ASA-based resin composition, method for producing same, and molded product comprising same

Abstract

The present invention relates to an ASA-based resin composition, a method for producing same, and a molded product comprising same. The present invention has the effect of providing an ASA-based resin composition and a molded product comprising same, with eco-friendly properties imparted to the ASA-based resin composition, and no deterioration in the balance between mechanical properties such as impact strength and hardness and physical properties such as heat resistance and weathering resistance.

Description

ASA resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0122495, dated September 14, 2023, and all contents of the document in that Korean patent application are incorporated herein by reference.

[0003] The present invention relates to an ASA resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to an ASA resin composition that adds environmentally friendly characteristics to an ASA resin composition without deteriorating the balance of mechanical properties such as impact strength and hardness and physical properties such as heat resistance and weather resistance, a method for producing the same, and a molded article comprising the same.

[0004] Acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as 'ASA resin') has various applications due to its excellent weather resistance, aging resistance, chemical resistance, and processability, and is widely used in automobiles, home appliances, leisure goods, construction materials, gardening goods, and building materials.

[0005] Research is actively being conducted to blend recycled ASA resin into the above ASA resin to improve its eco-friendly properties and reduce manufacturing costs. However, not only is it difficult to recover waste ASA resin, but the weather resistance of the recovered waste ASA resin is also poor, making it difficult to recycle.

[0006] Therefore, there is a need to develop an ASA resin composition that provides eco-friendly characteristics to ASA resin, facilitates the procurement of raw materials, reduces manufacturing costs, and does not deteriorate mechanical properties and property balance.

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] Korean Patent Publication No. 2022-0084326

[0010] The purpose of the present invention is to provide an ASA resin composition that has an excellent balance of properties between mechanical strength and heat resistance and weather resistance that is suitable or higher for automobile exterior materials, and a method for producing the same.

[0011] In addition, the present invention aims to provide a molded product manufactured from the ASA resin composition.

[0012] The above and other objects of the present invention can all be achieved by the present invention described below.

[0013] In order to achieve the above purpose, the present invention

[0014] (A) an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) a styrenic copolymer; and (C) a post-consumer recycled ABS resin;

[0015] The above (C) post-consumer recycled ABS resin provides an ASA-based resin composition characterized in that it is included in an amount of 20 to 70 wt%.

[0016] The above (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may include (A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 200 to 320 nm and (A-2) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 40 to 109 nm.

[0017] The above (B) styrenic copolymer may be a mixture of (B-1) a styrenic copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol and (B-2) a styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol.

[0018] The above (C) post-consumer recycled ABS resin may comprise 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 may have a weight average molecular weight of 100,000 to 300,000 g / mol, or may be a mechanically recycled resin.

[0019] The above (A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including acrylate rubber having an average particle diameter of 200 to 320 nm and the above (A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including acrylate rubber having an average particle diameter of 40 to 109 nm may be included in a weight ratio (A-1:A-2) of 1:0.8 to 1:1.5.

[0020] The above (A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including acrylate rubber having an average particle diameter of 200 to 320 nm may be formed by including, for example, 30 to 50 wt% of acrylate rubber, 40 to 60 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on a total of 100 wt%.

[0021] The above (A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including acrylate rubber having an average particle diameter of 40 to 109 nm can be formed by including, for example, 40 to 60 wt% of acrylate rubber, 25 to 45 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on a total of 100 wt%.

[0022] The above (B-1) styrene copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol may be formed by including 55 to 75 wt% of an aromatic vinyl compound and 25 to 45 wt% of a vinyl cyan compound based on 100 wt% of the total.

[0023] The above (B-2) styrene copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol may be formed by including 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound based on a total of 100 wt%.

[0024] The above ASA resin composition has a flow index (220°C, load 10 kg) measured according to ISO 1133 within the range of 8.8 to 9.8 g / 10 min, and an Izod impact strength measured according to ISO 179 within the range of 10.1 to 10.7 kJ / m. 2 Within the range, the HDT measured according to ISO 75-1,2 may be within the range of 84.2 to 86°C, the hardness measured according to ISO 2039 may be within the range of 102 to 104, or the weatherability (SCI △E) measured according to the SAE J2527 evaluation method may be within the range of 0.99 to 1.63.

[0025]

[0026] In addition, the present invention

[0027] (A-1) 5 to 22 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle diameter of 200 to 320 nm;

[0028] (A-2) 5 to 25 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle diameter of 40 to 109 nm;

[0029] (B-1) 30 to 60 wt% of a styrene copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol;

[0030] (B-2) 0 to 15 wt% of a styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol; and

[0031] (C) An ASA resin composition is provided, characterized in that it comprises 20 to 35 wt% of an aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer.

[0032] The above (C) aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer has a melt volume flow rate (MVR) of 10 cm measured for polymer melt at 220°C and 10 kg according to ISO 1133-1:2011. 3 / 10min or more; Vicat B / 50 softening point of 80℃ or more as measured according to ISO 306:2004; E-modulus of 1500 MPa or more as measured according to ISO 527; stress at yield of 30 MPa or more as measured according to ISO 527; strain at yield of 2% or more as measured according to ISO 527; Charpy notched impact strength of 2 kJ / m as measured according to notch type A at 23℃ according to EN-ISO 179-1. 2 or a Charpy notched impact strength of 2 kJ / m measured according to EN-ISO 179-1 at -30°C according to notch type A. 2 It could be strange.

[0033]

[0034] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and characterized by comprising 11 to 15 wt% of an alkyl acrylate, 26 to 34 wt% of an aromatic vinyl compound, and 25 to 33 wt% of an alkyl-substituted aromatic vinyl compound.

[0035]

[0036] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 10 to 20 wt% of alkyl acrylate, 20 to 40 wt% of aromatic vinyl compound, 20 to 30 wt% of vinyl cyanate compound, 1 to 10 wt% of conjugated diene compound, and 20 to 40 wt% of alkyl-substituted aromatic vinyl compound.

[0037]

[0038] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 11 to 15 wt% of alkyl acrylate, 26 to 34 wt% of aromatic vinyl compound, 23 to 24 wt% of vinyl cyanate compound, 3 to 6 wt% of conjugated diene compound, and 25 to 33 wt% of alkyl-substituted aromatic vinyl compound.

[0039]

[0040] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 13 to 15 wt% of alkyl acrylate, 27 to 32 wt% of aromatic vinyl compound, 23 to 24 wt% of vinyl cyanate compound, 3 to 6 wt% of conjugated diene compound, and 27 to 32 wt% of alkyl-substituted aromatic vinyl compound.

[0041]

[0042] In addition, the present invention

[0043] (A-1) 5 to 22 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle size of 200 to 320 nm; (A-2) 5 to 25 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle size of 40 to 109 nm; (B-1) 30 to 60 wt% of a styrenic copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol; (B-2) 0 to 15 wt% of a styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol; And (C) a post-consumer recycled ABS resin (post-consumer recycled ABS resin) 20 to 35 wt%; a step of kneading and extruding under conditions of 200 to 300° C. and 300 to 800 rpm is provided. A method for producing an ASA resin composition is provided.

[0044]

[0045] In addition, the present invention provides a molded article characterized by including the above-described ASA resin composition.

[0046] The above molded product may be an automobile part including an automobile exterior material.

[0047] The ASA resin composition according to the present invention is environmentally friendly and provides an excellent balance of physical properties between mechanical strength such as impact strength and hardness, and heat resistance and weather resistance at a level equivalent to or higher than that of conventional ASA resin compositions, and therefore can be used as a material for automobile parts in particular.

[0048] Therefore, the ASA resin composition according to the present invention and the molded article manufactured therefrom can be widely applied to the field of unpainted automobile parts, including radiator grills or pillar parts, which require excellent properties thereof.

[0049] To help understand the present invention, the present invention will be described in more detail below.

[0050] Terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, but should be construed as meanings and concepts that conform to the technical spirit of the present invention, taking into account that the inventor can appropriately define the concept of the term in order to explain the invention in the best way.

[0051] The inventors of the present invention confirmed that when post-consumer recycled ABS resin is included in ASA resin, a balance of mechanical strength, heat resistance, and weather resistance suitable for automobile parts is achieved, and further devoted themselves to research to complete the present invention.

[0052]

[0053] The ASA resin composition according to the present invention is characterized in that it includes post-consumer recycled ABS resin.

[0054] The term "post-consumer recycled ABS resin" used in this description is not particularly limited as long as it is a post-consumer recycled ABS resin generally recognized in the technical field to which the present invention belongs, and for example, it may be a mechanically recycled resin in which the purity is improved through a process of removing impurities and washing after selecting raw materials by changing the physical structure of ABS resin waste having a weight average molecular weight in the range of 100,000 to 300,000 g / mol without changing the chemical structure.

[0055]

[0056] Hereinafter, the ASA resin composition of the present invention will be described in detail by composition.

[0057]

[0058] post-consumer recycled ABS resin

[0059] In one embodiment of the present invention, the post-consumer recycled ABS resin is an ABS resin recycled from a product discarded from, for example, automobile equipment, household appliances, electrical equipment, etc., or a product discarded as a defective product during the manufacturing of the product.

[0060] In a specific example, the post-consumer recycled ABS resin may exhibit one or more of the following characteristics:

[0061] -Melt volume flow rate (MVR) measured for polymer melts at 220°C and 10 kg according to ISO 1133-1:2011: 10 cm 3 / 10 min or more, or 10~35 cm 3 / 10min

[0062] -Vicat B / 50 softening point measured according to ISO 306:2004: 80℃ or higher, or 80~100℃

[0063] - E-modulus measured according to ISO 527: 1500 MPa or more, or 2000 MPa or more

[0064] - Stress at yield measured by ISO 527: 30 MPa or more, or 30 to 50 MPa

[0065] -Strain at yield measured by ISO 527: 2% or more, or 2 to 3%

[0066] -Charpy notch impact strength measured according to EN-ISO 179-1 at 23°C with notch type A: 2 kJ / m 2 or 2–20 kJ / m 2

[0067] -Charpy notch impact strength measured according to EN-ISO 179-1 at -30°C with notch type A: 2 kJ / m 2 or 2–20 kJ / m 2

[0068]

[0069] The above post-consumer recycled ABS resin may be a recycled ABS resin comprising, for example, 55 wt% or more, or 55 to 65 wt%, of an aromatic vinyl monomer, 10 wt% or more, or 10 to 20 wt%, of a diene rubber, and 15 wt% or more, or 15 to 25 wt%, of a vinyl cyanide compound. When the above ranges are satisfied, even when included in an ASA-based resin composition, there is an advantage of providing an excellent balance of properties among excellent mechanical properties, heat resistance, and weather resistance.

[0070] The above post-consumer recycled ABS resin may have, for example, a weight average molecular weight of 100,000 g / mol or more, or within a range of 100,000 to 300,000 g / mol, and may improve mechanical properties within the above range.

[0071] Specifically, the above weight average molecular weight is prepared by putting tetrahydrofuran (THF) and the compound in a 1 ml glass bottle to prepare a sample sample with a concentration of 1 wt% of the compound, filtering the standard sample (polystyrene) and the sample sample through a filter (pore size of 0.45 μm), and then injecting them into a GPC injector, and comparing the elution time of the sample sample with the calibration curve of the standard sample to obtain the weight average molecular weight and molecular weight distribution of the compound. At this time, Infinity II 1260 (Agilient) can be used as the measuring device, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 ℃.

[0072] The above post-consumer recycled ABS resin may be a mechanically recycled resin that is reprocessed after raw material selection by changing the physical structure without changing the chemical structure.

[0073] The above raw material selection process may be a process of collecting waste home appliances, washing them, and classifying them by component and color.

[0074] The above reprocessing may be a process of pelletizing the recycled ABS resin classified as above through an extruder.

[0075] The above post-consumer recycled ABS resin may be included in an amount of 20 to 35 wt%, 20 to 32 wt%, preferably 22 to 32 wt%, and more preferably 22 to 26 wt%, based on 100 wt% of the total weight of the ASA-based resin composition. If the content is less than the above range, the amount of post-consumer recycled ABS resin used decreases, thereby diminishing the eco-friendly concept. If the content exceeds the above range, there are disadvantages of deterioration in mechanical properties and appearance quality.

[0076] The above post-consumer recycled ABS resin is not particularly limited as long as it follows the definition of the present invention, and can be manufactured and used through a method known in the art, or a commercially available material can be obtained and used.

[0077]

[0078] virgin resin

[0079] The virgin resin constituting the above ASA resin composition may be formed by including, for example, (A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 200 to 320 nm; (A-2) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 40 to 109 nm; and (B) one or more styrene-based copolymers.

[0080] As a specific example, the virgin resin constituting the ASA-based resin composition may include (A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 200 to 320 nm; (A-2) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 40 to 109 nm; and (B-1) a first styrene-based copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol.

[0081] As another example, the virgin resin constituting the ASA resin composition may include (A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 200 to 320 nm; (A-2) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 40 to 109 nm; (B-1) a first styrenic copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol; and (B-2) a second styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol.

[0082] In cases such as the above examples, there is an advantage of providing an excellent balance of mechanical properties, heat resistance, and weather resistance while including post-consumer recycled ABS resin.

[0083]

[0084] Hereinafter, the virgin resin constituting the ASA resin composition of the present invention will be described in detail by composition.

[0085] (A-1) Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising acrylate rubber having an average particle diameter of 200 to 320 nm

[0086] The acrylate rubber of the above (A-1) graft copolymer preferably has an average particle diameter of 200 to 320 nm, preferably 220 to 300 nm, more preferably 240 to 280 nm, and within this range, has excellent mechanical strength such as impact strength.

[0087] In this paper, the average particle size can be measured using dynamic light scattering, and specifically, it is measured as an intensity value in Gaussian mode using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). As a specific measurement example, 0.1 g of latex with a total solid content of 35 to 50 wt% is prepared by diluting 1,000 to 5,000 times with distilled water, and the measurement method is measured using a flow cell through auto-dilution. The measurement mode is dynamic light scattering / Intensity 300 KHz / Intensity-weight Gaussian Analysis, and the setting values ​​are temperature 23 ℃, measurement wavelength 632.8 nm, and channel width 10 μsec.

[0088]

[0089] The above (A-1) graft copolymer may be, for example, 5 to 22 wt%, 10 to 22 wt%, 15 to 22 wt%, or 18 to 21 wt% of the total 100 wt% of all components constituting the virgin resin, and within this range, it has the effect of providing superior appearance quality while having fluidity and weather resistance equivalent to or higher than that of a conventional ASA-based resin composition.

[0090] The above (A-1) graft copolymer comprises, for example, 30 to 50 wt% of acrylate rubber, 40 to 60 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on 100 wt% of the total, and preferably comprises 35 to 50 wt% of acrylate rubber, 40 to 55 wt% of aromatic vinyl compound, and 10 to 20 wt% of vinyl cyan compound, and within this range, excellent mechanical strength such as impact strength is achieved.

[0091] In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units in the polymerized polymer are derived from the compound.

[0092]

[0093] The above acrylate rubber may be formed by including an alkyl acrylate compound.

[0094] In the present invention, the alkyl acrylate compound may be, for example, an alkyl acrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, more preferably an alkyl acrylate including a chain alkyl group having 1 to 4 carbon atoms, and even more preferably butyl acrylate.

[0095]

[0096] In the present invention, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-bromo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene, and in this case, there is an effect of having appropriate fluidity, excellent processability, and excellent mechanical properties such as impact resistance.

[0097]

[0098] In the present invention, the vinyl cyanide compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

[0099]

[0100] The above (A-1) graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has excellent mechanical strength such as impact strength.

[0101] The above emulsion polymerization is not particularly limited if it is performed using an emulsion graft polymerization method commonly practiced in the technical field to which the present invention belongs.

[0102]

[0103] (A-2) Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising acrylate rubber having an average particle diameter of 40 to 109 nm

[0104] The acrylate rubber of the above (A-2) graft copolymer may have, for example, an average particle diameter of 40 to 109 nm, preferably 40 to 100 nm, more preferably 50 to 100 nm, and even more preferably 60 to 100 nm, and within this range, it can impart excellent impact strength and gloss to the ASA resin composition finally manufactured.

[0105]

[0106] The above (A-2) graft copolymer may be, for example, 5 to 25 wt%, preferably 10 to 25 wt%, more preferably 15 to 25 wt%, even more preferably 20 to 25 wt%, and even more preferably 23 to 25 wt%, of the total 100 wt% of all components constituting the virgin resin, and within this range, it has the effect of providing superior appearance quality while having fluidity and weather resistance equivalent to or higher than that of a conventional ASA-based resin composition.

[0107]

[0108] The above (A-2) graft copolymer comprises, for example, 40 to 60 wt% of acrylate rubber, 25 to 45 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on 100 wt% of the total, and preferably comprises 45 to 55 wt% of acrylate rubber, 30 to 45 wt% of aromatic vinyl compound, and 10 to 20 wt% of vinyl cyan compound, and within this range, excellent gloss and impact strength are achieved.

[0109]

[0110] The above acrylate rubber may be formed by including an alkyl acrylate compound.

[0111] The types of alkyl acrylate compounds, aromatic vinyl compounds, and vinyl cyan compounds included in the above (A-2) graft copolymer may be within the same category as the types of alkyl acrylate compounds, aromatic vinyl compounds, and vinyl cyan compounds included in the above-described (A-1) graft copolymer.

[0112]

[0113] The above (A-2) graft copolymer can be produced, for example, by emulsion polymerization, in which case it has excellent impact strength and gloss.

[0114] The above emulsion polymerization is not particularly limited if it is performed using an emulsion graft polymerization method commonly practiced in the technical field to which the present invention belongs.

[0115]

[0116] The total amount of the above (A-1) graft copolymer and the above (A-2) graft copolymer may be preferably 45 wt% or less, 30 to 45 wt%, and more preferably 40 to 44 wt%, of the total 100 wt% of all components constituting the virgin resin, and within this range, even if the post-consumer recycled ABS resin is included in the ASA-based resin composition, there is an advantage of providing an excellent balance of properties among mechanical properties, heat resistance, and weather resistance.

[0117]

[0118] (B-1) A first styrene copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol

[0119] The above (B-1) first styrene copolymer may be, for example, an aromatic vinyl compound-vinyl cyan compound copolymer.

[0120] The above aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of, for example, 85,000 to 100,000 g / mol, more preferably 90,000 to 100,000 g / mol, and even more preferably 92,000 to 98,000 g / mol, and within this range, excellent effects such as impact strength and hardness are achieved.

[0121] The above (B-1) aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, 30 to 60 wt%, 35 to 60 wt%, 40 to 60 wt%, or 45 to 59 wt% based on 100 wt% of the total components constituting the virgin resin, and within this range, impact resistance, heat resistance, and hardness are maintained at equivalent levels, while fluidity and appearance quality are improved.

[0122]

[0123] The above (B-1) aromatic vinyl compound-vinyl cyan compound copolymer can be formed by including, for example, an aromatic vinyl compound and a vinyl cyan compound, and in this case, it has the advantage of excellent impact resistance and suppressing the deterioration of heat resistance and weather resistance.

[0124] As a preferred example, the aromatic vinyl compound-vinyl cyan compound copolymer may comprise 55 to 75 wt% of the aromatic vinyl compound and 25 to 45 wt% of the vinyl cyan compound based on a total of 100 wt%, more preferably 60 to 80 wt% of the aromatic vinyl compound and 20 to 40 wt% of the vinyl cyan compound, and even more preferably 65 to 75 wt% of the aromatic vinyl compound and 25 to 35 wt% of the vinyl cyan compound. In this case, there is an advantage of excellent fluidity and suppressing deterioration of appearance quality.

[0125]

[0126] The types of aromatic vinyl compounds and vinyl cyan compounds included in the above (B-1) aromatic vinyl compound-vinyl cyan compound copolymer may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds included in the (A-1) graft copolymer of the present disclosure.

[0127] The above (B-1) aromatic vinyl compound-vinyl cyan compound copolymer can be produced by, for example, emulsion polymerization, solution polymerization or bulk polymerization, and in this case, it has excellent effects such as heat resistance and fluidity.

[0128] The above emulsion polymerization, solution polymerization and bulk polymerization are not particularly limited when performed using emulsion polymerization, solution polymerization and bulk polymerization methods commonly performed in the technical field to which the present invention belongs.

[0129]

[0130] (B-2) A second styrene copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol

[0131] The above (B-2) second styrene copolymer may be, for example, an aromatic vinyl compound-vinyl cyan compound copolymer.

[0132] The above aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of, for example, 150,000 to 200,000 g / mol, more preferably 155,000 to 195,000 g / mol, and even more preferably 160,000 to 180,000 g / mol, and within this range, excellent effects such as impact resistance and scratch resistance are achieved.

[0133] The above (B-2) aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, 15 wt% or less, 3 to 15 wt%, or 5 to 15 wt% based on 100 wt% of the total components constituting the virgin resin, and within this range, there is an advantage in that the fluidity and appearance quality are improved while the impact resistance, heat resistance, and hardness are maintained at equivalent levels.

[0134]

[0135] The above aromatic vinyl compound-vinyl cyan compound copolymer may comprise 60 to 80 wt% of the aromatic vinyl compound and 20 to 40 wt% of the vinyl cyan compound based on 100 wt% of the total, more preferably 65 to 80 wt% of the aromatic vinyl compound and 20 to 35 wt% of the vinyl cyan compound, and even more preferably 65 to 75 wt% of the aromatic vinyl compound and 25 to 35 wt% of the vinyl cyan compound. In this case, there is an advantage of excellent fluidity and suppressing deterioration of appearance quality.

[0136]

[0137] The types of aromatic vinyl compounds and vinyl cyan compounds included in the above (B-2) aromatic vinyl compound-vinyl cyan compound copolymer may be within the same category as the types of aromatic vinyl compounds and vinyl cyan compounds included in the (A-1) graft copolymer of the present disclosure.

[0138] The above (B-2) aromatic vinyl compound-vinyl cyan compound copolymer can be produced by, for example, emulsion polymerization, solution polymerization or bulk polymerization, and in this case, it has excellent effects such as heat resistance and fluidity.

[0139] The above emulsion polymerization, solution polymerization and bulk polymerization are not particularly limited when performed using emulsion polymerization, solution polymerization and bulk polymerization methods commonly performed in the technical field to which the present invention belongs.

[0140]

[0141] ASA resin composition

[0142] The above ASA resin composition may, for example, contain the contents of (A-1) and (A-2) in a weight ratio of 1:0.8 to 1:1.5, or a weight ratio of 1:0.8 to 1:1.5, and in this case, it has the advantage of providing an excellent balance of mechanical properties, heat resistance, and weather resistance while containing post-consumer recycled ABS resin.

[0143]

[0144] The above ASA resin composition may further include, for example, an active agent or an additive including the same.

[0145] The above additive may be at least one selected from the group consisting of an activator, a heat stabilizer, a UV stabilizer, an optical whitening agent, a chain extender, a 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.

[0146] The above additives may be further included, for example, in an amount of 0.01 to 5 wt%, preferably 0.05 to 3 wt%, and more preferably 0.1 to 3 wt%, based on 100 wt% of the total components (A+B+C+additive) constituting the ABS resin composition. In this case, the function of the additives is effectively implemented without deteriorating the original physical properties of the ASA resin composition of the present disclosure.

[0147] The above-mentioned active agent may be, for example, at least one selected from the group consisting of an alkyl acrylate polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, an ethylene copolymer comprising ethylene and a co-polymer, an olefin wax, and an aliphatic amide compound, and preferably at least one selected from the group consisting of an alkyl acrylate polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, and an olefin wax, and more preferably an alkyl acrylate polymer, and in this case, the active agent has an excellent balance of physical properties while exhibiting excellent scratch resistance and colorability, thereby providing an excellent appearance quality.

[0148] The above-mentioned active agent may be, for example, 0.1 to 3 wt%, preferably 0.5 to 2.5 wt%, and more preferably 0.7 to 2.2 wt%, based on 100 wt% of the total components (A+B+C+active agent) constituting the ABS resin composition, and within this range, both impact resistance and fluidity are excellent.

[0149] The above-mentioned alkyl acrylate polymer as an active agent may preferably be at least one selected from the group consisting of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate), and in this case, the formation of mold deposits is suppressed, so that the molded product has an attractive appearance and high gloss.

[0150] The above-mentioned alkyl acrylate polymer, which is an active agent, is not particularly limited as long as it is an alkyl acrylate polymer commonly used in the technical field to which the present invention belongs, and a product manufactured directly or commercially available can be used.

[0151] The above-mentioned styrene-acrylonitrile copolymer as the active agent preferably has a weight average molecular weight of 40,000 to 67,000 g / mol, more preferably 50,000 to 65,000 g / mol, and even more preferably 55,000 to 65,000 g / mol, and within this range, it has the effect of improving fluidity, thereby providing excellent processability and improving appearance quality.

[0152] The above-mentioned styrene-acrylonitrile copolymer, which is an active agent, may have a flow index (190°C, 5kg) measured according to ISO 1133 of, for example, 20 to 60 g / 10min, preferably 25 to 55 g / 10min, and within this range, it has excellent impact strength and flowability and excellent appearance quality.

[0153] The above-mentioned styrene-acrylonitrile copolymer, which is an active agent, may have a heat distortion temperature of, for example, 82 to 90°C, preferably 84 to 88°C, as measured according to ASTM D648, and within this range, has excellent impact strength and fluidity and excellent appearance quality.

[0154] The above ethylene copolymer may be at least one selected from the group consisting of, for example, an ethylene / 1-butene copolymer and an ethylene / n-butyl acrylate / carbon monoxide terpolymer, and in this case, it has the effect of excellent heat resistance and fluidity and superior appearance quality.

[0155] The above olefin wax may be, for example, at least one selected from the group consisting of polyethylene wax and polypropylene wax, and preferably polyethylene wax. In this case, it has the effect of excellent heat resistance and fluidity and superior appearance quality.

[0156] The above aliphatic amide compound may be at least one selected from the group consisting of stearamide, behanamide, ethylene bis(stearamide), ethylene bis 12-hydroxy stearamide, erucamide, oleamide, and ethylene bis oleamide, and preferably ethylene bis stearamide. In this case, the aliphatic amide compound has excellent impact strength and fluidity and excellent appearance quality.

[0157] The ASA resin composition of the present invention preferably does not contain a stearate-based lubricant, i.e., is stearate-based lubricant-free, and in this case, the molded product has an attractive appearance and high gloss.

[0158] The above stearate-based active agent may be, for example, at least one selected from the group consisting of barium stearate, calcium stearate, magnesium stearate, zinc stearate, and stearic acid.

[0159] In this description, ‘stearate-based lubricant-free’ means that no stearate-based lubricant is intentionally added during the manufacture of the ASA-based resin composition.

[0160]

[0161] Other additives other than the above-mentioned active agent may further include, for example, one or more additives selected from the group consisting of heat stabilizers, UV stabilizers, optical whitening agents, chain extenders, release agents, pigments, dyes, antibacterial agents, processing aids, metal deactivators, smoke suppressants, inorganic fillers, glass fibers, antifriction agents, and wear-resistant agents, for example, 0.1 to 5 wt%, preferably 1 to 3 wt%, of each additive relative to 100 wt% of the total components (A+B+C+other additives) constituting the ABS resin composition. In this case, there is an effect in which the function of the additive is well implemented without deteriorating the original physical properties of the ASA resin composition of the present disclosure.

[0162] The above heat stabilizer may be, for example, preferably 0.1 to 2 wt%, more preferably 0.2 to 1.5 wt%, based on 100 wt% of the total components (A+B+C+heat stabilizer) constituting the ABS resin composition, and has the effect of improving heat resistance within this range.

[0163] The above heat stabilizer may be, for example, at least one selected from the group consisting of a phenol-based heat stabilizer, a phosphite-based heat stabilizer, and a thioether-based heat stabilizer, and is preferably a phenol-based heat stabilizer and / or a phosphite-based heat stabilizer.

[0164] The above phenolic heat stabilizer may be, for example, at least one selected from the group consisting of tetrakis methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris-(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0165] The above phosphite-based heat stabilizer may be, for example, trisnonylphenyl phosphite, tris-(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0166] The above thioether-based heat stabilizer may be, for example, at least one selected from the group consisting of dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

[0167] The above UV stabilizer may be, for example, preferably 0.1 to 3 wt%, more preferably 0.5 to 1.5 wt%, based on 100 wt% of the total components (A+B+C+UV stabilizer) constituting the ABS resin composition, and in this case, there is an effect of improving weather resistance.

[0168] The UV stabilizer may be, for example, a hindered amine light stabilizer (HALS), and preferably, 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-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid. Condensation products, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-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-butane tetracarboxylate, 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, At least one selected from the group consisting of a linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, a 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-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], and more preferably Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate2-(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-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino] or a mixture thereof, and more preferably Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacade, 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 which case there is an advantage of significantly improving weather resistance without compromising impact resistance and fluidity.

[0169] The above pigment may be, for example, carbon black.

[0170] The pigment may be preferably present in an amount of 0.5 to 5 wt%, more preferably 1 to 4.5 wt%, and even more preferably 2 to 4.5 wt%, based on 100 wt% of the total components (A+B+C+pigment) constituting the ABS resin composition, and within this range, it has the advantage of excellent physical property balance and excellent coloring properties.

[0171]

[0172] In addition, the present invention provides an ASA resin composition characterized by comprising: 20 to 35 wt% of a post-consumer recycled ABS resin; 5 to 22 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 200 to 320 nm; 5 to 25 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 40 to 109 nm; 30 to 60 wt% of a styrenic copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol; and 0 to 15 wt% of a styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol.

[0173] The above post-consumer recycled ABS resin may be made of 55 to 65 wt% of an aromatic vinyl monomer, 10 to 20 wt% of a diene rubber, and 15 to 25 wt% of a vinyl cyanide compound, or may be a mechanically recycled resin obtained by reprocessing waste ABS resin having a weight average molecular weight in the range of 100,000 to 300,000 g / mol by changing its physical structure without changing its chemical structure and then sorting the raw materials.

[0174] The above ASA resin composition may include an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle size of 200 to 320 nm and an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle size of 40 to 109 nm in a weight ratio of 1:0.8 to 1:1.5.

[0175] The above ASA resin composition has a flow index of 8 g / 10 min or more, preferably 8.8 to 9.5 g / 10 min, measured at 220°C and 10 kg for 10 minutes using MI-4 from GOTTFEST according to ISO1133, and within this range, has excellent physical property balance, scratch resistance, and colorability, resulting in excellent appearance quality.

[0176] The above ASA resin composition has an Izod impact strength of 10 kJ / m measured at 23°C with a specimen thickness of 4 mm according to ISO 179. 2 Ideally, 10 to 15 kJ / m 2 It can be, and has the effect of excellent scratch resistance while having excellent physical property balance within this range.

[0177] The above ASA resin composition may have a heat distortion temperature (HDT) of 84°C or higher, preferably 84 to 86°C, as measured by an Auto HDT Tester 6A-2 (trade name, manufacturer: TOYOSEIKI) according to ISO 75-1,2, for example, and has excellent heat resistance characteristics without affecting mechanical strength within this range.

[0178] The above ASA resin composition may have a hardness of 100 or more, preferably 102 to 105, measured according to ISO 2039, and has excellent physical property balance and excellent scratch resistance within this range.

[0179] The above ASA resin composition can have a weather resistance (SCI △E) of 3 or less, preferably 0.99 to 1.63, calculated by irradiating a specimen with 2500 kJ of energy using the SAE J2527 evaluation method and then measuring the color before and after irradiation using a colorimeter SCI Mode, and has an excellent weather resistance while maintaining excellent physical property balance within this range.

[0180]

[0181] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 10 to 20 wt% of alkyl acrylate, 20 to 40 wt% of aromatic vinyl compound, 20 to 30 wt% of vinyl cyanate compound, 1 to 10 wt% of conjugated diene compound, and 20 to 40 wt% of alkyl-substituted aromatic vinyl compound.

[0182]

[0183] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 11 to 15 wt% of alkyl acrylate, 26 to 34 wt% of aromatic vinyl compound, 23 to 24 wt% of vinyl cyanate compound, 3 to 6 wt% of conjugated diene compound, and 25 to 33 wt% of alkyl-substituted aromatic vinyl compound.

[0184]

[0185] In addition, the present invention provides an ASA resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyanate compound graft copolymer and a vinyl cyanate compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that it comprises 13 to 15 wt% of alkyl acrylate, 27 to 32 wt% of aromatic vinyl compound, 23 to 24 wt% of vinyl cyanate compound, 3 to 6 wt% of conjugated diene compound, and 27 to 32 wt% of alkyl-substituted aromatic vinyl compound.

[0186]

[0187] Method for producing ASA resin composition

[0188] The present invention provides a method for producing an ASA resin composition, characterized in that it comprises, for example, a step of mixing and extruding an ASA resin and a post-consumer recycled ABS resin under conditions of 200 to 300°C and 300 to 800 rpm. In this case, there is an advantage of providing an excellent balance of mechanical properties, heat resistance, and weather resistance while including the post-consumer recycled ABS resin.

[0189]

[0190] As a preferred example, 20 to 35 wt% of a post-consumer recycled ABS resin; 5 to 22 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (ASA-based resin) comprising an acrylate rubber having an average particle size of 200 to 320 nm; 5 to 25 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (ASA-based resin) comprising an acrylate rubber having an average particle size of 40 to 109 nm; 30 to 60 wt% of a styrene-based copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol; And it is characterized by including a step of mixing and extruding under conditions of 200 to 300 ℃ and 300 to 800 rpm, including 0 to 15 wt% of a styrene-based copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol. In this case, there is an advantage of providing an excellent balance of mechanical properties, heat resistance, and weather resistance while including a post-consumer recycled ABS resin.

[0191] The method for manufacturing the above ASA resin composition shares all the technical characteristics of the aforementioned ASA resin composition. Therefore, a description of the overlapping portions will be omitted.

[0192]

[0193] The step of manufacturing pellets using the above extrusion mixer may preferably be performed at a temperature of 200 to 300°C with a size of 25 to 75 pi, more preferably at a temperature of 220 to 260°C with a size of 20 to 70 pi, and within this range, stable extrusion is possible and the mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder, and pi means the outer diameter (unit: mm).

[0194] The above extrusion mixer is not particularly limited as long as it is an extrusion mixer commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extrusion mixer.

[0195]

[0196] molded products

[0197] The molded article of the present invention is characterized by including, for example, the ASA-based resin composition of the present invention, and in this case, compared to a conventional ASA-based resin composition, it has the advantage of providing an excellent balance of properties among mechanical properties, heat resistance, and weather resistance while including post-consumer recycled ABS resin.

[0198]

[0199] The method for manufacturing a molded product of the present invention is characterized by including a step of injecting pellets manufactured by the method for manufacturing the ASA resin composition under the conditions of an injection temperature of 200 to 300°C, an injection pressure of 60 to 100 bar, and a holding pressure of 30 to 65 bar, and in this case, there is an advantage in that an injection molded product having high impact strength can be easily manufactured.

[0200] The above injection temperature is preferably 220 to 280°C, more preferably 230 to 270°C, and within this range, there is an advantage in that an injection molded product requiring a complex design can be easily manufactured.

[0201] The above injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and within this range, there is an advantage in that an injection molded product requiring a complex design can be easily manufactured.

[0202] The above pressure may preferably be 35 to 60 bar, more preferably 40 to 55 bar, and within this range, there is an advantage in that injection molded products requiring complex designs can be easily manufactured.

[0203]

[0204] The pellets manufactured by the method for manufacturing the above ASA resin composition may have a residual emulsifier content (based on weight) of 5,000 ppm or less, specifically 1,000 to 4,000 ppm, 1,000 to 3,000 ppm, or 1,000 to 1,900 ppm. In this case, the pellets may provide a luxurious appearance and high gloss while being capable of unpainted injection molding and having improved processability due to high fluidity.

[0205]

[0206] The above-mentioned molded product is, for example, an automobile exterior material, and preferably may be a radiator grill, a side mirror cover, a pillar part, etc.

[0207]

[0208] In describing the ASA resin composition, its manufacturing method, and molded product of this invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0209]

[0210] Hereinafter, preferred examples are presented to help understand the present disclosure; however, the following examples are merely illustrative of the present disclosure, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0211]

[0212] [Example]

[0213] The materials used in the following examples and additional examples are as follows.

[0214] * (A-1) Graft copolymer: ASA graft copolymer having an average particle size of 300 nm of acrylate rubber (40 wt% butyl acrylate, 46.5 wt% styrene, and 13.5 wt% acrylonitrile)

[0215] * (A-2) Graft copolymer: ASA graft copolymer having an average particle size of 90 nm of acrylate rubber (50 wt% butyl acrylate, 36.5 wt% styrene, and 13.5 wt% acrylonitrile)

[0216] * (B) Styrenic copolymer

[0217] (B-1) Aromatic vinyl compound-vinyl cyanide compound copolymer (70 wt% styrene and 30 wt% acrylonitrile, weight average molecular weight 95,000 g / mol)

[0218] (B-2) Aromatic vinyl compound-vinyl cyanide compound copolymer (73 wt% styrene and 27 wt% acrylonitrile, weight average molecular weight 130,000 g / mol)

[0219] * (C) Post-consumer recycled ABS resin: Mechanically recycled resin reprocessed after selecting raw materials without chemical structural change, comprising 60 parts by weight of styrene, 15 parts by weight of butadiene rubber, and 25 parts by weight of acrylonitrile (Product name: AB3010, Manufacturer: Daeil Resin)

[0220] * Additive 1: Ethylene bis(stearamide) lubricant

[0221] * Additive 2: UV stabilizer

[0222] * Additive 3: Black pigment

[0223]

[0224] Examples 1 to 4, and additional examples 1 to 4

[0225] The components and contents (parts by weight) described in Tables 1 and 2 below were fed into a twin-screw extruder. Additives 1, 2, and 3 were fed in corresponding parts by weight based on a total weight of 100 parts by weight of the aforementioned components (A-1), (A-2), (B-1), and (B-2).

[0226] Then, pellets were manufactured by kneading and extruding at a cylinder temperature of 240 ℃, and the flow index was measured using the manufactured pellets.

[0227] The manufactured pellets were injected using an injection molding machine (Engel's 120MT) at an injection temperature of 240°C to produce specimens for measuring physical properties.

[0228]

[0229] [Example Exam]

[0230] The properties of the specimens manufactured in Examples 1 to 4 and Additional Examples 1 to 4 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0231]

[0232] measurement method

[0233] * Izod impact strength (kJ / m) 2 ): Measurements were made at 23°C with a specimen thickness of 4 mm according to ISO 179.

[0234] * Flow index (g / 10min): Measured at 220℃, 10kg for 10 minutes using MI-4 from GOTTFERT according to ISO 1133.

[0235] * Heat deflection temperature (HDT, ℃): Measured using TOYOSEIKI Auto HDT Tester 6A-2 according to ISO 75-1,2.

[0236] * Hardness: Measured according to ISO 2039.

[0237] * Weatherability: The evaluation was conducted under SAE J2527 conditions for 2500 kJ of light, and the △E of the glossy surface of the specimen before and after the evaluation was measured.

[0238] Classification (weight part) Example 1 Example 2 Example 3 Example 4 (A-1) Graft copolymer 18182118 (A-2) Graft copolymer 24242124 (B-1) Styrenic copolymer 58485858 (B-2) Styrenic copolymer-10-- (C) Post-consumer recycled ABS resin 28282848 (C) Content (weight %) 22222232 (Additive 1) 1111 (Additive 2) 1111 (Additive 3) 4444 Izod impact strength 10.1 10.7 10.6 10.2 Flow index 8.8 9.4 8.7 9.8 Heat distortion Temperature 85.684.28685.2 Hardness 104102103104 Weatherability (△E) 0.991.21.11.63

[0239] Addition Example 1Addition Example 2Addition Example 3Addition Example 4(A-1) Graft copolymer 15182316(A-2) Graft copolymer 26241926(B-1) Styrenic copolymer 59585858(B-2) Styrenic copolymer----(C) Post-consumer recycled ABS resin (weight parts) 28682828(C) Content (weight%) 22402222(Additive 1) 1111(Additive 2) 1111(Additive 3) 4444Izod impact strength 9.69.811.78.8Flow index 10.210.88.09.8Heat deflection temperature 87.2828786Hardness 10610599105Weather resistance (△E) 0.753.152.00.9

[0240] (The content (weight%) of (C) in Tables 1 and 2 above is the value converted to weight% by taking the input amount (weight part) of (C) as 100 weight% of the total weight of (A-1), (A-2), (B-1), (B-2) and (C).)

[0241] Furthermore, the monomer composition ratios of Examples 1 to 4 of Table 1 and Additional Examples 1 to 4 of Table 2 were converted and shown in Table 3 below.

[0242] ClassificationEmbodiment 1Embodiment 2Embodiment 3Embodiment 4Additional Example 1Additional Example 2Additional Example 3Additional Example 4BA1515151315111515SM2732273126342726AN2323232323242323BD33353633AMS3227322833253232Total100100100100100100100100

[0243] (In Table 3 above, BA stands for butylacrylate, SM stands for styrene, AN stands for acrylonitrile, BD stands for butadiene, and AMS stands for alkylmethylstyrene.)

[0244] As shown in Tables 1 and 2 above, among the examples according to the present invention, examples 1 to 4 have hardness equivalent to or greater than that of additional examples 1 to 4, while having superior fluidity index, heat resistance, and Izod impact strength, and improved weather resistance, thereby preventing deterioration of surface properties that may occur during molding processing and confirming the effect of excellent appearance quality even in harsh external environments.

[0245] In particular, Example 2, which used a combination of two styrenic copolymers having different weight average molecular weights of (B-1) and (B-2) in the graft copolymers of (A-1) and (A-2), confirmed that the impact strength was improved compared to Example 1, which used only the styrenic copolymer of (B-1) in the graft copolymers of (A-1) and (A-2).

[0246] Meanwhile, additional example 1, in which the graft copolymer of (A-1) was used in a small amount outside the range according to the present invention and the graft copolymer of (A-2) was used in an excessive amount outside the range according to the present invention, had relatively poor impact strength.

[0247] In addition, additional example 2, which used an excessive amount of post-consumer recycled ABS resin (C) outside the appropriate range according to the present invention, had relatively low impact strength and heat resistance and poor weather resistance.

[0248] In addition, additional example 3, in which the graft copolymer of (A-1) was used in an excessive amount outside the appropriate range according to the present invention, had relatively poor fluidity and hardness.

[0249] In addition, additional example 4, in which the graft copolymer of (A-2) was used in an excessive amount outside the appropriate range according to the present invention, had relatively poor impact strength and fluidity.

[0250]

[0251] In summary of these results, even when using post-consumer recycled ABS resin, by including a graft copolymer containing an acrylate rubber having a different average particle size and a styrene copolymer having a predetermined weight average molecular weight range in a predetermined content ratio, the mechanical properties such as impact resistance and hardness, as well as heat resistance, fluidity, and weather resistance are improved due to the synergistic effect according to the combination, and it was confirmed that a resin composition is provided that has an eco-friendly effect compared to the conventional ASA resin composition, improves product properties, and further provides product reliability as an automobile exterior material.

Claims

1. (A) an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer; (B) a styrenic copolymer; and (C) a post-consumer recycled ABS resin; An ASA resin composition characterized in that the above (C) post-consumer recycled ABS resin is contained in an amount of 20 to 70 wt%.

2. In paragraph 1, An ASA resin composition characterized in that the (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises (A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 200 to 320 nm and (A-2) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 40 to 109 nm.

3. In paragraph 1, An ASA resin composition characterized in that the above (B) styrene copolymer is a mixture of (B-1) a styrene copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol and (B-2) a styrene copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol.

4. In any one of paragraphs 1 to 3, The above (C) post-consumer recycled ABS resin comprises 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 an ASA resin composition characterized in that it is a mechanically recycled resin.

5. In any one of paragraphs 1 to 3, An ASA resin composition characterized in that the (A-1) acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including an acrylate rubber having an average particle diameter of 200 to 320 nm and the (A-2) acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including an acrylate rubber having an average particle diameter of 40 to 109 nm are included in a weight ratio (A-1:A-2) of 1:0.8 to 1:1.

5.

6. In paragraph 2, An ASA resin composition characterized in that the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 200 to 320 nm (A-1) comprises, for example, 30 to 50 wt% of acrylate rubber, 40 to 60 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on a total of 100 wt%.

7. In paragraph 2, An ASA resin composition characterized in that the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 40 to 109 nm (A-2) comprises, for example, 40 to 60 wt% of acrylate rubber, 25 to 45 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, based on a total of 100 wt%.

8. In paragraph 3, An ASA resin composition characterized in that the above (B-1) styrene copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol comprises 55 to 75 wt% of an aromatic vinyl compound and 25 to 45 wt% of a vinyl cyan compound based on a total of 100 wt%.

9. In paragraph 3, An ASA resin composition characterized in that the above (B-2) styrene copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol comprises 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound based on a total of 100 wt%.

10. In paragraph 1, The above ASA resin composition has a flow index (220°C, load 10 kg) measured according to ISO 1133 within the range of 8.8 to 9.8 g / 10 min, and an Izod impact strength measured according to ISO 179 within the range of 10.1 to 10.7 kJ / m. 2 An ASA resin composition characterized in that the HDT measured according to ISO 75-1,2 is within the range of 84.2 to 86 ℃, the hardness measured according to ISO 2039 is within the range of 102 to 104, or the weather resistance (SCI △E) measured according to the SAE J2527 evaluation method is within the range of 0.99 to 1.

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

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

13. Including an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, An ASA resin composition comprising 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-1) 5 to 22 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle size of 200 to 320 nm; (A-2) 5 to 25 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle size of 40 to 109 nm; (B-1) 30 to 60 wt% of a styrenic copolymer having a weight average molecular weight of 80,000 to 100,000 g / mol; (B-2) 0 to 15 wt% of a styrenic copolymer having a weight average molecular weight of 150,000 to 200,000 g / mol; And (C) a method for producing an ASA resin composition, characterized by comprising a step of mixing and extruding under conditions of 200 to 300° C. and 300 to 800 rpm, including 20 to 35 wt% of a post-consumer recycled ABS resin.

15. A molded product characterized by comprising an ASA resin composition according to any one of claims 1 to 3 or claims 6 to 13.