KR20230034146A - Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

The present disclosure relates to a thermoplastic resin composition, a method for preparing the same, and a molded article comprising the same and, more specifically, to a thermoplastic resin composition, a method for preparing the same, and a molded article including the same, the thermoplastic resin composition comprising: (A) 35 to 50 wt% of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15 wt% of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing 23 to 35 wt% of a vinyl cyan compound; (D) 7 to 12 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer containing 26 to 40 wt% of a vinyl cyan compound; and (E) 20 to 37 wt% of a glass fiber containing 50 to 70 wt% of silica (SiO_2). According to the present invention, provided are a thermoplastic resin composition having excellent heat resistance, excellent fluidity, and excellent mechanical properties, such as impact strength, tensile strength, flexural strength, and flexural modulus, so as to be suitable as a material for automobile exterior materials and electric parts, a method for preparing the same, and a molded article comprising the same.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded products including the same

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded product including the same, and more particularly, a thermoplastic resin composition that has excellent heat resistance and excellent fluidity and mechanical properties, and thus can be applied in high quality to materials for automobile exterior materials and electric parts. , It relates to a manufacturing method thereof and a molded product including the same.

Polybutylene terephthalate (hereinafter referred to as 'PBT') resin is a crystalline material among engineering plastics. It has a fast crystallization rate and an appropriate molding temperature range, and has a better balance of physical properties than other materials. is known as For this reason, PBT resin is applied to products in a wide range of fields such as automobiles, electrical/electronic devices, and office equipment.

However, since PBT resin has low impact strength at room temperature and lower impact strength at low temperatures (-1 to -50 ° C), reinforced PBT materials containing additives such as glass fibers or rubber or impact modifiers are widely used to compensate for this.

However, the impact strength of the PBT resin is in a trade-off relationship with fluidity, so when the impact strength is improved, the flow characteristics are deteriorated.

Therefore, it is necessary to develop a material that can simultaneously improve flow characteristics along with impact strength, particularly low-temperature impact strength, as well as excellent heat resistance, which is an advantage of PBT materials.

Korean Registered Patent No. 0199159

In order to solve the problems of the prior art as described above, an object of the present substrate is to provide a thermoplastic resin composition having excellent heat resistance and excellent fluidity and mechanical properties.

In addition, an object of the present description is to provide a method for producing the above thermoplastic resin composition.

In addition, an object of the present substrate is to provide a molded article manufactured from the above thermoplastic resin composition.

All of the above and other objects of the present disclosure can be achieved by the present disclosure described below.

In order to achieve the above object, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; and (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ).

In addition, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers comprising 50 to 70% by weight of silica (SiO ₂ ); and, in accordance with ISO 1133, the melt flow rate measured at 260 ° C. and 2.16 kg is It is possible to provide a thermoplastic resin composition characterized in that 10 g / 10 min or more.

In addition, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers comprising 50 to 70% by weight of silica (SiO ₂ ); and, in accordance with ISO 180/1A, low temperature (-30 ℃) and specimen thickness of 4mm notched It is possible to provide a thermoplastic resin composition characterized in that the notched Izod impact strength measured by the specimen is 6 kJ/m ² or more.

In addition, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ); including melt-kneading and extruding under conditions of 200 to 300 ° C. and 100 to 300 rpm. It provides a method for producing a characterized thermoplastic resin composition.

In addition, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; and (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ); melt-kneaded and extruded under conditions of 200 to 300 °C and 100 to 300 rpm to prepare a thermoplastic resin composition. Including the step of doing, the prepared thermoplastic resin composition according to ISO 1133 to provide a method for producing a thermoplastic resin composition, characterized in that the melt flow rate (Melt Flow Rate) measured under 260 ℃ and 2.16 kg is 10 g / 10 min or more can

The (B) polyethylene terephthalate homo polymer may preferably have an intrinsic viscosity of 0.6 to 1.2 dl/g.

The acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 23 to 35 wt% of a vinyl cyan compound, 30 to 45 wt% of an acrylate-based rubber including acrylate, and 25 to 45 wt% of an aromatic vinyl compound It may be a graft copolymer comprising 40% by weight.

The thermoplastic resin composition may preferably include 4.1 to 5.5% by weight of a vinyl cyan compound based on the total weight thereof.

The glass fiber (E) preferably includes 50 to 70% by weight of silica (SiO ₂ ), 16 to 30% by weight of aluminum oxide (Al ₂ O ₃ ), 5 to 25% by weight of calcium oxide (CaO), and MaO. It may be made up of 5 to 20% by weight of other components.

The (E) glass fiber may preferably have an average particle diameter of 3 to 25 μm and an average length of 1 to 15 mm.

The thermoplastic resin composition may preferably include at least one selected from the group consisting of antioxidants, lubricants, and transesterification inhibitors.

In addition, the substrate includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; and (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ); melt-kneaded and extruded under conditions of 200 to 300 °C and 100 to 300 rpm to prepare a thermoplastic resin composition. Including the step of doing, the prepared thermoplastic resin composition has a notched Izod impact strength of 6 kJ / m ² or more measured at a low temperature (-30 ° C) and a notched specimen having a specimen thickness of 4 mm in accordance with ISO 180 / 1A Characterized in that It is possible to provide a method for producing a thermoplastic resin composition to be.

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

According to the present invention, a thermoplastic resin composition that has excellent heat resistance and excellent mechanical properties such as impact strength, tensile strength, and flexural strength at room temperature and low temperature and fluidity, so that it can be applied in high quality to materials for automobile exterior materials and electric parts, and manufacture thereof There is an effect of providing a method and a molded article comprising the same.

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

The present inventors have prepared a polybutylene terephthalate resin having a predetermined intrinsic viscosity, a polyethylene terephthalate homopolymer, an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, an aromatic vinyl compound-vinyl cyan compound copolymer, and glass fiber. content ratio, and the content of vinyl cyan compound in each of the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer and the silica content in the glass fiber are adjusted within a predetermined range It was confirmed that both mechanical properties and fluidity, such as impact strength and tensile strength, were improved while heat resistance was excellent, and based on this, further research was conducted to complete the present invention.

Looking at the thermoplastic resin composition according to the present substrate in detail is as follows.

The thermoplastic resin composition of the present disclosure includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; and (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ). It has excellent mechanical properties such as elastic modulus and fluidity, so it is suitable as a material for automobile exterior materials and electric parts.

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

(A) polybutylene terephthalate resin

The (A) polybutylene terephthalate resin is, for example, 35 to 50% by weight, preferably 37 to 47% by weight, more preferably 38 to 45% by weight, more preferably 38% by weight based on the total weight of the thermoplastic resin composition to 42% by weight, and within this range, mechanical properties such as impact strength, tensile strength, elongation, flexural strength and flexural modulus, fluidity, and heat resistance are all excellent.

The (A) polybutylene terephthalate resin may preferably have an intrinsic viscosity of 0.6 to 0.9 dl/g, more preferably 0.65 to 0.9 dl/g, and still more preferably 0.75 to 0.85 dl/g, The melt index is appropriate within the range, so there is an effect of excellent processability, molding processability and molding stability.

In this description, the intrinsic viscosity is a value obtained by completely dissolving a sample to be measured in methylene chloride and then filtering the filtrate using a filter at 20° C. using an Uberode viscometer, unless otherwise specified.

The (A) polybutylene terephthalate resin is not particularly limited in the case of a conventional polybutylene terephthalate resin, and may be, for example, a polycondensation polymer of 1,4-butanediol and dimethyl terephthalate.

The (A) method for producing the polybutylene terephthalate resin is not particularly limited if it is a method commonly used in the art to which the present invention belongs.

(B) Polyethylene Terephthalate Homo Polymer

The (B) polyethylene terephthalate homo polymer is, for example, 5 to 15% by weight, preferably 7 to 14% by weight, more preferably 9 to 13% by weight, and even more preferably 9 to 13% by weight, based on the total weight of the thermoplastic resin composition. It may be 10 to 13% by weight, and within this range, there is an effect of improving mechanical properties and fluidity and improving appearance quality.

In the present description, the polyethylene terephthalate homopolymer is not particularly limited in the case of a polyethylene terephthalate homopolymer commonly recognized in the art to which the present invention belongs, and refers to a polymer condensation-polymerized from a diacid compound and a dialcohol as a monomer, for example, , Specifically, it is a polymer condensation polymerized from terephthalic acid or terephthalic acid dimethyl, and ethylene glycol.

The polyethylene terephthalate homopolymer (B) preferably has an intrinsic viscosity of 0.6 to 1.2 dl/g, more preferably 0.6 to 1.1 dl/g, still more preferably 0.6 to 1 dl/g, even more preferably 0.7 dl/g. to 0.9 dl/g, and the melt index is appropriate within this range, resulting in excellent processability, molding processability and molding stability.

(C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The (C) graft copolymer may be, for example, 7 to 9% by weight, preferably 7.5 to 8.5% by weight, based on the total weight of the thermoplastic resin composition, and within this range, fluidity and mechanical properties, particularly at room temperature and low temperature It has excellent impact strength and excellent heat resistance.

The (C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be a graft copolymer comprising preferably 23 to 35% by weight, more preferably 25 to 33% by weight of a vinyl cyan compound And, within this range, there is an effect of excellent mechanical properties, especially impact strength at room temperature and low temperature, and excellent heat resistance.

The (C) graft copolymer is, for example, a graft copolymer comprising 23 to 35% by weight of a vinyl cyan compound, 30 to 45% by weight of an acrylate-based rubber, and 25 to 40% by weight of an aromatic vinyl compound, preferably is a graft copolymer comprising 25 to 33% by weight of a vinyl cyan compound, 35 to 43% by weight of an acrylate-based rubber, and 30 to 37% by weight of an aromatic vinyl compound, more preferably 25 to 31% by weight of a vinyl cyan compound , It may be a graft copolymer comprising 38 to 43% by weight of acrylate-based rubber and 30 to 35% by weight of an aromatic vinyl compound, and within this range, excellent fluidity and mechanical properties, especially impact strength at room temperature and low temperature It has an excellent heat resistance effect.

The acrylate-based rubber is a rubber containing acrylate, and may have, for example, an average particle diameter of 400 to 2500 Å, preferably 500 to 2000 Å, and more preferably 700 to 1500 Å, and within this range at room temperature and It has excellent impact strength at low temperatures.

In the present description, unless otherwise specified, the average particle diameter can be measured using dynamic light scattering, and in detail, Gaussian using a particle meter (product name: Nicomp 380, manufacturer: PSS) Mode is measured as an intensity value. At this time, as a specific measurement example, the sample was prepared by diluting 0.1 g of latex (TSC 35-50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, appropriately diluted so as not to deviate greatly from the intensity setpoint of 300 kHz, put in a glass tube, and measured. The method is auto-dilution and measurement with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting values are temperature 23 ℃, measurement wavelength 632.8nm, channel width It can be measured as 10 μsec.

The (C) graft copolymer may have, for example, a graft rate of 20 to 60%, preferably 25 to 55%, more preferably 30 to 50%, and still more preferably 30 to 40%, within this range It has excellent impact strength at room temperature and low temperature.

In this description, the graft rate is obtained by coagulating, washing, and drying the graft polymer latex to obtain a powder form, and 2 g of this powder is added to 300 ml of acetone and stirred for 24 hours. This solution is separated using an ultracentrifuge, and only the insoluble content that is not dissolved in acetone is collected, dried at 60 to 120 ° C., and the weight is measured and calculated according to Equation 1 below.

[Equation 1]

Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100

(The weight (g) of the grafted monomer in Equation 1 is the weight obtained by subtracting the weight (g) of rubber from the weight (g) of the insoluble material (gel) after dissolving the graft copolymer in acetone and centrifuging, The rubbery weight (g) is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.)

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

The acrylate of the present invention may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in an alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in an alkyl group, and more preferably butyl acrylate, ethylhexyl acrylate or a mixture thereof.

For example, the vinyl cyan compound of the present invention may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, and is preferably acrylonitrile. may be nitrile.

The aromatic vinyl compound of the present invention is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brovo styrene, ρ - may be at least one selected from the group consisting of bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene; Preferably it may be styrene.

The method for preparing the (C) graft copolymer is not particularly limited as long as it is a method commonly used in the technical field to which the present invention belongs, and may be, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. Preferably, it may be emulsion polymerization.

(D) aromatic vinyl compound-vinyl cyan compound copolymer

The (D) aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 7 to 12% by weight, preferably 7 to 11% by weight, more preferably 8 to 10% by weight, and still more preferably 8 to 10% by weight, based on the total weight of the thermoplastic resin composition. Preferably, it may be 8 to 9% by weight, and within this range, there is an advantage in that the heat deflection temperature is excellent in both high load and low load while excellent in flexural modulus among fluidity and mechanical properties.

The (D) aromatic vinyl compound-vinyl cyan compound copolymer preferably contains 26 to 40% by weight, more preferably 26 to 35% by weight, still more preferably 27 to 32% by weight of the vinyl cyan compound. It may be a composite, and within this range, there is an advantage in that the flexural modulus is excellent among fluidity and mechanical properties, and the heat deflection temperature is excellent at both high and low loads.

The (D) aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 100,000 to 180,000 g/mol, preferably 110,000 to 170,000 g/mol, more preferably 120,000 to 150,000 g/mol, Within this range, there is an effect of excellent processability and injection stability while maintaining mechanical properties and friction resistance at equal or higher levels.

In this description, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. It is a value obtained by applying the weight average molecular weight (Mw) in terms of polystyrene by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies). More specifically, it is measured using GPC (Gel Permeation Chromatography, Waters 2410 RI Detector, 515 HPLC pump, 717 Auto Sampler). After dissolving 20ml of THF (tetrahydrofuran) in 0.02g of each polymer, filter it through a 0.45㎛ filter and put it into a GPC vial (4ml) to make each sample. The solvent (THF) is injected at a rate of 1.0 mL/min from 1 hour before the measurement, the measurement time is 25 minutes, the injection volume is 150 μL, the flow rate is 1.0 ml/min, the isocratic pump mode, and the RI detector is measured under the conditions of 40. At this time, calibration may be performed using PS (Polystyrene) standard, and data may be processed using ChemStation.

The (C) aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof. , More preferably, it may be a styrene-acrylonitrile copolymer (SAN resin), and in this case, there is an advantage in that it has excellent heat resistance under both high load and low load while maintaining equal or higher mechanical properties and fluidity.

The method for producing the (D) aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited in the case of a method commonly used in the technical field to which the present invention belongs, and examples thereof include suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. It can be prepared, preferably bulk polymerization, and in this case, there is an excellent effect such as heat resistance and fluidity.

(E) glass fiber

The (E) glass fiber is, for example, 20 to 37% by weight, preferably 23 to 37% by weight, more preferably 25 to 35% by weight, and still more preferably 28 to 32% by weight based on the total weight of the thermoplastic resin composition. It may be, and within this range, there is an effect of excellent fluidity, mechanical properties and heat resistance.

The glass fiber (E) preferably contains 50 to 70% by weight, more preferably 51 to 65% by weight, and still more preferably 51 to 58% by weight of silica (SiO ₂ ) based on the total weight thereof. Within this range, while fluidity and impact strength are maintained, tensile strength, flexural strength, and flexural modulus are excellent, and heat resistance, particularly at low load, is more excellent.

Specifically, the glass fiber (E) preferably contains 50 to 70% by weight of silica (SiO ₂ ), 16 to 30% by weight of aluminum oxide (Al ₂ O ₃ ), 5 to 25% by weight of calcium oxide (CaO), and MaO Glass fiber comprising 5 to 20% by weight of other components including, more preferably 51 to 65% by weight of silica (SiO ₂ ), 17 to 28% by weight of aluminum oxide (Al ₂ O ₃ ), calcium oxide (CaO ) 10 to 24% by weight, and 8 to 18% by weight of other components including MaO, more preferably 51 to 58% by weight of silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) 17 to 24% by weight, 15 to 22% by weight of calcium oxide (CaO), and 10 to 15% by weight of other components including MaO, and the tensile strength while maintaining fluidity and impact strength within this range , Flexural strength and flexural modulus are excellent, and heat resistance, especially at low load, is more excellent.

The other component including MaO refers to one or more selected from the group consisting of MgO, Na ₂ O, K ₂ O, Li ₂ O, Fe ₂ O ₃ , B ₂ O ₃ and SrO.

The (E) glass fiber may have, for example, an average diameter of 3 to 25 μm, preferably 5 to 20 μm, and more preferably 8 to 15 μm, and within this range, the mechanical strength with the resin is improved while the final product It has excellent appearance characteristics.

The glass fiber (E) may have, for example, an average length of 1 to 15 mm, preferably 2 to 7 mm, and more preferably 2.5 to 5 mm, and within this range, the mechanical strength with the resin is improved while improving the final product. It has excellent appearance characteristics.

In this substrate, the average length and average diameter of the glass fibers are measured by SEM (Scanning Electron Microscope) by 30 each, and then the average value is calculated.

The glass fiber (E) may be, for example, chopped glass fiber, and in this case, there is an advantage in compatibility.

In the present description, the chopped glass fiber is not particularly limited if it is a chopped fiber glass commonly used in the technical field to which the present invention pertains.

The glass fiber (E) has, for example, an aspect ratio (L/D) of 200 to 550, preferably 220 to 450, more preferably 250 to 250 It may be 350, more preferably 270 to 320, and within this range, there is an advantage in that the surface appearance is excellent due to excellent compatibility with the resin.

The (E) glass fiber may be surface-treated with, for example, a silane-based compound or a urethane-based compound, and preferably at least one surface treatment agent selected from the group consisting of an amino silane-based compound, an epoxy silane-based compound, and a urethane-based compound A surface-treated material may be used, and more preferably, a surface-treated material with an epoxy silane-based compound. In this case, compatibility is improved and mechanical strength is improved by being uniformly dispersed in the resin composition.

The surface treatment agent is, for example, 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, and more preferably 0.1 to 3% by weight, based on 100% by weight of the total surface-treated glass fibers (glass fiber + surface treatment agent). Preferably it may be included in the range of 0.1 to 0.8% by weight, more preferably 0.2 to 0.5% by weight, and within this range, there is an effect of excellent mechanical properties, balance of physical properties and appearance of the final product.

The amino silane-based compound is not particularly limited in the case of amino silane generally used as a coating agent for glass fibers, but examples thereof include gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, and gamma-glycidoxypropyl trimethoxy silane. Glycidoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trime Toxy silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyltriethoxy silane, gamma-acetoacetate propyl tri It may be at least one selected from the group consisting of methoxysilane, acetoacetatepropyl triethoxy silane, gamma-cyanoacetyl trimethoxy silane, gamma-cyanoacetyl triethoxy silane, and acetoxy aceto trimethoxy silane, In this case, the mechanical properties and heat resistance are excellent, and the surface properties of the injection-molded product are excellent.

The epoxy silane-based compound is not particularly limited when it is an epoxy silane generally used as a coating agent for glass fibers, but examples thereof include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltriethoxysilane. -It may be at least one selected from the group consisting of glycidyloxypropyl (dimethoxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and in this case, the injection molding product has excellent mechanical properties and heat resistance. has excellent surface properties.

The glass fiber (E) may be appropriately selected and used within a range commonly used in the art as long as the definition of the present invention is followed, and a cross-sectional shape such as a cylinder or an ellipse is not particularly limited.

In the above description, the total weight of the thermoplastic resin composition is (A) polybutylene terephthalate resin, (B) polyethylene terephthalate homopolymer, (C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, (D ) It means the total weight of the aromatic vinyl compound-vinyl cyan compound copolymer and (E) glass fiber.

additive

The thermoplastic resin composition may include, for example, one or more additives selected from the group consisting of antioxidants, lubricants, and transesterification inhibitors, and in this case, the effect of improving processability, light resistance, and mechanical properties within this range is there is.

The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, or a mixture thereof, and may preferably be a phenol-based antioxidant. In this case, oxidation by heat is prevented during the extrusion process, and mechanical properties and heat resistance are improved. This has an excellent effect.

The phenolic antioxidant is, for example, N,N'-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)], pentaerythritol tetra Kiss[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy -hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy Benzylphosphonate-diethylester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and 1,3,5- It may be at least one selected from the group consisting of tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, and in this case, heat resistance can be greatly improved while maintaining a high physical property balance. .

The phosphorus antioxidant is, for example, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite Pite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl di Phenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) ) Octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, stearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , And it may be one or more selected from the group consisting of trimethyl phosphate.

The antioxidant may be included in preferably 0.05 to 1% by weight, more preferably 0.1 to 0.8% by weight, and even more preferably 0.2 to 0.6% by weight, based on the total weight of the thermoplastic resin composition, and the balance of physical properties within this range. It has an effect of improving heat resistance while being excellent.

When the thermoplastic resin composition includes additives, the total weight of the thermoplastic resin composition in the present description means (A) polybutylene terephthalate resin, (B) polyethylene terephthalate homopolymer, (C) acrylate-aromatic vinyl compound-vinyl It means the total weight of the cyan compound graft copolymer, (D) the aromatic vinyl compound-vinyl cyan compound copolymer, (E) glass fiber, antioxidant, lubricant, and transesterification inhibitor.

The lubricant may be, for example, at least one selected from the group consisting of polyethylene-based wax, sodium-neutralized ethylene-methacrylic acid copolymer, and sodium-neutralized Montanic acid wax, preferably polyethylene-based wax, and more Preferably, it may be oxidized high density polyethylene wax, and in this case, heat resistance and fluidity are improved.

The polyethylene-based wax is polar and penetrates between the inner polymers to make the chains slide well and to induce intermolecular flow.

For example, the lubricant may be included in an amount of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, and even more preferably 0.2 to 0.5% by weight, based on the total weight of the thermoplastic resin composition. Within this range, there is an effect of improving heat resistance and fluidity while having excellent mechanical properties.

The transesterification inhibitor may be, for example, a metal phosphate-based compound, and preferably monobasic sodium phosphate, monobasic potassium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tribasic potassium phosphate, and It is at least one selected from the group consisting of calcium phosphate, preferably monobasic sodium phosphate, and in this case, it has an effect of improving mechanical properties and fluidity while having excellent physical property balance.

The transesterification inhibitor is, for example, 0.01 to 3% by weight, preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, and still more preferably 0.05 to 0.5% by weight, based on the total weight of the thermoplastic resin composition. Within this range, there is an effect of improving mechanical properties and fluidity while having excellent physical property balance.

The thermoplastic resin composition optionally contains one or more selected from the group consisting of a UV stabilizer, a dye, a pigment, a flame retardant, and an inorganic filler, as needed, in a total of 100 parts by weight of the thermoplastic resin composition ((A) polybutylene terephthalate resin + (B) ) Polyethylene terephthalate homopolymer + (C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer + (D) aromatic vinyl compound-vinyl cyan compound copolymer + (E) glass fiber) 0.01 to 5 weight part, preferably from 0.05 to 3 parts by weight, more preferably from 0.1 to 2 parts by weight, and even more preferably from 0.5 to 1 part by weight, and within this range, the physical properties of the thermoplastic resin composition of the present substrate There is an effect that the necessary physical properties are well implemented without deteriorating.

The UV stabilizer, dye, pigment, flame retardant and inorganic filler are not particularly limited as long as they are commonly used in the art to which the present invention belongs.

thermoplastic resin composition

The thermoplastic resin composition is the total weight thereof ((A) polybutylene terephthalate resin + (B) polyethylene terephthalate homopolymer + (C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer + (D) aromatic For example, the vinyl cyan compound may be 4.1 to 5.5% by weight, preferably 4.1 to 5% by weight, more preferably 4.2 to 4.8% by weight, relative to the vinyl compound-vinyl cyan compound copolymer + (E) glass fiber) , within this range, there is an effect of excellent fluidity, mechanical properties and heat resistance.

The thermoplastic resin composition preferably has a heat distortion temperature measured in accordance with ISO 75 under a low load of 0.45 MPa of 205 ° C. or higher, more preferably 210 ° C. or higher, still more preferably 210 to 230 ° C., still more preferably may be 210 to 220 ° C., and within this range, all physical property balance is excellent, and heat resistance is excellent under low load.

The thermoplastic resin composition may preferably have a heat distortion temperature of 180 ° C. or higher, more preferably 190 ° C. or higher, and still more preferably 190 to 200 ° C., measured under a high load of 1.80 MPa according to ISO 75. It has excellent balance of all physical properties within the range and has excellent heat resistance especially under high load.

The thermoplastic resin composition preferably has a melt flow rate of 10 g / 10 min or more, more preferably 11 g / 10 min or more, and still more preferably 12 g / 10 min or more, more preferably 12.5 g / 10 min or more, particularly preferably 12.5 to 19.5 g / 10 min, particularly preferably 12.5 to 18 g / 10 min, and all physical property balance is excellent within this range It has excellent processability and injection moldability while doing so.

The thermoplastic resin composition preferably has an Izod impact strength of 7 kJ/m ² or more, more preferably 8 kJ/m ² or more, as measured by a notched specimen having a specimen thickness of 4 mm at room temperature in accordance with ISO 180/1A. More preferably, it may be 8 to 11 kJ/m ² , and even more preferably 8.4 to 10 kJ/m ² , and within this range, all physical property balances and mechanical strength are excellent.

In the present description, room temperature may be a point within the range of 20 ± 5 °C.

The thermoplastic resin composition preferably has a notched Izod impact strength of 6 kJ / m ² or more, more preferably 7 kJ / m ² or more, more preferably 7 to 10 kJ/m ² , and even more preferably 7.5 to 9 kJ/m ² , and within this range, all physical property balance and mechanical strength are excellent.

The thermoplastic resin composition preferably has a tensile strength of 140 MPa or more, more preferably 145 MPa or more, still more preferably 145 to 170 MPa, even more preferably, as measured under ISO 527 at a speed of 50 mm/min. It may be 148 to 160 MPa, and within this range, all physical property balance and mechanical strength have excellent effects.

The thermoplastic resin composition preferably has an elongation of 1% or more, more preferably 2% or more, still more preferably 2 to 4%, even more preferably 2.5%, as measured under ISO 527 at a speed of 50 mm/min. to 4%, and within this range, all physical property balances and mechanical strengths have excellent effects.

The thermoplastic resin composition preferably has a flexural strength of 180 MPa or more, more preferably 185 MPa or more, more preferably measured with a specimen having a thickness of 4 mm under a span of 64 mm and a speed of 2 mm / min in accordance with ISO 178. It may preferably be 185 to 210 MPa, more preferably 190 to 205 MPa, and within this range, there is an advantage in that all physical properties are excellent and mechanical strength is excellent.

The thermoplastic resin composition preferably has a flexural modulus of 8000 MPa or more, more preferably 8100 MPa or more, as measured by a specimen having a thickness of 4 mm under a span of 64 mm and a speed of 2 mm/min in accordance with ISO 178. Preferably it may be 8100 to 10000 MPa, more preferably 8200 to 9500 MPa, and within this range, there is an advantage in that all physical properties are excellent and mechanical strength is excellent.

The thermoplastic resin composition preferably has a density of 1.48 g/cm ³ or less, more preferably 1.44 to 1.48 g/cm ³ , more preferably 1.44 to 1.47 g/cm ³ , as measured according to ISO 1183-1. Within this range, there is an advantage of weight reduction while excellent physical property balance.

Manufacturing method of thermoplastic resin composition

The method for preparing the thermoplastic resin composition of the present disclosure includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers comprising 50 to 70% by weight of silica (SiO ₂ ); including melt-kneading and extruding under conditions of 200 to 300 ° C. and 100 to 300 rpm. In this case, it has excellent heat resistance, excellent mechanical properties and fluidity such as impact strength, tensile strength, flexural strength and flexural modulus, and thus has the advantage of being suitable as a material for automobile exterior materials and electric parts.

The kneading and extrusion may be performed, for example, through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, and in this case, the composition is uniformly dispersed, resulting in excellent compatibility.

The kneading and extrusion may be carried out, for example, at a barrel temperature of 200 to 300 °C, preferably 230 to 280 °C, more preferably 250 to 270 °C, and in this case, the throughput per unit time is excellent and the resin component There is an advantage of not causing problems such as thermal decomposition of

The kneading and extruding may be carried out, for example, under the condition that the number of rotations of the screw is 100 to 300 rpm, preferably 150 to 300 rpm, more preferably 200 to 300 rpm, and even more preferably 230 to 270 rpm, in this case While the throughput and process efficiency per unit time are excellent, there is an effect of suppressing excessive cutting of glass fibers.

The thermoplastic resin composition obtained through the extrusion may be made into pellets using, for example, a pelletizer.

molding

The molded article of the present substrate is characterized by comprising the thermoplastic resin composition of the present substrate as an example, and in this case, it has excellent heat resistance and excellent mechanical properties such as impact strength, tensile strength, flexural strength and flexural modulus and fluidity, so that automotive exterior materials and It has the advantage of being suitable as a material for electric parts.

The molded article may preferably be an automobile exterior material or an electric component, and in this case, it has excellent heat resistance and excellent mechanical properties such as impact strength, tensile strength, flexural strength and flexural modulus, and excellent fluidity.

The manufacturing method of the molded article preferably includes (A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers comprising 50 to 70% by weight of silica (SiO ₂ ); including 200 to 300 ℃ And preparing pellets by melt kneading and extruding under conditions of 100 to 300 rpm; And injecting the manufactured pellets using an extruder; characterized in that it includes, in this case, there is an advantage that the injection processability is excellent while the physical property balance is excellent within this range.

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 description, but the following examples are merely illustrative of the present description, and various changes and modifications are possible within the scope and spirit of the present description. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims.

[Example]

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

* A-1: polybutylene terephthalate having an intrinsic viscosity of 0.8 dl/g

* A-2: polybutylene terephthalate having an intrinsic viscosity of 1.0 dl/g

* A-3: polybutylene terephthalate having an intrinsic viscosity of 0.7 dl/g

* B-1: polyethylene terephthalate homopolymer having an intrinsic viscosity of 0.8 dl/g

* B-2: polyethylene terephthalate copolymer having an intrinsic viscosity of 0.8 dl/g

* C-1: Acrylates-styrene-acrylonitrile graft copolymer (a graft copolymer in which 41% by weight of butyl acrylate rubber, 34% by weight of styrene, and 25% by weight of acrylonitrile are graft-polymerized, graft rate 35%) )

* C-2: Acrylates-styrene-acrylonitrile graft copolymer (graft copolymer graft polymerized with 45% by weight of butyl acrylate rubber, 35% by weight of styrene, and 20% by weight of acrylonitrile, graft rate 45% )

* D-1: styrene-acrylonitrile copolymer (copolymer of 72% by weight of styrene and 28% by weight of acrylonitrile, weight average molecular weight 130,000 g/mol)

* D-2: styrene-acrylonitrile copolymer (copolymer of 76% by weight of styrene and 24% by weight of acrylonitrile, weight average molecular weight 120,000 g/mol)

* E-1: Glass fiber (average length 3 mm, average particle diameter 14 μm) comprising 48% by weight of Si0 ₂ , 12% by weight of Al ₂ O ₃ , 35% by weight of CaO, and 5% by weight of other components including MaO )

* E-2: Glass fiber (average length 3 mm, average particle diameter 10 μm) comprising 44% by weight of Si0 ₂ , 14% by weight of Al ₂ O ₃ , 36% by weight of CaO, and 6% by weight of other components including MaO )

* E-3: Glass fiber (average length 3 mm, average particle diameter 10 μm) comprising 52% by weight of Si0 ₂ , 18% by weight of Al ₂ O ₃ , 16% by weight of CaO, and 14% by weight of other components including MaO )

* F (phenolic antioxidant): Pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)

* G (Polyethylene Wax): LDPE Wax

* H (transesterification inhibitor): sodium phosphate monobasic (NaH ₂ PO ₄ )

Examples 1 to 11 and Comparative Examples 1 to 14

The ingredients and contents listed in Tables 1 to 4 were put into an extruder (42Ψ), melt-kneaded and extruded at 260 ° C. and 250 rpm to produce pellets, and then injected to prepare a specimen for characterization of physical properties. .

[Test Example]

The characteristics of the specimens prepared in Examples 1 to 11 and Comparative Examples 1 to 14 were measured in the following manner, and the results are shown in Tables 1 to 4 below.

measurement method

* Melt Flow Rate: Measured for 10 minutes at 260 ° C. and under a load of 2.16 kg in accordance with ISO 1133. Here, the fluidity unit is g/10min.

* Izod impact strength (KJ/m ² ): Measured under 23 °C and -30 °C, respectively, in accordance with ISO 180/1A using a notched specimen. At this time, the specimen thickness was 4 mm.

* Tensile strength (MPa) and elongation (%): measured under the condition of 50 mm/min in accordance with ISO 527.

* Flexural strength (MPa), flexural modulus (MPa): Measured under the conditions of a span of 64 mm and a test speed of 2 mm/min in accordance with ISO 178 using a specimen having a thickness of 4 mm.

* Heat deflection temperature (HDT, ℃): measured under 1.80 MPa (high load) and 0.45 MPa (low load) in accordance with ISO 75, respectively.

* Density (g/cm ³ ): Measured according to ISO 1183-1.

Classification (% by weight) Example One 2 3 4 5 6 A-1 44.2 40.2 38.2 43.2 41.2 45.2 A-2 A-3 B-1 9 13 13 11 11 13 B-2 C-1 8 8 8 7 9 8 C-2 D-1 8 8 10 8 8 8 D-2 E-1 E-2 E-3 30 30 30 30 30 25 F 0.4 0.4 0.4 0.4 0.4 0.4 G 0.3 0.3 0.3 0.3 0.3 0.3 H 0.1 0.1 0.1 0.1 0.1 0.1 Properties Fluidity (g/10min) 16.8 12.6 13.2 14.8 14.2 18.7 IMP (23℃, KJ/m ² ) 8.3 8.5 8.6 7.5 9.6 8.1 IMP(-30℃, KJ/m ² ) 7.4 7.5 7.4 6.3 8.2 7.0 Tensile strength (MPa) 147 150 149 148 148 140 Elongation (%) 2.2 2.5 2.5 2.4 2.5 2.8 Flexural strength (MPa) 193 191 188 192 191 184 Flexural modulus (MPa) 8310 8200 8130 8250 8230 7890 HDT (1.80 MPa, ℃) 193 191 194 192 192 186 HDT (0.45 MPa, ℃) 212 210 212 211 210 201 Density (g/cm ³ ) 1.46 1.46 1.46 1.46 1.46 1.41

Classification (% by weight) Example 7 8 9 10 11 A-1 35.2 42.2 38.2 46.2 A-2 A-3 40.2 B-1 13 13 13 13 7 B-2 C-1 8 8 8 8 8 C-2 D-1 8 8 8 8 8 D-2 E-1 E-2 E-3 35 28 32 30 30 F 0.4 0.4 0.4 0.4 0.4 G 0.3 0.3 0.3 0.3 0.3 H 0.1 0.1 0.1 0.1 0.1 Properties Fluidity (g/10min) 10.2 15.0 11.1 15.6 17.5 IMP (23 ℃, KJ/m ² ) 8.5 8.3 8.4 7.2 8.2 IMP (-30 ℃, KJ/m ² ) 7.8 7.2 7.5 6.5 7.4 Tensile strength (MPa) 156 145 150 148 146 Elongation (%) 1.7 2.5 2.4 2.7 2.2 Flexural strength (MPa) 199 192 196 189 190 Flexural modulus (MPa) 8650 8180 8450 8170 8150 HDT (1.80 MPa, ℃) 197 191 194 190 194 HDT (0.45 MPa, ℃) 218 210 213 209 213 Density (g/cm ³ ) 1.50 1.44 1.48 1.46 1.46

Classification (% by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 A-1 40.2 40.2 40.2 40.2 40.2 A-2 40.2 B-1 13 13 13 13 13 B-2 13 C-1 8 8 8 8 8 C-2 8 D-1 8 8 8 8 8 D-2 8 E-1 30 E-2 30 E-3 30 30 30 30 F 0.4 0.4 0.4 0.4 0.4 0.4 G 0.3 0.3 0.3 0.3 0.3 0.3 H 0.1 0.1 0.1 0.1 0.1 0.1 Properties Fluidity (g/10min) 12.8 12.3 8.2 12.4 12.7 15.1 IMP (23℃, KJ/m ² ) 8.3 8.1 9.2 6.3 8.2 8.6 IMP(-30℃, KJ/m ² ) 7.6 7.2 8.1 5.2 7.3 7.7 Tensile strength (MPa) 142 143 148 149 148 149 Elongation (%) 2.3 2.4 3.0 2.2 2.4 2.6 Flexural strength (MPa) 183 184 180 189 190 188 Flexural modulus (MPa) 7830 7850 8010 8120 8070 7950 HDT (1.80 MPa, ℃) 183 181 188 189 183 186 HDT (0.45 MPa, ℃) 201 198 207 208 201 205 Density (g/cm ³ ) 1.46 1.47 1.46 1.47 1.46 1.46

division
(weight%) Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 A-1 43.2 43.2 38.2 36.2 37.2 49.2 55.2 30.2 A-2 B-1 13 13 13 17 9 One 13 13 B-2 C-1 5 8 10 8 8 8 8 8 C-2 D-1 8 5 8 8 15 11 8 8 D-2 E-1 E-2 E-3 30 30 30 30 30 30 15 40 F 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 G 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Properties Fluidity (g/10min) 12.7 13.4 12.4 10.5 14.2 14.6 17.1 7.9 IMP (23℃, KJ/m ² ) 6.5 8.3 10.7 8.4 6.3 8.3 6.2 8.8 IMP(-30℃, KJ/m ² ) 5.4 7.7 9.4 7.3 5.2 7.1 5.5 7.7 Tensile strength (MPa) 153 151 146 149 148 145 94 160 Elongation (%) 2.4 2.3 2.3 2.1 2.2 2.4 3.2 1.4 Flexural strength (MPa) 193 187 185 189 195 184 144 205 Flexural modulus (MPa) 8440 8020 7890 8010 8420 7850 4680 8850 HDT (1.80 MPa, ℃) 189 187 191 181 198 197 169 199 HDT (0.45 MPa, ℃) 208 201 210 199 216 214 209 218 Density (g/cm ³ ) 1.46 1.46 1.46 1.47 1.44 1.47 1.36 1.53

As shown in Tables 1 to 4, Examples 1 to 11 prepared according to the present invention showed excellent effects in fluidity, mechanical properties, heat resistance and density compared to Comparative Examples 1 to 14 outside the scope of the present invention. there was. Here, in Examples 2 and 10, which differ only in the intrinsic viscosity of polybutylene terephthalate, (A-1) Example 2 including polybutylene terephthalate having an intrinsic viscosity of 0.8 dl/g has excellent fluidity, mechanical properties and heat resistance. was better.

Specifically, (E) Comparative Examples 1 and 2, in which the content of silica (SiO ₂ ) in the glass fiber was less than 50% by weight, had a low flexural modulus and decreased heat resistance under both high and low loads.

In addition, (A) Comparative Example 3 in which the intrinsic viscosity of the polybutylene terephthalate resin was 1.0 dl/g had poor processability due to reduced fluidity, and (C) acrylate-styrene-acrylonitrile graft copolymer in Comparative Example 3. Comparative Example 4 having a ronitrile content of less than 23% by weight had low Izod impact strength at room temperature and low temperature among mechanical properties.

In addition, (D) Comparative Example 5, in which the acrylonitrile content in the styrene-acrylonitrile copolymer was less than 26% by weight, had a lower heat deflection temperature under a lower load of 0.45 MPa, and (B-2) polyethylene terephthalate copolymer Comparative Example 6 including the lowered flexural modulus of mechanical properties.

In addition, (C) Comparative Example 7 including the acrylate-styrene-acrylonitrile graft copolymer below the scope of the present invention has poor Izod impact strength at both room temperature and low temperature, whereas (C) the graft copolymer Comparative Example 9, which was included beyond the scope of the present invention, had a low flexural modulus.

In addition, (D) Comparative Example 8 including the styrene-acrylonitrile copolymer below the scope of the present invention has poor heat resistance due to a low heat distortion temperature, especially at low load among heat distortion temperatures, and (D) styrene-acrylonitrile Comparative Example 11, in which the copolymer was used beyond the scope of the present invention, had low Izod impact strength at both room temperature and low temperature.

In addition, Comparative Example 10 including (B-1) homopolyethylene terephthalate in excess of the scope of the present invention had poor processability due to low fluidity and low heat deflection temperature at low load, and (B-1) homopolyethylene terephthalate Comparative Example 12 including less than the scope of the present invention was poor in flexural modulus.

In addition, (E-3) Comparative Example 13 using glass fibers within the range of the present invention showed all of the mechanical properties of Izod impact strength, tensile strength, flexural strength and flexural modulus at room temperature and low temperature, and heat deflection temperature under high load. (E-3) Comparative Example 13, in which the glass fibers were used beyond the scope of the present invention, did not achieve weight reduction due to low impact strength and fluidity at room temperature and low temperature and high density.

In conclusion, the polybutylene terephthalate resin according to the present invention, the polyethylene terephthalate homopolymer, the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including the vinyl cyan compound in a predetermined amount, and the vinyl cyan compound in a predetermined amount A thermoplastic resin composition prepared by adjusting an aromatic vinyl compound-vinyl cyan compound copolymer and silica in a predetermined content within a predetermined content ratio has excellent heat resistance and mechanical properties such as impact strength, tensile strength, flexural strength, and flexural modulus. It is effective to provide a thermoplastic resin composition suitable for a material for automobile exterior materials and electric parts due to its excellent flowability, a method for manufacturing the same, and a molded article including the same.

Claims (12)

(A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g;
(B) 5 to 15% by weight of a polyethylene terephthalate homo polymer;
(C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound;
(D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; and
(E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ );
Thermoplastic resin composition.
According to claim 1,
The (B) polyethylene terephthalate homo (Homo) polymer is characterized in that the intrinsic viscosity of 0.6 to 1.2 dl / g
Thermoplastic resin composition.
According to claim 1,
The acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer contains 23 to 35 wt% of vinyl cyan compound, 30 to 45 wt% of acrylate-based rubber including acrylate, and 25 to 40 wt% of aromatic vinyl compound Characterized in that it is a graft copolymer comprising
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that it comprises 4.1 to 5.5% by weight of a vinyl cyan compound based on the total weight thereof
Thermoplastic resin composition.
According to claim 1,
The glass fiber (E) contains 50 to 70 wt% of silica (SiO ₂ ), 16 to 30 wt% of aluminum oxide (Al ₂ O ₃ ), 5 to 25 wt% of calcium oxide (CaO), and other components including MaO. Characterized in that it comprises 5 to 20% by weight
Thermoplastic resin composition.
According to claim 1,
The glass fiber (E) is characterized in that the average particle diameter of 3 to 25 ㎛ and the average length of 1 to 15 mm
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that it comprises at least one selected from the group consisting of antioxidants, lubricants and transesterification inhibitors
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the melt flow rate (Melt Flow Rate) measured under 260 ℃ and 2.16 kg in accordance with ISO 1133 is 10 g / 10 min or more
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition has a notched Izod impact strength of 6 kJ / m ² or more as measured by a notched specimen having a low temperature (-30 ° C) and a specimen thickness of 4 mm in accordance with ISO 180 / 1A. Characterized in that
Thermoplastic resin composition.
(A) 35 to 50% by weight of a polybutylene terephthalate resin having an intrinsic viscosity of 0.6 to 0.9 dl/g; (B) 5 to 15% by weight of a polyethylene terephthalate homo polymer; (C) 7 to 9 wt % of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including 23 to 35 wt % of a vinyl cyan compound; (D) 7 to 12 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 26 to 40 wt % of a vinyl cyan compound; And (E) 20 to 37% by weight of glass fibers including 50 to 70% by weight of silica (SiO ₂ ); including melt-kneading and extruding under conditions of 200 to 300 ° C. and 100 to 300 rpm. characterized
A method for producing a thermoplastic resin composition.
It is characterized in that it comprises the thermoplastic resin composition of any one of claims 1 to 9
molding.
According to claim 11,
Characterized in that the molded article is an automobile exterior material or an electric component
molding.