KR20230047012A - Thermoplastic resin and article prepared therefrom - Google Patents

Abstract

The present invention provides a thermoplastic resin composition and a shaped article comprising the same. The thermoplastic resin composition comprises, at a predetermined content, (A) a base resin including polyalkylene terephthalate and polycarbonate, (B) an impact mitigator having a core-shell structure, (C) a halogenated epoxy-based flame retardant, (D) a compatibilizer, and (E) a transesterification inhibitor, has a flow index (250℃, 5 kg) is more than 7.0 g/10min, and has a WOM value of 70% or more measured according to UL 746C (f1 Class). The thermoplastic resin composition can have excellent mechanical strength, moldability, and flame retardancy, while also having excellent hot water resistance and weather resistance.

Description

Thermoplastic resin and molded article manufactured therefrom {THERMOPLASTIC RESIN AND ARTICLE PREPARED THEREFROM}

The present invention relates to a thermoplastic resin composition and a molded article manufactured by including the same, and more particularly, to a thermoplastic resin composition excellent in mechanical strength, molding processability and flame retardancy, as well as excellent in both hot water resistance and weather resistance, and a molded article manufactured by including the same. it's about

Polycarbonate (PC) resin has excellent mechanical, physical and optical properties and is used in various fields such as automobile interior and exterior materials and electric/electronic product housings. In particular, polycarbonate resin has excellent transparency and is applied to its application fields.

However, since polycarbonate resin has poor chemical resistance due to its amorphous nature, it is blended with a crystalline material to be used in parts that require it.

In particular, polybutylene terephthalate (PBT) resin is widely used as a PC/PBT alloy resin because it has excellent chemical resistance and stiffness similar to that of polycarbonate resin.

However, polybutylene terephthalate resin is hydrolyzed under a high-temperature and high-humidity environment, resulting in a decrease in physical properties, and this phenomenon occurs in the same way in alloy resins.

In addition, there is a problem in that a transesterification reaction occurs between the polycarbonate resin and the polybutylene terephthalate resin during blending, causing deterioration in physical properties.

On the other hand, in the case of electrical products, it is required to have flame retardancy of a certain level or higher due to the risk of fire. However, when an impact modifier is added to enhance mechanical strength, there is a problem in that the flame retardancy of the composition is lowered.

Moreover, in the case of outdoor electrical products such as electrical boxes, they have not only flame retardancy but also shock resistance to external shocks, various weather phenomena, harsh weather conditions and high temperature, high humidity, rainfall and UV due to exposure to sunlight for a long time. It is required to have durability against, and it is necessary to develop a material capable of satisfying all of these physical properties.

Korean Patent Publication No. 2003-0000778

In order to solve the problems of the prior art as described above, the present invention has excellent mechanical strength, molding processability and flame retardancy, as well as excellent hot water resistance and weather resistance. It aims at providing a thermoplastic resin composition.

In addition, an object of the present invention is to provide a molded article manufactured by including the thermoplastic resin composition.

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

In order to achieve the above object, the present invention (A) 100 parts by weight of a base resin containing 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate, (B) impact of core-shell structure 5.5 to 9 parts by weight of a reinforcing agent, (C) 10 to 30 parts by weight of a halogenated epoxy flame retardant, (D) 2 to 4.5 parts by weight of a compatibilizer, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor, according to ASTM D1238 A thermoplastic resin composition characterized in that the flow index measured under the conditions of a temperature of 250 ° C and a load of 5 kg is 7.0 g / 10 min or more, and the WOM value measured according to UL 746C (f1 Class) is 70% or more.

In addition, the present invention (A) 1 to 99% by weight of polyalkylene terephthalate having an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl / g, and a flow index measured under conditions of a temperature of 250 ° C and a load of 5 kg according to ASTM D1238 100 parts by weight of a base resin containing 1 to 99% by weight of a polycarbonate having 1 to 11 g/10 min, (B) 5.5 to 9 parts by weight of an impact modifier having a core-shell structure, (C) 10 to 90 parts by weight of a halogenated epoxy flame retardant 30 parts by weight, (D) 2 to 4.5 parts by weight of a compatibilizer, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor.

In addition, the present invention (A) 1 to 99% by weight of polyalkylene terephthalate having an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl / g, and a flow index measured under conditions of a temperature of 250 ° C and a load of 5 kg according to ASTM D1238 100 parts by weight of a base resin containing 1 to 99% by weight of a polycarbonate having 1 to 11 g/10 min, (B) 5.5 to 9 parts by weight of an impact modifier, (C) 10 to 30 parts by weight of a halogenated epoxy-based flame retardant, ( D) 2 to 4.5 parts by weight of a glycidyl methacrylate-based compatibilizer containing vinyl acrylate, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor that is a monobasic phosphate. provides

The thermoplastic composition may preferably have a WOM value of 70% or more measured according to UL 746C (f1 Class).

The thermoplastic composition may preferably have a warm water resistance index value of 50% or more measured according to UL 746C (f1 Class).

The polyalkylene terephthalate may preferably be polybutylene terephthalate.

The polyalkylene terephthalate may preferably have an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl/g.

The polycarbonate may preferably have a flow index of 1 to 11 g/10 min measured under conditions of a temperature of 250° C. and a load of 5 kg in accordance with ASTM D1238.

The base resin may preferably include 40 to 60% by weight of polyalkylene terephthalate and 40 to 60% by weight of polycarbonate, based on the total weight thereof.

The impact modifier may preferably be a butyl acrylic impact modifier.

The halogenated epoxy-based flame retardant may preferably be a brominated epoxy-based flame retardant.

The transesterification inhibitor may preferably be an inorganic phosphate-based compound, more preferably a monobasic phosphate, and more preferably NaH ₂ PO ₄ .

The thermoplastic resin composition may preferably include 2 to 8 parts by weight of a flame retardant agent based on 100 parts by weight of the base resin, and the flame retardant agent may preferably include antimony trioxide.

The compatibilizer may preferably include a glycidyl methacrylate-based compatibilizer, and the glycidyl methacrylate-based compatibilizer may preferably include vinyl acrylate. In this case, the vinyl acrylate may be preferably included in an amount of 1 to 20% by weight based on the total weight of the glycidyl methacrylate-based compatibilizer.

The thermoplastic resin composition may preferably include 0.05 to 3 parts by weight of a UV stabilizer based on 100 parts by weight of the base resin.

The UV stabilizer may be preferably a benzotriazole-based UV stabilizer.

The thermoplastic resin composition may preferably satisfy the f1 Class grade specified in UL 746C.

In addition, the present invention provides a molded article comprising the thermoplastic resin composition.

The molded article may preferably be an electrical box.

According to the present invention, mechanical strength, molding processability, and flame retardancy are secured at a certain level or higher, while hot water resistance and weather resistance are greatly improved, making it suitable for use as an outdoor electric appliance for a long period of time. There is an effect of providing a thermoplastic resin composition and a molded article manufactured therefrom.

1 and 2 are exemplary images of outdoor power packs.

Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article including the same will be described in detail.

the present inventors While researching a flame retardant PC/PBT alloy resin that can be used outdoors, when a predetermined amount of impact modifier, flame retardant, and compatibilizer is included, molding processability and While simultaneously raising the flame retardancy to a certain level or higher, it was confirmed that the weather resistance and durability to a high temperature and high humidity environment were greatly improved, and based on this, further research was conducted to complete the present invention.

The thermoplastic resin composition of the present invention includes (A) 100 parts by weight of a base resin including 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate, (B) 5.5 to 9 parts by weight of a core-shell structured impact modifier parts by weight, (C) 10 to 30 parts by weight of a halogenated epoxy flame retardant, (D) 2 to 4.5 parts by weight of a compatibilizer, and 0.1 to 2 parts by weight of a transesterification inhibitor, and a temperature of 250 according to ASTM D1238 It is characterized in that the flow index measured under the condition of ℃ and load 5kg is 7.0 / 10min or more, and the WOM value measured according to UL 746C (f1 Class) is 70% or more. In this case, the tensile strength, flexural modulus, flexural strength and Mechanical strength such as impact strength, molding processability, and flame retardancy are secured at a certain level or more, and both hot water resistance and weather resistance are excellent.

The thermoplastic resin composition of the present invention also includes (A) 100 parts by weight of a base resin including 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate, (B) 5.5 parts by weight of a core-shell structured impact modifier to 9 parts by weight, (C) 10 to 30 parts by weight of a halogenated epoxy flame retardant, (D) 2 to 4.5 parts by weight of a compatibilizer, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor, according to ASTM D1238 It is characterized in that the flow index measured under the conditions of a temperature of 250 ° C and a load of 5 kg is 7.0 g / 10 min or more, and the warm water index value measured in accordance with UL 746C (f1 Class) is 50% or more. While ensuring mechanical strength such as elastic modulus, flexural strength and impact strength, molding processability and flame retardancy at a certain level or higher, both hot water resistance and weather resistance are excellent.

The thermoplastic resin composition of the present invention also contains (A) 1 to 99% by weight of a polyalkylene terephthalate having an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl/g and, in accordance with ASTM D1238, under conditions of a temperature of 250° C. and a load of 5 kg. 100 parts by weight of a base resin containing 1 to 99% by weight of polycarbonate having a measured flow index of 1 to 11 g / 10 min, (B) 5.5 to 9 parts by weight of an impact modifier, (C) 10 to 30 parts by weight of a halogenated epoxy-based flame retardant parts by weight, (D) 2 to 4.5 parts by weight of a compatibilizer, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor, in this case, mechanical properties such as tensile strength, flexural modulus, flexural strength and impact strength While securing strength, molding processability, and flame retardancy at a certain level or higher, it has excellent effects in both hot water resistance and weather resistance.

The thermoplastic resin composition of the present invention also includes (A) 1 to 99% by weight of a polyalkylene terephthalate having an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl/g and measured under conditions of a temperature of 250° C. and a load of 5 kg according to ASTM D1238 100 parts by weight of a base resin containing 1 to 99% by weight of polycarbonate having a flow index of 1 to 11 g / 10 min, (B) 5.5 to 9 parts by weight of an impact modifier having a core-shell structure, (C) halogenated epoxy-based 10 to 30 parts by weight of a flame retardant, (D) 2 to 4.5 parts by weight of a glycidyl methacrylate-based compatibilizer containing vinyl acrylate, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor that is a monobasic phosphate. In this case, mechanical strength such as tensile strength, flexural modulus, flexural strength and impact strength, molding processability and flame retardancy are secured at a certain level or more, and both hot water resistance and weather resistance are excellent.

In this description, the flow index can be measured by setting a weight of 5 kg and a standard time of 10 minutes at 250 ° C in accordance with ASTM D1238. As a more specific example, a specimen is heated to a temperature of 250 ° C using GOETTFERT's melting index measuring equipment, put in a cylinder of a melt indexer, and melted for 10 minutes by applying a load of 5 kg with a piston It can be obtained by measuring the weight (g) of the resulting resin.

In this description, the WOM value measured in accordance with UL 746C (f1 Class) is, as a specific example, according to UL 746C (f1 Class) regulations, an accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000 , Xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiance 0.35 W/m ² at 340 nm, black panel temperature 60±3℃) applied, UV for 102 minutes for an impact specimen with a thickness of 3.2 mm It can be expressed as the retention rate (%) of the impact strength (according to ASTM D256) measured before and after the accelerated weathering test for a total of 1,000 hours, with simultaneous exposure to UV and water spray for 18 minutes as one cycle.

In this description, the value of the warm water resistance index measured according to UL 746C (f1 Class) is measured by completely immersing an impact specimen with a thickness of 3.2 mm in 70 ° C. deionized water according to UL 746C (f1 Class) as a specific example. After leaving it for a day, it is taken out and immersed in deionized water at 23 ° C. for 30 minutes, and the retention rate (%) of the impact strength measured before and after the warm water resistance test is performed (according to ASTM D256) can be expressed.

In this description, as a specific example, the impact strength is measured in an impact specimen with a thickness of 3.2 mm and a notch width of 2.54 mm obtained by injection under the conditions of an injection temperature (based on the inlet) of 250 ° C, a mold temperature of 60 ° C, a holding pressure of 60 MPa and an injection speed of 40 MPa. It can be measured according to ASTM D256 under a temperature of 23 ℃ using Toyoseiki's IMPACT TESTER.

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

(A) base resin

The base resin includes 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate based on 100 parts by weight of the base resin, and in a preferred example, 40 to 60% by weight of polyalkylene terephthalate and 40% by weight of polycarbonate to 60% by weight, more preferably 40 to 55% by weight of polyalkylene terephthalate and 45 to 60% by weight of polycarbonate, even more preferably 45 to 55% by weight of polyalkylene terephthalate and 45 to 55% by weight of polycarbonate %, and within this range, excellent mechanical strength, molding processability, hot water resistance and weather resistance have effects.

The polyalkylene terephthalate may be polybutylene terephthalate (PBT) as a preferred example, and in this case, molding processability, hot water resistance, and weather resistance are more excellent.

The polybutylene terephthalate is not particularly limited in the case of a conventional polybutylene terephthalate resin, and for example, 1,4-butanediol and terephthalic acid or dimethyl terephthalate are directly esterified or transesterified to condensation polymerization may be a polymer.

The polybutylene terephthalate is, for example, a copolymer copolymerized with an impact-improving compound such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, aliphatic polyester, aliphatic polyamide, or the like, or the polybutylene terephthalate as the impact-improving compound. Modified polybutylene terephthalate mixed with the compound may be used, and in this case, there is an advantage in that hot water resistance and weather resistance are further improved without deterioration of other physical properties.

As another example, the polyalkylene terephthalate may be at least one selected from the group consisting of polyethylene terephthalate (PET) and polytrimethylene terephthalate (PTT), or a mixture of polybutylene terephthalate and polybutylene terephthalate. There is an advantage that molding processability is further improved.

The polyalkylene terephthalate may have an intrinsic viscosity (I.V.) of, for example, 0.9 to 1.3 dl/g, preferably 0.9 to 1.25 dl/g, and more preferably 0.95 to 1.25 dl/g, within this range. Molding processability, tensile strength, flexural modulus and molding processability of the composition are more excellent.

The polyalkylene terephthalate may have an intrinsic viscosity (IV) of, for example, 1.1 to 1.5 dl/g, preferably 1.1 to 1.4 dl/g, and more preferably 1.2 to 1.4 dl/g, within this range. impact strength of the composition, Tensile strength, flexural modulus, and molding processability are more excellent.

Unless otherwise specified, the intrinsic viscosity in this description is obtained by completely dissolving the sample to be measured in a methylene chloride solvent at a concentration of 0.05 g/ml, and then filtering the filtrate using a filter using an Ubbelohde viscometer. It is the value measured at 20 ℃ using

The polyalkylene terephthalate may have, for example, a weight average molecular weight of 30,000 to 100,000 g/mol, 40,000 to 80,000 g/mol, or 45,000 to 70,000 g/mol, and excellent mechanical properties are effective within this range.

in this article The weight average molecular weight of polyalkylene terephthalate can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined. As an example, NaTFA (sodium trifluoroacetate) is used as an eluent at 0.01 N It can be measured as a relative value to a standard poly methyl methacrylate (PMMA) sample through GPC using a HFIP (hexafluoroisopropanol) solution containing At this time, a more specific measurement example is as follows.

(1) Measuring device: EcoSEC HLC-8320 GPC by Tosoh

(2) Detector: RI-detector

(3) Solvent: HFIP + NaTFA (0.01 N)

(4) Column model: 2 x TSKgel SuperAWM-H (Tosoh Co., Ltd., 6.0 x 150 mm)

(5) column temperature: 40°C

(6) Flow rate: 0.3 mL/min

(7) Sample concentration: 3 mg/mL

(8) Injection amount: 100 μl

(9) Data processing: EcoSEC software

(10) Standard sample: PMMA

The method for producing the alkylene terephthalate is not particularly limited in the case of a method commonly applied in the art, and commercially available products may be used as long as they follow the definition of the present invention.

The polycarbonate has a flow index of 1 to 1, measured under ISO 1133 at a temperature of 300 ° C and a load of 1.2 kg. 11 / 10min, preferably 3 to 10 g / 10min, or 1 to 8 g / 10min, more preferably 2 to 5 g / 10min, and within this range, there is an effect of excellent mechanical strength and molding processability .

The polycarbonate may have, for example, a weight average molecular weight of 2,000 to 40,000 g/mol, preferably 30,000 to 40,000 g/mol, and more preferably 32,000 to 38,000 g/mol, and mechanical strength and physical property balance within this range. has a better effect.

In the present description, the weight average molecular weight of polycarbonate can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, standard PS through GPC using THF (tetrahydrofuran) as an eluent. (standard polystyrene) can be measured as a relative value for the sample. At this time, as a more specific measurement example, solvent: THF, column temperature: 40 ℃, flow rate: 0.3ml / min, sample concentration: 20mg / ml, injection amount: 5μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing : Agilent ChemStation S/W, test method (Mn, Mw and PDI): OECD TG 118 condition can be measured.

The polycarbonate may have an intrinsic viscosity of, for example, 2.0 to 3.5 dl/g, preferably 2.2 to 3.3 dl/g, and more preferably 2.5 to 3.0 dl/g, and within this range, mechanical strength and physical property balance are It has a better effect.

The polycarbonate has, for example, an impact strength of 50 kg cm/cm or more, preferably 50 to 80 kg cm/cm, more preferably 50 to 80 kg cm/cm, more preferably Preferably, 65 to 75 kg cm/cm may be used, and within this range, there is an advantage in that mechanical properties are better without deterioration of other properties.

The type of the polycarbonate is not particularly limited, but may be, for example, a polymerized resin including a bisphenol-based monomer and a carbonate precursor.

The bispinol-based monomer is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3 ,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2 ,2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) )propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and α,ω-bis[3-(ο-hydroxyphenyl)propyl] It may be one or more selected from the group consisting of polydimethylsiloxane.

The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis ( diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate.

The polycarbonate may be, for example, at least one selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin, preferably a linear polycarbonate resin, , In this case, the fluidity is improved, so that the molding processability and appearance characteristics are more excellent.

The linear polycarbonate resin may be, for example, a bisphenol-A-based polycarbonate resin.

The manufacturing method of the polycarbonate is not particularly limited in the case of a manufacturing method commonly applied in the art, and commercially available products may be used as long as they follow the definition of the present invention.

(B) Impact modifier of core-shell structure

The core-shell structured impact modifier is included in 5.5 to 9 parts by weight, preferably 5.7 to 9 parts by weight, more preferably 6 to 8.8 parts by weight, and even more preferably 6 to 7.5 parts by weight, Within this range, there is an effect of excellent mechanical strength, molding processability, hot water resistance and weather resistance.

In the present description, the core-shell structure may follow a definition commonly applied in the art to which the present invention pertains, and may be defined as, for example, manufactured by a manufacturing method of graft polymerization of monomers in the presence of rubber, or TEM (Transmission Electron Microscope), SEM (Scanning Electron Microscope), etc. can be defined as a multi-layered structure of two or more layers confirmed by an analysis device.

The core-shell structured impact modifier may be, for example, a butyl acrylic impact modifier including a butyl acryl lake rubber core, and in this case, mechanical strength is excellent without deterioration of other physical properties.

The butyl acrylic impact modifier may include, for example, 50 to 80% by weight, preferably 55 to 75% by weight, and more preferably 60 to 75% by weight of butyl acrylate rubber based on the total weight thereof, in this case It has advantages of superior mechanical strength, warm water resistance and weather resistance.

The core-shell structured impact modifier includes, for example, a butyl acrylic impact modifier including a butyl acryl lake rubber core, but may not include an ethylene-(butyl) acrylate copolymer. In this case, ethylene-(butyl ) Compared to the case of including an acrylate copolymer-containing impact modifier, mechanical strength such as tensile strength, flexural modulus and flexural strength, and superior hot water resistance and weather resistance are superior.

The core included in the core-shell structured impact modifier may have, for example, a DLS average particle diameter of 80 to 200 nm, more preferably 90 to 150 nm, still more preferably 100 to 140 nm, even more preferably It may be 120 to 140 nm, and in this case, there are advantages of superior mechanical strength, hot water resistance and weather resistance.

The core included in the core-shell structured impact modifier may have an average TEM particle diameter of, for example, 50 to 140 nm, more preferably 60 to 110 nm, more preferably 70 to 100 nm, and even more preferably It may be 80 to 95 nm, and in this case, there are advantages of superior mechanical strength, hot water resistance and weather resistance.

In the present description, the DLS average particle diameter can be measured using dynamic light scattering, and as a specific measurement example, in Gaussian mode using a particle size distribution analyzer (Nicomp CW380, PPS Co.) in a latex state It can be measured as an intensity value. As a specific example, after preparing a sample by diluting 0.1 g of latex having a solid content of 35 to 50% by weight with 100 g of deionized water, using a particle size distribution analyzer (Nicomp CW380, PPS Co.) at 23 ° C., the measurement method is Auto-dilution and measured with a flow cell, and the measurement mode can be obtained by dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis.

In the present description, the TEM average particle diameter can be measured using TEM (transmission electron microscope) analysis, and as a specific example, it means the arithmetic mean value obtained by numerically measuring the particle size on a TEM high-magnification image. At this time, specific measurement examples are as follows:

- Sample preparation: thermoplastic resin (composition) prepared by an extrusion kneader

- Sample pretreatment: Timming (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO ₄ vapor staining (2 hours)

- Analysis device: TEM (JEM-1400, Jeol company)

- Analysis conditions: Acc. Volt 120 kV, SPOT Size 1 (X 10K, X 25K, X 50K)

- Size (average particle diameter) measurement: average of the longest diameters of the top 10% of the particles in diameter

Here, the average of the longest diameters of the particles in the top 10% of the diameter size means, for example, 100 or more particles are randomly selected from the TEM image, their longest diameters are measured, and the arithmetic mean value of the top 10% of the measured diameters is it means.

The core included in the core-shell structured impact modifier may be, for example, rubber having a glass transition temperature of -50 to -20°C, and the glass transition temperature is preferably -45 to -23°C, more preferably It may be -40 to -25 ° C, and within this range, there is an effect of better impact strength without deterioration of other physical properties.

In this substrate, the glass transition temperature can be measured at a heating rate of 10 °C/min using TA Instruments Q100 Differential Scanning Calorimetry (DSC) in accordance with ASTM D 3418.

The core-shell structured impact modifier may include, for example, a shell made of at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and alkyl methacrylates , preferably aromatic vinyl compounds and vinyl cyan compounds. In this case, there is an advantage of excellent mechanical strength.

In the present description, a polymer comprising a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.

In the present description, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, and is preferably styrene.

In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

In the present disclosure, the alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in an alkyl group, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , It may be at least one selected from the group consisting of 2-ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate.

The core-shell structured impact modifier may be prepared by, for example, emulsion polymerization, and in this case, excellent chemical resistance, weather resistance, fluidity, tensile strength and impact strength are obtained. The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.

As another example, the core-shell structured impact modifier may be a commercially available product as long as it follows the definition of the present invention.

(C) halogenated epoxy flame retardant

The halogenated epoxy-based flame retardant It is included in 10 to 30 parts by weight, preferably 12 to 27 parts by weight, more preferably 13 to 25 parts by weight, and within this range, mechanical strength, molding processability, hot water resistance and weather resistance are excellent.

The halogenated epoxy-based flame retardant may be, for example, a brominated epoxy-based flame retardant, and in this case, the composition has superior thermal stability and flame retardancy.

The brominated epoxy-based flame retardant is, for example, a bromine-substituted epoxy-based oligomer, more specifically, a bisphenol A-type compound unit having n bromine substituents and a bisphenol A-type glycidyl ether compound unit having m bromine substituents. It may be a copolymer comprising, where m and n are each independently an integer of 1 to 6, preferably an integer of 2 to 5, more preferably 4, in which case thermal stability and flame retardancy are more excellent There is an advantage.

The brominated epoxy-based flame retardant may, for example, have a weight average molecular weight of 800 to 5,000 g/mol, preferably 1,000 to 4,000 g/mol, and more preferably 1,100 to 3,000 g/mol, and within this range There is an advantage in that the flame retardancy improvement effect is excellent without deterioration of other physical properties.

The weight average molecular weight of the brominated epoxy-based flame retardant may be measured according to a method commonly practiced in the art to which the present invention belongs.

The manufacturing method of the halogenated epoxy-based flame retardant is not particularly limited in the case of a manufacturing method commonly applied in the art, and commercially available products may be used as long as they follow the definition of the present invention.

The thermoplastic resin composition of the present invention may further include, for example, a flame retardant aid in addition to the halogenated epoxy-based flame retardant, and the flame retardant aid may be included in an amount of 2 to 8 parts by weight, preferably 2 to 7 parts by weight, more Preferably, it may be included in 3 to 5 parts by weight, and in this case, there is an advantage in that flame retardancy is more excellent due to interaction with the halogenated epoxy-based flame retardant.

The flame retardant aid may use, for example, an antimony-based compound, and the antimony-based compound may preferably include antimony trioxide and/or antimony pentoxide, and more preferably may include antimony trioxide. There is an advantage that flame retardancy is more excellent without deterioration of physical properties.

(D) compatibilizer

The compatibilizing agent It is included in 2 to 4.5 parts by weight, preferably 2 to 4.3 parts by weight, more preferably 2 to 4.1 parts by weight, and even more preferably 2.0 to 3.2 parts by weight. Within this range, mechanical strength and molding processability , it has excellent effects on hot water resistance and weather resistance.

For example, the compatibilizer can further improve mechanical strength and molding processability by controlling the crystallization rate of polyalkylene terephthalate, which is a crystalline resin, while performing an impact reinforcing action through interaction with the base resin, for example. Through this, it can play a role in preventing the deterioration of the appearance quality that occurs during the injection process.

From this point of view, the compatibilizer may include a glycidyl methacrylate-based compatibilizer as a preferred example, and in this case, mechanical strength, particularly impact strength, is greatly improved, and flame retardancy reinforcing effect is excellent.

The content of the glycidyl methacrylate compound included in the total 100% by weight of the glycidyl methacrylate-based compatibilizer may be, for example, 20% by weight or less, preferably 3 to 20% by weight, more preferably 5 to 15% by weight, more preferably 8 to 12% by weight, and in this case, there is an excellent advantage in improving mechanical strength and flame retardancy.

The glycidyl methacrylate-based compatibilizer may include, for example, vinyl acrylate, and in this case, mechanical strength, hot water resistance, and weather resistance are superior.

The vinyl acrylate may be, for example, 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the total weight of the glycidyl methacrylate-based compatibilizer. In this case, there is an advantage that mechanical strength, hot water resistance and weather resistance are superior without deterioration of other physical properties.

The glycidyl methacrylate-based compatibilizer may be, for example, a copolymer comprising glycidyl methacrylate, an olefin-based compound, and vinyl acetate, and more preferably ethylene-glycol grafted with vinyl acetate. It may be a cydyl methacrylate copolymer, and in this case, mechanical strength, molding processability, flame retardancy, hot water resistance and weather resistance are more excellent without deterioration of other physical properties.

The glycidyl methacrylate-based compatibilizer may further include, for example, maleic acid or maleic anhydride, and in this case, heat resistance and physical property balance are better.

The compatibilizer has a flow index of 1 to 20 g / 10 min, preferably 1 to 15 g / 10 min, more preferably 5 to 10 It may be g/10min, and within this range, there is an effect of excellent mechanical strength and molding processability.

The compatibilizing agent may have, for example, a glass transition temperature of -50 to 0 °C, preferably -40 to -10 °C, and more preferably -35 to -20 °C, and within this range, mechanical strength and molding processability This has an excellent effect.

The method for preparing the glycidyl methacrylate-based compatibilizer is not particularly limited in the case of a method commonly applied in the art, and commercially available products may be used as long as they follow the definition of the present invention.

(E) transesterification inhibitor

The transesterification inhibitor may be included in an amount of 0.1 to 2.0 parts by weight, preferably 0.1 to 1.4 parts by weight, more preferably 0.2 to 0.8 parts by weight, and mechanical strength, molding processability, hot water resistance and weather resistance within this range. This has a great effect.

For example, the transesterification inhibitor may inhibit a transesterification reaction between a carbonate unit of polycarbonate and an ester unit of polyalkylene terephthalate included in the base resin, thereby preventing deterioration in physical properties. In addition, it may act to improve heat resistance and weather resistance according to the prevention of decomposition of the base resin.

The transesterification inhibitor may be, for example, a phosphate-based compound, preferably an inorganic phosphate-based compound, and in this case, the effect of preventing decomposition of the base resin and improving the hot water resistance is excellent, and it may occur during kneading and molding. Discoloration of the composition is suppressed, so it is easier to express a desired color and has an advantage of excellent appearance quality.

The inorganic phosphate-based compound may be preferably a monobasic phosphate, more preferably a monobasic alkali metal phosphate, and particularly preferably NaH ₂ PO ₄ , in which case the effect of preventing decomposition of the base resin is more excellent, and in particular, the hot water resistance can be greatly improved. In addition, in this case, discoloration of the composition that may occur during kneading and molding is suppressed, so that the desired color is more easily expressed and the appearance quality is excellent.

When the transesterification inhibitor includes, for example, an organic phosphate-based compound, the color may be darkened by reacting with the flame retardant aid during the kneading and molding process of the composition. In this case, due to the darkened pellet color, for example, pigments, etc. When added, it may be difficult to express the desired color. As a specific example, the organic phosphate-based compound may refer to a phosphate compound having at least one organic substituent such as an alkyl phosphate or an aryl phosphate.

For example, the transesterification inhibitor may further include at least one selected from the group consisting of carbodiimide, monobasic zinc phosphate, hydroxybenzophenone, and methyl salicylate, together with the monobasic alkali metal phosphate, In this case, there is an effect of excellent warm water resistance and mechanical strength.

(F) UV stabilizer

The thermoplastic resin composition may preferably further include a UV stabilizer, and as a specific example 0.1 to 2.0 parts by weight, preferably 0.1 to 1.4 parts by weight, and more preferably 0.2 to 0.8 parts by weight, and within this range, there is an advantage of excellent warm water resistance and weather resistance without deterioration of other physical properties.

The UV stabilizer consists of, for example, a benzotriazole-based UV stabilizer, a triazine-based UV stabilizer, a benzophenone-based UV stabilizer, a quinolinone-based UV stabilizer, a benzoate-based UV stabilizer, a cyanoacrylate-based UV stabilizer, and a benzoxazole-based UV stabilizer It may be at least one selected from the group, preferably at least one selected from the group consisting of benzotriazole-based UV stabilizers and triazine-based UV stabilizers, more preferably benzotriazole-based UV stabilizers, in this case without deterioration of other physical properties It has the advantage of superior weather resistance.

The benzotriazole-based UV stabilizer may be, for example, a hydroxybenzotriazole-based compound, preferably a 2-(2'-hydroxyphenyl)benzotriazole-based compound, and as a specific example, a 2-(3',5 '-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole (CAS NO. 2440-22- 4), 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole (CAS NO. 3147-75-9), 2-(3',5'- Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2 -(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-( 3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzo Triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert- Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy Roxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl Ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert- Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'- Methylphenyl) benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4- (1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], 2-(2 H -benzotriazol-2-yl)-4,6-bis(1-methyl -1-phenylethyl)phenol (CAS NO. 70321-86-7) and 1 selected from the group consisting of transesterification products of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol. It may be more than one species, more preferably 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethyl At least one selected from the group consisting of butyl) phenyl) benzotriazole and 2- (2 H -benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, and even more Preferably, it may be 2-(2 H -benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and in this case, weather resistance is superior without deterioration of other physical properties. there is

The triazine-based UV stabilizer may preferably be a trisaryl 1,3,5-triazine compound, and specific examples include Tinuvin 360 or UV 360; Tinuvin 1577 or UV 1577 (2-[4,6-Bis(2,4-dimthylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy) phenol); Cyasorb 1164 or UV 1164; Cyasorb 2908 or UV 2908; and Cyasorb UV-3346 or UV 3346; more preferably Tinuvin 1577 or UV 1577, and in this case, there is an advantage of excellent weather resistance without deterioration of other physical properties.

The benzophenone-based UV stabilizer is, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4- Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2-hydroxy-4- Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydride hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis( 5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 4 , 4'-bis (diethylamino) may be one or more selected from the group consisting of benzophenone.

The indole-based UV stabilizer may be, for example, 2-[(1-methyl-2-phenyl-1H-indol-3-yl) methylene] propanedinitrile.

The quinolinone-based UV stabilizer may be, for example, 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

The benzoate-based UV stabilizer is, for example, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butyl Phenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and n-octadecyl- It may be at least one selected from the group consisting of 3,5-di-t-butyl-4-hydroxybenzoate.

The cyanoacrylate-based UV stabilizer is, for example, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3-(3',4'-methylenedioxy) phenyl)-acrylate, or a mixture thereof.

The UV stabilizer may have, for example, a molecular weight of 350 to 600 g/mol, preferably 400 to 550 g/mol, more preferably 420 to 470 g/mol, and within this range 400 nm or less, preferably It has an advantage of excellent weatherability due to its high absorbance in the wavelength range of 280 to 360 nm.

The molecular weight of the UV stabilizer can be calculated from the molecular formula, but if necessary, it can be measured according to a method commonly practiced in the art to which the present invention belongs.

thermoplastic resin composition

The thermoplastic resin composition of the present invention has excellent molding processability with a flow index of 7.0 g / 10 min or more measured under the conditions of a temperature of 250 ° C and a load of 5 kg according to ASTM D1238 from the above-defined composition, and in accordance with UL 746C (f1 Class) The measured WOM value is 70% or more, which is characterized by excellent weather resistance.

The thermoplastic resin composition of the present invention also has excellent molding processability with a flow index of 7.0 g / 10 min or more measured under the conditions of a temperature of 250 ° C and a load of 5 kg according to ASTM D1238 from the above-defined composition, and according to UL 746C (f1 Class) The measured warm water resistance index value is 50% or more, which is characterized by excellent warm water resistance.

The thermoplastic resin composition of the present invention also contains (A) 1 to 99% by weight of a polyalkylene terephthalate having an intrinsic viscosity (I.V.) of 0.9 to 1.3 dl/g and measured under conditions of a temperature of 250° C. and a load of 5 kg according to ASTM D1238 100 parts by weight of a base resin containing 1 to 99% by weight of polycarbonate having a flow index of 1 to 11 g / 10 min, (B) 5.5 to 9 parts by weight of an impact modifier having a core-shell structure, (C) a halogenated epoxy flame retardant 10 to 30 parts by weight, (D) 2 to 4.5 parts by weight of a compatibilizing agent, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor. , hot water resistance and weather resistance are greatly improved, so it is suitable for use as an outdoor electrical appliance for a long period of time.

As a specific example, the thermoplastic resin composition of the present invention includes a brominated epoxy-based flame retardant as the halogenated epoxy-based flame retardant, additionally includes an antimony-based compound, preferably antimony trioxide, as a flame-retardant aid, and an inorganic phosphate-based transesterification inhibitor. A compound, preferably an organic phosphate-based compound containing an alkali metal phosphate salt and not containing an organic phosphate-based compound may be free, in which case discoloration is suppressed without deterioration of other physical properties, resulting in more excellent appearance quality There is an advantage.

Organic phosphate-based compound free in the present description means that the organic phosphate-based compound is not artificially included in the thermoplastic resin composition, and specifically means that it is included in less than 0.1% by weight or 0% by weight.

As a specific example, the thermoplastic resin composition of the present invention includes a butyl acrylic impact modifier as an impact modifier of the core-shell structure, but ethylene-(butyl) acrylate copolymer-free ethylene-(butyl) acrylate copolymer-free It may be, and there is an advantage that mechanical strength such as tensile strength, flexural modulus and flexural strength, and better resistance to hot water and weatherability.

The flow index (250 ° C, 5 kg) of the thermoplastic resin composition is, for example, 7.0 to 20 g / 10 min, preferably 7.0 to 17 g / 10 min, more preferably 7.3 to 17 g / 10 min, and even more preferably 8.2 to 14 g/10 min. In this case, there is an advantage in that molding processability and appearance quality of molded products are better without deterioration of other physical properties.

The WOM value measured according to UL 746C (f1 Class) of the thermoplastic resin composition may be preferably 70 to 100%, more preferably 75 to 95%, and still more preferably 80 to 93%, and even more Preferably it may be 81.1 to 90%, in a preferred embodiment it may be 78 to 99%, more preferably 85 to 98%, and even more preferably 90 to 98%, in which case mechanical strength, molding processability , flame retardancy, hot water resistance and weather resistance are more excellent.

The warm water resistance index value of the thermoplastic resin composition measured according to UL 746C (f1 Class) may be preferably 50 to 100%, more preferably 60 to 95%, and even more preferably 70 to 90% , In a preferred embodiment, it may be 75 to 98%, more preferably 78 to 95%, and even more preferably 80 to 93%, and in this case, mechanical strength, molding processability, flame retardancy, warm water resistance and weather resistance are more excellent There is an advantage.

The thermoplastic resin composition has, for example, excellent flame retardancy (under the condition of a specimen thickness of 0.8 mm) measured according to the UL 94 standard of V-1 grade or higher, more preferably V-0 grade or higher.

In the present description, flame retardancy can be measured under the condition of a specimen standard of 127 mm x 12.7 mm x 0.8 mm in accordance with the UL 94 standard (Vertical Burning Test) as a specific example.

The thermoplastic resin composition is a preferred example, based on UL 746C (f1 Class), before and after performing an accelerated weather resistance test in the same way as the WOM value measurement method for a flame retardant specimen having a thickness of 0.8 mm. Measured according to UL 94 standard The flame retardant grade may be the same, and in this case, flame retardancy is prevented from deterioration even when exposed to harsh weather conditions such as UV or precipitation, and there is an advantage in providing an outdoor molded article with excellent flame retardancy retention.

As a preferred example of the thermoplastic resin composition, in accordance with UL 746C (f1 Class), a flame retardant specimen having a thickness of 0.8 mm is subjected to a hot water resistance test in the same manner as the method for measuring the water resistance index value, and then the temperature is 23 ° C and the relative humidity is By performing additional conditioning for 2 weeks under 50% conditions, the flame retardancy rating measured according to the UL 94 standard before and after the hot water test and additional conditioning may be the same, in which case, even when exposed to high temperature hot water, deterioration in flame retardancy is prevented Thus, there is an advantage of providing an outdoor molded article having excellent flame retardancy retention.

As a preferred example, the thermoplastic resin composition has a WOM value of 70% or more and a warm water resistance index of 50% or more measured according to UL 746C (f1 Class) before and after the accelerated weather resistance test measured according to UL 746C (f1 Class) And, there is no change in the flame retardant grade before and after the hot water test and additional conditioning, so it can satisfy the f1 Class grade specified in UL 746C, and thus has an effect suitable for application as a high-impact flame retardant material for outdoor use.

As a preferred example, the thermoplastic resin composition has a tensile strength of 500 MPa or more, preferably 520 to 630 MPa, more preferably, measured under the conditions of a temperature of 23 ° C, a test speed of 50 mm / min, and a specimen thickness of 3.2 mm in accordance with ASTM D638. It may be 525 to 620 MPa, more preferably 535 to 600 MPa, and even more preferably 537 to 590 MPa, and within this range, there is an advantage of excellent mechanical strength without deterioration of other physical properties.

In this substrate, the tensile strength can be measured under the condition of a specimen standard length of 165 mm, width of 19 mm, thickness of 3.2 mm, and test speed of 50 mm/min at 23 ° C. temperature conditions according to ASTM D638 as a specific example.

The thermoplastic resin composition, as a preferred example, has a flexural modulus of 20,000 kgf/cm ² or more, preferably 20,000 to 25,000 kgf/cm, measured under the conditions of a test speed of 2.8 mm/min, SPAN 50, and specimen thickness of 3.2 mm in accordance with ASTM D790. ² , more preferably 21,000 to 24,000 kgf/cm ² , and even more preferably 21,000 to 23,000 kgf/cm ² , and within this range, there is an advantage in that mechanical strength is excellent without deterioration of other physical properties.

As a preferred example, the thermoplastic resin composition has a flexural strength of 800 kgf/cm ² or more, preferably 800 to 1,000 kgf/cm, measured under the conditions of a test speed of 2.8 mm/min, SPAN 50, and specimen thickness of 3.2 mm in accordance with ASTM D790. ² , more preferably 820 to 1,000 kgf/cm ² , and even more preferably 825 to 900 kgf/cm ² , and within this range, there is an advantage in that mechanical strength is excellent without deterioration of other physical properties.

In this substrate, the flexural modulus and flexural strength are, as a specific example, in accordance with ASTM D790, at room temperature of 23 ° C. Specimen standard length 127 mm, width 12.7 mm, thickness 3.2 mm, interval (SPAN) 50 mm, and test speed 2.8 mm / min conditions can be measured under

The thermoplastic resin composition has, for example, an impact strength of 70 kgf cm/cm or more, preferably 70 to 100 kgf cm/cm, more preferably 76 to 100 kgf cm/cm, as measured according to ASTM D256. , More preferably, it may be 80 to 95 kgf cm / cm, and within this range, there is an advantage of excellent mechanical strength without deterioration of other physical properties.

As described above, the thermoplastic resin composition of the present invention has excellent mechanical strength, molding processability, and room temperature flame retardancy at room temperature, and thus has advantages suitable for use in electrical products. In addition, as described above, the retention rate of impact strength and the retention rate of the flame retardant class before and after the weather resistance and hot water index tests satisfy the f1 Class class specified in UL 746C, and thus have the advantage of being suitable as an impact resistant flame retardant material for outdoor use.

The thermoplastic resin composition may have, for example, a specific gravity of 1.25 to 1.40, preferably 1.30 to 1.33, measured at 23 ° C. in accordance with ISO 1183, and has good mechanical properties within this range, making it suitable for electrical products, especially molded products for power packs. There are advantages that are desirable to apply as.

The thermoplastic resin composition optionally includes at least one selected from the group consisting of a lubricant, a heat stabilizer, a pigment, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a retardant, an anti-drip agent, an anti-friction agent, and an anti-abrasion agent, as needed. Other additives may be further included in an amount of 0.01 to 10 parts by weight, 0.05 to 7 parts by weight, 0.1 to 5 parts by weight, or 0.5 to 4.5 parts by weight based on 100 parts by weight of the base resin, and within this range, the thermoplastic resin of the present description There is an advantage in that the desired physical properties are well implemented without deteriorating the desired physical properties of the composition.

The lubricant may be, for example, at least one selected from the group consisting of a fatty acid amide-based compound, a montan-based wax, and an olefin-based wax, preferably an olefin-based wax, and more preferably a polyethylene wax, in which case molding processability And mold release properties are excellent, and noise and friction resistance can be further improved.

The fatty acid amide compound is, for example, stearamide (stearamide), behenamide (behenamide), ethylene bis stearamide [ethylene bis (stearamide)], ethylene bis 12-hydroxy stearamide [N, N'-ethylene bis (12 -hydroxystearamide], erucamide, oleamide, and ethylene bis oleamide.

The montan-based wax may be, for example, montan wax, montan ester wax, or a mixture thereof.

The olefin-based wax may be, for example, polyethylene wax, polypropylene wax, or a mixture thereof.

The lubricant is, for example, the (A) base resin, (B) core-shell structure impact modifier, (C) halogenated epoxy-based flame retardant, (D) compatibilizer, and (E) 100 parts by weight of the total of the transesterification inhibitor It may be included in 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, and more preferably 0.1 to 0.5 parts by weight, and within this range, the appearance quality of the molded article is excellent while the physical property balance is excellent.

The wax of the present description is not particularly limited in definition if it follows the form and/or properties of wax commonly recognized in the art to which the present invention pertains.

The heat stabilizer may include, for example, a phenol-based heat stabilizer (antioxidant), and in this case, oxidation by heat is prevented during an extrusion process, and mechanical properties and heat resistance are excellent.

The phenolic heat stabilizer is, for example, N,N'-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)], pentaerythritol tetrakis [3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate](pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], CAS No. 6683-19-8), N,N′-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3- t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl ) benzene, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, and at least one selected from the group consisting of hindered phenolic heat stabilizers In this case, the heat resistance can be greatly improved while the physical property balance is maintained high. The hindered phenolic heat stabilizer is, for example, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Octadecyl 3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate, CAS number 2082-79-3), 2,2'-methylenebis(4-methyl-6-t-butylphenol), hexamethylene glycol-bis(3,5-di-t-butyl- 4-hydroxyhydrocinnamate), triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenol) pro Cionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-3-methyl-phenol), distearyl -3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacrylic rate, and 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10 - It may be one or more selected from the group consisting of tetraoxaspiro [5,5] undecane. The heat stabilizer is preferably pentaerythritol tetrakis[3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert -butyl-4-hydroxyphenyl)propionate or a mixture thereof.

The heat stabilizer is, for example, the (A) base resin, (B) a core-shell structured impact modifier, (C) a halogenated epoxy-based flame retardant, (D) a compatibilizer, and (E) a total of 100 weight of a transesterification inhibitor It may be included in 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, and more preferably 0.1 to 0.5 parts by weight, and has an effect of improving heat resistance while excellent physical property balance within this range.

The pigment may be an inorganic pigment or an organic pigment.

The organic pigment is, for example, perinone-based, anthraquinone-based pigment, perylene-based pigment, phthalocyanine-based pigment, azo-based pigment, indigo-based pigment, dioxazine-based pigment, quinacridone-based pigment, methane-based pigment, quinoline-based pigment, isoindry It may be at least one selected from the group consisting of paddy-based pigments and phthalone-based pigments.

The inorganic pigment may be, for example, at least one selected from the group consisting of ultramarine-based pigments, titanium dioxide, zinc sulfide, zinc oxide, iron oxide, and carbon black.

The release agent may be used, for example, at least one selected from the group consisting of glycerin sterate, polyethylene tetra sterate, and the like, but is not limited thereto.

The antistatic agent may use one or more kinds of anionic surfactants, nonionic surfactants, and the like as an example, but it is specified that it is not limited thereto.

The anti-drip agent is, for example, PTFE (polytetrafluoroethylene), a mixture of PTFE and styrene-acrylonitrile (SAN) resin (PTFE / SAN), a mixture of PTFE and PMMA (PTFE / PMMA), polyamide, polysilicon, and TFE-HFP ( At least one selected from the group consisting of tetrafluoroethylene-hexafluoropropylene) copolymer may be used, and preferably at least one selected from the group consisting of PTFE/SAN and PTFE/PMMA. The PTFE/SAN and PTFE/PMMA may preferably be a mixture of PTFE and SAN resin or PMMA at a weight ratio of 1:0.5 to 1.5, respectively, and in one embodiment may be a mixture at a weight ratio of 1:1.

The antibacterial agent, processing aid, metal deactivator, inhibitor, anti-friction agent, anti-wear agent, etc. are not particularly limited as long as they are commonly used in the art to which the present invention belongs.

Manufacturing method of thermoplastic resin composition

The method for preparing the thermoplastic resin composition of the present invention includes (A) 100 parts by weight of a base resin containing 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate, (B) an impact modifier having a core-shell structure. 5.5 to 9 parts by weight, (C) 10 to 30 parts by weight of a halogenated epoxy flame retardant, (D) 2 to 4.5 parts by weight of a compatibilizing agent, and (E) 0.1 to 2 parts by weight of a transesterification inhibitor at 240 to 280 ° C. and 150 to 300 rpm It is characterized in that it comprises the steps of melt kneading and extruding under conditions. In this case, while securing all mechanical strength, molding processability, and flame retardancy, hot water resistance and weather resistance are greatly improved, so that there is an effect suitable for use as an outdoor electric product for a long period of time.

The manufacturing method of the thermoplastic resin composition shares all the technical characteristics of the thermoplastic resin composition described above. Therefore, the description of the overlapping part will be omitted.

In the melt-kneading and extruding step, for example, the temperature and the screw rotation speed of the extruder are respectively 240 to 280 ° C and 150 to 300 rpm, preferably 245 to 270 ° C and 170 to 260 rpm, more preferably 250 to 260 ° C And it may proceed under 190 to 220 rpm, and there is an advantage in sufficiently obtaining desired physical properties within this range.

The kneading and extruding step may be performed using, for example, at least one selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer, and using this, the composition is uniformly mixed and extruded, for example, in the form of pellets. It is possible to obtain a thermoplastic resin composition of, and in this case, there is an effect of preventing deterioration of mechanical properties and heat resistance, and having excellent appearance quality.

molding

The molded article of the present invention is characterized by comprising the thermoplastic resin composition of the present description, in this case It has excellent mechanical strength, molding processability and flame retardancy, as well as excellent hot water resistance and weather resistance.

The manufacturing method of the molded article may be manufactured by a method commonly used in the art. For example, injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, pressure molding method, heat bending molding method, compression molding method, calender molding method or rotation using the melt-kneaded product or pellets of the thermoplastic resin composition according to the present invention as a raw material A molding method such as a molding method can be applied. At this time, the size and thickness of the molded article may be appropriately adjusted according to the purpose of use.

As a specific example, the molded product may be manufactured by injecting a melt-kneaded product or pellets of the thermoplastic resin composition according to the present invention using an extruder.

In the step of injecting, for example, the melt-kneaded product or pellets are injected at an injection temperature of 240 to 280° C., preferably 245 to 270° C.; Mold temperature 40 to 80 ℃, preferably 50 to 70 ℃; and an injection speed of 10 to 50 mm/sec, preferably 20 to 40 mm/sec; It may be a step of injecting under.

The molded article has excellent mechanical strength, molding processability and flame retardancy, and is excellent in both hot water resistance and weather resistance, and is suitable for application as a product that is frequently used in high temperature environments and outdoors while requiring high mechanical strength and flame retardancy. As a specific example, for outdoor use It is suitable for application to electrical appliances, and can be particularly preferably applied to a power box.

1 and 2 are exemplary images of power packs having different shapes, respectively, showing a state in which a door is opened. When the molded article of the present invention is applied to such a power box, there is an advantage of excellent long-term durability without deterioration of long-term physical properties.

In describing the thermoplastic resin composition of the present description, its manufacturing method and molded article, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. do.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these changes and modifications fall within the scope of the appended claims.

[Example]

Materials used in the following Examples and Comparative Examples are as follows.

(A) base resin

(A-a1) Polyalkylene terephthalate: PBT resin having an intrinsic viscosity (20° C.) of 1.2 dl/g (weight average molecular weight of 95,000 g/mol)

(A-a2) Polyalkylene terephthalate: PBT resin having an intrinsic viscosity (20° C.) of 0.98 dl/g

(A-a3) Polyalkylene terephthalate: PBT resin having an intrinsic viscosity (20° C.) of 0.84 dl/g (weight average molecular weight of 75,000 g/mol)

(A-b1) Polycarbonate: Bisphenol A type PC resin (weight average molecular weight 70,000 g/mol) having a flow index (300°C, 1.2 kg load) of 3 g/10 min measured according to ISO 1133

(A-b2) Polycarbonate: Bisphenol A type PC resin having a flow index (300 ° C, 1.2 kg load) of 10 g / 10 min measured according to ISO 1133

(A-b3) Polycarbonate: Bisphenol A type PC resin (weight average molecular weight 44,000 g/mol) having a flow index (300°C, 1.2 kg load) of 15 g/10 min measured according to ISO 1133

(B-1) Impact modifier: BA impact modifier of core-shell structure containing 60% by weight of core (butyl acrylate rubber) and 40% by weight of shell (20% by weight of acrylonitrile and 80% by weight of styrene)

(B-2) Impact modifier: Non-core-shell poly(ethylene-butyl acrylate-glycidyl methacrylate) impact modifier (Elvaloy PTW from Dupont, butyl acrylate 27% by weight)

(C-a1) flame retardant: brominated epoxy oligomer flame retardant (CAS NO. 68928-70-1)

(C-a2) flame retardant: brominated aromatic carbonate oligomer flame retardant (C ₂₂ H ₁₅ Br ₇ Cl ₂ O ₄ )

(C-b1) flame retardant aid: Sb ₂ O ₃

(D-1) compatibilizer: ethylene-glycidyl methacrylate-vinyl acetate terpolymer (E-GMA-VA, GMA 12% by weight, VA 5% by weight)

(D-2) compatibilizer: ethylene-glycidyl methacrylate-n butyl acrylate terpolymer (E-GMA-BA, 5% by weight of GMA, 28% by weight of BA)

(E-1) transesterification inhibitor: NaH ₂ PO ₄

(E-2) transesterification inhibitor: Na ₂ HPO ₄

(E-3) transesterification inhibitor: diphenyl phosphate

(F) UV stabilizer: benzotriazole-based compound (molecular weight 448 g/mol, 300-350 nm wavelength absorption)

(G) Additional additives: The following additional additives (G-1) to (G-3) were mixed and added at the same weight ratio (1:1:1).

(G-1) Thermal stabilizer: phenolic antioxidant (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) propionate]methane)

(G-2) lubricant: PE wax (low molecular weight polyethylene wax)

(G-3) anti-drip agent (anti-drip agent): polytetrafluoroethylene/PMMA (weight ratio 1:1 mixture)

Examples 1 to 7 and Comparative Examples 1 to 14

(A) base resin, (B) impact modifier, (C) flame retardant, (D) compatibilizer, (E) transesterification inhibitor, (F) UV stabilizer, and (G) additional additives in Tables 1 to 3 below. The indicated contents are mixed using a super mixer and extruded with a twin-screw extruder (screw diameter 40 mm, L/D = 40) under extrusion conditions of an extrusion temperature of 260 ° C and a screw rotation speed of 250 rpm to form pellets. made in the form.

After drying the prepared thermoplastic resin composition in the form of pellets at 100 ° C. for more than 2 hours, specimens were prepared by injection molding under conditions of an injection temperature of 250 ° C., a mold temperature of 60 ° C. and an injection speed of 30 mm / sec in an injection machine, which was room temperature ( 20 to 26 ° C) after leaving it for 48 hours or more, and then measuring the physical properties.

[Test Example]

The physical properties of the specimens prepared in the Examples and Comparative Examples were measured in the following manner, and the results are shown in Tables 4 to 6 below.

* Specific gravity: measured using a specific gravity meter (Scott volumeter, model name: Version USP 616) in accordance with ASTM D792.

* Tensile strength (kgf / cm ² ): In accordance with ASTM D638, it was measured at 23 ° C under the conditions of a specimen standard length of 165 mm, width of 19 mm, thickness of 3.2 mm, and test speed of 50 mm / min.

* Flexural strength and flexural modulus (kgf/cm ² ): According to ASTM D790, specimen standard length 127 mm, width 12.7 mm, thickness 3.2 mm, span 50 mm, and test speed 2.8 mm/min at 23 °C conditions were measured.

* Impact strength (kgf cm/cm): measured at 23° C. under the condition of a specimen standard thickness of 3.2 mm and a notch width of 2.54 mm in accordance with ASTM D256.

* Melt flow index (g / 10min): In accordance with ASTM D1238, it was measured for 10 minutes under the conditions of a temperature of 250 ° C and a load of 5 kg using GOETTFERT's melting index measuring equipment.

* Flame retardancy: Measured in accordance with the UL 94 standard (Vertical Burning Test) with an injection-molded specimen having a width and length of 127 mm x 12.7 mm and a thickness of 0.8 mm.

* Appearance discoloration: It was determined whether or not discoloration was observed by visually checking the color of the prepared extruded pellets. Based on the natural pellet (NP) of the composition prepared according to the present invention, X (no discoloration) when the desired white color was observed, and O when discoloration was observed with the naked eye.

* f1 WOM (%): In accordance with UL 746C (f1 Class) regulations, an accelerated weathering test apparatus (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S.Boro ( outer) filter, irradiance 0.35 W/m ² at 340 nm, black panel temperature 60 ± 3 ° C) applied, exposure to UV for 102 minutes and simultaneous exposure to UV and water spray for 18 minutes for the impact specimen was 1 The accelerated weathering test was conducted for a total of 1,000 hours as a cycle, and the impact strength retention measured before and after the accelerated weathering test was expressed as %.

* f1 flame retardancy (WOM, grade): According to UL 746C (f1 Class) regulations, the flame retardancy test was performed on the flame retardant specimen, and then the flame retardancy was measured by the flame retardancy test method.

* f1 water resistance index (%): According to UL 746C (f1 Class) regulations, the impact specimen is completely immersed in 70 ° C deionized water and left for 7 days, and then immersed in 23 ° C deionized water for 30 minutes A hot water resistance test was performed, and the impact strength retention rate measured before and after the warm water resistance test was expressed in %.

* f1 flame retardancy (hot water resistance, grade): According to UL 746C (f1 Class) regulations, the hot water resistance test was conducted on the flame retardant specimen, and then conditioning was additionally performed for 2 weeks under conditions of a temperature of 23 ° C and a relative humidity of 50%. After that, the flame retardancy was measured by the above flame retardancy test method.

division
(parts by weight) Example One 2 3 4 5 6 7 (A-a1) PBT 49.3 49.7 48.3 49.7 48.6 - 49.3 (A-a2) PBT - - - - - 49.3 - (A-a3) PBT - - - - - - - (A-b1) PC 50.7 50.3 51.7 50.3 51.4 50.7 - (A-b2) PC - - - - - - 50.7 (A-b3) PC - - - - - - - (B-1) BA rubber-containing core-shell impact modifier 6.7 6.0 8.8 6.6 6.8 6.7 6.7 (B-2) non-core-shell impact modifier - - - - - - - (C-a1) brominated epoxy oligomer 17.3 17.2 17.7 17.2 17.6 17.3 17.3 (C-a2) brominated aromatic carbonate oligomer - - - - - - - (C-b1) Sb ₂ O ₃ 4.0 4.0 4.1 4.0 4.1 4.0 4.0 (D-1) E-GMA-VA 2.7 2.6 2.7 2.0 4.1 2.7 2.7 (D-2) E-GMA-BA - - - - - - - (E-1) NaH ₂ PO ₄ 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E-2) Na ₂ HPO ₄ - - - - - - - (E-3) diphenyl phosphate - - - - - - - (F) benzotriazole-based UV stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (G) additional additives 1.9 1.9 1.9 1.9 1.9 1.9 1.9

division
(parts by weight) comparative example One 2 3 4 5 6 7 (A-a1) PBT 50.6 50.3 50.0 49.3 49.3 50.6 49.3 (A-a2) PBT - - - - - - - (A-a3) PBT - - - - - - - (A-b1) PC 49.4 49.7 50.0 50.7 50.7 49.4 50.7 (A-b2) PC - - - - - - - (A-b3) PC - - - - - - - (B-1) BA rubber-containing core-shell impact modifier 6.5 6.5 6.6 6.7 6.7 3.9 - (B-2) non-core-shell impact modifier - - - - - - 6.7 (C-a1) brominated epoxy oligomer 16.9 17.0 17.1 17.3 - 16.9 17.3 (C-a2) brominated aromatic carbonate oligomer - - - - 17.3 - - (C-b1) Sb ₂ O ₃ 3.9 3.9 3.9 4.0 4.0 3.9 4.0 (D-1) E-GMA-VA - 0.7 1.3 - 2.7 2.6 2.7 (D-2) E-GMA-BA - - - 2.7 - - - (E-1) NaH ₂ PO ₄ 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E-2) Na ₂ HPO ₄ - - - - - - - (E-3) diphenyl phosphate - - - - - - - (F) benzotriazole-based UV stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (G) additional additives 1.8 1.8 1.8 1.9 1.9 1.8 1.9

division
(parts by weight) comparative example 8 9 10 11 12 13 14 (A-a1) PBT 47.6 49.3 47.9 - 49.3 - 49.3 (A-a2) PBT - - - - - - - (A-a3) PBT - - - 49.3 - 49.3 - (A-b1) PC 52.4 50.7 52.1 - 50.7 50.7 - (A-b2) PC - - - - - - - (A-b3) PC - - - 50.7 - - 50.7 (B-1) BA rubber-containing core-shell impact modifier 10.3 6.7 6.8 6.7 6.7 6.7 6.7 (B-2) non-core-shell impact modifier - - - - - - - (C-a1) brominated epoxy oligomer 17.9 17.3 17.8 17.3 17.3 17.3 17.3 (C-a2) brominated aromatic carbonate oligomer - - - - - - - (C-b1) Sb ₂ O ₃ 4.1 4.0 4.1 4.0 4.0 4.0 4.0 (D-1) E-GMA-VA 2.8 2.7 5.5 2.7 2.7 2.7 2.7 (D-2) E-GMA-BA - - - - - - - (E-1) NaH ₂ PO ₄ 0.4 - 0.4 0.4 - 0.4 0.4 (E-2) Na ₂ HPO ₄ - 0.4 - - - - - (E-3) diphenyl phosphate - - - - 0.4 - - (F) benzotriazole-based UV stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (G) additional additives 1.9 1.9 1.9 1.9 1.9 1.9 1.9

division Example One 2 3 4 5 6 7 importance 1.31 1.31 1.30 1.31 1.31 1.31 1.31 tensile strength
(kgf/cm ² ) 549 555 529 558 535 546 538 flexural modulus
(kgf/cm ² ) 21,600 21,800 20,300 21,700 21,200 21,850 21,650 Flexural strength (kgf/cm ² ) 848 854 823 857 829 850 847 impact strength
(kgfㆍcm/cm) 85 82 88 80 88 76 81 Flow rate (g/10min) 8.4 8.8 7.3 9.0 7.1 12.6 12.8 flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 discoloration X X X X X X X f1 Warm water index (%) 85.6 84.9 83.8 76.5 82.4 78.8 81.9 Warm water flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 WOM (%) 91.6 90.2 89.3 81.3 88.7 80.4 86.9 WOM flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

division comparative example One 2 3 4 5 6 7 importance 1.32 1.32 1.31 1.31 1.31 1.32 1.31 tensile strength
(kgf/cm ² ) 598 576 567 548 572 581 537 flexural modulus
(kgf/cm ² ) 22,500 22,150 21,900 21,500 21,350 22,000 20,700 flexural strength
(kgf/cm ² ) 896 877 868 845 884 887 826 impact strength
(kgfㆍcm/cm) 16 38 71 84 72 71 80 liquidity index
(g/10min) 12.2 11.3 9.8 6.3 6.4 10.1 8.8 flame retardant V-2 V-2 V-0 V-2 V-0 V-0 V-0 discoloration X X X X X X X f1 Warm water index (%) 85.0 44.4 36.1 82.1 75.3 23.9 68.4 Warm water flame retardancy V-2 V-2 V-0 V-2 V-0 V-0 V-0 WOM (%) 80.0 37.2 21.4 94.8 87.9 25.1 85.7 WOM flame retardant V-2 V-2 V-0 V-2 V-0 V-0 V-0

division comparative example 8 9 10 11 12 13 14 importance 1.29 1.31 1.30 1.31 1.31 1.31 1.31 tensile strength
(kgf/cm ² ) 518 555 521 550 551 527 525 flexural modulus
(kgf/cm ² ) 21,000 21,700 20,700 21,800 21,750 21,450 61,650 flexural strength
(kgf/cm ² ) 814 859 813 851 860 816 846 impact strength
(kgfㆍcm/cm) 89 80 90 78 77 62 74 liquidity index
(g/10min) 5.8 7.1 5.7 12.4 12.9 17.1 15.9 flame retardant V-2 V-0 V-0 V-0 V-0 V-0 V-0 discoloration X X X X O X X f1 Warm water index (%) 82.8 31.4 79.2 72.1 78.8 34.2 69.7 Warm water flame retardancy V-2 V-0 V-2 V-0 V-2 V-0 V-0 WOM (%) 88.7 86.9 85.1 47.5 82.4 36.8 68.1 WOM flame retardant V-2 V-0 V-0 V-2 V-0 V-0 V-2

As shown in Tables 1 to 6, Examples 1 to 7 prepared according to the present invention have a tensile strength of 529 kgf/cm ² or more, a flexural modulus of 20,300 kgf/cm ² or more, and a flexural strength of 823 kgf/cm ² or more, impact strength of 76 kgf·cm/cm or more, flow index of 7.1 g/10min or more, flame retardancy grade was all V-0, impact strength retention rate before and after the warm water test was 76.5% or more, accelerated weather resistance test The impact strength retention rate before and after was 80.4% or more, and in particular, there was no change in the flame retardant grade before and after the warm water resistance test and before and after the accelerated weather resistance test. It was confirmed that all of them had excellent weather resistance.

In addition, in the case of discoloration, it was confirmed that all of the pellets of Examples 1 to 7 were visually white, indicating that no discoloration occurred, whereas in Comparative Example 12, the pellet color was visually distinctly gray, It was confirmed that the appearance quality was deteriorated.

Therefore, it was confirmed that the thermoplastic resin composition of the present invention has mechanical strength, molding processability, and flame retardancy at a certain level or higher, and at the same time, hot water resistance and weather resistance are greatly improved, so that it is suitable for use as an outdoor electric product for a long period of time.

Claims (16)

(A) 100 parts by weight of a base resin containing 1 to 99% by weight of polyalkylene terephthalate and 1 to 99% by weight of polycarbonate;
(B) 5.5 to 9 parts by weight of a core-shell structured impact modifier;
(C) 10 to 30 parts by weight of a halogenated epoxy-based flame retardant;
(D) 2 to 4.5 parts by weight of a compatibilizer; and
(E) 0.1 to 2 parts by weight of a transesterification inhibitor;
According to ASTM D1238, the flow index measured under the condition of temperature 250 ℃ and load 5kg is 7.0 g / 10min or more,
Characterized in that the WOM value measured in accordance with UL 746C (f1 Class) is 70% or more
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition has a warm water resistance index value of 50% or more measured in accordance with UL 746C (f1 Class)
Thermoplastic resin composition.
According to claim 1,
Characterized in that the polyalkylene terephthalate has an intrinsic viscosity (IV) of 0.9 to 1.3 dl / g
Thermoplastic resin composition.
According to claim 1,
Characterized in that the polycarbonate has a flow index of 1 to 11 g / 10 min measured under the condition of a temperature of 250 ° C and a load of 5 kg according to ASTM D1238
Thermoplastic resin composition.
According to claim 1,
The base resin is characterized in that it comprises 40 to 60% by weight of polyalkylene terephthalate and 40 to 60% by weight of polycarbonate
Thermoplastic resin composition.
According to claim 1,
Characterized in that the impact modifier of the core-shell structure is a butyl acrylic impact modifier
Thermoplastic resin composition.
According to claim 1,
The halogenated epoxy-based flame retardant is characterized in that the brominated epoxy-based flame retardant
Thermoplastic resin composition.
According to claim 1,
The transesterification inhibitor is NaH ₂ PO ₄ , characterized in that
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition comprises 2 to 8 parts by weight of a flame retardant aid
Thermoplastic resin composition.
According to claim 9,
The flame retardant aid is characterized in that it contains antimony trioxide
Thermoplastic resin composition.
According to claim 1,
The compatibilizer is characterized in that it comprises a glycidyl methacrylate-based compatibilizer
Thermoplastic resin composition.
According to claim 11,
The glycidyl methacrylate-based compatibilizer is characterized in that it comprises vinyl acrylate
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition comprises 0.05 to 3 parts by weight of a UV stabilizer
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition satisfies the f1 Class grade specified in UL 746C
Thermoplastic resin composition.
It is characterized in that it is prepared by including the thermoplastic resin composition of any one of claims 1 to 14
molding.
According to claim 15,
Characterized in that the molded article is an electrical box
molding.

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