Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof

Abstract

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same. More specifically, the invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same, wherein the composition comprises: A) an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) a hard matrix polymer; wherein the rubber content is 25 to 31 weight% and the graft copolymer has a graft rate of 23 to 29.5%. According to the present invention, there is an effect of providing a thermoplastic resin composition that includes a rubber having a single average particle size, which has excellent impact resistance, gloss, weather resistance, and processability compared to a conventional case in which two types of rubber with different average particle sizes are included, and which can satisfy high added value and high efficiency, a method for manufacturing the same, and a molded article including the same.

Description

Technology Field

[0001] The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article including the same. More specifically, it relates to a thermoplastic resin composition having a single average particle size, which has significantly improved appearance characteristics such as impact resistance and gloss compared to a conventional ASA resin composition containing two types of rubber with different average particle sizes, a method for manufacturing the same, and a molded article including the same. Background Technology

[0003] Acrylonitrile-butadiene-styrene copolymers based on conjugated diene rubber (hereinafter referred to as "ABS resin") are widely used in components of electrical and electronic products, automobiles, small toys, furniture, and building materials due to their excellent processability, mechanical properties, and appearance properties. However, ABS resins have the disadvantage of poor weather resistance because they use butadiene polymers as rubber. To overcome this, acrylate compound-styrene-acrylonitrile copolymers (hereinafter referred to as "ASA resin"), which do not contain ethylene-based unsaturated polymers, have been developed. ASA resins have the advantage of excellent weather resistance, as well as excellent impact resistance and colorability.

[0004] Acrylate-based rubber used in ASA resins is characterized by varying adhesion, gloss, and impact resistance depending on the particle size. Small-diameter acrylate-based rubber with an average particle size of 50 to 150 nm has excellent colorability and gloss, whereas large-diameter acrylate-based rubber with an average particle size of 400 nm or more has excellent impact resistance. Therefore, most ASA resins achieve desired properties by mixing two types of rubber with different average particle sizes.

[0005] However, in order to manufacture two or more types of rubber with different particle sizes, losses and idle time occur during the polymerization process, which reduces productivity and makes it difficult to manufacture high-value-added ASA resins.

[0006] Therefore, in order to meet the demand for high value-added and high efficiency of ASA resins, there is a need to develop a thermoplastic resin composition that can achieve properties such as impact resistance, gloss, and weather resistance that are equivalent to or superior to those of an ASA resin composition using a mixture of two types of rubber with different particle sizes. Prior art literature

[0008] Korean Published Patent No. 2009-0016955 The problem to be solved

[0009] In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition containing an acrylate-based rubber having a single average particle size, which has excellent appearance characteristics such as impact resistance and gloss, and can satisfy high added value and high efficiency compared to a thermoplastic resin composition containing two types of acrylate-based rubber with different average particle sizes, a method for manufacturing the same, and a molded article containing the same.

[0010] The above purposes and other purposes of this description can all be achieved by the description below. means of solving the problem

[0012] To achieve the above objective, the present invention provides a thermoplastic resin composition comprising: A) an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) a hard matrix polymer; wherein the rubber content is 25 to 31 weight%, and the graft copolymer of A) has a graft rate of 23 to 29.5%.

[0014] In addition, the present invention provides a method for preparing a thermoplastic resin composition comprising the step of preparing a thermoplastic resin composition by kneading and extruding A) an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) a hard matrix polymer under conditions of 200 to 270°C and 200 to 300 rpm, wherein the prepared thermoplastic resin composition has a rubber content of 25 to 31 weight% relative to its total weight, and the graft copolymer A) has a graft rate of 23 to 29.5%.

[0016] In addition, the present invention provides a molded article characterized by comprising the above-mentioned thermoplastic resin composition. Effects of the invention

[0018] According to the present invention, a thermoplastic resin composition containing an acrylate-based rubber having a single average particle size has the effect of providing a thermoplastic resin composition having superior impact resistance while having appearance characteristics such as gloss, weather resistance, and processability at an equivalent level compared to a thermoplastic resin composition containing two types of acrylate-based rubbers having different average particle sizes, a method for manufacturing the same, and a molded article containing the same.

[0019] In particular, by including acrylate-based rubber with a uniform average particle size, it offers excellent effects on efficient production and process management, providing the advantage of meeting the needs for high added value and high efficiency. Specific details for implementing the invention

[0021] The thermoplastic resin composition, the method for manufacturing the same, and a molded article containing the same described herein will be described in detail below.

[0022] The inventors confirmed that when the graft rate of a graft copolymer containing an acrylate-based rubber having a single predetermined average particle size is adjusted to a predetermined range and the rubber content in a thermoplastic resin composition is adjusted to a predetermined range, the gloss, weather resistance, and processability are maintained compared to when two types of rubber with different average particle sizes are included, while the elongation and impact resistance are excellent. Based on this, they further devoted themselves to research and completed the present invention.

[0024] The thermoplastic resin composition according to the present description is described in detail as follows.

[0026] The thermoplastic resin composition of the present invention comprises A) an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) a hard matrix polymer; wherein the rubber content is 25 to 31 weight% and the graft copolymer A) has a graft rate of 23 to 29.5%, and in this case, the acrylate rubber having a single average particle size maintains colorability and gloss while significantly improving impact resistance, appearance characteristics, and weather resistance.

[0028] The thermoplastic resin composition of the present invention will be described in detail below according to its components.

[0030] A) Acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising acrylate rubber having an average particle size of 85 nm to 120 nm

[0031] The acrylate rubber of the graft copolymer A) above may, for example, have an average particle size of 85 to 120 nm, preferably 90 to 110 nm, more preferably 95 to 105 nm, and within this range, processability along with excellent gloss and weather resistance can be imparted to the thermoplastic resin composition finally manufactured.

[0032] In this description, the average particle size can be measured using dynamic light scattering, and specifically, using a particle meter (product name: Nicomp 380, manufacturer: PSS), it is measured as an intensity value in Gaussian mode. As a specific measurement example, a sample is prepared by diluting 0.1g of latex (TSC 35 to 50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, diluting it appropriately so as not to deviate significantly from the Intensity Setpoint of 300 kHz, and placing it in a glass tube. The measurement method is performed by auto-dilution using a flow cell, and the measurement mode is set to dynamic light scattering / Intensity 300 kHz / Intensity-weight Gaussian Analysis. The measurement can be performed with the setting values ​​of a temperature of 23℃, a measurement wavelength of 632.8 nm, and a channel width of 10 μsec.

[0034] The above A) graft copolymer may, for example, have a rubber content of 45 to 55 weight%, preferably 47 to 52 weight%, relative to its total weight, and within this range, it has excellent impact resistance and fluidity.

[0035] In the present invention, the rubber content is FT-IR or 1H It is measured through NMR analysis.

[0036] In the present invention 1H NMR analysis may be a method commonly measured in the technical field to which the present invention belongs, and as a specific measurement example, the equipment is a Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe and the measurement conditions are 1HNMR (zg30): ns = 32, d1 = 5s, TCE-d2, at room temperature.

[0037] In the present invention, FT-IR analysis may be a method commonly measured in the technical field to which the present invention belongs, and as a specific example of measurement, the equipment may be an Agilent Cary 660 and the measurement condition may be an ATR.

[0039] The above A) graft copolymer may, for example, have a graft rate of 23 to 29.5%, preferably 23.5 to 29.1%, more preferably 24 to 28%, and even more preferably 24.5 to 27.5%, and within this range, the rubber is uniformly dispersed within the hard matrix polymer, thereby having the effect of significantly improving the impact resistance, fluidity, and weather resistance of the thermoplastic resin composition. If the graft rate is below the above range, a problem of phase separation with the hard matrix polymer occurs.

[0041] In this description, the graft rate is calculated by adding acetone to the dry powder of the graft copolymer, stirring at room temperature for 24 hours, centrifuging at 18,000 rpm for 3 hours to collect only the insoluble matter that does not dissolve in acetone, drying it for 24 hours, and measuring its weight using the following mathematical formula 1.

[0042] [Mathematical Formula 1]

[0043] Graft rate (%) = [Weight of grafted monomer (g) / Weight of gum (g)] * 100

[0044] The weight (g) of the grafted monomer is the weight obtained by subtracting the rubber weight (g) from the weight of the insoluble (gel) after dissolving the graft polymer in acetone and centrifuging, and the rubber weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.

[0045] As a specific measurement example, 30g of acetone was added to 0.5g of dry graft copolymer powder, stirred at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075), and then centrifuged at 18,000 rpm at 0℃ for 3 hours using a centrifuge (Supra R30 from Hanil Science Co.) to collect only the insoluble matter that did not dissolve in acetone, dried using a forced convection oven (equipment name: Lab companion OF-12GW) at 85℃ for 12 hours, and then the weight was measured.

[0047] The physical properties of an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer are determined by the graft rate and the particle size of the acrylate rubber. As the graft rate increases, dispersibility within the matrix polymer improves, leading to enhanced gloss. As the particle size of the acrylate rubber increases, impact resistance improves, but weather resistance and gloss decrease. Conversely, as the particle size of the acrylate rubber decreases, weather resistance and gloss improve, but impact resistance decreases. Therefore, conventionally, desired impact resistance, weather resistance, and gloss are achieved by mixing two types of rubber with different particle sizes. However, the present invention reduces the dispersibility within the matrix polymer by lowering the graft rate of the graft copolymer in order to impart excellent impact resistance, weather resistance, and gloss using only one type of rubber with a small particle size. In such cases, aggregates of dry powders (DPs) of graft copolymers occur within the matrix polymer, and these aggregated dry powders of graft copolymers can improve impact resistance by acting as acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer powders with large rubber particle sizes. Additionally, dry powders of small-sized rubber graft copolymers partially dispersed within the matrix polymer can improve physical properties such as colorability, weather resistance, and gloss.

[0048] In this description, a single average particle size refers to the average particle size of a rubber of the same average particle size, which may mean the average particle size of a monomodal particle size distribution.

[0050] The above rubber may be, for example, 25 to 31 weight%, preferably 25.5 to 30.5 weight%, more preferably 26.5 to 29.5 weight% with respect to a total of 100 weight% of a thermoplastic resin composition (A) graft copolymer + B) hard matrix), and within this range, there is an advantage of excellent fluidity and weather resistance and a rapid increase in impact resistance while maintaining colorability and glossiness.

[0052] The above A) graft copolymer may, for example, comprise 45 to 55 weight% of acrylate-based rubber, 30 to 40 weight% of aromatic vinyl compound, and 5 to 20 weight% of vinyl cyanide compound, and preferably may comprise 47 to 52 weight% of acrylate-based rubber, 33 to 38 weight% of aromatic vinyl compound, and 10 to 15 weight% of vinyl cyanide compound, and within this range, both impact resistance and fluidity are excellent.

[0053] In this description, a polymer comprising a certain compound refers to a polymer polymerized including that compound, wherein the monomers within the polymerized polymer originate from that compound.

[0055] The above A) graft copolymer can be manufactured, for example, by emulsion polymerization, and in this case, it has excellent mechanical strength such as tensile strength, impact strength, and flexural strength.

[0056] The above emulsion polymerization is not particularly limited when carried out by an emulsion graft polymerization method commonly practiced in the technical field to which the present invention belongs.

[0058] The above acrylate may be, for example, one or more selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl group, and more preferably butyl acrylate or ethylhexyl acrylate.

[0059] The above aromatic vinyl compound may be, for example, one or more 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-brovostyrene, ρ-bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably may be styrene.

[0060] The vinyl cyanide compound may be one or more selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile and isopropylacrylonitrile, and preferably acrylonitrile.

[0062] The above method for manufacturing A) a graft copolymer may include, for example, a step of manufacturing a seed; a step of polymerizing a core in the presence of the seed; and a step of polymerizing a shell in the presence of the core.

[0064] The step of preparing the above seed can be polymerized by including, for example, 0.1 to 1 weight part of a crosslinking agent and 0.1 to 1 weight part of a grafting agent in 3 to 20 weight parts of an alkyl acrylate monomer based on 100 weight parts of a graft copolymer.

[0065] The above crosslinking agent may be, for example, one or more selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylol methane triacrylate.

[0066] The above grafting agent may be, for example, one or more selected from the group consisting of allyl methacrylate, trialyl isocyanurate, trialylamine, and dialylamine.

[0067] The polymerization reaction of the above seed can be carried out, for example, by emulsion polymerization alone or by mixing emulsion-free polymerization and emulsion polymerization, and the monomer input method can also be carried out by using batch input and continuous input individually or by combining both.

[0068] In this description, emulsion-free polymerization refers to a polymerization method using a monomer and an ionic hydrophilic initiator or an ionic comonomer without adding an emulsifier, i.e., a surfactant.

[0070] The step of polymerizing the core can, for example, be carried out by including 0.1 to 1 part by weight of a crosslinking agent and 0.01 to 3 parts by weight of a grafting agent in 25 to 52 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of a graft copolymer in the presence of the seed.

[0071] For example, the crosslinking agent and grafting agent may use the same material as that used in the seed manufacturing step.

[0072] The polymerization reaction of the above-mentioned core can be carried out, for example, by emulsion polymerization alone or by mixing emulsion polymerization and non-emulsion polymerization, and the monomer input method can also be carried out by using batch input and continuous input individually or by combining both.

[0074] The step of polymerizing the shell can, for example, be polymerized by including 30 to 40 parts by weight of an aromatic vinyl compound and 5 to 20 parts by weight of a vinyl cyanide compound based on 100 parts by weight of a graft copolymer in the presence of the core.

[0075] In this description, 100 parts by weight of graft copolymer refers to a standard where the total weight of the seed, core, and shell constituting the graft copolymer is set to 100 parts by weight, and it has the meaning of 100% by weight for the seed, core, shell, and monomers thereof.

[0077] The method for manufacturing the above graft shell is preferably emulsion polymerization, and it is also preferable to feed the mixed monomer containing the emulsifier during the graft reaction using a continuous feeding method.

[0078] To control the molecular weight of the above graft copolymer, a molecular weight regulator may be used, and preferably, a tertiary dodecyl mercaptan may be used.

[0080] The graft copolymer latex manufactured above can be coagulated by adding a coagulant, for example.

[0081] The above coagulant may be one or more selected from the group consisting of sulfuric acid, MgSO4, CaCl2, and Al2(SO4)3, for example, and preferably CaCl2.

[0083] The above aggregated graft copolymer latex can be prepared into a powder by, for example, washing, dehydrating, and drying.

[0085] B) Hard matrix polymer

[0086] The hard matrix polymer B) above is, for example, a hard matrix resin that can be melt-mixed with the dry powder (DP) of the graft copolymer A) above, and may have a glass transition temperature of at least 60°C, preferably 80 to 160°C, more preferably 90 to 150°C, and within this range, the moldability is further improved.

[0087] In this document, the glass transition temperature can be measured at a heating rate of 10°C using Perkin Elmer's Pyris DSC (Differential Scanning Calorimetry) in accordance with ASTM D 3418.

[0089] The above B) hard matrix polymer may be a polymerized polymer comprising one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth)acrylate alkyl ester compounds, for example, and in this case, it has excellent impact resistance and excellent colorability, gloss, and fluidity.

[0091] The hard matrix polymer B) above may specifically be an aromatic vinyl compound-vinyl cyanide compound copolymer, an (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer, or a mixture thereof, and preferably an aromatic vinyl compound-vinyl cyanide compound copolymer, in which case it has excellent impact resistance and excellent colorability, gloss, and fluidity.

[0093] The types of aromatic vinyl compounds and vinyl cyanide compounds included in the hard matrix polymer B) above may be within the same category as the types of aromatic vinyl compounds and vinyl cyanide compounds included in the graft copolymer A) described in this document.

[0095] Unless otherwise specified in this description, the (meth)acrylate alkyl ester compound means that both alkyl acrylate esters and alkyl methacrylate esters are possible, and may be one or more selected from the group consisting of, for example, methyl methacrylate ester, ethyl methacrylate ester, propyl methacrylate ester, 2-ethylhexyl methacrylate ester, decyl methacrylate ester, and lauryl methacrylate ester.

[0097] The above aromatic vinyl compound-vinyl cyanide compound copolymer may be, for example, a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, and preferably a styrene-acrylonitrile copolymer (SAN resin), in which case it has excellent processability, impact resistance, and colorability.

[0099] The above styrene-acrylonitrile copolymer (SAN resin) may preferably be a copolymer comprising 65 to 85 weight% of styrene and 15 to 35 weight% of acrylonitrile, and more preferably a copolymer comprising 70 to 80 weight% of styrene and 20 to 30 weight% of acrylonitrile, in which case it has excellent processability, impact resistance, and colorability.

[0101] The above aromatic vinyl compound-vinyl cyanide compound copolymer may, for example, have a weight-average molecular weight (Mw) of 100,000 to 150,000 g / mol, preferably 110,000 to 150,000 g / mol, and within this range, it has the advantage of excellent fluidity, colorability, and impact resistance.

[0102] Unless otherwise defined, the weight-average molecular weight in this description can be measured using Gel Permeation Chromatography (GPC, waters breeze). Specifically, it can be measured as a relative value to a standard polystyrene (PS) sample via Gel Permeation Chromatography (GPC, waters breeze) using Tetrahydrofuran (THF) as the eluent. In this case, as a specific measurement example, the measurement can be performed under the following conditions: solvent: THF, column temperature: 40℃, flow rate: 0.3ml / min, sample concentration: 20mg / ml, injection volume: 5µl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): OECD TG 118.

[0104] The above aromatic vinyl compound-vinyl cyanide compound copolymer can be prepared, for example, by suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and preferably by bulk polymerization, in which case it has excellent heat resistance and fluidity.

[0106] The above (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer may, for example, comprise 30 to 75 weight% of a (meth)acrylate alkyl ester compound, 20 to 60 weight% of an aromatic vinyl compound, and 5 to 15 weight% of a vinyl cyanide compound, and preferably may comprise 45 to 70 weight% of a (meth)acrylate alkyl ester compound, 20 to 50 weight% of an aromatic vinyl compound, and 5 to 10 weight% of a vinyl cyanide compound, and within this range, excellent processability, weather resistance, and colorability are achieved.

[0108] The above (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer may, for example, have a weight-average molecular weight of 50,000 to 150,000 g / mol, preferably 50,000 to 100,000 g / mol, more preferably 110,000 to 150,000 g / mol, and within this range, it has excellent fluidity, colorability, and impact resistance.

[0110] The above (meth)acrylate alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer may be prepared, for example, by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and preferably by bulk polymerization, and the above solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited when carried out by emulsion polymerization and suspension polymerization methods commonly practiced in the technical field to which the present invention belongs.

[0112] Thermoplastic resin composition

[0113] The above thermoplastic resin composition may, for example, comprise 30 to 70 weight% of A) an acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer and 30 to 70 weight% of B) a hard matrix polymer, and in this case, it has the effect of having excellent impact resistance, colorability, gloss, processability, and weather resistance.

[0114] Preferably, it may comprise 35 to 65 weight% of A) an acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer and 35 to 65 weight% of B) a hard matrix polymer, and in this case, it has the effect of having excellent impact resistance, colorability, gloss, processability, and weather resistance.

[0115] More preferably, it may comprise 40 to 60 weight% of A) an acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer and 40 to 60 weight% of B) a hard matrix polymer, and in this case, it has the effect of having excellent impact resistance, colorability, gloss, processability, and weather resistance.

[0117] The above thermoplastic resin composition may optionally include one or more additives selected from the group consisting of flame retardants, lubricants, antibacterial agents, release agents, nucleating agents, plasticizers, heat stabilizers, antioxidants, UV stabilizers, and compatibilizers as needed, and within this range, the necessary properties are well realized without degrading the inherent properties of the thermoplastic resin composition described herein.

[0118] The above additive may be included in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, and even more preferably 0.5 to 2 parts by weight, with respect to 100 parts by weight of a thermoplastic resin composition (A) acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer + B) hard matrix polymer, and within this range, the desired effect of the additive can be fully expressed without deteriorating the inherent physical properties of the resin composition.

[0120] The above lubricant may be, for example, one or more selected from the group consisting of alkylene bis stearamide, polyethylene oxidized wax, and magnesium stearate, and preferably may be alkylene bis stearamide, in which case it has the effect of improving the wettability of the composition of the present invention and at the same time having excellent mechanical properties.

[0122] The above lubricant may be, for example, 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, with respect to 100 parts by weight of a thermoplastic resin composition (A) acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer + B) hard matrix polymer), and in this case, it has the effect of improving the wettability of the composition described herein and simultaneously having excellent mechanical properties.

[0124] The above antioxidant may be, for example, a phenolic antioxidant, a phosphorus-based antioxidant, or a mixture thereof, and in this case, it prevents oxidation caused by heat during the extrusion process and has the effect of having excellent mechanical properties of the present invention.

[0125] The above antioxidant may be, for example, 0.001 to 3 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of the thermoplastic resin composition, and within this range, it prevents oxidation caused by heat during the extrusion process and has the effect of providing excellent mechanical properties of the present invention.

[0126] The above-mentioned phenolic antioxidants are, for example, 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl)propion ester, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion ester], thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propion ester, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propion ester]methane, 1,3,5-trimethyl-2,4,6'-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, calcium(3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propion ester], 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis[3,3-bis(4'hydroxy-3't-butylphenyl)butylic acid]glycol ester, tocopherol, 2,2'ethylidene bis(4,6-di-t-butylphenol), N,N'Hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenirpropionamide), 1,3,5-bis[2,4-bis(1,1-dimethyl ethyl)-6-methylphenyl]ethyl ester phosphonic acid, tetrakis(2,4-di-t-butyl phenyl)[1,1-biphenyl]-4,4'diylbisphosphonate, bis(2,4-di-t-butyl phenyl)pentaerythritol diphosphite, N,N'bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'oxamidebis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propion ester], 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-Tris(3'5'di-t-butyl-4'hydroxybenzyl)-S-triazine 2,4,6(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,It may be one or more selected from the group consisting of 5-di-t-butyl-4-hydroxyhydrocinnamic acid trieste, and 1,3,5-tris(2-hydroxyethyl)-S-triazine 2,4,6(1H,3H,5H).

[0128] The above phosphorus-based antioxidants are, for example, tris(mixed, mono, and gynolirnphenyl)phosphite, tris(2,3-di-t-butylphenyl)phosphite, 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphanite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythrityl-di-phosphite, and 2,2'-ethylidene bis(4,6-di-t-butyl It may be one or more selected from the group consisting of phenyl)-2-ethylhexyl-phosphite, bis(2,4,6-di-t-butylphenyl) pentaerythritol-di-phosphite, triphenylphosphite, diphenyldecyl phosphite, didecylphenyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonirphenir phosphite, and tridodecyl trithiophosphite.

[0130] The above thermoplastic resin composition may, for example, have an impact strength of 20.5 kgf·cm / cm or more, preferably 20.5 to 66 kgf·cm / cm, more preferably 35 to 65 kgf·cm / cm, and even more preferably 45 to 60 kgf·cm / cm, measured at room temperature (23℃) and thickness 1 / 8" according to ASTM D-256, and within this range, all physical properties and mechanical strength are excellent.

[0132] The above thermoplastic resin composition may, for example, have an impact strength of 23 kgf·cm / cm or more, preferably 23 to 46 kgf·cm / cm, more preferably 30 to 46 kgf·cm / cm, and even more preferably 35 to 44 kgf·cm / cm, measured at room temperature (23℃) with a thickness of 1 / 4" according to ASTM D-256, and within this range, all physical properties and mechanical strength are excellent.

[0134] The above thermoplastic resin composition may, for example, have a flow index of 8 to 12 g / 10 min, preferably 8.5 to 11 g / 10 min, more preferably 8.5 to 10.5 g / 10 min, even more preferably 9 to 10.5 g / 10 min, and even more preferably 9.5 to 10 g / 10 min, measured under conditions of 220°C and 10 kg according to ASTM D1238. Within this range, there is an excellent balance of all physical properties and excellent fluidity, which has the advantage of being easy to mold into various shapes.

[0136] The above thermoplastic resin composition may, for example, have a glossiness of 90 or higher, preferably 90 to 95, more preferably 90 to 92, measured at 45° according to ASTM D2457, and within this range, both appearance characteristics and physical property balance are excellent.

[0138] The above thermoplastic resin composition may, for example, have an elongation measured according to ASTM D638 of 35 to 65%, preferably 37 to 62%, more preferably 38 to 55%, and even more preferably 38 to 45%, and within this range, there is an excellent balance of physical properties and an effect of easily manufacturing a film.

[0140] For example, the above thermoplastic resin composition may have a weather resistance (△E) calculated by the following mathematical formula 2 after 2,000 hours of exposure to SAE J2527 conditions using an accelerated weathering test apparatus of 1.8 or less, preferably 1.7 or less, more preferably 1.5 or less, even more preferably 0 to 1.5, and even more preferably 0.3 to 1.2, and within this range, there is an effect of excellent balance of physical properties.

[0141] [Mathematical Formula 2]

[0142]

[0144] In this specification, weathering resistance (△E) is determined by an accelerated weathering test apparatus (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiance 0.55 W / m² 2 It can be evaluated by △E calculated by the above mathematical formula 2 after measuring for 2,000 hours under SAE J2527 conditions using (at 340 nm). The above △E is the arithmetic mean of the Hunter Lab(L, a, b) values ​​measured before and after the accelerated weathering test, and the closer △E is to 0, the better the weathering resistance.

[0146] Method for manufacturing a thermoplastic resin composition

[0147] The method for manufacturing a thermoplastic resin composition according to the present invention comprises the step of manufacturing a thermoplastic resin composition by kneading and extruding A) an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) a hard matrix polymer under conditions of 200 to 270°C and 200 to 300 rpm, wherein the manufactured thermoplastic resin composition has a rubber content of 25 to 31 weight% relative to its total weight, and the graft copolymer A) has a graft rate of 23 to 29.5%, and in this case, the acrylate rubber having a single average particle size has the effect of maintaining colorability and gloss while significantly improving impact resistance, weather resistance, and appearance characteristics.

[0149] The step of preparing a thermoplastic resin composition by kneading and extruding as described above may preferably be carried out at 200 to 270°C with a diameter of 20 to 80 phi, and more preferably at 210 to 260°C with a diameter of 25 to 75 phi, within which stable extrusion is possible and the kneading effect is excellent. At this time, the temperature is the temperature set in the cylinder, and phi refers to the outer diameter (unit: mm).

[0150] The extrusion mixer used for the above mixing and extrusion is not particularly limited to any extrusion mixer commonly used in the technical field to which the present invention belongs, and preferably, it may be a twin-screw extrusion mixer.

[0152] The method for manufacturing the above-mentioned thermoplastic resin composition shares all the technical features of the aforementioned thermoplastic resin composition. Therefore, the description of the overlapping parts will be omitted.

[0154] molded product

[0155] The molded article of the present invention is characterized by including, for example, the thermoplastic resin composition of the present invention, and in this case, has the effect of significantly improving impact resistance and appearance characteristics while maintaining colorability and gloss.

[0157] The step of manufacturing the above-mentioned molded product may, for example, include injection molding the manufactured pellets under conditions of an injection temperature of 200 to 260°C, an injection pressure of 60 to 100 bar, and a holding pressure of 25 to 55 bar, and in this case, there is an advantage that an injection-molded product with excellent mechanical properties such as impact strength can be easily manufactured.

[0158] The above injection temperature is preferably 200 to 230°C, more preferably 210 to 220°C, and within this range, there is an advantage of being able to easily manufacture injection-molded products with excellent mechanical properties such as impact strength.

[0159] The injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and within this range, there is an advantage of being able to easily manufacture injection-molded products with excellent mechanical properties such as impact strength.

[0160] The above holding pressure may preferably be 30 to 50 bar, and more preferably 35 to 50 bar, and within this range, there is an advantage of being able to easily manufacture injection-molded products with excellent mechanical properties such as impact strength.

[0162] In describing the thermoplastic resin composition, the method of manufacturing the same, and the molded article described herein, it is specified that other conditions or equipment not explicitly described may be appropriately selected within the scope of practices ordinarily carried out in the industry and are not particularly limited.

[0164] Hereinafter, preferred embodiments are presented to aid in understanding the description; however, the following embodiments are merely illustrative of the description, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the description, and that such variations and modifications fall within the scope of the appended claims.

[0166] [Example]

[0167] The materials used in the following examples and comparative examples are as follows.

[0168] * A-1) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 29.1%

[0169] * A-2) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 23.9%

[0170] * A-3) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 25.2%

[0171] * A-4) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 27%

[0172] * A-5) ASA graft copolymer: average particle size of acrylate rubber is 75 nm, butyl acrylate content is 50 wt%, and graft rate is 27.4%

[0173] * A-6) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 21.2%

[0174] * A-7) ASA graft copolymer: average particle size of acrylate rubber 100 nm, butyl acrylate content 50 wt%, and graft rate 33.4%

[0175] * A-8) ASA graft copolymer: average particle size of acrylate rubber 170 nm, butyl acrylate content 50 wt%, and graft rate 26.8%

[0176] * B) Hard matrix polymer: Styrene-acrylonitrile copolymer (LG Chem, 90HR)

[0178] Examples 1 to 8 and Comparative Examples 1 to 11

[0179] The ingredients and content listed in Table 1 below were fed into a twin-screw extruder and mixed and extruded at a cylinder temperature of 230°C to produce pellets. The produced pellets were injected into an injection molding machine at a barrel temperature of 220°C to produce specimens for measuring physical properties.

[0181] [Test Example]

[0182] The characteristics of the specimens prepared in Examples 1 to 8 and Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Table 2 below.

[0184] measurement method

[0185] * Rubber content (weight%): 1H It was measured via NMR analysis. As a specific measurement example, 1H NMR analysis was performed using a Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe. 1H NMR (zg30): ns = 32, d1 = 5s, TCE-d2, measured at room temperature.

[0186] * Graft rate (%): Acetone was added to the dry powder of the graft copolymer and stirred at room temperature for 24 hours. The mixture was then centrifuged at 18,000 rpm for 3 hours to collect only the insoluble matter that did not dissolve in acetone, dried for 24 hours, and weighed. The rate was calculated using the following mathematical formula 1.

[0187] [Mathematical Formula 1]

[0188] Graft rate (%) = [Weight of grafted monomer (g) / Weight of gum (g)] * 100

[0189] In the above mathematical formula 1, the weight (g) of the grafted monomer is the weight obtained by subtracting the weight of the rubbery substance (g) from the weight of the insoluble (gel) after dissolving the grafted polymer in acetone and centrifuging, and the weight of the rubbery substance (g) is the weight (g) of the theoretically added rubbery component in the grafted copolymer powder.

[0190] As a specific measurement example, 30g of acetone was added to 0.5g of dry graft copolymer powder, stirred at 210 rpm for 12 hours at room temperature using an orbital shaker (equipment name: Lab companion SKC-6075), and then centrifuged at 18,000 rpm at 0℃ for 3 hours using a centrifuge (Supra R30 from Hanil Science Co.) to collect only the insoluble matter that did not dissolve in acetone, dried using a forced convection oven (equipment name: Lab companion OF-12GW) at 85℃ for 12 hours, and then the weight was measured.

[0191] * Impact strength (kgf·cm / cm): Measured at room temperature (23℃) with thicknesses of 1 / 4" and 1 / 8" according to ASTM D256.

[0192] * Melt index (MI; g / 10min): The manufactured pellets were measured according to ASTM D1238 under conditions of 220℃ and 10 kg.

[0193] * Glossiness: Measured at 45° according to ASTM D2457.

[0194] * Elongation (%): Measured according to ASTM D638.

[0195] * Weathering (△E): Accelerated weathering test apparatus (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S.Boro (outer) filter, irradiance 0.55 W / m²) 2 After measuring for 2,000 hours under SAE J2527 conditions using (at 340 nm), it was evaluated as △E calculated by the following Equation 2. The following △E is the arithmetic mean of the Hunter Lab(L, a, b) values ​​measured before and after the accelerated weathering test, and the closer △E is to 0, the better the weathering resistance.

[0196] [Mathematical Formula 2]

[0197]

[0199] division Types of ASA resins Content of ASA resin in the composition (weight%) ASA resin rubber content (weight%) Rubber content in composition (weight%) rubber particle size (nm) Graft rate (%) Example 1 A-1 52 50 26 100 29.1 Example 2 A-1 56 50 28 100 29.1 Example 3 A-1 60 50 30 100 29.1 Example 4 A-2 60 50 30 100 23.9 Example 5 A-3 60 50 30 100 25.2 Example 6 A-4 52 50 26 100 27.0 Example 7 A-4 56 50 28 100 27.0 Example 8 A-4 60 50 30 100 27.0 Comparative Example 1 A-1 44 50 22 100 29.1 Comparative Example 2 A-1 68 50 34 100 29.1 Comparative Example 3 A-5 44 50 22 75 27.4 Comparative Example 4 A-5 60 50 30 75 27.4 Comparative Example 5 A-8 44 50 22 170 26.8 Comparative Example 6 A-8 60 50 30 170 26.8 Comparative Example 7 A-6 44 50 22 100 21.2 Comparative Example 8 A-6 60 50 30 100 21.2 Comparative Example 9 A-7 44 50 22 100 33.4 Comparative Example 10 A-7 60 50 30 100 33.4 Comparative Example 11 A-4 44 50 22 100 27.0

[0200] division Impact strength (1 / 8) Impact strength (1 / 4) Liquidity Index gloss elongation rate Weather resistance Example 1 21.0 24.5 10.0 91.8 39 1.6 Example 2 50.4 34.9 9.2 91.1 41 1.2 Example 3 62.9 41.2 8.3 90.5 60 0.9 Example 4 63.1 41.4 8.2 90.1 61 1.1 Example 5 63.7 43.5 8.7 90.3 61 1.0 Example 6 21.2 24.8 10.1 91.9 39 1.7 Example 7 50.8 36.7 9.7 91.5 41 1.3 Example 8 63.5 42.3 8.8 90.7 60 1.0 Comparative Example 1 4.2 12.9 11.5 92.3 35 1.8 Comparative Example 2 69.1 45.2 7.2 89.0 64 0.8 Comparative Example 3 3.0 4.2 8.2 89.3 30 2.0 Comparative Example 4 6.2 11.2 3.7 84.5 47 0.9 Comparative Example 5 6.3 14.0 10.3 89.2 33 3.5 Comparative Example 6 19.4 21.2 6.8 88.0 55 3.0 Comparative Example 7 4.4 9.1 8.5 88.3 28 2.4 Comparative Example 8 8.8 19.3 4.2 84.8 41 1.6 Comparative Example 9 4.1 10.3 9.7 95.6 31 2.1 Comparative Example 10 8.2 17.8 4.7 94.3 46 1.3 Comparative Example 11 6.5 13.6 11.7 92.5 35 2.1

[0202] As shown in Table 2 above, it was confirmed that Examples 1 to 8 according to the present invention maintained glossiness compared to Comparative Examples 1 to 11, while having excellent impact strength, fluidity, and weather resistance.

[0203] Specifically, Comparative Example 1, in which the rubber content in the composition is 22 wt%, showed significantly lower impact strength and lower weather resistance compared to Examples 1 to 8, and Comparative Example 2, in which the rubber content in the composition is 34 wt%, showed lower flow index and glossiness compared to Examples 1 to 8.

[0204] In addition, Comparative Example 3, in which the rubber content in the composition is 22 wt% and the rubber particle size is 75 nm, showed reduced impact strength, elongation, and weather resistance, and Comparative Example 4, in which the rubber content in the composition is 30 wt% and the rubber particle size is 75 nm, showed reduced impact strength, flow index, and flow index.

[0205] In addition, Comparative Example 5, in which the rubber content in the composition is 22 wt% and the rubber particle size is 170 nm, showed reduced impact strength and weather resistance, and Comparative Example 6, in which the rubber content in the composition is 30 wt% and the rubber particle size is 170 nm, showed reduced impact strength, glossiness, flow index, and weather resistance.

[0206] In addition, Comparative Example 7, in which the rubber content in the composition is 22 wt% and the graft rate is 21.2%, has poor impact strength, gloss, elongation, and weather resistance, and Comparative Example 8, in which the rubber content in the composition is 30 wt% and the graft rate is 21.2%, has lower impact strength, flow index, and gloss.

[0207] In addition, Comparative Example 9, in which the rubber content in the composition is 22 wt% and the graft rate is 33.4%, has poor impact strength, elongation, and weather resistance, and Comparative Example 10, in which the rubber content in the composition is 30 wt% and the graft rate is 33.4%, has lower impact strength and flow index.

[0208] In addition, Comparative Example 11, in which the rubber content in the composition was 22 wt% and the graft rate was 27%, had low impact strength, elongation, and weather resistance.

[0210] In conclusion, the thermoplastic resin composition according to the present invention, in which the average particle size and graft rate of the acrylate-based rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer and the rubber content in the composition are adjusted within a predetermined range, includes rubber having a single average particle size, and compared to conventional ASA resin compositions containing two types of rubber with different average particle sizes, it was possible to confirm that the impact strength, fluidity, gloss, elongation, and weather resistance are all significantly improved while satisfying high added value and high efficiency.

Claims

Claim 1 A thermoplastic resin composition comprising: A) 35 to 65 weight% of an acrylate rubber-aromatic vinyl compound-vinyl cyanide compound graft copolymer including an acrylate rubber having an average particle size of 85 nm to 120 nm; and B) 35 to 65 weight% of a hard matrix polymer, wherein the rubber content is 28 to 31 weight%, the graft rate of A) the graft copolymer is 25.2 to 27%, and the impact strength measured under a thickness of 1 / 4" at room temperature (23℃) according to ASTM D-256 is 23 kgf·cm / cm or higher. Claim 2 A thermoplastic resin composition according to claim 1, characterized in that the average particle size of the acrylate-based rubber included in the graft copolymer A) is 90 to 110 nm. Claim 3 A thermoplastic resin composition according to claim 1, wherein the graft copolymer A) comprises 45 to 55 weight% of acrylate-based rubber, 30 to 40 weight% of an aromatic vinyl compound, and 5 to 20 weight% of a vinyl cyanide compound. Claim 4 A thermoplastic resin composition according to claim 1, characterized in that the acrylate is one or more selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group. Claim 5 A thermoplastic resin composition according to claim 1, wherein B) the hard matrix polymer is a polymerized polymer comprising one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylate alkyl ester compounds. Claim 6 A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition has an impact strength of 20.5 kgf·cm / cm or more, measured at room temperature (23℃) with a thickness of 1 / 8" according to ASTM D-256. Claim 7 A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition has an impact strength of 35 to 46 kgf·cm / cm measured at room temperature (23℃) with a thickness of 1 / 4" in accordance with ASTM D-256. Claim 8 A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition has a flow index of 8 to 12 g / 10 min measured under conditions of 220°C and 10 kg in accordance with ASTM D1238. Claim 9 A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition has a glossiness of 90 or higher as measured at 45° in accordance with ASTM D2457. Claim 10 A thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition comprises one or more additives selected from the group consisting of flame retardants, lubricants, antibacterial agents, release agents, nucleating agents, plasticizers, heat stabilizers, antioxidants, UV stabilizers, and compatibilizers. Claim 11 A method for preparing a thermoplastic resin composition comprising the step of preparing a thermoplastic resin composition by kneading and extruding at conditions of 200 to 270°C and 200 to 300 rpm, wherein the prepared thermoplastic resin composition has a rubber content of 28 to 31 weight% relative to its total weight, the graft copolymer of A) has a graft rate of 25.2 to 27%, and the impact strength measured at room temperature (23°C) with a thickness of 1 / 4" according to ASTM D-256 is 23 kgf·cm / cm or higher. Claim 12 A molded article characterized by comprising a thermoplastic resin composition according to any one of claims 1 to 10.

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