KR20220004301A - Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article including the same. Particularly, the thermoplastic resin composition includes: (A) 20-48 wt% of a polyester resin; (B) 22-42 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18-45 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer, and shows a change (ΔE) in color difference of a gloss specimen of 1.2 or less, as determined according to MS210-05 or ISO 105 at a temperature of 89 ± 3℃ under a relative humidity of 50 ± 5% with an irradiation dose of 84 MJ/m^2 at an illuminance of 0.55 ± 0.02 W/m^2·nm (300-400 nm). The thermoplastic resin composition according to the present invention shows excellent environmental stress resistance, light resistance and frictional noise resistance, while maintaining mechanical properties and heat stability.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article comprising the same

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition having excellent chemical resistance, light resistance and friction noise resistance while maintaining mechanical properties and thermal stability, and a method for manufacturing the same And it relates to a molded article comprising the same.

ABS resin is an acrylonitrile-butadiene-styrene terpolymer, and has excellent impact resistance, rigidity, chemical resistance, and processability, and is used in various fields such as electricity and electronics, architecture, and automobiles. However, ABS resin lacks heat resistance compared to engineering plastics, so its use is limited for parts of electric and electronic products that require heat resistance and automotive interior materials.

In particular, PC/ABS material is widely used in various applications such as automobiles, electricity and electronics due to its excellent mechanical properties and economical price. It is widely applied, etc. However, in the case of PC/ABS, its use is limited because of its weak chemical resistance due to the amorphous nature of the material itself, and the environmental stress cracking (ESC) problem caused by chemical products in automobile interior materials is chronic and serious. is emerging as a problem. In particular, a lot of cracking problems occur for chemicals that are frequently used inside automobiles, and the demand for chemical-resistant materials that can prevent these problems in advance is increasing.

Therefore, there is a need to develop a material that maintains mechanical properties and thermal stability while improving chemical resistance, light resistance, friction noise resistance, etc. of the material used as an automobile interior material.

Korean Patent Registration No. 10-00334710000

In order to solve the problems of the prior art as described above, the present substrate is a very excellent thermoplastic resin composition with excellent environmental stress cracking (ESC), light resistance and friction noise resistance while maintaining mechanical properties and thermal stability. intended to provide

In addition, an object of the present disclosure is to provide a method for preparing the above-mentioned thermoplastic resin composition.

Another object of the present invention is to provide a molded article prepared from the above-mentioned thermoplastic resin composition.

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

In order to achieve the above object, the present substrate is (A) 20 to 48% by weight of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; according to MS210-05 or ISO 105, at a temperature of 89±3° C. and a relative humidity of 50±5%, an irradiation amount of 84 MJ/m ² and the irradiance 0.55 ± 0.02 W / m ² ·nm (300 ~ 400nm) to provide a thermoplastic resin composition, characterized in that the color difference change (ΔE) of the glossy specimen is 1.2 or less.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer; wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is 25 to 30 wt% of the vinyl cyanide compound based on the total weight thereof and, based on MS210-05 or ISO 105, at a temperature of 89±3° C. and a relative humidity of 50±5%, an irradiation amount of 84MJ/m ² and an irradiation intensity of 0.55±0.02W/m ² nm (300-400 nm ), it is possible to provide a thermoplastic resin composition, characterized in that the color difference change (ΔE) of the glossy specimen measured as 1.2 or less.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer has a residual monomer content measured by gas chromatography (GPC) 500 ppm or less, in accordance with MS210-05 or ISO 105, at a temperature of 89±3° C. and a relative humidity of 50±5%, an irradiation dose of 84MJ/m ² and an irradiance of 0.55±0.02W/m ² nm (300-400 nm) It is possible to provide a thermoplastic resin composition, characterized in that the color difference change (ΔE) of the glossy specimen measured with is 1.2 or less.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer; wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is 25 to 30 wt% of the vinyl cyanide compound based on the total weight thereof The (C) aromatic vinyl compound-vinyl cyan compound copolymer has a residual monomer content of 500 ppm or less as measured by gas chromatography (GPC), and according to MS210-05 or ISO 105, temperature 89 The color difference change (ΔE) of the glossy specimen measured at ±3°C and 50±5% relative humidity at an irradiation dose of 84MJ/m ² and an irradiance of 0.55±0.02W/m ^{2 nm (300 to 400 nm) is 1.2 or less.} A thermoplastic resin composition can be provided.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; And (C) aromatic vinyl compound-vinyl cyan compound copolymer 18 to 45% by weight; containing, based on the environmental stress cracking resistance (Environmental Stress Cracking; ESC) test tensile strength according to ASTM D638 in a stress 2.0% jig After fixing the same specimen (length 165mm, width 19mm, thickness 3.2mm) as the specimen for measuring It is possible to provide a thermoplastic resin composition characterized in that no cracks or cracks occur 2 hours after application with a pipette.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; according to ISO 178, using a specimen thickness of 1/8″ under the conditions of a span of 64 mm and a test speed of 2 mm/min. It is possible to provide a thermoplastic resin composition, characterized in that the measured flexural strength is 53 MPa or more.

In addition, (A) 20 to 48 wt% of the polyester resin, (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and (C) an aromatic vinyl compound-vinyl cyan compound air A thermoplastic resin composition comprising the steps of kneading and extruding 18 to 45% by weight of the coalescing at 200 to 250° C. and 200 to 300 rpm conditions, wherein the thermoplastic resin composition is at a temperature of 89 according to MS210-05 or ISO 105 The color difference change (ΔE) of the glossy specimen measured at ±3°C and 50±5% relative humidity at an irradiation dose of 84MJ/m ² and an irradiance of 0.55±0.02W/m ^{2 nm (300 to 400 nm) is 1.2 or less.} It provides a method for producing a thermoplastic resin composition.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin, (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and (C) an aromatic vinyl compound-vinyl cyan A thermoplastic resin composition comprising 18 to 45 wt% of the compound copolymer, kneading and extruding at 200 to 250 °C and 200 to 300 rpm conditions, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is its 25 to 30% by weight of the vinyl cyan compound is included based on the total weight, and the (C) aromatic vinyl compound-vinyl cyan compound copolymer has a residual monomer content of 500 ppm or less as measured by gas chromatography (GPC), According to MS210-05 or ISO 105, at a temperature of 89±3℃ and a relative humidity of 50±5%, an irradiation dose of 84MJ/m ² and an irradiance of 0.55±0.02W/m ² nm (300~400nm). It is possible to provide a method for producing a thermoplastic resin composition, characterized in that the color difference change (ΔE) of 1.1 or less.

In addition, the present substrate comprises (A) 20 to 48 wt% of a polyester resin, (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and (C) an aromatic vinyl compound-vinyl cyan A thermoplastic resin composition is prepared, including kneading and extruding 18 to 45% by weight of the compound copolymer under 200 to 250° C. and 200 to 300 rpm conditions, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is dehydrated It is possible to provide a method for producing a thermoplastic resin composition, characterized in that produced by performing the process twice or more.

In addition, the present substrate provides a molded article, characterized in that produced from the thermoplastic resin composition.

According to the present invention, there is an effect of providing a thermoplastic resin composition suitable for automobile interior materials, a method for manufacturing the same, and a molded article including the same, in particular, having excellent chemical resistance, light resistance and friction noise resistance while maintaining mechanical properties and thermal stability.

1 is a diagram schematically illustrating a method for measuring environmental stress cracking (ESC).
2 is a diagram schematically illustrating a method for measuring friction noise resistance.

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

The present inventors included a polyester resin, a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and an aromatic vinyl compound-vinyl cyan compound copolymer within a predetermined content range and when the light resistance is adjusted within a predetermined range, the impact strength It was confirmed that both chemical resistance and friction noise resistance were improved while maintaining mechanical properties such as , tensile strength, elongation, and thermal stability, and based on this, further research was completed and the present invention was completed.

A detailed look at the thermoplastic resin composition according to the present disclosure is as follows.

The thermoplastic resin composition of the present invention comprises (A) 20 to 48% by weight of a polyester resin; (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and (C) 18 to 45 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; according to MS210-05 or ISO 105, at a temperature of 89±3° C. and a relative humidity of 50±5%, an irradiation amount of 84 MJ/m ² and the irradiance 0.55±0.02 W/m ² nm (300-400 nm) is characterized in that the color difference change (ΔE) of the shiny specimen is 1.2 or less, and in this case, the mechanical properties and thermal stability are maintained while chemical resistance, It has the effect of improving light resistance and friction noise resistance.

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

(A) polyester resin

The (A) polyester resin is, for example, 20 to 48% by weight, preferably 24 to 46% by weight, more preferably 31 to 41% by weight, even more preferably 31 to 37% by weight based on the total weight of the thermoplastic resin composition It may be a weight %, and there is an effect of improving chemical resistance, light resistance and friction noise resistance while maintaining mechanical properties and thermal stability within this range.

The intrinsic viscosity of the (A) polyester resin may be, for example, 0.6 to 1.8 dl/g, preferably 0.7 to 1.3 dl/g, more preferably 0.9 to 1.3 dl/g, and mechanical properties within this range and excellent workability and, in particular, excellent friction noise resistance.

In the present description, unless otherwise specified, the intrinsic viscosity is a value measured at 20° C. using a Uberode viscometer for the filtrate filtered using a filter after completely dissolving the sample to be measured in methylene chloride.

The (A) polyester resin is, for example, polyethylene adipate (PEA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and at least one selected from the group consisting of polyethylene naphthalate (PEN), preferably polybutylene terephthalate. have.

The polybutylene terephthalate resin is not particularly limited if it is a conventional polybutylene terephthalate resin, and may be, for example, a polycondensation polymer of 1,4-butanediol and dimethyl terephthalate.

(B) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer

The (B) graft copolymer is, for example, 22 to 42 wt%, preferably 23 to 40 wt%, more preferably 27 to 35 wt%, even more preferably 27 to 42 wt%, based on the total weight of the thermoplastic resin composition It may be 31% by weight, and while maintaining mechanical properties and thermal stability within this range, there is an excellent effect in chemical resistance, light resistance and friction noise resistance.

The (B) graft copolymer may be, for example, a graft copolymer obtained by graft polymerization of 10 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound in 40 to 80% by weight of a conjugated diene rubber, Preferably, 50 to 70% by weight of the conjugated diene rubber may be a graft copolymer in which 20 to 35% by weight of an aromatic vinyl compound and 1 to 15% by weight of a vinyl cyanide compound are graft-polymerized, and more preferably, a conjugated diene rubber 55 To 65% by weight, 25 to 35% by weight of the aromatic vinyl compound and 5 to 15% by weight of the vinyl cyanide compound may be a graft copolymer, which has excellent mechanical properties and processability within this range.

The (B) graft copolymer may have, for example, a graft rate of 30 to 50%, preferably 35 to 45%, and has excellent mechanical properties and processability within this range.

In the present 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 the separated acetone solution is dropped into methanol to obtain an ungrafted portion. It is dried at 60 to 120° C., weighed, and calculated according to the following Equation 1.

[Equation 1]

Graft rate (%) = (weight of monomer component grafted to rubber polymer/total weight of copolymer)*100

The conjugated diene rubber may have, for example, an average particle diameter of 600 to 3,500 Å, preferably 1,000 to 3,000 Å, more preferably 1,500 to 2,500 Å, and within this range, mechanical properties and processability are improved.

In this description, unless otherwise specified, the average particle diameter can be measured using dynamic light scattering, and in detail, in Gaussian mode using Nicomp 380 equipment (product name, manufacturer: PSS). Measure 　 by the value of intensity 　.

The (B) graft copolymer may have, for example, a weight average molecular weight of 70,000 to 100,000 g/mol, preferably 75,000 to 85,000 g/mol, and has adequate fluidity within this range, thereby providing excellent processability and excellent impact resistance. It works.

In this description, the weight average molecular weight is relative to a standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40° C. through gel chromatography (GPC) filled with porous silica as a column packing material. can be measured.

(C) Aromatic vinyl compound-vinyl cyan compound copolymer

The (C) copolymer is, for example, 18 to 45% by weight, or 20 to 43% by weight, preferably 28 to 42% by weight, more preferably 33 to 38% by weight, even more with respect to the total weight of the thermoplastic resin composition Preferably, it may be 35 to 42 wt%, and while maintaining mechanical properties, thermal stability and noise and friction resistance within this range, environmental stress cracking resistance (ESC), processability and injection moldability are excellent. have.

The (C) copolymer, for example, comprises 25 to 30 wt% of a vinyl cyanide compound based on the total weight thereof, and preferably comprises 27 to 29 wt%, and has friction noise resistance within this range. and excellent light resistance.

As a specific example, the copolymer (C) is a copolymer polymerized including 25 to 30% by weight of a vinyl cyan compound and 70 to 85% by weight of an aromatic vinyl compound, preferably 27 to 29% by weight of a vinyl cyanide compound and an aromatic vinyl It may be a copolymer polymerized by including 71 to 73% by weight of the compound, and within this range, there is an excellent effect of friction noise resistance and light resistance.

The copolymer (C) may be, for example, a styrene-acrylonitrile copolymer (SAN resin), α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, more preferably styrene- It may be an acrylonitrile copolymer (SAN resin), and in this case, there is an effect excellent in processability and light resistance.

The copolymer (C) may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, preferably bulk polymerization, and in this case, heat resistance and fluidity are excellent.

The copolymer (C) preferably has a residual monomer content measured by gas chromatography (GPC) of 500 ppm or less, more preferably 450 ppm or less, still more preferably 350 to 450 ppm, in this range It has excellent flexural strength, flexural modulus, thermal deformation temperature and light resistance.

In this description, the residual monomer content is determined by dissolving 2 g of the copolymer in 10 ml of chloroform, precipitating it with 30 ml of methanol, taking the supernatant, filtering (0.2 μm disc syringe filter), and then gas chromatography ( GC) can be analyzed and measured with ALS-GC/FID (Automatic Liquid Sampler-Gas Chromatography/Flame Ionization Detector).

In the present description, the conjugated diene compound is, for example, selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene. There may be more than one type.

In the present description, the vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.

In the present description, the aromatic vinyl compound is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ -bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene may be at least one selected from the group consisting of.

Thermoplastic resin composition

The thermoplastic resin composition is, for example, based on MS210-05 or ISO 105, at a temperature of 89±3° C., a relative humidity of 50±5%, an irradiation amount of 84MJ/m ² and an irradiance of 0.55±0.02W/m ² nm (300~ 400 nm), the change in color difference (ΔE) of the glossy specimen may be 1.2 or less, preferably 1.1 or less, more preferably 0.5 to 1.1, and within this range, all physical property balances have an excellent effect.

In the present description, the color difference change (ΔE) is obtained by measuring the color of the specimen using a Hunter Lab color meter, and ΔE is obtained by Equation 3 below.

[Equation 3]

In addition, the thermoplastic resin composition is, for example, based on MS210-05 or ISO 105, at a temperature of 89±3° C. and a relative humidity of 50±5%, an irradiation amount of 84MJ/m ² and an irradiation intensity of 0.55±0.02W/m ² ·nm ( The color difference change (ΔE) of the embossed specimen measured at 300 to 400 nm) may be 1.0 or less, preferably 0.5 to 1.0, and all properties have an excellent balance within this range.

Specimens for measuring light resistance in the present substrate are manufactured at an injection temperature of 230 to 250° C. and a mold temperature of 50° C. with a mold that is mirror-treated with 2,000 to 40,000 grit. to 21 μm is formed in a mold.

The thermoplastic resin composition used as an automobile interior material is generally required to have a color difference change (ΔE) of 2 or less of a glossy specimen and an embossed specimen measured in accordance with MS210-05 or ISO 105, but the thermoplastic resin composition according to the present invention has a color difference change (ΔE) is very low as 1.2 or less and 1.0 or less in the specimen and the embossed specimen, respectively, and has excellent light resistance compared to the conventional thermoplastic resin composition.

The thermoplastic resin composition is an example of the same size as the specimen for measuring tensile strength according to ASTM D638 on a stress 2.0% jig based on an Environmental Stress Cracking (ESC) test (length 165mm, width 19mm, thickness) 3.2 mm), 25 μl of fragrance (a mixture of isoamyl acetate, limonene and linaroul in a volume ratio of 4:1:1) was applied with a micropipette and then cracked or cracked 2 hours later ) may not have occurred, and within this range, all physical property balances have an excellent effect.

In the present substrate, environmental stress cracking resistance refers to a phenomenon in which cracks and fractures occur on the surface of plastics in contact with chemicals in the presence of continuous, internal and external stresses.

1 is a view schematically showing a method for measuring environmental stress cracking resistance. After 2 hours after applying a fragrance to a specimen of the same size as a specimen for measuring tensile strength according to ASTM D638 on a stress 2.0% jig, the It shows a series of processes to observe the surface. "Normal" is the surface of the specimen without craze or cracks, "Craze & Crack" is the surface of the specimen with crazes or cracks, and "Crack & Break" is when the specimen is fractured by cracks. will be. In addition, the right figure of FIG. 1 schematically illustrates a process in which crazes or cracks are generated and fractured on the surface of the specimen.

^{The thermoplastic resin composition has an Izod impact strength of 13 J/m 2} or more, preferably 13 to 25 J/m ² , more preferably 15 as measured at 23° C. as a notched specimen according to ISO 180/1A, for example. to 20 J/m ² may be, and within this range, all physical property balances have an excellent effect.

The thermoplastic resin composition may have, for example, a tensile strength of 36.5 MPa or more, preferably 36.5 to 45 MPa, more preferably 40 to 43 MPa, measured under 50 mm/min according to ISO 527, all within this range. There is an excellent effect of the physical property balance.

The thermoplastic resin composition may have, for example, an elongation of 8% or more, preferably 8 to 40%, more preferably 15 to 35%, measured under 50 mm/min according to ISO 527, and all physical properties within this range There is an excellent effect of balance.

The thermoplastic resin composition has, for example, a flexural strength of 53 MPa or more, preferably 53 to 65 MPa, more preferably measured under a specimen thickness of 1/8", a 64 mm interval (SPAN), and a speed of 2 mm/min in accordance with ISO 178. may be 60 to 63 MPa, and all properties have an excellent balance.

The thermoplastic resin composition has, for example, a flexural modulus of 1300 MPa or more, preferably 1300 to 2000 MPa, more preferably measured under a specimen thickness of 1/8", a 64 mm interval (SPAN), and a speed of 2 mm/min according to ISO 178 may be 1780 to 1990 MPa, and all properties have an excellent balance within this range.

The thermoplastic resin composition may have, for example, a heat deflection temperature of 89° C. or higher, preferably 89 to 100° C., more preferably 90 to 95° C., measured under 0.45 MPa in accordance with ISO 75, all within this range. It has excellent physical property balance and, in particular, has excellent heat resistance.

The thermoplastic resin composition may have, for example, a density of 1.11 g/cm ³ or less, preferably 1.00 to 1.11 g/cm ³ , measured according to ISO 1183, and is light within this range and has an excellent balance of all physical properties. have.

The thermoplastic resin composition is, for example, using a flat specimen of 70 x 60 mm and 25 x 50 mm with a Ziegler SSP-04 equipment under the conditions of a load of 10N and a motion condition of 1 mm / s of the specimen. Acceleration, impulse , Frequency, friction, and fluctuation are measured, respectively, and friction noise calculated as a RPN (Risk Priority Number) value according to the following Equation 2 is 3 or less, preferably 1 to 3 may be, and within this range, the balance of all physical properties has an excellent effect.

The thermoplastic resin composition is, for example, using a flat specimen of 70 x 60 mm and 25 x 50 mm, with a Ziegler SSP-04 equipment under a load of 10N and a motion condition of 4 mm / s. Acceleration, impulse , Frequency, friction, and fluctuation are measured, respectively, and friction noise calculated as a RPN (Risk Priority Number) value according to Equation 2 is 2 or less, preferably 1 to 2 may be, and within this range, the balance of all physical properties has an excellent effect.

The thermoplastic resin composition is, for example, using a flat specimen of 70 x 60 mm and 25 x 50 mm, with a Ziegler SSP-04 equipment under a load of 40 N and a motion condition of 1 mm / s. Acceleration, impulse , Frequency, Friction, and Fluctuation are measured, respectively, and the Stick-Slip Noise calculated by the RPN (Risk Priority Number) value according to Equation 2 below is 2 or less. , may preferably be 1 to 2, and within this range, all physical property balances have an excellent effect.

The thermoplastic resin composition is, for example, using a flat specimen of 70 x 60 mm and 25 x 50 mm with Ziegler SSP-04 equipment under the conditions of a load of 40 N and a motion condition of 4 mm / s of the specimen. Acceleration, impulse , Frequency, Friction, and Fluctuation are measured, respectively, and the Stick-Slip Noise calculated by the RPN (Risk Priority Number) value according to Equation 2 below is 1 or less. and all physical property balances within this range have an excellent effect.

[Equation 2]

<Evaluation of friction noise properties>

RPN 1 or more and 3 or less: good (the possibility of friction noise is very low),

RPN 4 or more and 5 or less: Partially good

RPN 6 or more and 10 or less: Not good

In the present invention, friction noise property measures BSR (Buzz, Squeak, Rattle) generated in a vehicle, and BSR is a representative characteristic value of emotional quality. Here, the buzz is caused by structural vibration, and the panel of the parts itself makes a drum-like noise, the squeak is the noise generated by friction in the shear direction between parts, and the rattle is the vertical direction between parts. noise caused by bumping into

2 is a view schematically showing a method of measuring friction noise with a Ziegler SSP-04 equipment, and a specimen of 70 x 60 mm on a flat specimen of 25 x 50 mm (10N, 1mm/s), (10N , 4mm/s), (40N, 1mm/s) and (40N, 4mm/s) are measured under four loads and motion conditions.

The thermoplastic resin composition may include, for example, at least one selected from the group consisting of a lubricant, a heat stabilizer, and a UV stabilizer, and in this case, there is an effect of improving processability, light resistance, noise and friction resistance and chemical resistance.

The lubricant may be included if necessary to ensure releasability during injection of the molded article using the thermoplastic resin composition.

The lubricant may be, for example, at least one selected from the group consisting of fatty acid amide-based compounds, montan-based waxes, and olefin-based waxes, preferably olefin-based waxes, and more preferably polyethylene waxes, and in this case, miscibility and excellent releasability, and noise friction resistance may be further improved.

The fatty acid amide compound is, for example, steramide (stearamide), behanamide (behanamide), ethylene bis steramide [ethylene bis (stearamide)], ethylene bis 12-hydroxy steramide [N,N'-ethylene bis(12-hydroxystearamide)], erucamide, oleamide, and ethylene bis oleamide may be at least one selected from the group consisting of.

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

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

The lubricant may be, for example, 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the thermoplastic resin composition, and has excellent balance of properties within this range It has the effect of improving noise friction properties.

The thermal stabilizer may include, for example, a phenol-based thermal stabilizer, a phosphorus-based thermal stabilizer, or a mixture thereof, preferably a phenol-based thermal stabilizer, and in this case, prevents oxidation due to heat during the extrusion process, and mechanical properties and heat resistance This has an excellent effect.

The phenolic heat stabilizer 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-hydroxyl -hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy Benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and 1,3,5-tris It may be at least one member selected from the group consisting of (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, and in this case, heat resistance may be greatly improved while maintaining a high balance of physical properties.

The phosphorus-based thermal stabilizer is, for example, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite Phite, 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) ) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, stearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate And it may be at least one selected from the group consisting of trimethyl phosphate.

The heat stabilizer may be, for example, 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, based on 100 parts by weight of the thermoplastic resin composition, and has excellent balance of properties within this range It has the effect of improving heat resistance.

The ultraviolet absorber is, for example, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a quinolinone-based ultraviolet absorber, a benzoate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a benzoxazole-based ultraviolet absorber. It may be at least one selected from the group, preferably a benzotriazole-based UV absorber, and in this case, the physical property balance is excellent and light resistance is further improved.

The triazine-based UV absorber is, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2 -Hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2 ,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)- 1,3,5-triazine, 2,6-diphenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-( 2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5- Triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-pro Foxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris( 2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine; 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-dodecyloxyphenyl)- 1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxyl) -4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine; 2,4,6-tris(2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-methoxycarbonyl) Propyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, 2,4 ,6-tris(2-hydroxyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4 ,6-tris (2-hydroxy-3-methyl-4-ethoxyphenyl) -1,3,5-triazine, 2,4,6- Tris(2-hydroxy-3-methyl-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-butoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-octyloxyphenyl)- 1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-ethoxyethoxyphenyl) )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4, 6-tris(2-hydroxy-3-methyl-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4- Methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-ethoxycarbonylethyloxyphenyl)-1,3, 5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)- 1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and It may be at least one selected from the group consisting of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol have.

The benzophenone-based UV absorber 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-sulfoxytrihydrate benzophenone, 2-hydroxy-4- Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydro Roxybenzophenone, 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 It may be at least one selected from the group consisting of ,4'-bis(diethylamino)benzophenone.

The benzotriazole-based UV absorber is, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-2'-hydroxy-3',2-(2'-hydroxy-3'- tert-Butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenyl-benzotriazole, 2 -(2'-hydroxyl-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxyl-3'-tert-butyl-5'-methylphenyl)-5 -Chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5 '-di-tert-amyl)-benzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'-hydride Roxy-3'-(3",4",5",6"-tetrahydrophthalimidemethyl)-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di- tert-pentylphenyl), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl) -6-(2H-benzotriazol-2-yl)phenol] may be at least one selected from the group consisting of.

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

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

The benzoate-based UV absorber 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 absorber 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 ultraviolet absorber may be, for example, 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, based on 100 parts by weight of the thermoplastic resin composition, and has excellent balance of properties within this range There is an effect that the light resistance is further improved.

Method for producing a thermoplastic resin composition

The method for preparing the thermoplastic resin composition of the present invention comprises (A) 20 to 48 wt% of a polyester resin, (B) 22 to 42 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and (C) aromatic A thermoplastic resin composition comprising the steps of kneading and extruding 18 to 45 wt% of a vinyl compound-vinyl cyan compound copolymer under 200 to 250 ° C and 200 to 300 rpm conditions, wherein the thermoplastic resin composition is MS210-05 or ISO 105, the change in color difference (ΔE) of the glossy specimen measured ^{at an irradiation dose of 84 MJ/m 2} and an irradiance of 0.55±0.02 W/m ² nm (300-400 nm) at a temperature of 89±3° C. and a relative humidity of 50±5% (ΔE ) is 1.2 or less, and in this case, mechanical properties, thermal stability and noise and friction resistance are maintained, while chemical resistance, processability and injection moldability are very excellent.

The method for preparing the thermoplastic resin composition may include, for example, (B) preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer.

The step of (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer is prepared, for example, in 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, ion-exchanged water 70 to 200 After polymerization by adding parts by weight, 0.1 to 2 parts by weight of an initiator, 0.1 to 2 parts by weight of an emulsifier, and 0.05 to 1.5 parts by weight of a molecular weight regulator, the polymerization reaction is terminated at a polymerization conversion rate of 93 to 99% by weight to prepare a graft copolymer latex Then, it may be a step of coagulation, dehydration and drying.

As a specific example, the step (B) for preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer comprises 40 to 80 parts by weight of the conjugated diene rubber latex based on 100 parts by weight of the conjugated diene rubber, the aromatic vinyl compound and the vinyl cyan compound. % (based on solid content), 60 to 150 parts by weight of ion-exchanged water, 10 to 40 wt% of an aromatic vinyl compound mixed in a separate mixing device, 1 to 20 wt% of a vinyl cyanide compound, 10 to 50 parts by weight of ion-exchanged water, A mixed solution containing 0.09 to 1.5 parts by weight of an initiator, 0.1 to 2 parts by weight of an emulsifier, and 0.05 to 1.5 parts by weight of a molecular weight regulator is added at 65 to 75° C. for 2 to 4 hours, and then 0.01 to 0.5 parts by weight of the initiator is added and 30 minutes to After raising the temperature to 75 to 80 °C over 90 minutes, and then terminating the graft polymerization at a polymerization conversion rate of 93 to 99 wt% to prepare a graft copolymer latex, it may be a step of agglomeration, dehydration and drying, in this case It has excellent mechanical properties and processability.

The (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer contained in the conjugated diene rubber latex is, for example, 100 parts by weight of the conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 emulsifiers It can be prepared by adding and polymerizing parts by weight, 0.01 to 0.5 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator, and 0.1 to 1 parts by weight of initiator, and in this case, excellent impact resistance is obtained.

As another example, the conjugated diene rubber latex is 100 parts by weight of the conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, 0.2 to 0.4 parts by weight of a molecular weight regulator, and an initiator By adding 0.3 to 0.8 parts by weight and polymerization, a conjugated diene rubber latex can be prepared, and in this case, the impact resistance is excellent.

The emulsifier used in the production of the graft copolymer latex and/or the conjugated diene rubber latex is, for example, a metal salt of rosin acid, an alkyl aryl sulfonate, an alkalimethyl alkyl sulfate, a sulfonated alkyl ester, and a metal salt of an unsaturated fatty acid. It may be at least one selected from

The electrolyte used in the preparation of the graft copolymer latex and/or the conjugated diene rubber latex is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ It may be at least one selected from the group consisting of _{P 2} O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ and Na ₂ HPO _{4 .}

The initiator used in the preparation of the graft copolymer latex and/or the conjugated diene rubber latex may include, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and as the water-soluble persulfate polymerization initiator may be, for example, at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and the fat-soluble polymerization initiator is, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutyl It may be at least one selected from the group consisting of ronitrile, t-butyl hydroperoxide, paramethane hydroperoxide and benzoyl peroxide, and examples of the oxidation-reduction catalyst system include diumformaldehyde sulfoxylate, sodium ethylenediamine tetra It may be at least one selected from the group consisting of acetate, ferrous sulfate, dextrose, sodium pyrrolate and sodium sulfite.

In addition to the above-described description, other reaction conditions such as reaction time, reaction temperature, pressure, time of input of reactants, etc. in the production method of the graft copolymer and rubber latex are not particularly limited if within the range commonly used in the technical field to which the present invention pertains. and may be appropriately selected and implemented according to need.

In the step (C) of preparing the aromatic vinyl compound-vinyl cyan compound copolymer, for example, the dehydration process may be performed two or more times after polymerization, and specifically, the dehydration process is performed two or more times after washing once after polymerization. Preferably, the dehydration process is performed 2 to 5 times, and more preferably, the dehydration process is performed twice and then dried. In this case, residual monomers, emulsifiers, etc. are removed to further improve mechanical properties, heat resistance and light resistance has the effect of being

The residual monomer content measured by gas chromatography (GPC) after dehydrating the copolymer (C) two or more times is, for example, 500 ppm or less, more preferably 450 ppm or less, even more preferably 350 to 450 ppm. Within this range, flexural strength, flexural modulus, thermal deformation temperature, light resistance and fluidity are excellent.

In general, when the aromatic vinyl compound-vinyl cyan compound copolymer is washed once after polymerization and then dehydrated once, the residual monomer content measured by gas chromatography (GPC) is, for example, about 1600 to 1900 ppm, but the present invention Silver is dehydrated twice or more to significantly lower the residual monomer content to 500 ppm or less.

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

The kneading and extrusion may be performed, for example, at a barrel temperature of 200 to 250 ° C., preferably 210 to 240 ° C. In this case, the throughput per unit time may be adequate and sufficient melt kneading may be possible, and thermal decomposition of the resin component There is an effect that does not cause such problems.

The kneading and extrusion, for example, may be performed under the condition that the screw rotation speed is 200 to 300 rpm, preferably 230 to 270 rpm. there is

molded product

The molded article of the present substrate may, for example, be prepared from the thermoplastic resin composition of the present substrate, and in this case, there is an effect of improving chemical resistance, processability and injection moldability while maintaining mechanical properties, thermal stability and noise and friction resistance.

The molded article may be, for example, an automobile interior, specifically, a center fascia and a door trim.

In describing the thermoplastic resin composition of the present disclosure, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.

Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present disclosure, It goes without saying that such 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): polybutylene terephthalate (intrinsic viscosity 1.0dl/g)

* (B): acrylonitrile-butadiene-styrene graft copolymer (butadiene rubber 50% by weight, styrene 30% by weight and acrylonitrile 10% by weight are graft-polymerized, grafting ratio 39% by weight, weight average molecular weight 78,000 g/mol)

* (C-1): styrene-acrylonitrile copolymer (28 wt% of acrylonitrile, dehydrated twice, the residual monomer content measured by GPC is 425 to 442 ppm)

* (C-2): styrene-acrylonitrile copolymer (acrylonitrile 24% by weight, dehydration performed once, residual monomer content measured by GPC is 1600 to 1900 ppm)

* (C-3): styrene-acrylonitrile copolymer (29 wt% of acrylonitrile, dehydrated once, the residual monomer content measured by GPC is 1600 to 1900 ppm)

* (C-4): styrene-acrylonitrile copolymer (32 wt% of acrylonitrile, dehydrated once, the residual monomer content measured by GPC is 1600 to 1900 ppm)

* Lubricant: Polyethylene Wax

* Heat stabilizer: phenolic heat stabilizer

* UV absorber: Hydroxyphenyl benzotriazole UV absorber

Example 1

(A) 31 parts by weight of polybutylene terephthalate resin, (B) 27 parts by weight of acrylonitrile-butadiene-styrene graft copolymer, and (C-1) styrene-acrylonitrile copolymer 42 parts by weight of lubricant 0.3 parts by weight Part, 0.4 parts by weight of a heat stabilizer, and 0.3 parts by weight of a UV absorber were added and put into an extruder (42Ψ, barrel temperature 230° C.) to prepare a resin in a pellet state, followed by injection to prepare a specimen.

Examples 2 to 5 and Comparative Examples 1 to 9

It was carried out in the same manner as in Example 1, except that the components and contents of Tables 1 and 2 below were used to prepare the thermoplastic resin composition in Example 1.

[Test Example]

The properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 9 were measured in the following manner, and the results are shown in Tables 1 and 2 below.

How to measure

* Izod impact strength (KJ/m ² ): It was measured at 23° C. in accordance with ISO 180/1A using a notched specimen.

* Tensile strength (MPa): It was measured under the condition of 50mm/min according to ISO 527.

* Elongation (%): It was measured under the conditions of 50 mm/min according to ISO 527.

* Flexural strength, flexural modulus (MPa): Measured under the conditions of a span of 64mm and a test speed of 2mm/min in accordance with ISO 178 using a specimen thickness of 1/8″.

* Thermal deformation temperature (℃): It was measured under 0.45 MPa in accordance with ISO 75.

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

* ESC test: After fixing a specimen (length 165mm, width 19mm, thickness 3.2mm) of the same size as the specimen for tensile strength measurement according to ASTM D638 on a stress 2.0% jig, a fragrance (isoamyl acetate, limonene and linaroul) After applying 25 μl of the mixed solution in a volume ratio of 4:1:1) with a micropipette, visually measure whether cracks or cracks occur 2 hours later. (craze) or crack (crack) occurred was marked with "X".

* Stick-Slip Noise: Acceleration and impulse at 23℃ and 50% relative humidity with Ziegler SSP-04 using flat specimens of 70 X 60mm and 25 X 50mm , frequency, friction, and fluctuation are measured, respectively, and RPN (Risk Priority Number) value is calculated according to Equation 2 below, and then friction noise property is evaluated according to the following criteria . The load and motion conditions of the specimen were performed under four conditions: (10N, 1mm/s), (10N, 4mm/s), (40N, 1mm/s) and (40N, 4mm/s).

[Equation 2]

<Evaluation of friction noise properties>

RPN 1 or more and 3 or less: good (the possibility of friction noise is very low),

RPN 4 or more and 5 or less: Partially good

RPN 6 or more and 10 or less: Not good

* Light resistance: According to MS210-05 or ISO 105, at a temperature of 89±3℃ and a relative humidity of 50±5%, the irradiance is 84MJ/m ² and the irradiance is 0.55±0.02W/m ² nm (300~400nm) The color difference change (ΔE) of each of the specimen and the embossed specimen was measured. The specimen was manufactured at an injection temperature of 230 to 250 ° C. and a mold temperature of 50 ° C. with a mold with 2,000 to 40,000 grit, and the embossed specimen was prepared in the same manner as the above specimen, but an embossed size of 15 to 21 μm was formed on the surface. .

The color difference change (ΔE) was obtained by measuring the color of the specimen using a Hunter Lab color meter, and ΔE was obtained by Equation 3 below.

[Equation 3]

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 (A) PBT 31 37 37 41 34 37 37 (B) ABS 27 27 35 29 28 35 35 (C-1) SAN 42 36 28 30 38 (C-2) SAN 28 (C-3) SAN 28 (C-4) SAN lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 heat stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 UV absorber 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Properties Izod impact strength 16.5 13.9 20.4 14.4 17.2 11.1 13.2 The tensile strength 42.5 40.5 36.5 41.1 42.2 36.5 36.5 elongation 35 15.2 8.2 10.2 10 7.8 8.4 flexural strength 61.2 61 53.6 56.1 61.7 54.3 52.9 flexural modulus 1890 1780 1330 1430 1940 1570 1565 heat deflection temperature 93 92.8 91.2 89.1 90.7 92.4 90.7 density 1.1 1.11 1.11 1.14 1.11 1.05 1.1 ESC ○ ○ ○ ○ ○ ○ ○ friction
noise 10N, 1mm/s 3 3 3 3 3 3 3 10N, 4mm/s 2 2 2 2 2 2 2 40N, 4mm/s 2 2 2 2 2 2 2 40N, 4mm/s One One One One One One One light fastness Psalter 1.1 1.1 1.1 1.1 1.3 1.1 1.3 embossed specimen 0.9 1.0 1.0 1.0 1.0 1.0 1.0

division Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 (A) PBT 37 16 51 26 41 24 46 (B) ABS 35 37 29 44 20 30 40 (C-1) SAN 47 20 30 39 46 14 (C-2) SAN (C-3) SAN (C-4) SAN 28 lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 heat stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 UV absorber 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Properties Izod impact strength 12.7 39.4 10.4 37 12.6 32.3 20.7 The tensile strength 36.8 37.5 34.6 36 36.1 32.4 28.9 elongation 8.1 23.1 14.4 12 8.2 6.3 13.8 flexural strength 63.0 52.8 53.3 48.9 53.6 48.9 43.8 flexural modulus 1640 1540 1485 1410 1525 1390 1480 heat deflection temperature 93.8 95.8 89.2 90.3 91.2 93.8 88.4 density 1.06 1.06 1.15 1.1 1.14 1.1 1.14 ESC ○ X ○ X ○ X ○ friction
noise 10N, 1mm/s 3 3 3 3 3 3 3 10N, 4mm/s 3 3 2 2 2 2 2 40N, 4mm/s 2 2 2 2 2 2 2 40N, 4mm/s One 2 One One One One One light fastness polished specimen 1.3 1.3 1.3 1.3 1.3 1.3 1.3 embossed specimen 1.0 1.0 1.0 1.0 1.0 1.0 1.0

As shown in Tables 1 and 2 above, Examples 1 to 5 prepared according to the present invention compared to Comparative Examples 1 to 9 out of the scope of the present invention, while maintaining mechanical properties and thermal stability, ESC, light resistance and friction resistance It was confirmed that the effect of the voice was very good.

The content of acrylonitrile in the styrene-acrylonitrile copolymer was outside the scope of the present invention, and Comparative Examples 1 and 3 had an excessive residual monomer content, and the impact strength and light resistance were lowered, and the residual monomer content of the styrene-acrylonitrile copolymer In Comparative Example 2, which is excessive, not only light resistance but also impact strength, flexural strength, and heat deflection temperature were lowered.

In addition, (A) Comparative Example 4 containing a small amount of PBT and (C-1) SAN in an excessive amount had lowered flexural strength, ESC, light resistance (specimen), and friction noise (10N, 4mm/s), (A ) In Comparative Example 5 in which PBT was contained in an excessive amount, the impact strength, density and light resistance (glossy specimen) were decreased.

In addition, (B) Comparative Example 6 containing an excessive amount of ABS had lower tensile strength, flexural strength, ESC and light resistance (specimen), and (B) Comparative Example 7 containing a small amount of ABS had impact strength, tensile strength, Density and light resistance (glossy specimens) were reduced.

In addition, (C-1) Comparative Example 8 containing an excess of SAN had lowered tensile strength, elongation, flexural strength, ESC and light resistance (glossy specimen), and (C-1) Comparative Example 9 containing a small amount of SAN was deteriorated in tensile strength, flexural strength, thermal deformation temperature, density and light resistance (glossy specimen).

Claims (15)

(A) 20 to 48% by weight of a polyester resin;
(B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; and
(C) 18 to 45% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer;
According to MS210-05 or ISO 105, at a temperature of 89±3℃ and a relative humidity of 50±5%, an irradiation dose of 84MJ/m ² and an irradiance of 0.55±0.02W/m ² nm (300~400nm). characterized in that the color difference change (ΔE) of is 1.2 or less
Thermoplastic resin composition.
According to claim 1,
The (A) polyester resin is polyethylene adipate (PEA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene Characterized in that at least one selected from the group consisting of naphthalate (PEN)
Thermoplastic resin composition.
According to claim 1,
The (A) polyester resin is characterized in that the intrinsic viscosity is 0.5 to 2 dl / g
Thermoplastic resin composition.
According to claim 1,
The (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer is a graft polymerization of 10 to 40 wt% of an aromatic vinyl compound and 1 to 20 wt% of a vinyl cyanide compound to 40 to 80 wt% of a conjugated diene rubber characterized in that it is a copolymer
Thermoplastic resin composition.
According to claim 1,
The (C) aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that it comprises 25 to 30 wt % of the vinyl cyan compound based on the total weight thereof.
Thermoplastic resin composition.
According to claim 1,
The (C) aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that the residual monomer content measured by gas chromatography (GPC) is 500 ppm or less
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is the same as the specimen (length 165mm, width 19mm, thickness 3.2mm) for measuring tensile strength according to ASTM D638 on a stress 2.0% jig based on an Environmental Stress Cracking (ESC) test ), 25 μl of fragrance (a mixture of isoamyl acetate, limonene and linaroul in a volume ratio of 4:1:1) was applied with a micropipette, and after 2 hours, cracks or cracks characterized by not occurring
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition has a flexural strength of 53 MPa or more measured under conditions of a span of 64 mm and a test speed of 2 mm/min using a specimen thickness of 1/8″ in accordance with ISO 178.
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the tensile strength measured under 50 mm / min according to ISO 527 is 36 MPa or more
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 a lubricant, a heat stabilizer and a UV stabilizer.
Thermoplastic resin composition.
(A) 20 to 48 wt% of a polyester resin, (B) 22 to 42 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and (C) 18 to 42 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer To prepare a thermoplastic resin composition comprising the step of melt-kneading 45% by weight under 200 to 300 ℃ conditions,
The thermoplastic resin composition is based on MS210-05 or ISO 105, at a temperature of 89±3° C., a relative humidity of 50±5%, an irradiation dose of 84MJ/m ² and an irradiation intensity of 0.55±0.02W/m ² nm (300-400 nm) Characterized in that the color difference change (ΔE) of the glossy specimen measured with
A method for producing a thermoplastic resin composition.
12. The method of claim 11,
The (C) aromatic vinyl compound-vinyl cyan compound copolymer is prepared by performing the dehydration process twice or more
A method for producing a thermoplastic resin composition.
Claims 1 to 10, characterized in that prepared from any one of the thermoplastic resin composition
molded article.
14. The method of claim 13,
The molded article is characterized in that the automobile interior material
molded article.
15. The method of claim 14,
The vehicle interior material, characterized in that the center fascia (center fascia) or door trim (door trim)
molded article.

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