Thermoplastic resin composition containing mineral filler and having a metallic texture, and molded article containing the same

Abstract

The present invention relates to a thermoplastic resin composition having a metallic texture containing a mineral filler, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition containing a specific fixed content ratio of polycarbonate resin, acrylonitrile-butadiene-styrene resin, a flame retardant, coal ash filler, a block copolymer containing (meth)acrylic acid ester units, and plate-like metal particles, which exhibits an excellent metallic texture and an excellent appearance due to reduced weld lines during injection molding, and can provide a molded article with an excellent balance of dimensional stability, flame retardancy, impact resistance, and heat resistance, and a molded article containing the same.

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition having a metallic texture containing a mineral filler, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition containing a specific content ratio of polycarbonate resin, acrylonitrile-butadiene-styrene resin, a flame retardant, coal ash filler, a block copolymer containing (meth)acrylic acid ester units, and plate-like metal particles, which exhibits an excellent metallic texture and an excellent appearance due to reduced weld lines during injection molding, and can provide a molded article with an excellent balance of dimensional stability, flame retardancy, impact resistance, and heat resistance, and a molded article containing the same. [Background technology]

[0002] Injection molding is one of the applications of thermoplastic resins with a metallic texture. Generally, thermoplastic resins are injection molded to be delivered to consumers as various products such as electrical and electronic products and automotive parts.

[0003] Traditionally, injection-molded products with a metallic texture are designed through post-processing such as painting after injection molding. However, this is fundamentally uneconomical due to the additional cost of the painting process, and increases production costs due to masking, defects, and handling difficulties in the post-processing. Furthermore, the use of volatile organic compounds poses problems of adverse effects on the human body and the environment.

[0004] Therefore, there is a growing demand for environmentally friendly paint-free materials that can achieve the same metallic appearance as metal paint without the need for a painting process, i.e., metal materials.For this reason, development of metal materials in which metal particles are painted on the thermoplastic resin itself is being continued.In addition, molded products used in electrical and electronic products such as televisions tend to be thinner, and molded products are required to have dimensional stability and high impact strength.

[0005] To improve the appearance of paint-free molded products with a metallic texture produced from compositions in which metal particles are added to a thermoplastic base resin, methods have been attempted to reduce flow marks and weld lines in the molded products by increasing the affinity between the base resin and the metal particles. However, the molded products obtained using this method lack impact resistance, flame retardancy, and heat resistance, and in particular, have poor dimensional stability, limiting their application to parts such as back covers and bezels for televisions, which are becoming thinner and more complex. As an alternative, attempts have been made to achieve a metallic appearance and improve mechanical properties by applying a metal layer to a molded product through double injection or extrusion molding, but these methods have drawbacks such as increased processing costs due to the double processing and the associated pre-treatment work, and a significant reduction in the degree of freedom in product design. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a molded article that has a metallic texture similar to that of a coated metal product and exhibits an appearance with reduced flow marks and weld lines, without requiring a painting process, and to provide a thermoplastic resin composition that has an excellent balance of dimensional stability, flame retardancy, impact resistance, and heat resistance, and a molded article containing the same. [Means for solving the problem]

[0007] One aspect of the present invention provides a thermoplastic resin composition comprising the following components: (A) a polycarbonate resin; (B) an acrylonitrile-butadiene-styrene resin; (C) a flame retardant; (D) a coal ash filler; (E) a block copolymer containing (meth)acrylic acid ester units; and (F) plate-shaped metal particles, wherein, relative to 100 parts by weight of the total amount of the composition, the content of the (A) component is greater than 41.5 parts by weight and less than 71 parts by weight, the content of the (B) component is greater than 5 parts by weight and less than 20 parts by weight, the content of the (C) component is greater than 9 parts by weight and less than 17 parts by weight, the content of the (D) component is greater than 8 parts by weight and less than 20 parts by weight, the content of the (E) component is greater than 1 part by weight and less than 8 parts by weight, and the content of the (F) component is greater than 0.5 parts by weight and less than 3 parts by weight.

[0008] According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention. [Effects of the Invention]

[0009] When the thermoplastic resin composition of the present invention is injection molded, the distribution of plate-shaped metal particles on the surface of the injection-molded product increases, and the spherical coal ash acts to reduce weld lines, providing an excellent metallic appearance and improving dimensional stability, flame retardancy, impact resistance, and heat resistance. Therefore, the thermoplastic resin composition of the present invention is very useful for molded products such as TV back covers and bezels, which require a metallic appearance without the need for painting and excellent levels of all of the above physical properties. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram schematically illustrating a situation in which flow marks and weld lines occur in a molded product obtained by injection molding a conventional resin composition containing only plate-shaped metal particles (left diagram), and a situation in which flow marks and weld lines do not occur or are reduced when a resin composition according to one embodiment of the present invention containing both plate-shaped metal particles and coal ash filler (spherical) is injection molded (right diagram). [Figure 2]1 shows photographs showing typical appearances corresponding to scores of 1 to 5 in appearance evaluations (weld lines) carried out in Examples and Comparative Examples of the present invention. [Figure 3] Photographs of surfaces having metallic textures measured for each flop index are shown, so that the difference in metallic texture depending on the flop index value can be seen. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will now be described in more detail.

[0012] The thermoplastic resin composition of the present invention comprises (A) a polycarbonate resin; (B) an acrylonitrile-butadiene-styrene resin; (C) a flame retardant; (D) a coal ash filler; (E) a block copolymer containing (meth)acrylic acid ester units; and (F) plate-like metal particles.

[0013] The thermoplastic resin composition of the present invention contains the polycarbonate resin component (A) in an amount of more than 41.5 parts by weight and less than 71 parts by weight, based on 100 parts by weight of the total composition. If the content of the component (A) is 41.5 parts by weight or less, a molded article produced from the resin composition may suffer from a deterioration in metallic texture and an increase in weld lines, resulting in a poor appearance and a poor dimensional stability. On the other hand, if the content is 71 parts by weight or more, the number of weld lines in the molded article may increase rapidly, resulting in a significant deterioration in appearance and a significant decrease in impact strength.

[0014] In one embodiment, the (A) component may be contained in an amount of, for example, more than 41.5 parts by weight, 41.6 parts by weight or more, 42 parts by weight or more, 42.5 parts by weight or more, 43 parts by weight or more, or 43.5 parts by weight or more, relative to 100 parts by weight of the total amount of the thermoplastic resin composition of the present invention, or may be contained in an amount of less than 71 parts by weight, 70.9 parts by weight or less, 70 parts by weight or less, 69 parts by weight or less, 68 parts by weight or less, 67 parts by weight or less, or 66.5 parts by weight or less, but is not particularly limited to these amounts.

[0015] The thermoplastic resin composition of the present invention contains the acrylonitrile-butadiene-styrene resin component (B) in an amount of more than 5 parts by weight and less than 20 parts by weight, based on 100 parts by weight of the total amount of the composition. If the content of the component (B) in 100 parts by weight of the total amount of the composition is 5 parts by weight or less, the impact strength of a molded article produced from the resin composition may be significantly reduced. Also, if the content is 20 parts by weight or more, the impact strength of the molded article may be significantly reduced.

[0016] In one embodiment, the (B) component may be contained in an amount of, for example, more than 5 parts by weight, 5.1 parts by weight or more, 5.5 parts by weight or more, 6 parts by weight or more, 6.5 parts by weight or more, or 7 parts by weight or more, or may be contained in an amount of less than 20 parts by weight, 19.9 parts by weight or less, 19.5 parts by weight or less, 19 parts by weight or less, 18.5 parts by weight or less, or 18 parts by weight or less, based on a total of 100 parts by weight of the thermoplastic resin composition of the present invention, but is not limited to these amounts.

[0017] The thermoplastic resin composition of the present invention contains the flame retardant component (C) in an amount of more than 9 parts by weight and less than 17 parts by weight, based on 100 parts by weight of the total composition. If the content of the component (C) is 9 parts by weight or less, based on 100 parts by weight of the total composition, the flame retardancy of a molded article produced from the resin composition may be significantly reduced, while if the content is 17 parts by weight or more, the impact strength of the molded article may be significantly reduced, and the heat resistance may also be reduced.

[0018] In one embodiment, the (C) component may be contained in an amount of, for example, more than 9 parts by weight, 9.1 parts by weight or more, 9.5 parts by weight or more, 10 parts by weight or more, 10.5 parts by weight or more, or 11 parts by weight or more, relative to 100 parts by weight of the total amount of the thermoplastic resin composition of the present invention, or may be contained in an amount of less than 17 parts by weight, 16.9 parts by weight or less, 16.5 parts by weight or less, or 16 parts by weight or less, but is not particularly limited to these amounts.

[0019] The thermoplastic resin composition of the present invention contains the coal ash filler component (D) in an amount of more than 8 parts by weight and less than 20 parts by weight, based on 100 parts by weight of the total composition. If the content of the component (D) is 8 parts by weight or less, the molded article produced from the resin composition may experience a rapid increase in weld lines, resulting in a significant deterioration in appearance, a significant deterioration in dimensional stability, and a significant decrease in impact strength. On the other hand, if the content is 20 parts by weight or more, the metallic texture of the molded article may be significantly deteriorated and the impact strength may also be significantly reduced.

[0020] In one embodiment, the (D) component may be contained in an amount of, for example, more than 8 parts by weight, 8.1 parts by weight or more, 8.5 parts by weight or more, 9 parts by weight or more, 9.5 parts by weight or more, or 10 parts by weight or more, or may be contained in an amount of less than 20 parts by weight, 19.9 parts by weight or less, 19.5 parts by weight or less, 19 parts by weight or less, 18.5 parts by weight or less, or 18 parts by weight or less, relative to 100 parts by weight of the total amount of the thermoplastic resin composition of the present invention, but is not particularly limited to these amounts.

[0021] The thermoplastic resin composition of the present invention contains the block copolymer component (E) containing (meth)acrylic acid ester units in an amount of more than 1 part by weight and less than 8 parts by weight per 100 parts by weight of the total composition. If the content of the component (E) per 100 parts by weight of the total composition is 1 part by weight or less, the impact strength of a molded article produced from the resin composition may be significantly reduced, while if the content is 8 parts by weight or more, the flame retardancy and heat resistance of the molded article may be significantly deteriorated, and the dimensional stability may also be reduced.

[0022] In one embodiment, the (E) component may be contained in an amount of, for example, more than 1 part by weight, 1.1 parts by weight or more, 1.3 parts by weight or more, 1.5 parts by weight or more, 1.7 parts by weight or more, 1.9 parts by weight or more, or 2 parts by weight or more, or may be contained in an amount of less than 8 parts by weight, 7.9 parts by weight or less, 7.5 parts by weight or less, 7 parts by weight or less, 6.5 parts by weight or less, 6 parts by weight or less, 5.5 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the total amount of the thermoplastic resin composition of the present invention, but is not particularly limited to these amounts.

[0023] The thermoplastic resin composition of the present invention contains the plate-like metal particle component (F) in an amount of more than 0.5 parts by weight and less than 3 parts by weight per 100 parts by weight of the total composition. If the content of the component (F) per 100 parts by weight of the total composition is 0.5 parts by weight or less, the metallic texture of a molded article produced from the resin composition may be significantly reduced, while if the content is 3 parts by weight or more, the impact strength of the molded article may be reduced.

[0024] In one embodiment, the (F) component may be contained in an amount of, for example, more than 0.5 parts by weight, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, or 1 part by weight or more, or may be contained in an amount of less than 3 parts by weight, 2.9 parts by weight or less, 2.8 parts by weight or less, 2.7 parts by weight or less, 2.6 parts by weight or less, or 2.5 parts by weight or less, relative to 100 parts by weight of the total amount of the thermoplastic resin composition of the present invention, but is not particularly limited to these amounts.

[0025] The above components are described in more detail below.

[0026] (A) Polycarbonate resin The polycarbonate resin contained in the resin composition of the present invention is preferably an aromatic polycarbonate resin, but there are no particular limitations on the type of polycarbonate resin as long as the technical idea of ​​the present invention can be realized, and any thermoplastic aromatic polycarbonate resin conventionally used in this field can be used.

[0027] In one embodiment, the aromatic polycarbonate resin can be produced from a dihydric phenol, a carbonate precursor, and a molecular weight modifier. The dihydric phenol is one of the monomers constituting the aromatic polycarbonate resin, and is represented by the following formula (1): [ka] (In the formula, X represents a linear, branched, or cyclic alkylene group having no functional group; or a linear, branched, or cyclic alkylene group containing one or more functional groups selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, and isobutylphenyl. More specifically, X may be a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 6 carbon atoms. R1 and R2 each independently represent a halogen atom or an alkyl group, for example, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms); n and m each independently represent an integer of 0 to 4.)

[0028] Non-limiting examples of the dihydric phenol include bisphenol (more specifically, 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A)), hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. Examples of halogenated bisphenols include bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis(4-hydroxyphenyl)decane, and 2-methyl-1,1-bis(4-hydroxyphenyl)propane, with bisphenol A being preferred.

[0029] The carbonate precursor is another monomer that constitutes the aromatic polycarbonate resin, and non-limiting examples thereof include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate, etc., with carbonyl chloride (phosgene) being preferred.

[0030] As the molecular weight modifier, a conventionally known compound, that is, a monofunctional compound similar to the monomer used in the production of a thermoplastic aromatic polycarbonate resin, can be used.

[0031] Non-limiting examples of the molecular weight regulator include phenol derivatives (e.g., p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, p-isononylphenol, etc.), aliphatic alcohols, etc., and preferably p-tert-butylphenol (PTBP) is used.

[0032] Examples of aromatic polycarbonate resins produced from such dihydric phenols, carbonate precursors, and molecular weight modifiers include linear polycarbonate resins, branched polycarbonate resins, copolycarbonate resins, polyester carbonate resins, and silicone copolymer polycarbonates. These resins can be used alone or in combination of two or more.

[0033] The viscosity average molecular weight (Mv, measured in a methylene chloride solution) (g / mol) of the aromatic polycarbonate resin is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and most preferably 20,000 to 30,000. If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 15,000, mechanical properties such as impact strength and tensile strength may decrease, while if it exceeds 40,000, the melt viscosity increases, which may cause problems in resin processing.

[0034] (B) Acrylonitrile-butadiene-styrene resin The resin composition of the present invention can be any acrylonitrile-butadiene-styrene resin that can be applied to metal materials that do not require painting, without any particular limitations. In one embodiment, the acrylonitrile-butadiene-styrene resin may be, but is not limited to, an acrylonitrile-butadiene-styrene (ABS) resin, a modified acrylonitrile-butadiene-styrene (mABS) resin, or a mixture thereof.

[0035] (C) Flame retardants The flame retardant contained in the resin composition of the present invention may be a non-halogen flame retardant, more specifically, a phosphorus-based flame retardant.

[0036] In one embodiment, non-limiting examples of the phosphorus-based flame retardant include phosphate ester compounds, and more specifically, compounds represented by the following formula (2): [ka] (Wherein R1, R2, R3 and R4 are each independently C1-C8 alkyl, C5-C6 cycloalkyl, C6-C 20 Aryl or C7-C 20 and aralkyl. Particularly preferred aryl groups are cresyl, phenyl, hexylenyl, propylphenyl, and butylphenyl. n may independently be 0 or 1, and is preferably 1. N is 0 to 10, preferably 0.3 to 8, and more preferably 0.5 to 5. X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms, and is preferably diphenylphenol, bisphenol A, resorcinol, or hydroquinone.

[0037] The phosphate ester compound is preferably represented by the following formula (3): [ka] (wherein R1, R2, R3, R4, n, and N are as defined in formula (2), and Y is C1-C7 alkylidene, C1-C7 alkylene, C5-C 12 Cycloalkylene, C5-C 12 Y represents cycloalkylidene, -O-, -S-, -SO-, -SO2- or -CO-, and a represents an integer of 0 to 2. Y is preferably a C1-C7 alkylidene, more preferably isopropylidene or methylene.

[0038] The phosphoric acid ester compound that can be used as the phosphorus-based flame retardant in the present invention may be a monophosphate (N=0), an oligophosphate (N=1 to 10), or a mixture of monophosphate and oligophosphate.

[0039] In one embodiment, the phosphorus-based flame retardant may be one or more selected from resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), and N,N'-bis[di-(2,6-xylyl)phosphoryl]-piperazine.

[0040] (D) Coal ash filler Coal ash, generated in thermal power plants, is a combustion waste product generated by the combustion of pulverized coal. Coal ash generally accumulates on the floor and walls of the combustion chamber and is divided into bottom ash, which is collected from the bottom of the combustion chamber, and fly ash, which is collected from the exhaust gas.

[0041] The coal ash used in the present invention means powdered fly ash, and the fly ash produced by coal combustion can be classified or pulverized according to particle size before use.

[0042] The coal ash is a spherical particle, and spherical particles also include particles that are not perfectly spherical. In one embodiment, the coal ash includes particles having an aspect ratio (longest diameter / shortest diameter of a particle) of 1 to 1.8, and particles having such an aspect ratio may account for 80% or more of the total number of particles. The particle shape can be measured and evaluated by a conventional method in this technical field, for example, by analyzing images taken with a scanning electron microscope (SEM).

[0043] In one embodiment, the coal ash may have an average particle size of 0.1 μm to 50 μm, more preferably 5 μm to 25 μm. If the particle size is too small, weld lines may become noticeable in injection-molded products, while if the particle size is too large, the unnotched impact strength may decrease to 40 or less.

[0044] The average particle size can be measured by a conventional method in the art, for example, a laser diffraction particle size distribution measurement method or image analysis.

[0045] In one embodiment, the coal ash may be surface-treated with a silane coupling agent, which may be selected from, but is not limited to, alkyl silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, and sulfide silane coupling agents.

[0046] Examples of the alkylsilane coupling agent include, but are not limited to, methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltriethoxysilane, decylmethyldiethoxysilane, and octadecyltriethoxysilane.

[0047] Examples of the aminosilane coupling agent include, but are not limited to, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

[0048] Examples of the epoxy silane coupling agent include, but are not limited to, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, glycidylbutyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0049] Examples of the vinyl silane coupling agent include, but are not limited to, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane.

[0050] Examples of the styrylsilane coupling agent include, but are not limited to, p-styryltrimethoxysilane.

[0051] Examples of the acrylate silane coupling agent include, but are not limited to, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane.

[0052] Examples of the ureidosilane coupling agent include, but are not limited to, 3-ureidopropyltriethoxysilane.

[0053] Examples of the mercaptosilane coupling agent include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane.

[0054] The isocyanate silane coupling agent may be, but is not limited to, 3-isocyanate propyl trimethoxy silane.

[0055] Examples of the sulfide silane coupling agent include, but are not limited to, bis(triethoxysilylpropyl) disulfide and bis(triethoxysilylpropyl) tetrasulfide.

[0056] In one embodiment, in order to improve the compatibility of coal ash with resin, the silane coupling agent may be used in an amount of 0.01 to 0.1% by weight based on the total weight of coal ash, but is not particularly limited thereto.

[0057] (E) Block copolymer containing (meth)acrylic acid ester units The resin composition of the present invention can be any block copolymer containing (meth)acrylic acid ester units that can be applied to metal materials that do not require painting, without any particular limitations.

[0058] In one embodiment, the (meth)acrylic acid ester may be, but is not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl acrylate, nonyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate, or a combination thereof.

[0059] In one embodiment, the block copolymer may include a block including a methacrylate-based unit and a block including an acrylate-based unit.

[0060] In one embodiment, the block copolymer may be an XYX type, YXY type, (XY)n type, (YX)nY type, or X(YX)n type block copolymer, where X and Y are polymer blocks and n is an integer.

[0061] In one embodiment, the block copolymer may be an XYX triblock copolymer. The X block is a hard block having a higher glass transition temperature (Tg) than the Y block, and the Y block is a soft block having a lower glass transition temperature (Tg) than the X block. In one embodiment, the Tg of the X hard block may be 30°C or higher or 50°C or higher, and the Tg of the Y soft block may be 0°C or lower or -20°C or lower.

[0062] In the XYX triblock copolymer, both outer X's may be the same or different and may contain methacrylic acid ester units. The methacrylic acid ester may be, for example, but not limited to, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, or a combination thereof. In the XYX triblock copolymer, Y may contain acrylic acid ester units. The acrylic acid ester may be, for example, but not limited to, n-butyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, or a combination thereof.

[0063] In one embodiment, in the XYX triblock copolymer, X may comprise poly(methyl methacrylate) and Y may comprise n-butyl acrylate-derived units. For example, the block copolymer may be a poly(methyl methacrylate)-poly(n-butyl acrylate)-poly(methyl methacrylate) triblock copolymer.

[0064] In one embodiment, the weight average molecular weight (g / mol) of the block copolymer is 10 3 ~107 More specifically, 10 4 ~10 6 It may be, but is not limited to these.

[0065] The block copolymer is a commercially available product, and examples of such commercially available products include Nanostrength M51, M52, M53, M22, 52N, 22N, and SM4032XM10 manufactured by Arkema, and KURARITY LA1114, LA2140e, LA2330, LA2250, and LA4285 manufactured by Kuraray.

[0066] (F) Plate-shaped metal particles The material of the plate-shaped metal particles contained in the resin composition of the present invention is not particularly limited, and the material of the metal particles may be selected depending on the metallic appearance required for the molded product to which the thermoplastic resin composition of the present invention is applied.

[0067] In one embodiment, the plate-shaped metal particles may be any metal or alloy of any two or more metals, specifically, but not limited to, aluminum or an aluminum-based alloy. The surfaces of the metal particles may be coated or surface-treated, and in this case, silica or a silane-based coupling agent may be used as the coating or surface treatment agent, but is not limited to these.

[0068] In one embodiment, the average particle size of the plate-like metal particle component may be, but is not limited to, 1 to 100 μm, more specifically 10 to 90 μm, and even more specifically 15 to 70 μm.

[0069] In one embodiment, the thickness of the plate-shaped metal particle component may be 0.2 to 1 μm, more specifically 0.4 to 1 μm, but is not particularly limited thereto. In one embodiment, the aspect ratio of the plate-shaped metal particle component may be 8 to 120.

[0070] Further optional ingredients that can be used In addition to the components described above, the resin composition of the present invention may further contain one or more other additives conventionally used in thermoplastic resin compositions.

[0071] In one embodiment, the resin composition of the present invention may further include a fluidizing agent to improve the fluidity of the composition to improve the metallic texture and workability.

[0072] The fluidizing agent is not particularly limited as long as it is applicable to the thermoplastic resin composition, and examples thereof include, but are not limited to, methyl methacrylate-based compounds, naphthalene-based compounds, lignin-based compounds, ethylene vinyl acetate-based compounds, melamine-based compounds, polycarboxylic acid-based compounds, and mixtures of two or more thereof.

[0073] When the resin composition of the present invention further contains the fluidizing agent, the content thereof may be, for example, 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more, relative to 100 parts by weight of the total amount of the composition, or 5 parts by weight or less, 4.5 parts by weight or less, or 4 parts by weight or less, but is not particularly limited to these.

[0074] In one embodiment, the resin composition of the present invention may further include a light diffusing agent.

[0075] The light diffusing agent contained in the resin composition of the present invention may be organic or inorganic particles. More specifically, the organic particles may be acrylic (e.g., methyl methacrylate (MMA)-based) crosslinked particles, silicone crosslinked particles, styrene crosslinked particles, or a mixture of two or more thereof. The inorganic particles may be, but are not limited to, calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, mica particles, magnesium oxide particles, zinc oxide particles, or a mixture of two or more thereof. The organic particles and inorganic particles may be used alone or in combination.

[0076] In one embodiment, the average particle size of the light diffusing agent component may be 3 to 60 μm, more specifically 3 to 20 μm, even more specifically 3 to 10 μm, and even more specifically 3 to 5 μm.

[0077] When the resin composition of the present invention further contains the light diffusing agent, the content thereof may be, for example, 0.05 to 5 parts by weight, more specifically 0.5 to 2 parts by weight, relative to 100 parts by weight of the total amount of the composition, but is not particularly limited thereto.

[0078] In addition to the above-mentioned components, the resin composition of the present invention may further contain one or more additives conventionally used in thermoplastic resin compositions for injection molding or extrusion molding. The resin composition of the present invention may further contain one or more additives selected from the group consisting of inorganic fillers, antioxidants, lubricants, UV absorbers, light stabilizers, impact modifiers, quenchers, mold release agents, nucleating agents, antistatic agents, pigments, dyes, or mixtures of two or more thereof.

[0079] Specifically, the inorganic filler may be plate glass, mica, graphite, talc, pearl particles, wollastonite, TiO2, or a combination thereof, and more specifically, TiO2. The inorganic filler may have an average particle size of 10 to 200 μm and a thickness of 0.1 to 10 μm.

[0080] Specifically, the antioxidant may be a phenol-based compound, a phosphite-based compound, a thioester-based compound, or a mixture of two or more of these.

[0081] Specifically, the lubricant may be a polyethylene-based compound, an ethylene-ester-based compound, an ethylene glycol-glycerin ester-based compound, a montan-based compound, an ethylene glycol-glycerin montanic acid ester-based compound, or a mixture of two or more of these.

[0082] As the ultraviolet absorber, commercially available ones can be used without any particular limitation.

[0083] Specifically, the light stabilizer may be a benzotriazole-based compound, a hydroxyphenyltriazine-based compound, a pyrimidine-based compound, a cyanoacrylate-based compound, or a mixture of two or more of these compounds.

[0084] Specifically, the quencher may be inorganic or organic particles. More specifically, the inorganic quencher may be silica, magnesium oxide, zirconia, alumina, titania, or a mixture of two or more thereof. The organic particle quencher may be a cross-linked vinyl copolymer. The monomer of the vinyl copolymer may be one or more selected from styrene, acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc.

[0085] The content of the other additives is not particularly limited, and may be any amount that can impart additional functionality to the thermoplastic resin composition of the present invention without impairing the desired physical properties. For example, the content of the other additives may be 0.05 to 5 parts by weight, more specifically 0.5 to 2 parts by weight, relative to 100 parts by weight of the total amount of the composition, but is not particularly limited thereto.

[0086] In one embodiment, the thermoplastic resin composition of the present invention may have a flop index (metallic texture (Flop index)) of 12 or more (for example, 12 to 18).

[0087] In one embodiment, the thermoplastic resin composition of the present invention can exhibit flame retardancy of V-0 at a thickness of 1.5 mm in a UL94 flame retardancy test.

[0088] In one embodiment, the thermoplastic resin composition of the present invention may have an impact strength (Izod, unnotched type) measured in accordance with ASTM D256 of 70 kgf*cm / cm or more (e.g., 70 to 100 kgf*cm / cm), more specifically 80 kgf*cm / cm or more (e.g., 80 to 100 kgf*cm / cm).

[0089] In one embodiment, the thermoplastic resin composition of the present invention has a molding shrinkage of 0.3% or less as measured on a 3 mm test piece in accordance with ASTM D955, and exhibits excellent dimensional stability.

[0090] According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

[0091] The molded article may be an extrusion molded article of the thermoplastic resin composition of the present invention, or an injection molded article obtained by injection molding, and more preferably an injection molded article.

[0092] The present invention will be described in more detail below with reference to the following examples, which, however, are not intended to limit the scope of the present invention.

[0093] Examples and Comparative Examples The components used in the present examples and comparative examples are as follows: (A): Aromatic polycarbonate resin produced from bisphenol A and phosgene (melt index: 34 g / 10 min, viscosity average molecular weight: 17,000) (TRIREX 3017PJ, manufactured by SAMYANG CORPORATION) (B): Acrylonitrile-butadiene-styrene (ABS) resin (melt index (220°C / 10 kg): 35) (Terluran (registered trademark) GP-35, manufactured by BASF) (C): Non-halogen phosphorus flame retardant (metal phosphinate) (Exolit OP1240, manufactured by Clariant) (D): Long-chain alkylsilane-treated spherical porous coal ash (average particle size: 25 μm, recycled product, manufactured by Yedam Chemical Co., Ltd.) (D-Comp.): Talc (E): Block copolymer containing (meth)acrylic acid ester units (linear methyl methacrylate / butyl acrylate triblock copolymer) (LA4285, manufactured by Kurary Co., Ltd.) (E-Comp.): Core / shell structured methacrylate-butadiene-styrene (MBS) impact modifier (EM500, manufactured by LG Chem) (F): Amorphous plate-shaped aluminum particles (average particle size: 20 μm) (manufactured by Eckart) (F-Comp.1): Spherical aluminum particles (average particle size: 30μm) (manufactured by Silver-line) (F-Comp.2): Spherical glass bead particles (average particle size: 100 μm)

[0094] Examples 1 to 11 and Comparative Examples 1 to 16 The components shown in Table 1 below were mixed and uniformly dispersed in a Henschel mixer. The mixture was then extruded in a twin-screw melt mixer with an L / D of 48 mm and a diameter of 25 mm under the following conditions: melt temperature of 220°C, screw rotation speed of 200 rpm, first vent pressure of approximately -600 mmHg, and self-feed rate of 20 kg / h. The extruded strand was cooled in water and then cut with a rotary cutter to produce pellets. The pellets were dried with hot air at 70-90°C for 4 hours and then injection molded at 260-280°C to produce test specimens. Rectangular multi-layer test specimens measuring 900 mm x 650 mm were prepared for evaluation of metallic texture and appearance (weld line).

[0095] Physical property evaluation The physical properties of each of the prepared specimens were measured or evaluated by the following methods, and the results are shown in Table 2 below.

[0096] (1) Metallic texture The flop index (metallic texture) was measured using a BYK-Maci spectrophotometer manufactured by BYK. Specifically, the luminance of reflected light at angles of 15°, 45°, and 110° was measured for a normal region and a weld region of the injection-molded specimens manufactured from the thermoplastic resin compositions of the Examples and Comparative Examples, and the flop index was calculated by substituting the results into the following equation (1):

number

[0097] The flop index of an object surface without a metallic texture is 0, the flop index of an actual metallic surface is 15 or more (e.g., 15-17), and the flop index of a surface that can be recognized as metallic with the naked eye is 6.5 or more. A flop index of 12 or more is considered to have achieved the desired level of metallic texture.

[0098] FIG. 3 is a photograph showing the flop index values ​​measured on the surface of a metal surface, and the metal texture can be seen according to the flop index value.

[0099] (2) Appearance evaluation (weld line) Appearance was evaluated by visual observation. Specifically, 10 subjects visually observed the weld lines of injection-molded specimens manufactured from the thermoplastic resin compositions of the Examples and Comparative Examples, and evaluated them on a scale of 1 to 5, with the average score of the 10 subjects recorded. A higher score indicates a thicker and darker weld line and poorer appearance. A score of 2 or less is considered to have achieved the desired level of appearance.

[0100] FIG. 1 is a diagram showing a state in which flow marks and weld lines occur in a molded product when a conventional resin composition containing only plate-shaped metal particles is injection molded (left diagram), and a state in which flow marks and weld lines do not occur or are reduced when a resin composition containing both plate-shaped metal particles and coal ash filler (spherical) according to one embodiment of the present invention is injection molded (right diagram). FIG. 2 shows photographs of appearance examples corresponding to appearance evaluation (weld line) scores of 1 to 5, respectively.

[0101] (3) Dimensional stability To evaluate the dimensional stability of injection-molded specimens prepared from the thermoplastic resin compositions of the Examples and Comparative Examples, the mold shrinkage (unit: %) of 3 mm specimens was measured in accordance with ASTM D955. Specifically, specimens measuring 350 mm (width) x 100 mm (length) x 3 mm thick were injection-molded under the same conditions as above and left in an atmosphere of 23°C and 50% relative humidity for 24 hours. The mold shrinkage was then measured and calculated using a 3D measuring device. It was considered that the lower the mold shrinkage, the better the dimensional stability.

[0102] (4) Flame retardancy Measurements were carried out using a 1.5mm thick test piece based on the UL94 V test method.

[0103] (5) Heat resistance The heat distortion temperature (HDT, unit: °C) was measured according to ASTM D648.

[0104] (6) Impact strength (kgf*cm / cm) The impact strength (Izod, unnotched type) of the injection molded specimens produced from the thermoplastic resin compositions of the Examples and Comparative Examples was measured in accordance with ASTM D256.

[0105] (7) Flow index (g / 10 min) Flow index (MI) was calculated according to ASTM D1238 by measuring the amount of resin composition that flows out in 5 minutes at 300°C using a 1.2 kg weight.

[0106] [Table 1]

[0107] [Table 2]

[0108] As is clear from Table 2, the resin compositions of Examples 1 to 11 according to the present invention all had excellent metallic texture (flop index value of 12 or more) and appearance (weld line score of 2 or less), while also maintaining a good balance in dimensional stability (mold shrinkage of 0.3% or less), flame retardancy (V-0 grade), heat resistance (heat distortion temperature of 80°C or more), unnotched impact strength (70 kgf*cm / cm or more), and flow index (35 or more). In contrast, the compositions of Comparative Examples 1 to 16 were inferior to the Examples in one or more of the measured physical properties, and in particular, the metallic texture, appearance (weld line score), dimensional stability, flame retardancy, heat resistance, and impact strength were unbalanced compared to the Examples, which may have significantly reduced the various properties of the final product.

Claims

1. A thermoplastic resin composition with a metallic texture, (A) a polycarbonate resin; (B) an acrylonitrile-butadiene-styrene resin; (C) a flame retardant; (D) a coal ash filler; (E) a block copolymer containing a (meth)acrylic acid ester-based unit; and (F) plate-like metal particles; Based on 100 parts by weight of the total amount of the composition, The content of the component (A) is more than 41.5 parts by weight and less than 71 parts by weight, The content of the (B) component is more than 5 parts by weight and less than 20 parts by weight, The content of the (C) component is more than 9 parts by weight and less than 17 parts by weight, The content of the (D) component is more than 8 parts by weight and less than 20 parts by weight, The content of the component (E) is more than 1 part by weight and less than 8 parts by weight, The content of the (F) component is more than 0.5 parts by weight and less than 3 parts by weight. Thermoplastic resin composition.

2. 2. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin.

3. 2. The thermoplastic resin composition according to claim 1, wherein the acrylonitrile-butadiene-styrene resin is an acrylonitrile-butadiene-styrene resin, a modified acrylonitrile-butadiene-styrene resin, or a mixture thereof.

4. 2. The thermoplastic resin composition according to claim 1, wherein the flame retardant is a non-halogen flame retardant.

5. 2. The thermoplastic resin composition according to claim 1, wherein the coal ash filler is treated with an alkylsilane.

6. The thermoplastic resin composition according to claim 1, wherein the block copolymer containing a (meth)acrylic acid ester unit is a triblock copolymer of poly(methyl methacrylate) / poly(n-butyl acrylate) / poly(methyl methacrylate).

7. 2. The thermoplastic resin composition according to claim 1, wherein the plate-like metal particles are aluminum or an aluminum-based alloy.

8. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7.

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