Thermoplastic resin composition and molded article manufactured using same

Abstract

The present invention relates to a thermoplastic resin composition and a molded article manufactured using same, the thermoplastic resin composition comprising (D) 0.5-5 parts by weight of an oil having a triglyceride structure on the basis of 100 parts by weight of a base resin comprising (A) 15-25 wt% of a first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer in which the average particle diameter of a rubber polymer is 250-350 nm, (B) 10-20 wt% of a second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer in which the average particle diameter of a rubber polymer is 100-200 nm, (C) 50-70 wt% of an aromatic vinyl-vinyl cyanide copolymer containing 25-35 wt% of a vinyl cyanide compound-derived component, and (D) 4-10 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer in which the average particle diameter of a rubber polymer is 500-1,000 nm, wherein the weight ratio of (A) to (B) is 2:1 to 1:1.

Description

Thermoplastic resin composition and molded article manufactured therefrom

[0001] It relates to a thermoplastic resin composition and a molded article manufactured therefrom.

[0002] Blow molding is a method of manufacturing a molded product by forming a parison by injection or extrusion and injecting air into it. Examples include extrusion blow molding, injection blow molding, and injection stretch blow molding.

[0003] Specifically, extrusion blow molding uses an extruder to melt resin, attach a die that can form a hollow shape like a hollow pipe to the end of the extruder to form a parison, and then vertically lower the parison into an open blow mold, close the mold to cut the parison, and then blow air into the parison to manufacture the desired molded product.

[0004] Due to the nature of blow molding, scrap (other than the manufactured molded product) is mixed with the resin raw material and reused. Over the course of repeated reuse, the proportion of scrap mixed with the resin raw material can reach up to 90 wt%. Generally, resin decomposes as it experiences thermal stress, and each decomposition reduces its melt strength, thereby reducing blow moldability.

[0005] If the melt strength of the resin is low, sagging may occur when the parison is lowered vertically during extrusion blow molding, preventing blow molding with a uniform thickness. This may cause a problem in which a relatively thin area is torn during the air injection process.

[0006] To prevent this, methods have been attempted of adding excessive amounts of additives such as antioxidants or adding lubricants that can reduce thermal history, but there is a problem that the mechanical properties of the molded product deteriorate or the appearance characteristics deteriorate due to the addition of additives and lubricants.

[0007] Therefore, there is a need to develop a thermoplastic resin composition that can maintain blow moldability even when scrap is reused.

[0008] Provided are a thermoplastic resin composition having excellent overall physical properties, including impact resistance, and excellent blow moldability even when scrap is reused, and a molded product manufactured therefrom.

[0009] According to one embodiment, (A) 15 to 25 wt% of a first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of 250 to 350 nm of a rubber polymer, (B) 10 to 20 wt% of a second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of 100 to 200 nm of a rubber polymer, (C) 50 to 70 wt% of an aromatic vinyl-vinyl cyanide copolymer having a content of a cyanide-derived component of 25 to 35 wt% of a cyanide-derived component, and (D) 4 to 10 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average particle size of 500 to 1,000 nm of a rubber polymer, (E) 0.5 to 5 wt% of an oil having a triglyceride structure, relative to 100 wt% of a base resin, A thermoplastic resin composition is provided in which the weight ratio of (A):(B) is 2:1 to 1:1.

[0010] The above (A) first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may have a core-shell structure including a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0011] The above (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.

[0012] The above (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may have a core-shell structure including a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a cyanide vinyl compound onto the core.

[0013] The above (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.

[0014] The above (C) aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 150,000 to 250,000 g / mol.

[0015] The above (C) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.

[0016] The above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer may have a structure in which a dispersed phase including a butadiene-based rubber polymer is dispersed in a continuous phase including an aromatic vinyl-vinyl cyanide copolymer.

[0017] The above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer may comprise 10 to 40 wt% of a dispersed phase comprising the butadiene-based rubber polymer and 60 to 90 wt% of a continuous phase comprising the aromatic vinyl-vinyl cyanide copolymer, based on 100 wt%.

[0018] The above (D) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer may be an acrylonitrile-butadiene-styrene copolymer.

[0019] The oil comprising the above (E) triglyceride structure may comprise a structure represented by the following chemical formula 1:

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1, R1, R2, and R3 may be the same or different from each other, and R1, R2, and R3 are each a C4 to C30 aliphatic hydrocarbon group that is saturated or unsaturated, and any carbon in the aliphatic hydrocarbon group may be substituted with a hydroxy group.

[0023] The oil comprising the above (E) triglyceride structure may be at least one of castor oil, palm oil, soybean oil, canola oil, corn oil, rapeseed oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, sesame oil, rice bran oil, palm kernel oil, camellia oil, olive oil, coconut oil, beef tallow, lard, safflower oil, fish oil, whale oil, tuna oil, and waste oils thereof.

[0024] The oil comprising the above (E) triglyceride structure may comprise a structure represented by the following chemical formula 2:

[0025] [Chemical Formula 2]

[0026]

[0027] The thermoplastic resin composition may further include at least one additive selected from among a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, a colorant, and an impact modifier.

[0028] Meanwhile, according to another embodiment, a molded article manufactured from the thermoplastic resin composition described above is provided.

[0029] A thermoplastic resin composition according to an embodiment has excellent blow moldability and mechanical properties such as impact resistance even when scrap is reused.

[0030] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, which is defined solely by the appended claims.

[0031] Unless specifically stated herein, “copolymerization” means block copolymerization, random copolymerization, and graft copolymerization, and “copolymer” means block copolymer, random copolymer, and graft copolymer.

[0032] Unless otherwise specified herein, the average particle size of a rubber polymer is a volume average diameter and refers to the Z-average particle size measured using a dynamic light scattering analyzer.

[0033] Unless otherwise specified herein, the weight average molecular weight is measured by dissolving a powder sample in an appropriate solvent and using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (Shodex polystyrene is used as the standard sample).

[0034] According to one embodiment, the thermoplastic resin composition comprises (A) 15 to 25 wt% of a first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of 250 to 350 nm of a rubbery polymer, (B) 10 to 20 wt% of a second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of 100 to 200 nm of a rubbery polymer, (C) 50 to 70 wt% of an aromatic vinyl-vinyl cyanide copolymer having a content of a cyanide-derived component of 25 to 35 wt% of a cyanide-derived component, and (D) 4 to 10 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average particle size of 500 to 1,000 nm of a rubbery polymer, with respect to 100 parts by weight of a base resin comprising (D) 0.5 to 10 wt% of an oil comprising a triglyceride structure. Contains 5 parts by weight, and the weight ratio of (A):(B) is 2:1 to 1:1.

[0035] Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

[0036] (A) A first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer having an average particle diameter of 250 to 350 nm.

[0037] In one embodiment, (A) a first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer (hereinafter, the first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer) having an average particle diameter of 250 to 350 nm imparts excellent impact resistance and blow moldability to a thermoplastic resin composition.

[0038] In one embodiment, the (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may have a core-shell structure in which a core is formed of a butadiene-based rubber polymer component and a shell is formed by graft polymerizing an aromatic vinyl compound and a cyanide vinyl compound onto the core.

[0039] According to one embodiment, the (A) first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer can be manufactured by adding an aromatic vinyl compound and a vinyl cyanide compound to a butadiene-based rubber polymer and graft polymerizing them using a conventional polymerization method such as emulsion polymerization or bulk polymerization.

[0040] The above butadiene-based rubber polymer may be selected from the group consisting of butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

[0041] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0042] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0043] In the above (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer, the average particle diameter of the butadiene-based rubber polymer may be, for example, 250 to 350 nm, for example, 250 to 300 nm, for example, 300 to 350 nm. When the above range is satisfied, the thermoplastic resin composition can exhibit excellent impact resistance and blow moldability.

[0044] With respect to 100 wt% of the (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer, the butadiene-based rubber polymer may be included in an amount of 40 to 70 wt%, for example, 40 to 60 wt%, for example, 50 to 60 wt%. Meanwhile, the weight ratio of the aromatic vinyl compound and the cyanide vinyl compound graft-polymerized onto the core made of the butadiene-based rubber polymer component may be 6:4 to 8:2.

[0045] In one embodiment, the (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.

[0046] The above (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be included in an amount of 15 to 25 wt%, for example, 15 to 20 wt%, for example, 20 to 25 wt%, based on 100 wt% of the base resin. A thermoplastic resin composition including it in the above wt% range may have excellent impact resistance and a balance of overall physical properties.

[0047] (B) A second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer having an average particle size of 100 to 200 nm.

[0048] In one embodiment, (B) the second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer (hereinafter, the second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer) having an average particle diameter of 100 to 200 nm imparts excellent appearance, impact resistance, and blow moldability to the thermoplastic resin composition.

[0049] In one embodiment, the second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer (B) may have a core-shell structure in which a core is formed of a butadiene-based rubber polymer component and a shell is formed by graft polymerizing an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0050] According to one embodiment, the second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer (B) can be manufactured by adding an aromatic vinyl compound and a cyanide vinyl compound to a butadiene-based rubber polymer and performing graft polymerization using a conventional polymerization method such as emulsion polymerization or bulk polymerization.

[0051] The above butadiene-based rubber polymer may be selected from the group consisting of butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

[0052] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0053] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0054] The average particle size of the butadiene-based rubber polymer of the second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer of the above (B) may be, for example, 100 to 200 nm, for example, 100 to 150 nm, for example, 150 to 200 nm. When the above range is satisfied, the thermoplastic resin composition can exhibit excellent appearance, impact resistance, and blow moldability.

[0055] With respect to 100 wt% of the (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer, the butadiene-based rubber polymer may be included in an amount of 40 to 70 wt%, for example, 40 to 60 wt%, for example, 50 to 60 wt%. Meanwhile, the weight ratio of the aromatic vinyl compound and the cyanide vinyl compound graft-polymerized onto the core made of the butadiene-based rubber polymer component may be 6:4 to 8:2.

[0056] In one embodiment, the (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.

[0057] The above (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be included in an amount of 10 to 20 wt%, for example, 10 to 15 wt%, for example, 15 to 20 wt%, based on 100 wt% of the base resin. A thermoplastic resin composition including it in the above wt% range may have excellent appearance, impact resistance, and overall physical property balance.

[0058] The weight ratio of the above component (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer to the above component (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be 2:1 to 1:1. Within the above weight ratio range, the melt strength of a thermoplastic resin composition including the same is improved, so that the blow moldability can be excellent even when repeatedly reused.

[0059] (C) Aromatic vinyl-vinyl cyanide copolymer having a content of 25 to 35 wt% of a component derived from a vinyl cyanide compound

[0060] In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (hereinafter, aromatic vinyl-vinyl cyanide copolymer) having a content of 25 to 35 wt% of a component derived from a (C) cyanide compound can improve the fluidity of the thermoplastic resin composition and the compatibility between each component.

[0061] In one embodiment, the (C) aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 150,000 g / mol or more, for example, 160,000 g / mol or more, for example, 170,000 g / mol or more, for example, 250,000 g / mol or less, for example, 240,000 g / mol or less, for example, 230,000 g / mol or less, for example, 150,000 to 250,000 g / mol, for example, 170,000 to 230,000 g / mol.

[0062] In one embodiment, the (C) aromatic vinyl-vinyl cyanide copolymer can be prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound using a conventional polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

[0063] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0064] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0065] The above (C) aromatic vinyl-vinyl cyanide copolymer contains 65 to 75 wt% of the aromatic vinyl compound-derived component and 25 to 35 wt% of the cyanide vinyl compound-derived component based on 100 wt%. Within the above weight range, compatibility between each component of the thermoplastic resin composition can be further improved.

[0066] In one embodiment, the (C) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0067] In one embodiment, the (C) aromatic vinyl-vinyl cyanide copolymer may be included in an amount of 50 to 70 wt%, for example 50 to 60 wt%, for example 60 to 70 wt%, based on 100 wt% of the base resin. In the above wt% range, the fluidity of a thermoplastic resin composition including it and the compatibility between each component may be excellent.

[0068] (D) Butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average particle size of 500 to 1,000 nm

[0069] In one embodiment, (D) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average particle diameter of 500 to 1,000 nm (hereinafter, (D) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer) imparts excellent impact resistance and melt strength to a thermoplastic resin composition.

[0070] In one embodiment, the (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer may have a structure in which a dispersed phase including a butadiene-based rubber polymer is dispersed in a continuous phase including an aromatic vinyl-vinyl cyanide copolymer.

[0071] The above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer can be manufactured by introducing a mixture of an aromatic vinyl compound and a vinyl cyanide compound in the presence of a butadiene-based rubber polymer and using a conventional continuous polymerization method such as continuous emulsion polymerization, continuous bulk polymerization, or continuous solution polymerization.

[0072] The above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer may comprise, based on 100 wt%, a dispersed phase comprising the butadiene-based rubber polymer in an amount of 10 to 40 wt%, for example, 10 to 30 wt%, for example, 20 to 30 wt%, and a continuous phase comprising the aromatic vinyl-vinyl cyanide copolymer in an amount of 60 to 90 wt%, for example, 70 to 90 wt%, for example, 70 to 80 wt%. Within the above range, the impact resistance and fluidity of the thermoplastic resin composition may be excellent.

[0073] The above butadiene-based rubber polymer may be selected from the group consisting of butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

[0074] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0075] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0076] The above butadiene-based rubber polymer has an average particle diameter of 500 to 1000 nm, and by having an average particle diameter in the above range, the melt strength of the thermoplastic resin composition can be further improved.

[0077] In one embodiment, the (D) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer may be an acrylonitrile-butadiene-styrene copolymer.

[0078] The above (D) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer may be included in an amount of 4 to 10 wt%, for example, 5 to 10 wt%, based on 100 wt% of the base resin. A thermoplastic resin composition including it within the above range may have excellent blow moldability.

[0079] (E) Oil containing triglyceride structure

[0080] In one embodiment, the oil comprising (E) a triglyceride structure can further improve the blow moldability of the thermoplastic resin composition by minimizing the thermal history between blow molding processes.

[0081] The oil comprising the above (E) triglyceride structure may comprise a structure represented by the following chemical formula 1:

[0082] [Chemical Formula 1]

[0083]

[0084] In the above chemical formula 1, R1, R2, and R3 may be the same or different from each other, and R1, R2, and R3 are each a C4 to C30 aliphatic hydrocarbon group that is saturated or unsaturated, and any carbon in the aliphatic hydrocarbon group may be substituted with a hydroxy group.

[0085] In one embodiment, R1, R2, and R3 of the above chemical formula 1 may each be a C12 to C20 aliphatic hydrocarbon group that is saturated or unsaturated.

[0086] In one embodiment, the oil comprising the (E) triglyceride structure may comprise a structure represented by the following chemical formula 2:

[0087] [Chemical Formula 2]

[0088]

[0089] The oil comprising the above (E) triglyceride structure may be a natural oil or a synthetic oil, and in one embodiment, the oil comprising the above (E) triglyceride structure may be a natural oil.

[0090] In one embodiment, the natural oil may be a vegetable oil or an animal oil.

[0091] In one embodiment, the oil comprising the (E) triglyceride structure may be at least one of castor oil, palm oil, soybean oil, canola oil, corn oil, rapeseed oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, sesame oil, rice bran oil, palm kernel oil, camellia oil, olive oil, coconut oil, beef tallow, lard, safflower oil, fish oil, whale oil, tuna oil, and waste oils thereof.

[0092] In one embodiment, the oil comprising the (E) triglyceride structure may be castor oil.

[0093] The oil containing the above (E) triglyceride structure may be included in an amount of 0.5 to 5 parts by weight, for example, 1 to 5 parts by weight, for example, 1 to 3 parts by weight, based on 100 parts by weight of the base resin. Within the above range of parts by weight, the blow moldability of a thermoplastic resin composition containing the same may be further improved.

[0094] (F) Additives

[0095] A thermoplastic resin composition according to one embodiment may further include, in addition to the components (A) to (E), one or more additives required depending on the final use of the thermoplastic resin composition.

[0096] Specifically, the additive may be at least one selected from among a nucleating agent, a coupling agent, a filler, a plasticizer, an activator, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, a colorant, and an impact modifier.

[0097] These additives may be appropriately included within a range that does not impair the properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less per 100 parts by weight of the base resin, but is not limited thereto.

[0098] The thermoplastic resin composition according to the present invention can be manufactured by a known method for manufacturing a thermoplastic resin composition.

[0099] For example, the thermoplastic resin composition according to the present invention can be manufactured in the form of pellets by mixing the components of the present invention and other additives and then melting / mixing them in an extruder.

[0100] A molded article according to one embodiment of the present invention can be manufactured from the thermoplastic resin composition described above using a known molding method or blow molding method. For example, the molded article can be manufactured using methods such as extrusion blow molding or injection blow molding, but is not limited thereto.

[0101] The above molded product may have a notched Izod impact strength of 20 kgf·cm / cm or more, for example, 21 kgf·cm / cm or more, for example, 22 kgf·cm / cm or more, for example, 23 kgfcm / cm or more, measured on a 1 / 4 inch thick specimen according to ASTM D256.

[0102] The above molded product is formed by dry-blending 90 wt% of scrap crushed into pellets from scrap generated during molding and 10 wt% of new material pellets, and then molding the parison into a pipe shape with a diameter of approximately 40 mm using a single screw extrusion blow molding machine at a molding temperature of 200°C and a screw rotation speed of 30 rpm, and then measuring the time until the previously molded parison falls freely when the screw rotation speed is adjusted to 0 rpm to stop additional parison molding, and then comparing the result with the result measured when 100 wt% of new material is used, the moldability reduction rate calculated may be 20% or less.

[0103] The above molded product is formed by dry-blending 90 wt% of scrap crushed into pellet size from scrap generated during molding and 10 wt% of new pellets, and then using a single screw extrusion blow molding machine capable of forming a pipe-shaped parison having a diameter of approximately 40 mm, forming the parison under the conditions of a molding temperature of 200°C and a screw rotation speed of 30 rpm, adjusting the screw rotation speed to 0 rpm to stop additional parison forming, and then measuring the time until the previously molded parison falls freely, and comparing the result with the result measured when 100 wt% of new material was used, the calculated parison length increase rate may be 20% or less.

[0104] Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the following examples and comparative examples are for the purpose of explanation and are not intended to limit the present invention.

[0105] Examples 1 to 3 and Comparative Examples 1 to 8

[0106] The thermoplastic resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8 were prepared according to the component content ratios described in Table 1 below.

[0107] In Table 1, (A), (B), (C), and (D) are included in the base resin and are expressed in weight % based on the total weight of the base resin, and (E1) to (E4) are added to the base resin and are expressed in weight parts based on 100 weight parts of the base resin.

[0108] The components listed in Table 1 were dry mixed, and general additives such as heat stabilizers and antioxidants were added, and then melted / kneaded using a twin-screw extruder (L / D=29, Φ=45 mm) at a barrel temperature of approximately 230°C to produce a thermoplastic resin composition in the form of pellets. Subsequently, the pelletized thermoplastic resin composition was dried at approximately 80°C for approximately 4 hours, and then specimens for property evaluation were produced using a 6 oz. injection molding machine with a cylinder temperature of approximately 230°C and a mold temperature of approximately 60°C.

[0109] Classification Implementation Preliminary Comparison Example 123412345678(A)2217222222222222222331122(B)1116111111111111111-2211(C)626262576262626267626262(D)555105555-555(E1)1131----1117(E2) -----1------(E3) ------1-----(E4) -------1----

[0110] The description of each component listed in Table 1 above is as follows: (A) First butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer

[0111] Acrylonitrile-butadiene-styrene graft copolymer (Lotte Chemical Co.) comprising a core (average particle size: about 270 nm) made of a butadiene rubber polymer and a shell formed by graft polymerization of acrylonitrile and styrene (the weight ratio of acrylonitrile to styrene is about 25:75) onto about 60 wt% of the core.

[0112] (B) Second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer

[0113] Acrylonitrile-butadiene-styrene graft copolymer (Lotte Chemical Co.) comprising a core (average particle size: about 130 nm) made of a butadiene rubber polymer and a shell formed by graft polymerization of acrylonitrile and styrene (the weight ratio of acrylonitrile to styrene is about 29:71) onto about 48 wt% of the core.

[0114] (C) Aromatic vinyl-vinyl cyanide copolymer

[0115] A styrene-acrylonitrile copolymer having a weight average molecular weight of about 170,000 g / mol, copolymerized from a monomer mixture containing about 28 wt% acrylonitrile and about 72 wt% styrene (Lotte Chemical Co., Ltd.)

[0116] (D) Butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer

[0117] An acrylonitrile-butadiene-styrene copolymer (SINOPEC) manufactured by a continuous polymerization method, wherein a dispersed phase containing a butadiene rubber polymer (average particle size: approximately 800 nm) is dispersed in a styrene-acrylonitrile continuous phase, and has a melt flow index of approximately 15 g / 10 min measured under conditions of 230°C and 10 kg according to ASTM D1238.

[0118] (E1) Oil containing triglyceride structure

[0119] Castor oil (Lotte Wellfood Co.)

[0120] (E2) Ethylene bis stearamide

[0121] LC 140B (Lion Chemtech)

[0122] (E3) Montanic acid ester wax

[0123] Luwax® E Powder (BASF)

[0124] (E4) Calcium stearate

[0125] SONGSTAB™ SC-110 (Songwon Industrial Co., Ltd.)

[0126] Experimental example

[0127] The experimental results are shown in Table 2 below.

[0128] (1) Impact resistance (unit: kgf·cm / cm): Notched Izod impact strength was measured on 1 / 4 inch thick specimens according to ASTM D256.

[0129] (2) Blow moldability (unit: sec)

[0130] After dry-blending 90 wt% of scrap crushed into pellets from the scrap generated during molding and 10 wt% of virgin pellets, a single screw extrusion blow molding machine capable of molding a pipe-shaped parison with a diameter of approximately 40 mm was used to mold the parison under the conditions of a molding temperature of 200°C and a screw rotation speed of 30 rpm, and the screw rotation speed was adjusted to 0 rpm to stop additional parison molding. The time until the previously molded parison fell freely (hanging time) was measured. At this time, if the melt strength is low, the falling time will be short, and if the melt strength is high, the falling time will be long, so the blow moldability was judged based on the falling time.

[0131] (3) Parison length (unit: mm)

[0132] In the above blow moldability evaluation, the length of the free-falling parison was measured. Since a longer length of the free-falling parison indicates more severe deformation, it was determined that a shorter parison length indicates better blow moldability.

[0133] (4) Formability reduction rate (unit: %)

[0134] The parison hanging time measured using 90 wt% of the above scrap and 10 wt% of the virgin material was compared with the parison hanging time measured using 100 wt% of the virgin material, and the formability degradation rate was evaluated based on the case where 100 wt% of the virgin material was used.

[0135] (5) Parison length increase rate (unit: %)

[0136] The free-fall length of the parison measured using 90 wt% of the above scrap and 10 wt% of the new material was compared with the free-fall length of the parison measured using 100 wt% of the new material, and the parison length increase rate was evaluated based on the case where 100 wt% of the new material was used.

[0137] Classification Preliminary Comparison Example 123412345678 Izod Impact Strength 262330282019192023311630 Hanging Time 270280280280260260250260220210280220 Parison Length 250260260240260270270260300310250310 Formability Decrease Rate 151010155055505025301530 Parison Length Increase Rate 201515206055606030252025

[0138] From the above Tables 1 and 2, it can be confirmed that the thermoplastic resin compositions comprising (A) a first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of the rubber polymer of 250 to 350 nm, (B) a second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer having an average particle size of the rubber polymer of 100 to 200 nm, (C) an aromatic vinyl-vinyl cyanide copolymer having a content of a vinyl cyanide compound-derived component of 25 to 35 wt%, (D) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average particle size of the rubber polymer of 500 to 1,000 nm, and (E) an oil including a triglyceride structure in an optimal content, as in Examples 1 to 4, have excellent physical properties such as impact resistance, and have excellent blow moldability even when the scrap content is increased to 90 wt% and reused. Although the present invention has been described above through preferred embodiments as described above, it is not limited thereto, and those skilled in the art will readily understand that various modifications and variations are possible without departing from the concept and scope of the patent claims described below.

Claims

1. (A) 15 to 25 wt% of a first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer having an average particle diameter of 250 to 350 nm; (B) 10 to 20 wt% of a second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer having an average particle diameter of 100 to 200 nm; (C) 50 to 70 wt% of an aromatic vinyl-vinyl cyanide copolymer having a content of 25 to 35 wt% of a component derived from a vinyl cyanide compound; and (D) 100 parts by weight of a base resin containing 4 to 10 wt% of a butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer having an average particle size of 500 to 1,000 nm. (E) A thermoplastic resin composition comprising 0.5 to 5 parts by weight of an oil having a triglyceride structure, wherein the weight ratio of (A):(B) is 2:1 to 1:

1.

2. In paragraph 1, The above (A) first butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a thermoplastic resin composition having a core-shell structure including a core made of a butadiene-based rubber polymer and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

3. In paragraph 1 or 2, A thermoplastic resin composition, wherein the above (A) first butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer.

4. In any one of paragraphs 1 to 3, The above (B) second butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a thermoplastic resin composition having a core-shell structure including a core made of a butadiene-based rubber polymer and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

5. In any one of paragraphs 1 to 4, A thermoplastic resin composition, wherein the above (B) second butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer.

6. In any one of paragraphs 1 to 5, A thermoplastic resin composition wherein the above (C) aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of 150,000 to 250,000 g / mol.

7. In any one of paragraphs 1 to 6, A thermoplastic resin composition wherein the above (C) aromatic vinyl-vinyl cyanide copolymer is a styrene-acrylonitrile copolymer.

8. In any one of paragraphs 1 to 7, The above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition having a structure in which a dispersed phase including a butadiene-based rubber polymer is dispersed in a continuous phase including an aromatic vinyl-vinyl cyanide copolymer.

9. In paragraph 8, A thermoplastic resin composition comprising, based on 100 wt% of the above (D) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer, 10 to 40 wt% of a dispersed phase comprising the butadiene-based rubber polymer and 60 to 90 wt% of a continuous phase comprising the aromatic vinyl-vinyl cyanide copolymer.

10. In any one of paragraphs 1 to 7, A thermoplastic resin composition wherein the above (D) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer is an acrylonitrile-butadiene-styrene copolymer.

11. In any one of paragraphs 1 to 10, The oil comprising the above (E) triglyceride structure is a thermoplastic resin composition comprising a structure represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1, R2, and R3 may be the same or different from each other, and R1, R2, and R3 are each a C4 to C30 aliphatic hydrocarbon group that is saturated or unsaturated, and any carbon in the aliphatic hydrocarbon group may be substituted with a hydroxy group.

12. In any one of paragraphs 1 to 11, A thermoplastic resin composition, wherein the oil containing the above (E) triglyceride structure is at least one of castor oil, palm oil, soybean oil, canola oil, corn oil, rapeseed oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, sesame oil, rice bran oil, palm kernel oil, camellia oil, olive oil, coconut oil, beef tallow, lard, safflower oil, fish oil, whale oil, tuna oil, and waste oils thereof.

13. In any one of paragraphs 1 to 10, The oil comprising the above (E) triglyceride structure is a thermoplastic resin composition comprising a structure represented by the following chemical formula 2: [Chemical Formula 2] 14. In any one of paragraphs 1 to 13, A thermoplastic resin composition further comprising at least one additive selected from among a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, a colorant, and an impact modifier.

15. A molded product manufactured from a thermoplastic resin composition according to any one of claims 1 to 14.

Images