Thermoplastic resin composition and molded article manufactured therefrom

Abstract

The present invention relates to a thermoplastic resin composition and a molded article manufactured from the thermoplastic resin composition, the thermoplastic resin composition comprising, on the basis of 100 parts by weight of a base resin comprising (A) 70-90 wt% of a polycarbonate resin and (B) 10-30 wt% of a styrene-acrylonitrile copolymer: (C) 5-15 parts by weight of a core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or a core-shell structured acrylonitrile-butadiene-styrene graft copolymer; and (D) 1-10 parts by weight of purified castor oil having an acid value of at least 0.1.

Description

Thermoplastic resin composition and molded article manufactured therefrom

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

[0002] PC / ABS resin, a blend of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS), boasts high impact and heat resistance, making it a versatile material for a wide range of applications. For example, it can be used in the mobility industry as interior and exterior materials for vehicles and as safety equipment for drivers. Special-purpose products, such as helmets and other safety equipment, require high stability and require enhanced impact resistance compared to standard PC / ABS resin.

[0003] To enhance the impact resistance of PC / ABS resins, methods such as adding impact modifiers or increasing the molecular weight of the PC resin being mixed are being used. However, increasing the content of impact modifiers in PC / ABS resins or increasing the molecular weight of the PC resin can lead to reduced fluidity of the PC / ABS resin or to products manufactured from such PC / ABS resins easily delaminating.

[0004] Therefore, a thermoplastic resin composition is required that can secure a certain level of fluidity while maintaining or increasing impact resistance and also manufacture a molded product with excellent appearance.

[0005] One embodiment provides a thermoplastic resin composition capable of producing a molded product having excellent impact resistance while simultaneously having excellent fluidity.

[0006] Another embodiment provides a molded article having an excellent appearance and reduced unpleasant odor, manufactured from the thermoplastic resin composition.

[0007] According to one embodiment, a thermoplastic resin composition comprises 100 parts by weight of a base resin including (A) 70 to 90 parts by weight of a polycarbonate resin; and (B) 10 to 30 parts by weight of a styrene-acrylonitrile copolymer; (C) 5 to 15 parts by weight of a core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or a core-shell structured acrylonitrile-butadiene-styrene graft copolymer; and (D) 1 to 10 parts by weight of refined castor oil having an acid value of 0.1 or higher.

[0008] The acid value of the above (D) refined castor oil may be 0.1 or more and 2.0 or less.

[0009] The above (D) refined castor oil may include a compound represented by the following chemical formula 1:

[0010] [Chemical Formula 1]

[0011]

[0012] The above (B) styrene-acrylonitrile copolymer may contain 15 to 40 wt% of acrylonitrile structural units based on the total weight of the copolymer.

[0013] The above (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer may include a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerizing methyl methacrylate and styrene onto the core.

[0014] The acrylonitrile-butadiene-styrene graft copolymer having the above (C) core-shell structure may include a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerizing acrylonitrile and styrene onto the core.

[0015] The core made of the above butadiene-based rubber polymer may have an average particle diameter of 200 to 400 nm.

[0016] The above (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or core-shell structured acrylonitrile-butadiene-styrene graft copolymer may comprise 30 to 60 wt% of a core made of a butadiene-based rubber polymer based on the total weight of each copolymer.

[0017] The weight average molecular weight of the above (A) polycarbonate resin may be 10,000 to 100,000 g / mol.

[0018] The weight average molecular weight of the above (B) styrene-acrylonitrile copolymer may be 50,000 to 500,000 g / mol.

[0019] The thermoplastic resin composition may have a melt flow index of more than 15 g / 10 min, measured according to ASTM D1238 under conditions of 250°C and 10 kg.

[0020] The thermoplastic resin composition may further include at least one additive selected from among flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, mineral fillers, antibacterial agents, release agents, heat stabilizers, antioxidants, pigments, dyes, and antistatic agents.

[0021] According to another embodiment, a molded article is manufactured from a thermoplastic resin composition according to the above embodiment.

[0022] The above molded product may have an odor level of 7 to 8 as measured according to the odor evaluation method of GEELY automobiles.

[0023] The above molded article may have a notched Izod impact strength of greater than 80 kgf·cm / cm at 1 / 8 inch thickness, as measured in accordance with ASTM D256.

[0024] A thermoplastic resin composition according to one embodiment may have excellent fluidity and thus be easy to mold.

[0025] A molded article manufactured from a thermoplastic resin composition according to one embodiment has excellent fluidity, appearance properties and impact resistance, and can have a reduced unpleasant odor.

[0026] 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.

[0027] Unless specifically stated herein, 'copolymer' includes random copolymerization, block copolymerization, and graft copolymerization, and 'copolymer' includes random copolymer, block copolymer, and graft copolymer.

[0028] Unless otherwise specified herein, '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).

[0029] Unless otherwise specified herein, 'average particle size' is the volume average diameter and refers to the Z-average particle size measured using a dynamic light scattering (DLS) analyzer.

[0030] According to one embodiment, a thermoplastic resin composition is provided, comprising (A) 70 to 90 wt% of a polycarbonate (PC) resin; and (B) 10 to 30 wt% of a styrene-acrylonitrile copolymer (SAN), relative to 100 wt% of a base resin, (C) 5 to 15 wt% of a core-shell structured methyl methacrylate-butadiene-styrene graft copolymer (MBS) or a core-shell structured acrylonitrile-butadiene-styrene graft copolymer (g-ABS); and (D) 1 to 10 wt% of a refined castor oil (Oil) having an acid value of 0.1 or higher.

[0031] To enhance the impact resistance of conventional PC / ABS resins, attempts have been made to manufacture molded articles by adding core-shell impact modifiers. While the impact resistance of molded articles manufactured from these compositions was improved, the resulting compositions suffered from reduced fluidity, making them difficult to manufacture. Furthermore, the molded articles exhibited poor appearance and were prone to peeling.

[0032] The inventors of the present invention have confirmed that the fluidity of the resin composition does not decrease even when an impact modifier of (C) a core-shell structured methyl methacrylate-butadiene-styrene graft copolymer (MBS) or a core-shell structured acrylonitrile-butadiene-styrene graft copolymer (g-ABS) is used together with (D) a refined castor oil having an acid value of 0.1 or more by adding (A) a polycarbonate resin and (B) a styrene-acrylonitrile copolymer to the base resin. Therefore, a thermoplastic resin composition according to one embodiment comprising (C) an impact modifier and (D) a refined castor oil having an acid value of 0.1 or more in the base resin comprising (A) and (B) has excellent fluidity, and the impact resistance of a molded article manufactured therefrom is excellent. In addition, the molded article has an excellent appearance and does not easily peel off. In addition, the molded article does not emit an unpleasant odor.

[0033] Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

[0034]

[0035] (A) Polycarbonate resin

[0036] (A) Polycarbonate (PC) resin is a polyester having a carbonate bond, and its type is not particularly limited, and any polycarbonate resin available in the field of thermoplastic resin compositions can be used. Polycarbonate resin has excellent properties such as impact resistance, heat resistance, and light weight, and thus a molded product manufactured from a thermoplastic resin composition containing the same can have excellent impact resistance.

[0037] For example, (A) polycarbonate resin can be produced by reacting a diphenol represented by the following chemical formula X with a compound selected from the group consisting of phosgene, halogen acid ester, carbonic acid ester, or a combination thereof.

[0038] [chemical formula X]

[0039]

[0040] In the above chemical formula X,

[0041] A is a linking group selected from the group consisting of a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group, a substituted or unsubstituted C1 to C30 haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C10 cycloalkylidene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a halogen acid ester group, a carbonic acid ester group, C=O, S and SO2, and R 1 and R 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and n1 and n2 are each independently an integer from 0 to 4.

[0042] In the above chemical formula X, A is, for example, a single bond, or a substituted or unsubstituted C1 to C10 alkylene group, and R 1 and R 2 are each independently a substituted or unsubstituted C1 to C10 alkyl group, and n1 and n2 are each independently 0 or 1, but are not limited thereto.

[0043] Two or more types of diphenols represented by the above chemical formula X may be combined to form a repeating unit of a polycarbonate resin.

[0044] Specific examples of the above diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also called 'bisphenol-A'), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, Examples thereof include bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)ether. Among the above diphenols, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)cyclohexane is preferably used. 2,2-bis(4-hydroxyphenyl)propane is more preferably used.

[0045] The above (A) polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. In addition, the above (A) polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like.

[0046] A specific example of the linear polycarbonate resin may be a bisphenol-A polycarbonate resin. A specific example of the branched polycarbonate resin may be a resin produced by reacting a polyfunctional aromatic compound, such as trimellitic anhydride or trimellitic acid, with diphenols and carbonates. The polyester carbonate copolymer resin may be produced by reacting a difunctional carboxylic acid with diphenols and carbonates, and the carbonate used here may be a diaryl carbonate, such as diphenyl carbonate, or ethylene carbonate.

[0047] The above (A) polycarbonate resin may have a weight average molecular weight of 10,000 to 100,000 g / mol, for example, 20,000 to 100,000 g / mol, 10,000 to 80,000 g / mol, 10,000 to 60,000 g / mol, 10,000 to 50,000 g / mol, 10,000 to 30,000 g / mol, or 15,000 to 30,000 g / mol, but is not limited thereto. When the weight average molecular weight of the above (A) polycarbonate resin is within the above range, a thermoplastic resin composition comprising the same can realize excellent impact resistance and fluidity.

[0048] The above (A) polycarbonate resin may be included in an amount of 70 to 90 wt%, for example, 75 to 90 wt%, for example, 70 to 85 wt%, based on 100 wt% of the base resin comprising (A) polycarbonate resin and (B) styrene-acrylonitrile copolymer described below. In the above weight range, the thermoplastic resin composition of the present invention and the molded article manufactured therefrom may exhibit excellent impact resistance.

[0049] The above (A) polycarbonate resin may have a melt flow index of 5 to 40 g / 10 min, for example, 5 to 30 g / 10 min, measured according to ASTM D1238 under conditions of 250°C and 10 kg. When a polycarbonate resin having a melt flow index within the above range is used, the thermoplastic resin composition and the molded article manufactured therefrom may exhibit excellent moldability and excellent impact resistance.

[0050] The above (A) polycarbonate resin can be used by mixing two or more polycarbonate resins having different weight average molecular weights or melt flow indices. By mixing and using polycarbonate resins having different weight average molecular weights or melt flow indices, it is easy to control the thermoplastic resin composition to have the desired fluidity.

[0051]

[0052] (B) Styrene-acrylonitrile copolymer

[0053] A thermoplastic resin composition according to one embodiment can improve the fluidity of the thermoplastic resin composition and maintain compatibility between components at a certain level by including (B) a styrene-acrylonitrile (SAN) copolymer.

[0054] The above (B) styrene-acrylonitrile copolymer comprises styrene structural units and acrylonitrile structural units. The acrylonitrile structural unit may be included in an amount of 15 to 40 wt%, for example, 20 to 40 wt%, or 15 to 35 wt%, based on the total weight of the (B) styrene-acrylonitrile copolymer, but is not limited thereto.

[0055] The weight average molecular weight of the above (B) styrene-acrylonitrile copolymer may be 50,000 to 500,000 g / mol. For example, it may be 50,000 to 400,000 g / mol, 50,000 to 300,000 g / mol, 100,000 to 500,000 g / mol, 100,000 to 400,000 g / mol, 100,000 to 300,000 g / mol, or 100,000 to 200,000 g / mol, but is not limited thereto. When the weight average molecular weight of the above (B) styrene-acrylonitrile copolymer is within the above range, the fluidity of a thermoplastic resin composition including the same can be improved and compatibility between components can be maintained.

[0056] The above (B) styrene-acrylonitrile copolymer may be included in an amount of 10 to 30 wt%, for example, 10 to 25 wt%, 15 to 30 wt%, based on 100 wt% of the base resin comprising (A) the polycarbonate resin and (B) the styrene-acrylonitrile copolymer. By including the (B) styrene-acrylonitrile copolymer in the above range in the base resin, compatibility with the (A) polycarbonate resin is excellent, and the fluidity of the thermoplastic resin composition including the same can be improved.

[0057]

[0058] (C) Core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or core-shell structured acrylonitrile-butadiene-styrene graft copolymer

[0059] According to one embodiment, a thermoplastic resin composition can enhance the impact resistance of the thermoplastic resin composition and improve the appearance properties of a molded article manufactured from the thermoplastic resin composition by including a methyl methacrylate-butadiene-styrene graft copolymer having a core-shell structure or an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure.

[0060] In one embodiment, the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer may include a core formed of a butadiene-based rubbery polymer and a shell formed by graft polymerizing methyl methacrylate and styrene onto the core. For example, the shell may be formed by adding methyl methacrylate and / or styrene to the core formed of the butadiene-based rubbery polymer and graft copolymerizing the core using a conventional polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization.

[0061] For example, the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer may be a graft copolymer including a core made of a butadiene-based rubber polymer and a shell formed by graft polymerization of methyl methacrylate and styrene.

[0062] As another example, the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer may be a graft copolymer formed by grafting methyl methacrylate onto a butadiene-based rubber polymer core to form a primary shell, and then grafting styrene to form a secondary shell.

[0063] As another example, the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer may be a graft copolymer formed by grafting styrene onto a butadiene-based rubber polymer core to form a primary shell, and then grafting methyl methacrylate to form a secondary shell.

[0064] The acrylonitrile-butadiene-styrene graft copolymer having the above (C) core-shell structure may include a shell formed by graft polymerization of acrylonitrile and styrene onto a core made of a butadiene-based rubber polymer. The graft polymerization may be performed using a conventional polymerization method as described above.

[0065] The above butadiene-based rubber polymer may be, for example, butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, or a combination thereof, but is not limited thereto.

[0066] The core made of the above butadiene-based rubber polymer may have an average particle diameter of 200 to 400 nm, for example, 150 to 400 nm, 120 to 400 nm, or 200 to 380 nm, but is not limited thereto. Since the core of the (C) core-shell structured graft copolymers has an average particle diameter within the above range, the impact resistance of the thermoplastic resin composition containing the core can be enhanced, and the appearance characteristics of a molded article manufactured from the thermoplastic resin composition can be improved.

[0067] The (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or the core-shell structured acrylonitrile-butadiene-styrene graft copolymer may contain, based on the total weight of each copolymer, 30 to 60 wt%, for example, 35 to 60 wt%, 40 to 60 wt%, of a core made of a butadiene-based rubber polymer, but is not limited thereto. By containing the core of the (C) core-shell structured graft copolymer in the above range, the impact resistance of a thermoplastic resin composition containing the same can be enhanced, and the appearance properties of a molded article manufactured from the composition can be improved.

[0068] The (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or the core-shell structured acrylonitrile-butadiene-styrene graft copolymer may be included in an amount of 5 to 15 parts by weight, for example, 7 to 15 parts by weight, or 5 to 13 parts by weight, based on 100 parts by weight of the base resin, but is not limited thereto. By including the (C) core-shell structured graft copolymer in an amount within the above range of parts by weight, the impact resistance of the thermoplastic resin composition including the same can be enhanced, and the appearance characteristics of a molded article manufactured from the thermoplastic resin composition can be improved.

[0069]

[0070] (D) Refined castor oil

[0071] According to one embodiment, a thermoplastic resin composition includes refined castor oil, so that even if the thermoplastic resin composition includes an impact modifier, the fluidity thereof is not reduced, the appearance characteristics of a molded product manufactured from the thermoplastic resin composition are improved, and the generation of an unpleasant odor can be suppressed.

[0072] According to one embodiment, a thermoplastic resin composition can improve the fluidity of the thermoplastic resin composition without deteriorating its mechanical properties by using refined castor oil, thereby improving the appearance characteristics of a molded article manufactured from the composition. In contrast, the use of unrefined oil can deteriorate the appearance characteristics or mechanical properties of the thermoplastic resin composition due to residual minerals, etc.

[0073] The above (D) refined castor oil may be refined castor oil having an acid value of 0.1 or more. The acid value of the above (D) refined castor oil may be 0.1 or more, for example, 0.2 or more, 0.3 or more, and 2.0 or less, 1.8 or less, 1.6 or less, 1.5 or less, and for example, 0.1 or more and 2.0 or less, 0.1 or more and 1.8 or less, 0.1 or more and 1.6 or less, 0.1 or more and 1.5 or less, but is not limited thereto.

[0074] The above (D) refined castor oil may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base resin, for example, 1 to 8 parts by weight, 1 to 7 parts by weight, 1 to 5 parts by weight, or 2 to 5 parts by weight, but is not limited to these ranges. By including the above (D) refined castor oil in the above content range, fluidity is imparted to the thermoplastic composition according to one embodiment, while the molded article manufactured therefrom has a reduced occurrence of an unpleasant odor, and further, peeling of the molded article can be suppressed and the appearance characteristics can be improved.

[0075] The above (D) refined castor oil may include a compound represented by the following chemical formula 1:

[0076] [Chemical Formula 1]

[0077]

[0078]

[0079] (E) Other additives

[0080] A thermoplastic resin composition according to one embodiment may further include, in addition to the components (A) to (D), one or more additives necessary to balance the properties under conditions of maintaining excellent fluidity and impact resistance, or depending on the final use of the thermoplastic resin composition.

[0081] In one embodiment, the additive may be at least one selected from among flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, mineral fillers, antibacterial agents, release agents, heat stabilizers, antioxidants, pigments, dyes, and antistatic agents.

[0082] These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and may be included in an amount of, for example, 0.1 to 20 parts by weight, 0.1 to 15 parts by weight, or 0.1 to 10 parts by weight relative to 100 parts by weight of the base resin, but are not limited thereto.

[0083]

[0084] The thermoplastic resin composition described above may have a melt flow index measured according to ASTM D1238 at 250°C and 10 kg of more than 15 g / 10 min, for example, more than 16 g / 10 min, more than 17 g / 10 min, or more than 20 g / 10 min, but is not limited thereto. A molded article manufactured from a thermoplastic resin composition having a fluidity within the above range may exhibit excellent impact resistance, excellent moldability, and may not be easily peeled off.

[0085]

[0086] Another embodiment of the present invention provides a molded article manufactured from the thermoplastic resin composition described above. The molded article exhibits excellent impact resistance and appearance, and emits virtually no unpleasant odor. Therefore, the molded article according to one embodiment can be advantageously applied to products requiring excellent appearance and high impact resistance, such as body protection equipment.

[0087] The above-mentioned molded article can be manufactured by molding the thermoplastic resin composition according to one embodiment using a known method. For example, the molded article according to one embodiment can be manufactured in the form of pellets by mixing the components of the thermoplastic resin composition according to one embodiment and other additives, and then melting / mixing them with an extruder. The manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding, and such molding methods are well known to those skilled in the art to which the present invention pertains.

[0088] The above-mentioned molded product may have an odor level of 7 to 8, as measured by the odor evaluation method for GEELY automobiles. Molded products having the above odor level can be used as safety equipment that can be worn on the body, such as helmets. The odor evaluation method for GEELY automobiles is described in detail in the examples below.

[0089] The above molded article may have a notched Izod impact strength of greater than 80 kgf·cm / cm, for example, greater than 85 kgf·cm / cm, greater than 90 kgf·cm / cm, or greater than 95 kgf·cm / cm, as measured in accordance with ASTM D256 at 1 / 8 inch thickness, but is not limited thereto.

[0090] Hereinafter, preferred embodiments of the present invention are described. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0091]

[0092] Examples 1 to 3 and Comparative Examples 1 to 5

[0093] The thermoplastic resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared according to the component content ratios described in Table 1 below.

[0094] Specifically, a mixture of the components in Table 1 below was continuously fed into a twin-screw extruder (L / D = 29, diameter = 45 mm) to be melted / kneaded and processed to obtain a thermoplastic resin composition in the form of pellets. At this time, the barrel temperature of the twin-screw extruder was set to about 260°C. Subsequently, the pelletized thermoplastic resin composition was dried at about 80°C for about 4 hours, and then a 6-ounce (oz) injection molding machine with a cylinder temperature of about 270°C and a mold temperature of about 60°C was used to manufacture a specimen for measuring physical properties.

[0095] In Table 1 below, (A) and (B) represent the weight % of each component among 100 weight % of the base resin, and (C), (D), (x), and (y) represent weight parts based on 100 weight parts of the base resin ((A) + (B)).

[0096] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) Polycarbonate resin 8080808080808080 (B) Styrene-acrylonitrile copolymer 2020202020202020 (C) Impact modifier 11010101015101010 (x) Impact modifier 2-----5-- (D) Refined castor oil 1 Acid value: 0.11510----- (y) Refined castor oil 2 Acid value: 0.05------5- (z) Unrefined castor oil 3 Acid value: 0.1-------5

[0097]

[0098] Each component listed in Table 1 above is as follows.

[0099] (A) Polycarbonate resin

[0100] Bisphenol-A polycarbonate resin from Lotte Chemical Co., Ltd. with a weight average molecular weight of approximately 28,000 g / mol was used.

[0101] (B) Styrene-acrylonitrile copolymer

[0102] A styrene-acrylonitrile copolymer from Lotte Chemical Co., Ltd. with a weight average molecular weight of approximately 135,000 g / mol and an acrylonitrile structural unit of approximately 32 wt% was used.

[0103] (C) Shock absorber 1

[0104] Lotte Chemical Co., Ltd.'s core-shell structured acrylonitrile-butadiene-styrene graft copolymer (g-ABS) having an average particle diameter of the butadiene-based rubber polymer core of about 260 nm and a butadiene-based rubber polymer content of about 58 wt% was used.

[0105] (x) Shock absorber 2

[0106] As an ethylene-methyl methacrylate copolymer, Elvaloy AC 1330 from Dow was used.

[0107] (D) Refined castor oil 1

[0108] We used refined castor oil from Lotte Wellfood Co., Ltd. with an acid value of approximately 0.1.

[0109] (y) Refined castor oil 2

[0110] We used refined castor oil from Lotte Wellfood Co., Ltd. with an acid value of approximately 0.05.

[0111] (z) Unrefined castor oil 3

[0112] Unrefined castor oil from Lotte Wellfood Co., Ltd. with an acid value of approximately 0.1 was used.

[0113]

[0114] evaluation

[0115] The following evaluation was performed on specimens for measuring physical properties manufactured from thermoplastic resin compositions according to the above examples and comparative examples, and the results are as shown in Table 3 below.

[0116] (1) Impact resistance evaluation: Notched Izod impact strength (unit: kgf·cm / cm) was measured for 1 / 8 inch specimens according to ASTM D256 standard.

[0117] (2) Fluidity evaluation: The melt flow index was measured according to ASTM D1238 at 250℃ and 10 kg.

[0118] (3) Appearance Characteristics Evaluation: The appearance characteristics were sensorily evaluated by the presence or absence of flow marks on 50 mm x 200 mm x 2 mm sized specimens injection-molded using a mold with a pin-point gate structure. If no flow marks occurred at the end opposite the gate of the specimen, the appearance characteristics were evaluated as excellent (○), and if flow marks occurred at the end of the specimen, the appearance characteristics were evaluated as poor (X).

[0119] (4) Odor Evaluation: For 100 g of pellets of thermoplastic resin composition in pellet form, in accordance with the Q / JLY J7110538C standard, which is the odor evaluation method of GEELY automobiles, five trained evaluators with experience in evaluating the standard evaluation method more than 10 times evaluated the odor grade according to the criteria in Table 2 below, and the odor grades of each evaluator were averaged including decimal points, and then the final grade was selected. According to Table 2 below, the lower the grade, the more unpleasant the odor.

[0120] Grade Detailed Description Human Senses 10 No smell Comfortable 9 Hardly noticeable, difficult to identify the type of smell 8 Sensing the presence of smell, slightly comfortable 7 Non-irritating smell, clearly detected Certain irritation, tolerable 6 Slightly irritating smell, clearly detected 5 Moderately irritating smell, clearly detected Somewhat annoying and intolerable 4 Unpleasant smell, slightly less disgusting 3 Irritating smell, disgusting Irritating, nausea 2 Irritating smell, very disgusting 1 Feeling short of breath, unbearable

[0121] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Impact strength 85961108083857050 Melt flow index 1725451512153040 Appearance characteristics ○○○○○XXX Odor rating 78866655

[0122] Referring to Tables 1 to 3 above, the melt flow indices of the thermoplastic resin compositions including (A) a polycarbonate resin, (B) a styrene-acrylonitrile copolymer, (C) an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure, and (D) refined castor oil having an acid value of 0.1 or more were all high, and the impact strengths of the specimens manufactured from these thermoplastic resin compositions were all high, such as 80 kgf·cm / cm or more. In addition, it can be seen that the specimens have excellent appearance characteristics and good odor ratings.

[0123] On the other hand, in the case of a thermoplastic resin composition in which any one of the above components is excluded, has an acid value of less than 0.1, or uses unrefined castor oil, it can be confirmed that the melt flow index is low and / or the appearance characteristics and / or odor grade are also inferior to those of the examples, even though the impact strength is good.

[0124] Although the present invention has been described above through preferred embodiments as described above, the present invention is not limited thereto, and those engaged in the technical field to which the present invention pertains 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) 70 to 90 wt% of polycarbonate resin; and (B) 10 to 30 wt% of styrene-acrylonitrile copolymer; For 100 parts by weight of base resin containing (C) 5 to 15 parts by weight of a core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or a core-shell structured acrylonitrile-butadiene-styrene graft copolymer; and (D) 1 to 10 parts by weight of refined castor oil having an acid value of 0.1 or higher A thermoplastic resin composition comprising:

2. In paragraph 1, the acid value of the refined castor oil (D) is a thermoplastic resin composition of 0.1 or more and 2.0 or less.

3. A thermoplastic resin composition in paragraph 1 or paragraph 2, wherein the purified castor oil (D) comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] 4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the (B) styrene-acrylonitrile copolymer contains 15 to 40 wt% of an acrylonitrile structural unit based on the total weight of the copolymer.

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer comprises a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerization of methyl methacrylate and styrene onto the core.

6. A thermoplastic resin composition in any one of paragraphs 1 to 5, wherein the (C) core-shell structured acrylonitrile-butadiene-styrene graft copolymer comprises a core made of a butadiene-based rubber polymer, and a shell formed by graft polymerizing acrylonitrile and styrene onto the core.

7. A thermoplastic resin composition in claim 5 or 6, wherein the core made of the butadiene-based rubber polymer has an average particle diameter of 200 to 400 nm.

8. A thermoplastic resin composition in any one of claims 1 to 7, wherein the (C) core-shell structured methyl methacrylate-butadiene-styrene graft copolymer or core-shell structured acrylonitrile-butadiene-styrene graft copolymer comprises a core made of a butadiene-based rubber polymer in an amount of 30 to 60 wt% based on the total weight of each copolymer.

9. A thermoplastic resin composition according to any one of claims 1 to 8, wherein the weight average molecular weight of the polycarbonate resin (A) is 10,000 to 100,000 g / mol.

10. A thermoplastic resin composition according to any one of claims 1 to 9, wherein the weight average molecular weight of the (B) styrene-acrylonitrile copolymer is 50,000 to 500,000 g / mol.

11. A thermoplastic resin composition according to any one of claims 1 to 10, wherein the thermoplastic resin composition has a melt flow index of more than 15 g / 10 min, measured according to ASTM D1238 under conditions of 250°C and 10 kg.

12. A thermoplastic resin composition according to any one of claims 1 to 11, wherein the thermoplastic resin composition further comprises at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, glass fiber, a plasticizer, a lubricant, a mineral filler, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, a pigment, a dye, and an antistatic agent.

13. A molded product manufactured from a thermoplastic resin composition according to any one of claims 1 to 12.

14. In paragraph 13, the molded product is a molded product having an odor generation level of 7 to 8 as measured according to the odor evaluation method of GEELY automobiles.

15. In paragraph 13 or 14, the molded product has a notched Izod impact strength of more than 80 kgf·cm / cm measured according to ASTM D256 at a thickness of 1 / 8 inch.

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