ASA-based resin composition, method for preparing same, and molded article comprising same

Abstract

The present invention relates to an ASA-based resin composition, a method for preparing the same, and a molded article comprising the same. According to the present invention, an effect of the present invention is to provide an ASA-based resin composition having environmental protection characteristics without reducing mechanical properties (such as impact strength and hardness) and having a physical property balance between heat resistance and weather resistance, and a molded article comprising the ASA-based resin composition.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority of Korean Patent Application No. 10 - 2023 - 0122495, filed on September 14, 2023, with the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference. Technical field

[0003] The present invention relates to an ASA - type resin composition, a method for preparing the same, and a molded article comprising the composition. More particularly, the present invention relates to an ASA - type resin composition having environmental - friendly characteristics and capable of preventing deterioration of the physical property balance between mechanical properties such as impact strength and hardness, and heat resistance and weather resistance, a method for preparing the same, and a molded article comprising the ASA - type resin composition. Background art

[0004] Acrylate - styrene - acrylonitrile graft copolymer (hereinafter referred to as ASA resin) has weather resistance, aging resistance, chemical resistance, and processability, and is widely used in vehicles, household appliances, leisure goods, building materials, gardening supplies, and construction materials.

[0005] In order to obtain environmental - friendly characteristics and reduce manufacturing costs, active research is being conducted on mixing ASA resin with recycled ASA resin. However, it is difficult to recycle waste ASA resin. In addition, the recycled waste ASA resin has poor weather resistance, which limits its recycling.

[0006] Therefore, there is a need to develop an ASA - type resin composition that can endow ASA resin with environmentally friendly characteristics, reduce manufacturing costs, prevent deterioration of the balance between mechanical properties and physical properties, and is abundant in quantity.

[0007] [Prior art documents]

[0008] [Patent documents]

[0009] KR 2022 - 0084326 A Summary of the invention

[0010] Technical problem

[0011] Therefore, the present invention aims to solve the above problems, and one of the objects of the present invention is to provide an ASA - type resin composition capable of achieving an excellent physical property balance between mechanical strength applicable to vehicle exterior materials and heat resistance and weather resistance, and a method for preparing the same.

[0012] Another object of the present invention is to provide a molded article manufactured using the ASA - type resin composition.

[0013] The above objects and other objects can be achieved by the present invention described below.

[0014] Technical solution

[0015] According to one aspect of the present invention, there is provided an ASA resin composition comprising:

[0016] An acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A); a styrenic copolymer (B); and a post-consumer recycled ABS resin (C),

[0017] wherein the content of the post-consumer recycled ABS resin (C) is 20% to 70% by weight.

[0018] The acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) may include an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200 nm to 320 nm and an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40 nm to 109 nm.

[0019] The styrenic copolymer (B) may be a mixture of a styrenic copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol and a styrenic copolymer (B-2) having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol.

[0020] The post-consumer recycled ABS resin (C) may contain 55 to 65 parts by weight of an aromatic vinyl monomer, 10 to 20 parts by weight of a diene rubber, and 15 to 25 parts by weight of a vinyl cyanide, or may have a weight average molecular weight of 100,000 g / mol to 300,000 g / mol, or may be a mechanically recycled resin.

[0021] The weight ratio (A-1:A-2) of the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200 nm to 320 nm to the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40 nm to 109 nm included may be 1:0.8 to 1:1.5.

[0022] An acrylate - aromatic vinyl compound - vinyl cyanide compound graft copolymer (A - 1) based on a total of 100% by weight of an acrylate rubber having an average particle size of 200 nm to 320 nm, which may contain 30% to 50% by weight of the acrylate rubber, 40% to 60% by weight of the aromatic vinyl compound, and 5% to 20% by weight of the vinyl cyanide compound.

[0023] An acrylate - aromatic vinyl compound - vinyl cyanide compound graft copolymer (A - 2) based on a total of 100% by weight of an acrylate rubber having an average particle size of 40 nm to 109 nm, which may contain 40% to 60% by weight of the acrylate rubber, 25% to 45% by weight of the aromatic vinyl compound, and 5% to 20% by weight of the vinyl cyanide compound.

[0024] A styrenic copolymer (B - 1) based on a total of 100% by weight having a weight - average molecular weight of 80,000 g / mol to 100,000 g / mol, which may contain 55% to 75% by weight of the aromatic vinyl compound and 25% to 45% by weight of the vinyl cyanide compound.

[0025] A styrenic copolymer (B - 2) based on a total of 100% by weight having a weight - average molecular weight of 150,000 g / mol to 200,000 g / mol, which may contain 60% to 80% by weight of the aromatic vinyl compound and 20% to 40% by weight of the vinyl cyanide compound.

[0026] The melt flow index (220 °C, load: 10 kg) of the ASA - type resin composition measured according to ISO 1133 may be 8.8 g / 10 min to 9.8 g / 10 min, the Izod impact strength measured according to ISO 179 may be 10.1 kJ / m 2 to 10.7 kJ / m 2 The HDT measured according to ISO 75 - 1,2 may be 84.2 °C to 86 °C, the hardness measured according to ISO 2039 may be 102 to 104, or the weather resistance (SCI△E) measured using the SAE J2527 evaluation method may be 0.99 to 1.63.

[0027] According to another aspect of the present invention, there is provided an ASA - type resin composition comprising:

[0028] 5% to 22% by weight of an acrylate - aromatic vinyl compound - vinyl cyanide compound graft copolymer (A - 1) containing an acrylate rubber having an average particle size of 200 nm to 320 nm;

[0029] 5% to 25% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing acrylate rubber with an average particle size of 40 nm to 109 nm;

[0030] 30% to 60% by weight of a styrenic copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol;

[0031] 0% to 15% by weight of a styrenic copolymer (B-2) having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol; and

[0032] 20% to 35% by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer (C).

[0033] The aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer (C) may have: a melt volume flow rate (MVR) measured using a polymer melt at 220 °C and 10 kg according to ISO 1133-1:2011 of 10 cm 3 / 10 min or more; a Vicat B / 50 softening point measured according to ISO 306:2004 may be 80 °C or more; an E modulus measured according to ISO 527 may be 1500 MPa or more; a yield stress measured according to ISO 527 may be 30 MPa or more; a yield strain measured according to ISO 527 may be 2% or more; a Charpy notched impact strength measured according to A-type notch at 23 °C according to EN-ISO 179-1 may be 2 kJ / m 2 or more; a Charpy notched impact strength measured according to A-type notch at -30 °C according to EN-ISO 179-1 may be 2 kJ / m 2 or more.

[0034] According to another aspect of the present invention, there is provided an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, wherein the ASA resin composition comprises 11% to 15% by weight of an alkyl acrylate, 26% to 34% by weight of an aromatic vinyl compound, and 25% to 33% by weight of an alkyl-substituted aromatic vinyl compound.

[0035] According to another aspect of the present invention, there is provided an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, wherein the ASA resin composition comprises 10% to 20% by weight of an alkyl acrylate, 20% to 40% by weight of an aromatic vinyl compound, 20% to 30% by weight of a vinyl cyanide compound, 1% to 10% by weight of a conjugated diene compound, and 20% to 40% by weight of an alkyl-substituted aromatic vinyl compound.

[0036] According to another aspect of the present invention, there is provided an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, wherein the ASA resin composition comprises 11% to 15% by weight of an alkyl acrylate, 26% to 34% by weight of an aromatic vinyl compound, 23% to 24% by weight of a vinyl cyanide compound, 3% to 6% by weight of a conjugated diene compound, and 25% to 33% by weight of an alkyl-substituted aromatic vinyl compound.

[0037] According to another aspect of the present invention, there is provided an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, wherein the ASA resin composition comprises 13% to 15% by weight of an alkyl acrylate, 27% to 32% by weight of an aromatic vinyl compound, 23% to 24% by weight of a vinyl cyanide compound, 3% to 6% by weight of a conjugated diene compound, and 27% to 32% by weight of an alkyl-substituted aromatic vinyl compound.

[0038] According to another aspect of the present invention, there is provided a method for preparing an ASA resin composition, which comprises:

[0039] The following components are kneaded and extruded under the conditions of 200°C to 300°C and 300 rpm to 800 rpm: 5% to 22% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle diameter of 200 nm to 320 nm; 5% to 25% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle diameter of 40 nm to 109 nm; 30% to 60% by weight of a styrenic copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol; 0% to 15% by weight of a styrenic copolymer (B-2) having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol; and 20% to 35% by weight of a post-consumer recycled ABS resin (C).

[0040] According to another aspect of the present invention, there is provided a molded article comprising the above ASA resin composition.

[0041] The molded article may be a vehicle part, including vehicle exterior materials.

[0042] Advantageous Effects

[0043] The ASA resin composition of the present invention is environmentally friendly. In addition, the ASA resin composition of the present invention has mechanical strengths such as impact strength and hardness equivalent to or more excellent than those of conventional ASA resin compositions, and has an excellent balance of physical properties between heat resistance and weather resistance. Therefore, the ASA resin composition of the present invention can be used as a material for vehicle parts.

[0044] Therefore, the ASA resin composition of the present invention and the molded article manufactured using the composition can be widely used for unpainted vehicle parts including radiator grilles and pillar parts. Detailed Description

[0045] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0046] The terms and words used in this specification and the appended claims should not be construed as limited to the conventional meanings or dictionary meanings, but should be construed as having meanings and concepts matching the technical spirit of the present invention in order to describe the present invention in the best way.

[0047] The present inventors confirmed that when post-consumer recycled ABS is added to an ASA resin, a mechanical strength suitable as a material for vehicle parts and a balance of physical properties between heat resistance and weather resistance are achieved. Based on these findings, the present inventors conducted further research to complete the present invention.

[0048] The ASA resin composition of the present invention contains post-consumer recycled ABS resin.

[0049] In the present invention, the post-consumer recycled ABS resin known in the art to which the present invention pertains can be used as the "post-consumer recycled ABS resin" of the present invention without particular limitation. For example, the post-consumer recycled ABS resin can be a mechanically recycled resin with high purity, which is obtained by changing the physical structure of waste ABS resin with a weight-average molecular weight of 100,000 g / mol to 300,000 g / mol without changing its chemical structure, sorting raw materials, removing impurities, and performing a washing process.

[0050] Each component of the ASA resin composition of the present invention will be described in detail below.

[0051] Post-consumer recycled ABS resin

[0052] In one embodiment of the present invention, the post-consumer recycled ABS resin can be an ABS resin obtained from discarded vehicle equipment, household appliances, electrical equipment, or an ABS resin obtained by recycling defective products discarded during the manufacturing process.

[0053] As a specific example, the post-consumer recycled ABS resin can exhibit one or more of the following characteristics.

[0054] - Melt volume flow rate (MVR) measured using a polymer melt at 220 °C and 10 kg according to ISO 1133-1:2011: 10 cm 3 / 10 min or more, or 10 cm 3 / 10 min to 35 cm 3 / 10 min

[0055] - Vicat B / 50 softening point measured according to ISO 306:2004: 80 °C or more, or 80 °C to 100 °C

[0056] - E modulus measured according to ISO 527: 1500 MPa or more, or 2000 MPa or more

[0057] - Yield stress measured according to ISO 527: 30 MPa or more, or 30 to 50 MPa

[0058] - Yield strain measured according to ISO 527: 2% or more, or 2% to 3%

[0059] - The Charpy notched impact strength measured according to the A-type notch at 23 °C according to EN-ISO 179-1 is 2 kJ / m 2 or more, or 2 to 20 kJ / m 2

[0060] - The Charpy notched impact strength measured according to the A-type notch at -30 °C according to EN-ISO 179-1 is 2 kJ / m 2 or more, or 2 to 20 kJ / m 2

[0061] For example, the post-consumer recycled ABS resin may be a recycled ABS resin containing 55% by weight or more, or 55% to 65% by weight of an aromatic vinyl monomer, 10% by weight or more, or 10% to 20% by weight of a diene rubber, and 15% by weight or more, or 15% to 25% by weight of a vinyl cyanide compound. Within this range, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can be provided even though it is contained in the ASA resin composition.

[0062] For example, the weight-average molecular weight of the post-consumer recycled ABS resin may be 100,000 g / mol or more, or 100,000 g / mol to 300,000 g / mol. Within this range, the mechanical properties can be improved.

[0063] When measuring the weight-average molecular weight, tetrahydrofuran (THF) and the compound are placed in a 1 ml glass bottle to prepare a sample with a concentration of 1% by weight. Then, the standard sample (polystyrene) and the sample are filtered through a filter (pore size: 0.45 μm), and the filtered sample is injected into the GPC syringe. Then, by comparing the elution time of the sample with the calibration curve of the standard sample, the molecular weight and molecular weight distribution of the compound can be obtained. At this time, Infinity II 1260 (Agilent Corporation) can be used as the measuring instrument, the flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 °C.

[0064] The post-consumer recycled ABS resin may be a mechanically recycled resin obtained by changing the physical structure, sorting the raw materials, and then reprocessing without changing the chemical structure.

[0065] The raw material sorting process may be a process of collecting waste household appliances, cleaning the waste household appliances, and sorting the household appliances according to components and colors.

[0066] The reprocessing may involve using an extruder to make the sorted recycled ABS resin into pellets.

[0067] Based on a total of 100% by weight of the ASA resin composition, the content of post-consumer recycled ABS resin can be 20% to 35% by weight, preferably 20% to 32% by weight, more preferably 22% to 32% by weight, and even more preferably 22% to 26% by weight. When the content is below this range, as the content of post-consumer recycled ABS resin decreases, the environmental protection concept gradually fades. When the content exceeds this range, the mechanical properties and appearance quality may be poor.

[0068] As long as the post-consumer recycled ABS resin meets the definition of the present invention, there are no special restrictions. The post-consumer recycled ABS resin can be prepared by methods known and used in the art or commercially available products can be used.

[0069] Virgin resin

[0070] For example, the virgin resin constituting the ASA resin composition may include: an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing acrylate rubber with an average particle size of 200 nm to 320 nm; an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing acrylate rubber with an average particle size of 40 nm to 109 nm; and one or more styrenic copolymers (B).

[0071] As a specific example, the virgin resin constituting the ASA resin composition may include: an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing acrylate rubber with an average particle size of 200 nm to 320 nm; an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing acrylate rubber with an average particle size of 40 nm to 109 nm; and a first styrenic copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol.

[0072] As another example, the virgin resin constituting the ASA resin composition may include: an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing acrylate rubber with an average particle size of 200 nm to 320 nm; an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing acrylate rubber with an average particle size of 40 nm to 109 nm; a first styrenic copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol; and a second styrenic copolymer (B-2) having a weight average molecular weight of 15,000 g / mol to 200,000 g / mol.

[0073] In this case, even though it contains post-consumer recycled ABS resin, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can still be provided.

[0074] Hereinafter, each component of the virgin resin constituting the ASA resin composition of the present invention will be described in detail.

[0075] (A-1) Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing acrylate rubber with an average particle size of 200 nm to 320 nm compound-vinyl cyanide compound graft copolymer

[0076] The average particle diameter of the acrylate rubber of the graft copolymer (A-1) can be 200 nm to 320 nm, preferably 220 nm to 300 nm, more preferably 240 nm to 280 nm. Within this range, excellent mechanical strength, such as impact strength, can be achieved.

[0077] In the present invention, the average particle diameter is measured by the dynamic light scattering method. Specifically, the average particle diameter is measured at an intensity value in the Gaussian mode using a Nicomp 380 particle size analyzer (manufacturer: PSS). As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (total solid content: 35 wt% to 50 wt%) 1000 to 5000 times with distilled water. Then, the average particle diameter of the sample is measured using an automatic dilution flow cell in a measurement mode of dynamic light scattering / intensity 300 kHz / intensity-weight Gaussian analysis. At this time, the set values are as follows: temperature: 23 °C; measurement wavelength: 632.8 nm; channel width: 10 microseconds.

[0078] For example, based on a total of 100 wt% of all components constituting the virgin resin, the content of the graft copolymer (A-1) can be 5 wt% to 22 wt%, 10 wt% to 22 wt%, 15 wt% to 22 wt%, or 18 wt% to 21 wt%. Within this range, fluidity and weather resistance equivalent to or more excellent than those of conventional ASA resin compositions can be achieved, and the appearance quality can be excellent.

[0079] For example, based on a total of 100 wt%, the graft copolymer (A-1) can contain 30 wt% to 50 wt% of acrylate rubber, 40 wt% to 60 wt% of aromatic vinyl compound, and 5 wt% to 20 wt% of vinyl cyanide, preferably 35 wt% to 50 wt% of acrylate rubber, 40 wt% to 55 wt% of aromatic vinyl compound, and 10 wt% to 20 wt% of vinyl cyanide. Within this range, excellent mechanical strength, such as impact strength, can be achieved.

[0080] In the present invention, a polymer containing a specific compound means a polymer prepared by polymerizing the compound, and the units in the polymer are derived from the compound.

[0081] The acrylate rubber may contain an alkyl acrylate compound.

[0082] In the present invention, the alkyl acrylate compound may include: an alkyl acrylate having an alkyl group with 1 to 15 carbon atoms, preferably one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, lauryl acrylate, more preferably an alkyl acrylate having a linear alkyl group with 1 to 4 carbon atoms, and still more preferably butyl acrylate.

[0083] In the present invention, for example, the aromatic vinyl compound may include one or more selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably one or more selected from the group consisting of styrene and α-methylstyrene, and more preferably styrene. In this case, due to the appropriate flow properties, excellent processability and mechanical properties, such as impact resistance, can be obtained.

[0084] In the present invention, for example, the vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0085] For example, the graft copolymer (A-1) can be prepared by emulsion polymerization. In this case, excellent mechanical properties, such as impact strength, can be obtained.

[0086] The emulsion graft polymerization method commonly used in the field of the present invention can be used for the emulsion polymerization of the present invention without particular limitation.

[0087] (A-2) Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing acrylate rubber with an average particle size of 40 nm to 109 nm compound-vinyl cyanide compound graft copolymer

[0088] For example, the average particle size of the acrylate rubber of the graft copolymer (A-2) can be 40 nm to 109 nm, preferably 40 nm to 100 nm, more preferably 50 nm to 100 nm, and still more preferably 60 nm to 100 nm. Within this range, excellent impact strength and gloss can be imparted to the finally prepared ASA resin composition.

[0089] For example, based on a total of 100% by weight of all components constituting the base resin, the content of the graft copolymer (A-2) can be 5% to 25% by weight, preferably 10% to 25% by weight, more preferably 15% to 25% by weight, more preferably 20% to 25% by weight, and even more preferably 23% to 25% by weight. Within this range, comparable or more excellent fluidity and weather resistance to conventional ASA resin compositions can be achieved, and the appearance quality can be excellent.

[0090] For example, based on a total of 100% by weight, the graft copolymer (A-2) can contain 40% to 60% by weight of an acrylate rubber, 25% to 45% by weight of an aromatic vinyl compound, and 5% to 20% by weight of a vinyl cyanide, preferably 45% to 55% by weight of an acrylate rubber, 30% to 45% by weight of an aromatic vinyl compound, and 10% to 20% by weight of a vinyl cyanide. Within this range, excellent gloss and impact strength can be obtained.

[0091] The acrylate rubber can contain an alkyl acrylate compound.

[0092] The alkyl acrylate compound, aromatic vinyl compound, and vinyl cyanide compound contained in the graft copolymer (A-2) can be the same as the alkyl acrylate compound, aromatic vinyl compound, and vinyl cyanide compound contained in the graft copolymer (A-1).

[0093] For example, the graft copolymer (A-2) can be prepared by emulsion polymerization. In this case, excellent impact strength and gloss can be obtained.

[0094] The emulsion graft polymerization method commonly used in the field of the present invention can be used for the emulsion polymerization of the present invention without particular limitation.

[0095] Based on a total of 100% by weight of all components constituting the base resin, the total amount of the graft copolymer (A-1) and the graft copolymer (A-2) can preferably be 45% by weight or less, preferably 30% to 45% by weight, and more preferably 40% to 44% by weight. Within this range, although the ASA resin composition contains post-consumer recycled ABS resin, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can still be provided.

[0096] (B-1) First styrenic copolymer with a weight-average molecular weight of 80,000 g / mol to 100,000 g / mol

[0097] For example, the first styrenic copolymer (B-1) can be an aromatic vinyl compound-vinyl cyanide copolymer.

[0098] For example, the weight-average molecular weight of the aromatic vinyl compound-vinyl cyanide copolymer (B) may be from 85,000 g / mol to 100,000 g / mol, more preferably from 90,000 g / mol to 100,000 g / mol, and still more preferably from 92,000 g / mol to 98,000 g / mol. Within this range, excellent impact strength and hardness can be achieved.

[0099] For example, based on all components constituting the base resin in a total of 100% by weight, the content of the aromatic vinyl compound-vinyl cyanide copolymer (B-1) may be from 30% by weight to 60% by weight, from 35% by weight to 60% by weight, from 40% by weight to 60% by weight, or from 45% by weight to 59% by weight. Within this range, fluidity and appearance quality can be improved while maintaining impact resistance, heat resistance, and hardness.

[0100] For example, the aromatic vinyl compound-vinyl cyanide copolymer (B-1) may contain an aromatic vinyl compound and vinyl cyanide. In this case, excellent impact resistance can be achieved, and deterioration of heat resistance and weather resistance can be prevented.

[0101] As a preferred example, based on a total of 100% by weight, the aromatic vinyl compound-vinyl cyanide copolymer (B) may contain from 55% by weight to 75% by weight of an aromatic vinyl compound and from 25% by weight to 45% by weight of vinyl cyanide, preferably from 60% by weight to 80% by weight of an aromatic vinyl compound and from 20% by weight to 40% by weight of vinyl cyanide, and still more preferably from 65% by weight to 75% by weight of an aromatic vinyl compound and from 25% by weight to 35% by weight of vinyl cyanide. In this case, due to excellent fluidity, deterioration of appearance quality can be prevented.

[0102] The types of the aromatic vinyl compound and vinyl cyanide contained in the aromatic vinyl compound-vinyl cyanide copolymer (B-1) may be the same as those contained in the graft copolymer (A-1) of the present invention.

[0103] For example, the aromatic vinyl compound-vinyl cyanide copolymer (B-1) can be prepared by emulsion polymerization, solution polymerization, or bulk polymerization. In this case, excellent heat resistance and fluidity can be achieved.

[0104] Emulsion polymerization, solution polymerization, and bulk polymerization can be carried out using emulsion polymerization, solution polymerization, and bulk polymerization commonly used in the technical field to which the present invention pertains, but are not limited thereto.

[0105] (B-2) Second styrenic copolymer with a weight-average molecular weight of 150,000 g / mol to 200,000 g / mol

[0106] For example, the second styrenic copolymer (B-2) can be an aromatic vinyl compound-vinyl cyanide copolymer.

[0107] For example, the weight-average molecular weight of the aromatic vinyl compound-vinyl cyanide copolymer (B) can preferably be from 150,000 g / mol to 200,000 g / mol, more preferably from 155,000 g / mol to 195,000 g / mol, and still more preferably from 160,000 g / mol to 180,000 g / mol. Within this range, excellent impact resistance and scratch resistance can be achieved.

[0108] For example, based on all components constituting the base resin in a total of 100% by weight, the content of the aromatic vinyl compound-vinyl cyanide copolymer (B-2) can be 15% by weight or less, 3% by weight to 15% by weight, or 5% by weight to 15% by weight. Within this range, fluidity and appearance quality can be improved while maintaining impact resistance, heat resistance, and hardness.

[0109] For example, based on its total of 100% by weight, the aromatic vinyl compound-vinyl cyanide copolymer can contain 60% by weight to 80% by weight of the aromatic vinyl compound and 20% by weight to 40% by weight of the vinyl cyanide compound, more preferably 65% by weight to 80% by weight of the aromatic vinyl compound and 20% by weight to 35% by weight of the vinyl cyanide compound, and still more preferably 65% by weight to 75% by weight of the aromatic vinyl compound and 25% by weight to 35% by weight of the vinyl cyanide compound. In this case, due to excellent fluidity, deterioration of appearance quality can be prevented.

[0110] The types of the aromatic vinyl compound and the vinyl cyanide compound contained in the aromatic vinyl compound-vinyl cyanide copolymer (B-2) can be the same as those of the aromatic vinyl compound and the vinyl cyanide compound contained in the graft copolymer (A-1) of the present invention.

[0111] For example, the aromatic vinyl compound-vinyl cyanide copolymer (B-2) can be prepared by emulsion polymerization, solution polymerization, or bulk polymerization. In this case, excellent heat resistance and fluidity can be achieved.

[0112] Emulsion polymerization, solution polymerization, and bulk polymerization can be carried out using emulsion polymerization, solution polymerization, and bulk polymerization commonly used in the technical field to which the present invention pertains, but are not limited thereto.

[0113] ASA resin composition

[0114] For example, the ASA-based resin composition may contain (A-1) and (A-2) in a weight ratio of 1:0.8 to 1:1.5 or 1:0.8 to 1:1.5. In this case, although it contains post-consumer recycled ABS resin, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can still be provided.

[0115] For example, the ASA-based resin composition may further contain a lubricant or may contain a lubricant and additives.

[0116] The additives may include one or more of a lubricant, a heat stabilizer, an ultraviolet stabilizer, a fluorescent brightening agent, a chain extender, a mold release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke suppressant, an inorganic filler, glass fiber, an antifriction agent, and an antiwear agent.

[0117] For example, based on all components (A + B + C + additives) constituting the ABA-based resin composition in a total of 100% by weight, the content of each additive may be 0.01% to 5% by weight, preferably 0.05% to 3% by weight, more preferably 0.1% to 3% by weight. In this case, the functions of the additives can be effectively exerted without reducing the inherent physical properties of the ASA-based resin composition of the present invention.

[0118] For example, the lubricant may contain one or more selected from an acrylic alkyl ester-based polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 g / mol to 70,000 g / mol, an ethylene-based copolymer composed of ethylene and a comonomer, an olefin wax, and an aliphatic amide compound, preferably may contain one or more selected from an acrylic alkyl ester-based polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 g / mol to 70,000 g / mol, and an olefin wax, more preferably an acrylic alkyl ester-based polymer. In this case, an excellent physical property balance, scratch resistance, colorability, and appearance quality can be achieved.

[0119] For example, based on all components (A + B + C + lubricant) constituting the ABS-based resin composition in a total of 100% by weight, the content of the lubricant may be 0.1% to 3% by weight, preferably 0.5% to 2.5% by weight, more preferably 0.7% to 2.2% by weight. Within this range, excellent impact resistance and fluidity can be achieved.

[0120] The acrylic alkyl ester-based polymer as the lubricant may contain one or more selected from methyl acrylate, ethyl acrylate, and butyl acrylate. In this case, the formation of mold deposits is inhibited, so that the appearance of the molded article can be made beautiful and a high gloss can be achieved.

[0121] As the acrylic alkyl ester-based polymer used as a lubricant, acrylic alkyl ester lubricants commonly used in the field to which the present invention pertains can be used without particular limitation. Alternatively, the acrylic alkyl ester-based polymer can be directly prepared and used, or a commercially available product can be used.

[0122] The weight-average molecular weight of the styrene-acrylonitrile copolymer used as a lubricant can preferably be from 40,000 g / mol to 67,000 g / mol, more preferably from 50,000 g / mol to 65,000 g / mol, and still more preferably from 55,000 g / mol to 65,000 g / mol. Within this range, the fluidity can be improved, thereby improving the processing performance and appearance quality.

[0123] For example, the melt flow index (190 °C, 5 kg) of the styrene-acrylonitrile copolymer used as a lubricant can be measured to be from 20 g / 10 min to 60 g / 10 min according to ISO 1133, preferably from 25 g / 10 min to 55 g / 10 min. Within this range, excellent impact strength, fluidity, and appearance quality can be achieved.

[0124] For example, the heat distortion temperature of the styrene-acrylonitrile copolymer used as a lubricant according to ASTM D648 can be from 82 °C to 90 °C, preferably from 84 °C to 88 °C. Within this range, excellent impact strength, fluidity, and appearance quality can be achieved.

[0125] For example, the ethylene copolymer can include one or more selected from ethylene / 1-butene copolymer, ethylene / n-butyl acrylate / carbon monoxide terpolymer. In this case, excellent heat resistance, fluidity, and appearance quality can be achieved.

[0126] For example, the olefin wax can include one or more selected from polyethylene wax, polypropylene wax, preferably polyethylene wax. In this case, excellent heat resistance, fluidity, and appearance quality can be achieved.

[0127] For example, the aliphatic amide compounds can include one or more selected from stearamide, behenamide, ethylene bisstearamide, N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, ethylene bisoleamide, preferably ethylene bisstearamide. In this case, excellent impact strength, fluidity, and appearance quality can be achieved.

[0128] The ASA resin composition of the present invention preferably does not contain a stearate lubricant, that is, there is no stearate lubricant. In this case, a molded article with a beautiful appearance and high gloss can be obtained.

[0129] For example, the stearate lubricant may include one or more selected from barium stearate, calcium stearate, magnesium stearate, zinc stearate, and stearic acid.

[0130] In the present invention, "without stearate lubricant" means that no stearate lubricant is added during the preparation of the ASA resin composition.

[0131] For example, other additives except the lubricant may include one or more selected from heat stabilizers, UV stabilizers, fluorescent brighteners, chain extenders, mold release agents, pigments, dyes, antibacterial agents, processing aids, metal deactivators, smoke suppressants, inorganic fillers, glass fibers, antifriction agents, and antiwear agents. For example, based on a total of 100% by weight of all components (A + B + C + other additives) constituting the ABS-based resin composition, the content of other additives may be 0.1% to 5% by weight, preferably 1% to 3% by weight. In this case, the functions of the additives can be effectively exerted without reducing the inherent physical properties of the ASA resin composition of the present invention.

[0132] For example, based on a total of 100% by weight of all components (A + B + C + heat stabilizer) constituting the ABS-based resin composition, the content of the heat stabilizer may preferably be 0.1% to 2% by weight, more preferably 0.2% to 1.5% by weight. Within this range, the heat resistance can be improved.

[0133] For example, the heat stabilizer may include one or more selected from phenolic heat stabilizers, phosphite heat stabilizers, and thioether heat stabilizers, preferably phenolic heat stabilizers and / or phosphite heat stabilizers.

[0134] For example, the phenolic heat stabilizer may include one or more of tetramethylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate methane, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0135] For example, the phosphite heat stabilizer may be tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, or a mixture thereof.

[0136] For example, the thioether-based heat stabilizer may include one or more selected from dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

[0137] For example, based on the total of all components (A + B + C + ultraviolet stabilizer) constituting the ABS-based resin composition being 100% by weight, the content of the ultraviolet stabilizer may preferably be from 0.1% to 3% by weight, more preferably from 0.5% to 1.5% by weight. In this case, the heat resistance can be improved.

[0138] For example, the ultraviolet stabilizer may include hindered amine light stabilizers (HALS), preferably selected from 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzoyl malonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino], more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino] or a mixture thereof, more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino] or a mixture thereof. In this case, the weather resistance can be significantly improved without reducing the impact resistance and fluidity.,

[0139] For example, the pigment may be carbon black.

[0140] For example, based on all components (A + B + C + pigment) constituting the ABS-based resin composition in a total of 100% by weight, the content of the pigment may preferably be 0.5% to 5% by weight, more preferably 1% to 4.5% by weight, and further preferably 2% to 4.5% by weight. Within this range, excellent physical property balance and colorability can be achieved.

[0141] In addition, the present invention provides an ASA resin composition comprising: 20% to 35% by weight of a post-consumer recycled ABS resin; 5% to 22% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylate rubber having an average particle size of 200 nm to 320 nm; 5% to 25% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylate rubber having an average particle size of 40 nm to 109 nm; 30% to 60% by weight of a styrenic copolymer having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol; 0% to 15% by weight of a styrenic copolymer having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol.

[0142] The post-consumer recycled ABS resin may contain 55% to 65% by weight of an aromatic vinyl monomer, 10% to 20% by weight of a diene rubber, and 15% to 25% by weight of a vinyl cyanide. Alternatively, the post-consumer recycled ABS resin may be a mechanically recycled resin obtained by sorting and reprocessing raw materials by changing the physical structure of waste ABS resin having a weight average molecular weight of 100,000 g / mol to 300,000 g / mol without changing its chemical structure.

[0143] The ASA resin composition may comprise: an acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylate rubber having an average particle size of 200 nm to 320 nm and an acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer containing an acrylate rubber having an average particle size of 40 nm to 109 nm, with a weight ratio of 1:0.8 to 1:1.5.

[0144] For example, the melt flow index of the ASA resin composition measured for 10 minutes at 220 °C and 10 kg using MI-4 (GOTTFEST Corporation) according to ISO 1133 can be 8 g / 10 min or more, preferably 8.8 g / 10 min to 9.5 g / 10 min. Within this range, excellent physical property balance, scratch resistance, colorability, and appearance quality can be achieved.

[0145] For example, according to ISO 179, when measured at 23 °C using a sample with a thickness of 4 mm, the Izod impact strength of the ASA resin composition can be 10 kJ / m 2 or more, preferably 10 kJ / m 2 to 15 kJ / m 2 . Within this range, excellent physical property balance and scratch resistance can be achieved.

[0146] For example, the heat distortion temperature (HDT) of the ASA resin composition measured according to ISO 75-1,2 using an automatic HDT tester 6A-2 (manufacturer: TOYOSEIKI) can be 84 °C or more, preferably 84 °C to 86 °C. Within this range, excellent heat resistance can be achieved without affecting mechanical strength.

[0147] The hardness of the ASA resin composition measured according to ISO 2039 can be 100 or more, preferably 102 to 105. Within this range, excellent physical property balance and scratch resistance can be achieved.

[0148] When evaluating according to the SAE J2527 evaluation method, irradiating the specimen with 2500 kJ of energy, measuring the color before and after irradiation using a color difference meter in the sci mode, and calculating the weather resistance (SCI△E), the weather resistance (SCI△E) of the ASA resin composition is 3 or less, preferably 0.99 to 1.63. Within this range, excellent physical property balance and weather resistance can be achieved.

[0149] Furthermore, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and comprising 10% to 20% by weight of an alkyl acrylate, 20% to 40% by weight of an aromatic vinyl compound, 20% to 30% by weight of a vinyl cyanide compound, 1% to 10% by weight of a conjugated diene compound, and 20% to 40% by weight of an alkyl-substituted aromatic vinyl compound.

[0150] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and comprising 11% to 15% by weight of an alkyl acrylate, 26% to 34% by weight of an aromatic vinyl compound, 23% to 24% by weight of a vinyl cyanide compound, 3% to 6% by weight of a conjugated diene compound, and 25% to 33% by weight of an alkyl-substituted aromatic vinyl compound.

[0151] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and comprising 13% to 15% by weight of an alkyl acrylate, 27% to 32% by weight of an aromatic vinyl compound, 23% to 24% by weight of a vinyl cyanide compound, 3% to 6% by weight of a conjugated diene compound, and 27% to 32% by weight of an alkyl-substituted aromatic vinyl compound.

[0152] Method for preparing ASA resin composition

[0153] For example, the method for preparing an ASA resin composition of the present invention includes a step of kneading and extruding an ASA resin and a post-consumer recycled ABS resin at 200°C to 300°C and 300 rpm to 800 rpm. In this case, although it contains a post-consumer recycled ABS resin, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can still be provided.

[0154] As a preferred example, the method of the present invention may include kneading and extruding the following components under the conditions of 200 °C to 300 °C and 300 rpm to 800 rpm: 20% to 35% by weight of a post-consumer recycled ABS resin; 5% to 22% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (ASA resin) containing acrylate rubber with an average particle size of 200 nm to 320 nm; 5% to 25% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (ASA resin) containing acrylate rubber with an average particle size of 40 nm to 109 nm; 30% to 60% by weight of a styrenic copolymer having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol; and 0% to 15% by weight of a styrenic copolymer having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol. In this case, despite containing a post-consumer recycled ABS resin, excellent mechanical properties and an excellent physical property balance between heat resistance and weather resistance can still be provided.

[0155] The method for preparing the ASA resin composition has all the technical features of the above ASA resin composition. Therefore, the description of the repeated parts will be omitted.

[0156] The step of preparing the granules using an extrusion kneader is preferably carried out at 200 °C to 300 °C and a size of 25 pi to 75 pi, more preferably at 220 °C to 260 °C and a size of 20 pi to 70 pi. Within this range, stable extrusion can be achieved and the mixing effect is excellent. Here, the temperature is the temperature set inside the barrel, and pi refers to the outer diameter (unit: mm).

[0157] The present invention can use an extrusion kneader commonly used in the technical field to which the present invention belongs, and there is no particular limitation. Preferably, a twin-screw extrusion kneader can be used.

[0158] Molded article

[0159] For example, the molded article of the present invention contains the ASA resin composition of the present invention. In this case, compared with a conventional ASA resin composition, although it contains a post-consumer recycled ABS resin, it can have excellent mechanical properties and a physical property balance between heat resistance and weather resistance.

[0160] The method for manufacturing a molded article of the present invention includes the step of injecting the granules manufactured by the method for preparing the ASA resin composition under the conditions of an injection temperature of 200 °C to 300 °C, an injection pressure of 60 bar to 100 bar, and a holding pressure of 30 bar to 65 bar. In this case, an injection molded article having excellent impact strength can be easily manufactured.

[0161] The injection temperature can be preferably 220°C to 280°C, more preferably 230°C to 270°C. Within this range, injection molded articles with complex designs can be easily manufactured.

[0162] The injection pressure can be preferably 70 bar to 90 bar, more preferably 75 bar to 85 bar. Within this range, injection molded articles with complex designs can be easily manufactured.

[0163] The holding pressure can be preferably 35 bar to 60 bar, more preferably 40 bar to 55 bar. Within this range, injection molded articles with complex designs can be easily manufactured.

[0164] The residual emulsifier content (by weight) of the pellets obtained by the method for preparing the ASA resin composition can be 5000 ppm or less, with specific examples being 1000 ppm to 4000 ppm, 1000 ppm to 3000 ppm, or 1000 ppm to 1900 ppm. In this case, a luxurious appearance and high gloss can be achieved, injection molding without painting can be carried out, and the processing performance can be improved due to high fluidity.

[0165] For example, the molded article can be an exterior material for a vehicle, preferably a radiator grille, a rearview mirror cover, a pillar member, etc.

[0166] When describing the ASA resin composition of the present invention, the method for preparing the thermoplastic resin composition, and the molded article containing the thermoplastic resin composition, it should be noted that other conditions or equipment not explicitly described herein can be appropriately selected within the range commonly practiced in the art without particular limitation.

[0167] Hereinafter, the present invention will be described in more detail with reference to the following preferred embodiments. However, these examples are for illustrative purposes only and should not be construed as limiting the scope and spirit of the present invention. In addition, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention, and these changes and modifications are also within the scope of the appended claims.

[0168] Examples

[0169] The materials used in the following examples and additional examples are as follows.

[0170] *Graft copolymer (A-1): ASA graft copolymer (butyl acrylate: 40% by weight, styrene: 46.5% by weight, and acrylonitrile: 13.5% by weight), which contains acrylate rubber with an average particle size of 300 nm

[0171] *Graft copolymer (A-2): ASA graft copolymer (butyl acrylate: 50 wt%, styrene: 36.5 wt%, and acrylonitrile: 13.5 wt%), which contains acrylate rubber with an average particle size of 90 nm

[0172] *Styrenic copolymer (B)

[0173] Aromatic vinyl compound-vinyl cyanide copolymer (B-1) (styrene: 70 wt%, and acrylonitrile: 30 wt%, weight average molecular weight: 95000 g / mol)

[0174] Aromatic vinyl compound-vinyl cyanide copolymer (B-2) (styrene: 73 wt%, and acrylonitrile: 27 wt%, weight average molecular weight: 130000 g / mol)

[0175] *Post-consumer recycled ABS resin (C):

[0176] Mechanical recycled resin (product name: AB3010, manufacturer: Daeil Suji), which contains 60 parts by weight of styrene, 15 parts by weight of butadiene rubber, and 25 parts by weight of acrylonitrile, and is obtained by sorting and reprocessing raw materials without changing their chemical structures

[0177] *Additive 1: Ethylene bis(stearamide) lubricant

[0178] *Additive 2: UV stabilizer

[0179] *Additive 3: Black pigment

[0180] Examples 1 to 4 and Additional Examples 1 to 4

[0181] According to the contents (parts by weight) shown in Table 1 and Table 2 below, the components shown in Table 1 and Table 2 are fed into a twin-screw extruder. Based on a total of 100 parts by weight of the above components (A-1), (A-2), (B-1), and (B-2), the corresponding amounts (parts by weight) of Additives 1, 2, and 3 are added.

[0182] Then, kneading and extrusion are carried out at a barrel temperature of 240 °C to obtain pellets, and the melt flow index is measured using the obtained pellets.

[0183] The obtained pellets are injected using an injection molding machine (Engel, 120 MT) at an injection temperature of 240 °C to manufacture samples for measuring physical properties.

[0184] Test examples

[0185] The properties of the samples manufactured in Examples 1 to 4 and Additional Examples 1 to 4 are measured by the following methods, and the results are shown in Table 1 and Table 2 below.

[0186] Measurement method

[0187] *Izod impact strength (kJ / m 2 ):The Izod impact strength is measured at 23 °C using a 4 mm thick sample according to ISO 179.

[0188] *Melt flow index (g / 10 min): The melt flow index is measured according to ISO 1133 using an MI-4 (GOTTFERT) at 220 °C with a load of 10 kg for 10 minutes.

[0189] *Heat deflection temperature (HDT, °C): The heat deflection temperature is measured using an automatic HDT tester 6A-2 device (TOYOSEIKI) according to ISO 75-1,2.

[0190] *Hardness: The hardness is measured according to ISO 2039.

[0191] *Weather resistance: It is evaluated with 2500 kJ of light under SAE J2527 conditions, and ΔE of the glossy surface of the sample is measured before and after the evaluation.

[0192] [Table 1]

[0193] Classification (parts by weight) Example 1 Example 2 Example 3 Example 4 Graft copolymer (A-1) 18 18 21 18 Graft copolymer (A-2) 24 24 21 24 Styrenic copolymer (B-1) 58 48 58 58 Styrenic copolymer (B-2) - 10 - - Post-consumer recycled ABS resin (C) 28 28 28 48 (C) Content (wt%) 22 22 22 32 (Additive 1) 1 1 1 1 (Additive 2) 1 1 1 1 (Additive 3) 4 4 4 4 Izod impact strength 10.1 10.7 10.6 10.2 Melt flow index 8.8 9.4 8.7 9.8 Heat distortion temperature 85.6 84.2 86 85.2 Hardness 104 102 103 104 Weather resistance (△E) 0.99 1.2 1.1 1.63

[0194] [Table 2]

[0195]

[0196] In Table 1 and Table 2, the content (% by weight) of (C) is a value obtained by converting the input amount (parts by weight) of (C) into % by weight based on a total of 100% by weight of (A-1), (A-2), (B-1), (B-2), and (C).

[0197] In addition, the ratios of the monomer compositions of Examples 1 to 4 in Table 1 and Additional Examples 1 to 4 in Table 2 are converted as shown in Table 3 below.

[0198] [Table 3]

[0199]

[0200] In Table 3, BA represents butyl acrylate, SM represents styrene, AN represents acrylonitrile, BD represents butadiene, and AMS represents alkyl methyl styrene.

[0201] As shown in Table 1 and Table 2, in the embodiments of the present invention, the hardness of Embodiments 1 to 4 is equal to or better than that of Additional Embodiments 1 to 4. In addition, the melt flow index, heat resistance, and Izod impact strength of Embodiments 1 to 4 are excellent, and the weather resistance is improved. Therefore, the deterioration of surface properties that may occur in the molding process is prevented, and the appearance quality is excellent even in a harsh external environment.

[0202] In particular, in the case of Embodiment 2 using a combination of graft copolymers (A-1) and (A-2) and two styrene copolymers (B-1) and (B-2) having different weight average molecular weights, the impact strength is improved compared to Embodiment 1 using graft copolymers (A-1) and (A-2) and only styrene copolymer (B-1).

[0203] In addition, in the case of Additional Embodiment 1, the amount of graft copolymer (A-1) is lower than the scope of the present invention, and the amount of graft copolymer (A-2) exceeds the scope of the present invention, resulting in poor impact strength.

[0204] In addition, in the case of Additional Embodiment 2, the amount of post-consumer recycled ABS resin (C) exceeds the scope of the present invention, resulting in reduced impact strength and heat resistance and poor weather resistance.

[0205] In addition, in the case of Additional Embodiment 3, the amount of graft copolymer (A-1) exceeds the scope of the present invention, resulting in poor fluidity and hardness.

[0206] In addition, in the case of Additional Embodiment 4, the amount of graft copolymer (A-2) exceeds the scope of the present invention, resulting in poor impact strength and fluidity.

[0207] In summary, despite using post-consumer recycled ABS resin, by containing a post-consumer recycled ABS resin in a predetermined content ratio, a graft copolymer containing acrylate rubber with different average particle sizes, and a styrene copolymer having a predetermined weight average molecular weight, due to the synergistic effect of this combination, a resin composition can be provided that has excellent mechanical properties such as impact resistance and hardness, heat resistance, fluidity, and weather resistance, has an environmentally friendly effect compared to conventional ASA resin compositions, has improved physical properties, and is suitable for vehicle exterior materials.

Claims

1. An ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A); a styrene copolymer (B); and post-consumer recycled ABS resin (C), in, The content of the post-consumer recycled ABS resin (C) is 20 wt % to 70 wt %.

2. The ASA-based resin composition according to claim 1, wherein The acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) comprises: an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200nm to 320nm and an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40nm to 109nm.

3. The ASA-based resin composition according to claim 1, wherein The styrene copolymer (B) is a mixture of a styrene copolymer (B-1) having a weight average molecular weight of 80,000 to 100,000 g / mol and a styrene copolymer (B-2) having a weight average molecular weight of 150,000 to 200,000 g / mol.

4. The ASA-based resin composition according to any one of claims 1 to 3, wherein The post-consumer recycled ABS resin (C) contains 55 to 65 parts by weight of an aromatic vinyl monomer, 10 to 20 parts by weight of a diene rubber and 15 to 25 parts by weight of a vinyl cyanide compound, or has a weight average molecular weight of 100,000 to 300,000 g / mol, or is a mechanically recycled resin.

5. The ASA-based resin composition according to any one of claims 1 to 3, wherein The weight ratio (A-1:A-2) of the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing acrylate rubber having an average particle size of 200nm to 320nm and the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing acrylate rubber having an average particle size of 40nm to 109nm is 1:0.8 to 1:1.

5.

6. The ASA-based resin composition according to claim 2, wherein Based on a total of 100 wt % of the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200 nm to 320 nm, the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) contains 30 wt % to 50 wt % of the acrylate rubber, 40 wt % to 60 wt % of the aromatic vinyl compound and 5 wt % to 20 wt % of the vinyl cyanide compound.

7. The ASA-based resin composition according to claim 2, wherein Based on a total of 100 wt % of the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40 nm to 109 nm, the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) contains 40 wt % to 60 wt % of the acrylate rubber, 25 wt % to 45 wt % of the aromatic vinyl compound and 5 wt % to 20 wt % of the vinyl cyanide compound.

8. The ASA-based resin composition according to claim 3, wherein The styrene copolymer (B-1) contains 55 to 75 wt % of an aromatic vinyl compound and 25 to 45 wt % of a vinyl cyanide compound, based on 100 wt % in total of the styrene copolymer (B-1) having a weight average molecular weight of 80,000 to 100,000 g / mol.

9. The ASA-based resin composition according to claim 3, wherein The styrene copolymer (B-2) contains 60 to 80 wt % of an aromatic vinyl compound and 20 to 40 wt % of a vinyl cyanide compound, based on 100 wt % in total of the styrene copolymer (B-2) having a weight average molecular weight of 150,000 to 200,000 g / mol.

10. The ASA-based resin composition according to claim 1, wherein The ASA-based resin composition has a melt flow index (220° C., load: 10 kg) of 8.8 g / 10 min to 9.8 g / 10 min measured according to ISO 1133, and an Izod impact strength of 10.1 kJ / m 2 Up to 10.7 kJ / m 2 , HDT measured according to ISO 75-1,2 is 84.2℃ to 86℃, hardness measured according to ISO 2039 is 102 to 104, or weather resistance (SCI△E) measured using SAE J2527 evaluation method is 0.99 to 1.

63.

11. An ASA-based resin composition, comprising: 5 to 22% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200 to 320 nm; 5 to 25% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40 to 109 nm; 30 to 60 wt % of a styrene copolymer (B-1) having a weight average molecular weight of 80,000 to 100,000 g / mol; 0 to 15 wt% of a styrene-based copolymer (B-2) having a weight average molecular weight of 150,000 to 200,000 g / mol; and 20 to 35 wt% of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer (C).

12. The ASA-based resin composition according to claim 11, wherein The aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer (C) has a melt volume flow rate (MVR) measured at 220° C. and 10 kg using a polymer melt according to ISO 1133-1:2011 of 10 cm 3 / 10min or more; Vicat B / 50 softening point measured according to ISO 306:2004 is 80℃ or more; E modulus measured according to ISO 527 is 1500MPa or more; Yield stress measured according to ISO 527 is 30MPa or more; Yield strain measured according to ISO 527 is 2% or more; Charpy notched impact strength measured according to A-notch at 23℃ according to EN-ISO 179-1 is 2kJ / m 2 or above; or the Charpy notched impact strength measured at -30°C according to type A notch is 2 kJ / m according to EN-ISO 179-1 2 above.

13. An ASA-based resin composition, comprising: Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, in, The ASA-based resin composition contains 10 to 20 wt % of an alkyl acrylate, 20 to 40 wt % of an aromatic vinyl compound, 20 to 30 wt % of a vinyl cyanide compound, 1 to 10 wt % of a conjugated diene compound, and 20 to 40 wt % of an alkyl-substituted aromatic vinyl compound.

14. A method for preparing an ASA-based resin composition, comprising kneading and extruding the following ingredients under the conditions of 200° C. to 300° C. and 300 rpm to 800 rpm: 5 wt % to 22 wt % of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-1) containing an acrylate rubber having an average particle size of 200 nm to 320 nm; 5 wt % to 25 wt % of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A-2) containing an acrylate rubber having an average particle size of 40 nm to 109 nm; 30 wt % to 60 wt % of a styrene-based copolymer (B-1) having a weight average molecular weight of 80,000 g / mol to 100,000 g / mol; 0 wt % to 15 wt % of a styrene-based copolymer (B-2) having a weight average molecular weight of 150,000 g / mol to 200,000 g / mol; and 20 wt % to 35 wt % of post-consumer recycled ABS resin (C). 15 . A molded article comprising the ASA-based resin composition according to any one of claims 1 to 3 or claims 6 to 13 .

Images