Metallic thermoplastic resin composition containing mineral filler and molded article containing same

Abstract

The present invention relates to a metallic thermoplastic resin composition comprising a mineral filler, and a molded article comprising the same, and more particularly, to a metallic thermoplastic resin composition comprising a mineral filler, the present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition comprising a polycarbonate resin, an acrylonitrile-butadiene-styrene resin, a flame retardant, a fly ash filler, a block copolymer comprising (meth) acrylate derived units, and sheet-like metal particles in combination at a specific content ratio, and exhibiting an excellent appearance due to excellent metallic texture and reduced weld lines during injection molding, the thermoplastic resin composition can provide a molded article having an excellent balance of dimensional stability, flame retardancy, impact resistance, and heat resistance, and a molded article comprising the same.

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition containing a mineral filler and having a metallic texture, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition containing a polycarbonate resin, an acrylonitrile-butadiene-styrene resin, a flame retardant, a fly ash filler, a block copolymer containing (meth)acrylate-derived units, and flaky metal particles in a specific content ratio. During injection molding, the composition exhibits an excellent appearance due to its excellent metallic texture and reduced weld lines, and can provide a molded article having an excellent balance of dimensional stability, flame retardancy, impact resistance, and heat resistance, and a molded article containing the composition. Background Art

[0002] One application area for metallic thermoplastic resins is injection molding. Typically, thermoplastic resins are injection molded into a variety of products, including electronic and electrical products and automotive parts, and delivered to consumers.

[0003] Injection-molded products with a metallic texture are usually designed after injection molding through post-processing such as painting. This is not only basically uneconomical due to the additional painting processing costs, but also increases manufacturing costs due to masking, defects, and handling difficulties during post-processing. In addition, the use of volatile organic compounds poses problems that are harmful to humans and the environment.

[0004] Therefore, demand is increasing for environmentally friendly, paint-free materials—materials that achieve a metallic appearance similar to that achieved with metal coatings without requiring a coating process. Consequently, development of metallic materials that incorporate metal particles within thermoplastic resins is ongoing. Furthermore, as molded products used in electronic devices such as televisions become thinner, there is a growing demand for dimensional stability and high impact strength.

[0005] To improve the appearance of metallic, unpainted molded products made from compositions containing metal particles added to thermoplastic base resins, attempts have been made to reduce flow marks and weld lines by increasing the affinity between the base resin and the metal particles. However, these molded products suffer from deficiencies in impact resistance, flame retardancy, and heat resistance, particularly poor dimensional stability. This limits their application in components such as back cases and bezels for increasingly thinner and more complex television designs.

[0006] As an alternative, attempts have been made to form a metallic layer on the molded product through double injection molding or extrusion to achieve a metallic appearance and improve mechanical properties. However, this method has the problem of increased processing costs and a significant reduction in product design freedom due to the double processing and its pre-treatment work. Summary of the Invention

[0007] (1) Technical issues to be resolved

[0008] An object of the present invention is to provide a thermoplastic resin composition and a molded article containing the same, wherein the thermoplastic resin composition has a metallic texture similar to that of metal-coated products without coating, exhibits an appearance with reduced flow marks and weld lines, and exhibits excellent balanced dimensional stability, flame retardancy, impact resistance, and heat resistance.

[0009] (2) Technical solution

[0010] One aspect of the present invention is to provide a metallic thermoplastic resin composition, which comprises: (A) a polycarbonate resin; (B) an acrylonitrile-butadiene-styrene resin; (C) a flame retardant; (D) a fly ash filler; (E) a block copolymer containing (meth)acrylate-derived units; and (F) flaky metal particles. Based on 100 parts by weight of the total composition, the content of the component (A) is greater than 41.5 parts by weight and less than 71 parts by weight, the content of the component (B) is greater than 5 parts by weight and less than 20 parts by weight, the content of the component (C) is greater than 9 parts by weight and less than 17 parts by weight, the content of the component (D) is greater than 8 parts by weight and less than 20 parts by weight, the content of the component (E) is greater than 1 part by weight and less than 8 parts by weight, and the content of the component (F) is greater than 0.5 parts by weight and less than 3 parts by weight.

[0011] According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

[0012] (3) Beneficial effects

[0013] When the thermoplastic resin composition of the present invention is injection molded, the distribution of flaky metal particles on the surface of the molded product increases, and the spherical fly ash reduces weld lines, thereby providing the molded product with an excellent metallic appearance while also improving its dimensional stability, flame retardancy, impact resistance, and heat resistance. Therefore, it can be very useful in molded products that require an unpainted metallic appearance and excellent physical properties, such as TV back covers or frames. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The diagram schematically illustrates the situation in which a conventional resin composition containing only flaky metal particles produces flow marks and weld lines when injection-molded (left figure), and the situation in which a resin composition containing flaky metal particles and a fly ash filler (spherical) according to one embodiment of the present invention produces no or fewer flow marks and weld lines when injection-molded (right figure).

[0015] Figure 2These are photographs of exemplary appearances corresponding to scores of 1 to 5 in the appearance evaluation (weld line) performed in Examples and Comparative Examples of the present invention.

[0016] Figure 3 These are photos showing the measured sparkle indices for various metallic surfaces, allowing users to verify the differences in metallic textures based on the sparkle index values. DETAILED DESCRIPTION

[0017] The present invention is described in detail below.

[0018] 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 fly ash filler; (E) a block copolymer comprising (meth)acrylate-derived units; and (F) flake metal particles.

[0019] The thermoplastic resin composition of the present invention comprises a 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 component (A) is less than 41.5 parts by weight of the total composition, the metallic texture of a molded article made from the resin composition may be reduced, weld lines may increase, the appearance may deteriorate, and dimensional stability may also deteriorate. Conversely, if the content of component (A) is greater than 71 parts by weight, the weld lines of the molded article may increase significantly, the appearance may deteriorate significantly, and the impact strength may also be very poor.

[0020] In a specific embodiment, the component (A) may be contained in an amount of 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, based on 100 parts by weight of the total thermoplastic resin composition of the present invention, and 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 thereto.

[0021] 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 composition. If the content of the component (B) is 5 parts by weight or less, the impact strength of a molded article made from the resin composition may be very poor. Conversely, if the content of the component (B) is 20 parts by weight or more, the impact strength of the molded article may be very poor.

[0022] In a specific embodiment, the component (B) may be included in an amount of 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, based on 100 parts by weight of the total thermoplastic resin composition of the present invention. The component (B) may also be included 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, but is not particularly limited thereto.

[0023] 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, the flame retardancy of a molded article made from the resin composition may be very poor. Conversely, if the content of the component (C) is 17 parts by weight or more, the impact strength of the molded article may be very poor, and the heat resistance may also be deteriorated.

[0024] In a specific embodiment, the component (C) may be contained in an amount of 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, based on 100 parts by weight of the total thermoplastic resin composition of the present invention, and 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 thereto.

[0025] The thermoplastic resin composition of the present invention contains the fly 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 less than 8 parts by weight per 100 parts by weight of the total composition, the weld line of a molded article made from the resin composition will increase dramatically, significantly deteriorating its appearance, and potentially also significantly reducing its dimensional stability and impact strength. Conversely, if the content of the component (D) is greater than 20 parts by weight, the molded article will have a very low metallic feel and may also suffer from poor impact strength.

[0026] In a specific embodiment, the component (D) may be contained in an amount of 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, based on 100 parts by weight of the total thermoplastic resin composition of the present invention, and 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, but is not particularly limited thereto.

[0027] The thermoplastic resin composition of the present invention comprises the block copolymer component (E) comprising (meth)acrylate-derived units in an amount of greater than 1 part by weight and less than 8 parts by weight, based on 100 parts by weight of the total composition. If the content of the component (E) is less than 1 part by weight per 100 parts by weight of the total composition, the impact strength of a molded article made from the resin composition may be significantly poor. Conversely, if the content of the component (E) is greater than 8 parts by weight, the flame retardancy and heat resistance of the molded article may be significantly poor, and the dimensional stability may also be deteriorated.

[0028] In a specific embodiment, the component (E) may be contained in an amount of 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, and 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, based on 100 parts by weight of the thermoplastic resin composition of the present invention, but is not particularly limited thereto.

[0029] The thermoplastic resin composition of the present invention contains the flaky metal particles (F) in an amount of more than 0.5 parts by weight and less than 3 parts by weight, based on 100 parts by weight of the total composition. If the content of the component (F) is 0.5 parts by weight or less, the metallic texture of a molded article made from the resin composition may be very low. Conversely, if the content of the component (F) is 3 parts by weight or more, the impact strength of the molded article may be deteriorated.

[0030] In a specific embodiment, the component (F) may be contained in an amount of 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, and 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, based on 100 parts by weight of the thermoplastic resin composition of the present invention, but is not particularly limited thereto.

[0031] The above components are described in more detail below.

[0032] (A) Polycarbonate resin

[0033] The polycarbonate resin contained in the resin composition of the present invention is preferably an aromatic polycarbonate resin, but its type is not particularly limited as long as the technical concept of the present invention can be achieved. Thermoplastic aromatic polycarbonate resins commonly used in the art can be used.

[0034] In a specific embodiment, the aromatic polycarbonate resin can be prepared from dihydric phenol, a carbonate precursor, a molecular weight regulator, etc. The dihydric phenol, as one of the monomers constituting the aromatic polycarbonate resin, can be a substance represented by the following chemical formula 1.

[0035] [Chemical Formula 1]

[0036]

[0037] In the chemical formula 1, 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 sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, or isobutylphenyl. More specifically, X can 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 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 independently represent integers from 0 to 4.

[0038] Non-limiting examples of the dihydric phenols 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, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and the like. Phenol, 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, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, and the like can be preferably used.

[0039] Non-limiting examples of the carbonate precursor as another monomer constituting the aromatic polycarbonate resin include phosgene, phosgene bromide, bishaloformates, diphenyl carbonate, dimethyl carbonate, etc. Preferably, phosgene can be used.

[0040] The molecular weight regulator can be a substance known in the art, that is, a monofunctional compound similar to the monomers used in the preparation of thermoplastic aromatic polycarbonate resins. Non-limiting examples of the molecular weight regulator include phenol-based derivatives (e.g., p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, p-isononylphenol, etc.), aliphatic alcohols, etc., and p-tert-butylphenol (PTBP) can be preferably used.

[0041] The aromatic polycarbonate resin prepared from the dihydric phenol, carbonate precursor and molecular weight modifier described above may be, for example, linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin, polyester carbonate resin, silicone copolycarbonate, etc., used alone or in combination of two or more.

[0042] The aromatic polycarbonate resin preferably has a viscosity-average molecular weight (Mv, measured in a methylene chloride solution) (g / mol) of 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 be reduced. If the viscosity-average molecular weight exceeds 40,000, problems may arise in resin processing due to increased melt viscosity.

[0043] (B) Acrylonitrile-butadiene-styrene resin

[0044] The acrylonitrile-butadiene-styrene resin contained in the resin composition of the present invention can be used without limitation as long as it can be used as an uncoated metallic material.

[0045] In a specific embodiment, the acrylonitrile-butadiene-styrene resin may be acrylonitrile-butadiene-styrene (ABS) resin, modified acrylonitrile-butadiene-styrene (mABS) resin or a mixture thereof, but is not particularly limited thereto.

[0046] (C) Flame retardant

[0047] The flame retardant included in the resin composition of the present invention may be a halogen-free flame retardant, and more specifically, may be a phosphorus-based flame retardant.

[0048] In a specific embodiment, non-limiting examples of the phosphorus-based flame retardant include phosphate compounds, more specifically, phosphate compounds represented by the following Chemical Formula 2:

[0049] [Chemical Formula 2]

[0050]

[0051] In the chemical formula 2, R1, R2, R3 and R4 are independently C1-C8 alkyl, C5-C6 cycloalkyl, C6-C 20 Aryl or C7-C 20 Aralkyl. Particularly preferred aryl groups are cresol, phenyl, xylyl, propylphenyl, or butylphenyl. n can independently be 0 or 1, preferably 1. N is 0 to 10, preferably 0.3 to 8, and more preferably 0.5 to 5. X is a mononuclear aromatic group or a polynuclear aromatic group having 6 to 30 carbon atoms, preferably diphenylphenol, bisphenol A, resorcinol, or hydroquinone.

[0052] The phosphate compound is also preferably a phosphate compound of the following Chemical Formula 3:

[0053] [Chemical Formula 3]

[0054]

[0055] In the chemical formula 3, R1, R2, R3, R4, n and N are as defined in the chemical formula 8, and Y represents a C1-C7 alkylene, a C1-C7 alkylene, a C5-C 12 Cycloalkylene, C5-C 12 Cycloalkylene, -O-, -S-, -SO-, -SO2- or -CO-, a represents an integer from 0 to 2. Preferably, Y is a C1-C7 alkylene, more preferably an isopropylidene or methylene group.

[0056] The phosphate compound that can be used as the phosphorus-based flame retardant in the present invention can be a monophosphate (N=0), an oligophosphate (N=1-10), or a mixture of a monophosphate and an oligophosphate.

[0057] In a specific embodiment, the phosphorus-based flame retardant may be one or more selected from resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or N,N′-bis[di-(2,6-xylyl)phosphoryl]-piperazine.

[0058] (D) Fly ash filler

[0059] The ash produced by thermal power plants is a combustion waste generated by the combustion of pulverized coal. It is generally divided into bottom ash, which is deposited on the bottom or wall of the combustion chamber and collected in the lower part of the combustion chamber, and fly ash, which is collected from the exhaust gas.

[0060] The fly ash used in the present invention refers to fly ash in a powdery state, and the fly ash generated by coal combustion can be used after being classified or pulverized according to particle size.

[0061] The fly ash is spherical, including particles that are not completely spherical. In one embodiment, the fly ash includes particles having an aspect ratio (longest diameter / shortest diameter) of 1 to 1.8, and the proportion of particles having such an aspect ratio in the total number of particles can be greater than 80%. The particle shape can be measured and evaluated by conventional methods in the art, for example, by analyzing images captured by a scanning electron microscope (SEM).

[0062] In a specific embodiment, the average particle size of the fly ash may be 0.1 μm to 50 μm, more preferably 5 μm to 25 μm. If the particle size is too small, weld lines may be noticeable on the injection molded product. Conversely, if the particle size is too large, the unnotched impact strength may drop below 40.

[0063] The average particle size can be measured by conventional methods in the art, for example, by laser diffraction particle size distribution measurement or image analysis.

[0064] In a specific embodiment, the fly ash may be surface-treated with a silane coupling agent. The silane coupling agent may be, for example, one selected from an alkyl silane coupling agent, an amino silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, a styryl silane coupling agent, an acrylate silane coupling agent, a urea silane coupling agent, a mercapto silane coupling agent, an isocyanate silane coupling agent, and a sulfide silane coupling agent, but is not particularly limited thereto.

[0065] Examples of the alkylsilane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltriethoxysilane, decylmethyldiethoxysilane, octadecyltriethoxysilane, and the like, but are not particularly limited thereto.

[0066] Examples of the aminosilane coupling agent include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, but are not particularly limited thereto.

[0067] Examples of the epoxy silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, glycidylbutyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0068] Examples of the vinylsilane coupling agent include vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and the like, but are not particularly limited thereto.

[0069] Examples of the styrylsilane coupling agent include p-styryltrimethoxysilane, but are not particularly limited thereto.

[0070] Examples of the acrylic silane coupling agent include, but are not limited to, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane.

[0071] Examples of the ureidosilane coupling agent include 3-ureidopropyltriethoxysilane, but are not particularly limited thereto.

[0072] Examples of the mercaptosilane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane, but are not particularly limited thereto.

[0073] Examples of the isocyanate silane coupling agent include 3-isocyanatepropyltrimethoxysilane, but are not particularly limited thereto.

[0074] Examples of the sulfide silane coupling agent include bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide, but are not particularly limited thereto.

[0075] In a specific embodiment, in order to improve the compatibility between fly ash and resin, the silane coupling agent can be used in an amount of 0.01 to 0.1 wt % based on the total weight of the fly ash, but is not particularly limited thereto.

[0076] (E) Block copolymer containing (meth)acrylate-derived units

[0077] The block copolymer containing a (meth)acrylate-derived unit contained in the resin composition of the present invention can be used without limitation as long as it can be applied as an uncoated metallic texture material.

[0078] In a specific embodiment, the (meth)acrylate can be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (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, but is not particularly limited thereto.

[0079] In a specific embodiment, the block copolymer may include blocks comprising methacrylate-derived units and blocks comprising acrylate-derived units.

[0080] In a specific embodiment, the block copolymer may be an XYX type, YXY type, (XY)n type, (YX)nY type or X(YX)n type block copolymer, wherein X and Y are polymer blocks and n represents an integer.

[0081] 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 above 30°C or above 50°C, and the Tg of the Y soft block may be below 0°C or below -20°C.

[0082] In the XYX triblock copolymer, the Xs on both sides may be the same or different and may include methacrylate-derived units. The methacrylate may be, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, or a combination thereof, but is not particularly limited thereto. Furthermore, in the XYX triblock copolymer, Y may include an acrylate-derived unit. In this case, the acrylate may be, for example, n-butyl acrylate, methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, or a combination thereof, but is not particularly limited thereto.

[0083] In a specific embodiment, in the XYX triblock copolymer, X may include polymethyl methacrylate and Y may include n-butyl acrylate derived units. For example, the block copolymer may be a triblock copolymer of polymethyl methacrylate-polyn-butyl acrylate-polymethyl methacrylate.

[0084] In a specific embodiment, the weight average molecular weight (g / mol) of the block copolymer can be 10 3 to 10 7 , more specifically it can be 10 4 to 10 6 , but is not limited to this.

[0085] The block copolymers are commercially available, and such commercial products include, for example, Nanostrength M51, M52, M53, M22, 52N, 22N, and SM4032XM10 from Arkema and KURARITY LA1114, LA2140e, LA2330, LA2250, and LA4285 from Kuraray.

[0086] (F) Flake metal particles

[0087] The material of the flaky metal particles contained in the resin composition of the present invention is not particularly limited, and the material of the metal particles can be selected based on the metallic appearance required for the molded article to which the thermoplastic resin composition of the present invention is applied.

[0088] In a specific embodiment, the flaky metal particles can be any metal or an alloy of two or more metals, specifically aluminum or an aluminum-based alloy, but are not limited thereto. Furthermore, the surface of the metal particles can be coated or surface treated. In this case, silica or a silane-based coupling agent can be used as the coating or surface treatment agent, but are not limited thereto.

[0089] In a specific embodiment, the average particle size of the flaky metal particles is 1-100 μm, more specifically 10-90 μm, and even more specifically 15-70 μm, but is not limited thereto.

[0090] In one embodiment, the thickness of the flaky metal particles may be 0.2-1 μm, more specifically 0.4-1 μm, but is not particularly limited thereto. In one embodiment, the aspect ratio of the flaky metal particles may be 8-120.

[0091] Any additional ingredients you may use

[0092] The resin composition of the present invention may further contain one or more additives commonly used in thermoplastic resin compositions in addition to the above-mentioned components.

[0093] In a specific embodiment, the resin composition of the present invention may further comprise a fluidizing agent in order to increase fluidity, thereby improving metallic texture and processability.

[0094] As the fluidizing agent, any fluidizing agent can be used without limitation as long as it can be applied to the thermoplastic resin composition. For example, methyl methacrylate-based compounds, naphthyl compounds, lignin-based compounds, ethylene-vinyl acetate-based compounds, melamine-based compounds, polycarboxylic acid-based compounds, or a mixture of two or more thereof can be used, but the invention is not particularly limited thereto.

[0095] In the resin composition of the present invention, when the fluidizing agent is further included, it can be included in an amount of, for example, 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more, based on 100 parts by weight of the total composition, and can be included in an amount of 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 thereto.

[0096] In a specific embodiment, the resin composition of the present invention may further include a light diffusing agent.

[0097] The light diffuser that may be included in the resin composition of the present invention may be an organic or inorganic particle. More specifically, the organic particle may be an acrylic (e.g., methyl methacrylate (MMA)-based) crosslinked particle, a silicon-based crosslinked particle, a styrene-based crosslinked particle, or a mixture of two or more thereof. The inorganic particle may be calcium carbonate particles, barium sulfate particles, titanium dioxide particles, aluminum hydroxide particles, silicon dioxide particles, glass particles, mica particles, magnesium oxide particles, zinc oxide particles, or a mixture of two or more thereof, but is not particularly limited thereto. The organic particles and the inorganic particles may be used alone or in combination.

[0098] In a specific embodiment, the average particle size of the light diffuser component may be 3-60 μm, more specifically 3-20 μm, further specifically 3-10 μm, and further specifically 3-5 μm.

[0099] In the resin composition of the present invention, when the light diffusing agent is further included, its content can be, for example, 0.05-5 parts by weight, more specifically 0.5-2 parts by weight, based on 100 parts by weight of the total composition, but is not particularly limited thereto.

[0100] In addition to the above-mentioned components, the resin composition of the present invention may further comprise one or more other additives commonly added to thermoplastic resin compositions for injection molding or extrusion molding. For example, the resin composition of the present invention may further comprise one or more additives selected from inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, light stabilizers, impact enhancers, matting agents, mold release agents, nucleating agents, antistatic agents, pigments, dyes, or mixtures of two or more thereof.

[0101] Specifically, the inorganic filler can be flake glass, mica, graphite, talc, pearl particles, wollastonite, TiO2 or a combination thereof, more specifically TiO2. In addition, the inorganic filler can have an average particle size of 10-200 μm and a thickness of 0.1-10 μm.

[0102] Specifically, the antioxidant may be a phenol-based compound, a phosphite-based compound, a thioester-based compound, or a mixture of two or more thereof.

[0103] Specifically, the lubricant may be a polyethylene-based compound, an ethylene-ester-based compound, an ethylene glycol-glycerol ester-based compound, a lignite-based compound, an ethylene glycol-glycerol montanate-based compound, or a mixture of two or more thereof.

[0104] As the ultraviolet absorber, commercially available products can be used without particular limitation.

[0105] 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 thereof.

[0106] Specifically, the matting agent may be an inorganic matting agent or an organic matting agent. More specifically, the inorganic matting agent may be silicon dioxide, magnesium oxide, zirconium oxide, aluminum oxide, titanium dioxide or a mixture of two or more thereof. The organic matting agent 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 or butyl (meth)acrylate.

[0107] The content of the other additives is not particularly limited and can be used in an amount sufficient to impart additional functionality, within a range that does not impair the desired physical properties of the thermoplastic resin composition of the present invention. For example, the content of each of the other additives can be 0.05-5 parts by weight, more specifically 0.5-2 parts by weight, based on 100 parts by weight of the total composition, but is not particularly limited thereto.

[0108] In a specific embodiment, the thermoplastic resin composition of the present invention may have a Flop index of 12 or more (eg, 12 to 18).

[0109] In a specific embodiment, the thermoplastic resin composition of the present invention can exhibit a flame retardant property of V-0 at a thickness of 1.5 mm in a UL94 flame retardancy test.

[0110] In one embodiment, the thermoplastic resin composition of the present invention may have an impact strength (Izod, Unnotched type) of 70 kgf, as measured according to ASTM D256. cm / cm or more (e.g., 70-100kgf cm / cm), more specifically 80 kgf cm / cm or more (e.g., 80-100kgf cm / cm).

[0111] In a specific embodiment, the thermoplastic resin composition of the present invention has a mold shrinkage of 0.3% or less as measured on a 3 mm specimen according to ASTM D955, exhibiting excellent dimensional stability.

[0112] According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

[0113] The molded article may be an extrusion-molded article or an injection-molded article of the thermoplastic resin composition of the present invention, and is more preferably an injection-molded article.

[0114] Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

[0115] [Examples and Comparative Examples]

[0116] The specific components used in the present examples and comparative examples are as follows.

[0117] (A): Aromatic polycarbonate resin made from bisphenol A and phosgene (melt index: 34 g / 10 min, viscosity average molecular weight: 17,000) (TRIREX 3017PJ, Samyang Corporation)

[0118] (B): Acrylonitrile butadiene styrene (ABS) resin (melt index (220°C / 10kg): 35) (Terluran ® GP-35, BASF

[0119] (C): Halogen-free phosphorus-based flame retardant (metal phosphinate) (Exolit OP1240, Clariant)

[0120] (D): Spherical porous fly ash treated with long-chain alkylsilane (average particle size: 25 μm, recycled product, Yedam Chemical)

[0121] (D-Comp.): Talc

[0122] (E): Block copolymer containing (meth)acrylate-derived units (linear structure methyl methacrylate / butyl acrylate triblock copolymer) (LA4285, Kurary)

[0123] (E-Comp.): Core / shell structured methacrylate-butadiene-styrene (MBS)-based impact enhancer (EM500, LG Chem)

[0124] (F): Amorphous flaky aluminum particles (average particle size: 20 μm) (Eckart)

[0125] (F-Comp.1): Spherical aluminum particles (average particle size: 30 μm) (Silver-line)

[0126] (F-Comp.2): Spherical glass beads (average particle size: 100 μm)

[0127] Examples 1 to 11 and Comparative Examples 1 to 16

[0128] The ingredients in the amounts shown in Table 1 below were mixed and uniformly dispersed using a Henschel mixer. The mixture was then extruded in a twin-screw melt-mixing extruder with an L / D ratio of 48 and a diameter of 25 mm at a melt temperature of 220°C, a screw speed of 200 rpm, a first vent pressure of approximately -600 mmHg, and a feed rate of 20 kg / hour. The extruded strands were cooled in water and then cut into pellets using a rotary cutter. The pellets were then hot-air dried at 70-90°C for 4 hours and injection molded at 260-280°C to produce test specimens. The injection-molded specimens used for evaluation of metallic texture and appearance (weld lines) were rectangular, multi-segment specimens measuring 900 mm x 650 mm.

[0129] Evaluation of physical properties

[0130] The physical properties of the samples prepared above were measured or evaluated by the following methods. The results are shown in Table 2 below.

[0131] (1) Metallic texture

[0132] The Flop Index was measured using a BYK-Mac i spectrophotometer from BYK. Specifically, the luminance of reflected light at angles of 15°, 45°, and 110° was measured for the normal and welded areas of injection-molded specimens made from the thermoplastic resin compositions of Examples and Comparative Examples. The luminance was then substituted into the following formula (1) to calculate the Flop Index.

[0133] [Mathematical formula 1]

[0134]

[0135] L 15° = Brightness of reflected light measured at an angle of 15°

[0136] L 45° = Brightness of reflected light measured at a 45° angle

[0137] L 110° = Brightness of reflected light measured at an angle of 110°

[0138] The sparkle index of a surface without a metallic texture is 0, the sparkle index of an actual metal surface is 15 or higher (e.g., 15 to 17), and the sparkle index of a surface that can be perceived as metallic by the naked eye is 6.5 or higher. A sparkle index of 12 or higher indicates that the desired level of metallic texture has been achieved.

[0139] Figure 3 This is a photograph of the sparkle index measured on a metallic surface. You can confirm the difference in metallic texture based on the sparkle index value.

[0140] (2) Appearance evaluation (weld line)

[0141] Appearance was evaluated visually. Specifically, ten subjects visually observed the weld lines of injection-molded specimens made from the thermoplastic resin compositions of Examples and Comparative Examples and rated them on a scale of 1 to 5. The average of the ten subjects' scores was recorded. Higher scores indicated thicker and more pronounced weld lines and poorer appearance. Scores of 2 or less were considered to have achieved the desired level of appearance.

[0142] Figure 1 The diagram schematically illustrates the occurrence of flow marks and weld lines in injection-molded articles of conventional resin compositions containing only flaky metal particles (left figure), and the occurrence of no or reduced flow marks and weld lines in injection-molded articles of a resin composition containing flaky metal particles and a spherical fly ash filler according to one embodiment of the present invention (right figure). Figure 2The following are photographs of exemplary appearances corresponding to scores of 1 to 5 in the appearance evaluation (weld line).

[0143] (3) Dimensional stability

[0144] To evaluate the dimensional stability of injection-molded specimens made from the thermoplastic resin compositions of the Examples and Comparative Examples, mold shrinkage (%) was measured on 3 mm specimens according to ASTM D955. Specifically, specimens measuring 350 mm (width) x 100 mm (length) x 3 mm thick were injection molded under the same conditions described above. After 24 hours of storage at 23°C and 50% relative humidity, mold shrinkage was measured and calculated using a 3D measuring instrument. Lower mold shrinkage indicates superior dimensional stability.

[0145] (4) Flame retardancy

[0146] According to the UL94V test method, the measurement is performed using a specimen with a thickness of 1.5 mm.

[0147] (5) Heat resistance

[0148] The heat distortion temperature (HDT, unit: °C) was measured according to ASTM D648.

[0149] (6) Impact strength (kgf) cm / cm)

[0150] For injection-molded specimens made from the thermoplastic resin compositions of Examples and Comparative Examples, impact strength (Izod, unnotched type) was measured in accordance with ASTM D256.

[0151] (7) Flow index (g / 10 minutes)

[0152] According to ASTM D1238, the amount of the resin composition that flowed out within 5 minutes was measured using a 1.2 kg weight at 300° C. to calculate the flow index (MI).

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] As shown in Table 2, the resin compositions of Examples 1 to 11 of the present invention all have excellent metallic texture (sparkle index value of 12 or more) and appearance (weld line score of 2 or less), and have good dimensional stability (mold shrinkage of 0.3% or less), flame retardancy (V-0 grade), heat resistance (heat deformation temperature of 80°C or more), and unnotched impact strength (70kgf cm / cm or more) and flow index (35 or more) also exhibited an excellent balance. In contrast, the compositions of Comparative Examples 1 to 16 exhibited poorer than the Examples in one or more of the measured physical properties, particularly in terms of metallic texture, appearance (weld line fraction), dimensional stability, flame retardancy, heat resistance, and impact strength. These compositions exhibited unbalanced properties compared to the Examples, which could significantly reduce the properties of the final product.

Claims

1. A thermoplastic resin composition, which is a metallic thermoplastic resin composition, comprising: (A) a polycarbonate resin; (B) an acrylonitrile-butadiene-styrene resin; (C) a flame retardant; (D) a fly ash filler; (E) a block copolymer comprising (meth)acrylate-derived units; and (F) flake metal particles, Wherein, based on 100 parts by weight of the composition in total, 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 component (B) is more than 5 parts by weight and less than 20 parts by weight. The content of the component (C) is more than 9 parts by weight and less than 17 parts by weight. The content of the component (D) 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 component (F) is more than 0.5 parts by weight and less than 3 parts by weight.

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

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

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

5. The thermoplastic resin composition according to claim 1, wherein The fly ash filler is treated with alkyl silane.

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

7. The thermoplastic resin composition according to claim 1, wherein The flaky metal particles are aluminum or an aluminum-based alloy. 8 . A molded article comprising the thermoplastic resin composition according to claim 1 .

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