRF method. Atmosphere was carried out in the atmosphere, SEA 1000A ID2445 was used as a measuring instrument.

(7) Surface characteristics of the appearance: 3 mm thick specimens were injection molded, and the ends of the thin-film molded articles lacking flowability were observed, and it was visually judged whether the glass fibers protruded from the surface (according to the visual observation of the surface). Relatively graded as ◎ -excellent, ○ -good, X-poor].

(8) Moldability: The ease and difficulty of continuous extrusion due to the decrease in strength of the swell and strand generated in the extruder die during extrusion of the composition under the same conditions were evaluated by the number of times the strand was broken. (Relatively rated as [◎ -continuous extrudable, ○ -comparative continuous processable, X-continuous machinability weak]].

[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 were superior in flame retardancy at various thicknesses than Comparative Examples 1 to 5 to which flame retardants of different compositions were added. The mechanical properties (thermal deformation temperature, tensile strength, flexural strength, impact strength), surface properties and workability were also good.

Claims (11)

Based on the total weight of the composition
(A) 38 to 74 wt% polyester resin;
(B) 2 to 9% by weight of a phosphonate flame retardant;
(C) 5 to 9% by weight of a phosphinate-based flame retardant;
(D) 1 to 4% by weight of the nitrogen-based flame retardant; And
(E) 15 to 40% by weight of the inorganic filler;
Non-halogen flame-retardant polyester resin composition comprising a. The non-halogen flame-retardant polyester resin composition according to claim 1, wherein the polyester resin component (A) is selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin and mixtures thereof. . The non-halogen flame-retardant polyester resin composition of Claim 1 whose intrinsic viscosity (IV) in 25 degreeC of a polyester resin component (A) is 0.45-1 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 general formula (1):
[Formula 1]

The non-halogen flame retardant according to claim 1, wherein the phosphinate flame retardant component (C) is a monophosphinate represented by the following formula (2), a diphosphinate represented by the following formula (3), or a mixture thereof. Polyester resin composition:
(2)

(3)

In the above, R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ is a linear or branched C ₁ -C ₁₀ alkylene, C ₆ Arylene, C ₆ substituted with one or more C ₁ -C ₁₀ alkyl Arylene, or one or more C ₆ C ₁ -C ₁₀ alkylene substituted with aryl, M is calcium, magnesium, zinc or aluminum, m is 2 or 3, n is 1-3 and X is 1 or 2. The method of claim 1, wherein the nitrogen-based flame retardant component (D) is selected from melamine, melamine cyanurate, triphenyl isocyanurate, melamine polyphosphonate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkylamine phosphate, blood Non-halogen flame-retardant polyester resin composition, characterized in that it is selected from ferridic acid polyphosphate and mixtures thereof. 2. The ratio of claim 1, wherein the inorganic filler component (E) is at least one selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, clay, kaolin, talc, mica, calcium carbonate and barium sulfate. Halogen flame retardant polyester resin composition. The non-halogen flame retardant polyester resin composition according to claim 1, further comprising 3 to 5% by weight of the (F) polysiloxane-polycarbonate copolymer based on the total weight of the composition. The non-halogen flame retardant polyester resin composition according to claim 8, wherein the polysiloxane-polycarbonate copolymer component (F) has a structure shown in the following formula (4) or (5):
[Chemical Formula 4]

[Chemical Formula 5]

In the above, R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, R ₂ independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms, and R ₃ independently represents 2 carbon atoms An alkylene group of 8 to 8, R ₄ represents an aromatic hydrocarbon group of 6 to 30 carbon atoms unsubstituted or substituted with alkyl, cycloalkyl, alkenyl, alkoxy, halogen atom, or nitro, and l is 1 to 20, m is 0-10 and n represent the integer of 2-1000. The molded article manufactured by processing the non-halogen flame-retardant polyester resin composition of any one of Claims 1-9. The molded article according to claim 10, which is used in a housing of a printer fixing unit.