Thermoplastic resin composition and molded article comprising same

Abstract

The present invention relates to a thermoplastic resin composition and a molded article comprising same and, more specifically, to a thermoplastic resin composition and a molded article comprising same, wherein the thermoplastic resin composition comprises: (A) two or more kinds of acrylic graft resins having different average particle sizes; (B) a first copolymer containing an alkyl-substituted styrene, a (meth)acrylate, and a vinyl cyanide compound; (C) a second copolymer containing an alkyl-unsubstituted styrene, a (meth)acrylate, and a vinyl cyanide compound; and (D) a (meth)acrylate polymer, 40 to 59 wt% of (meth)acrylates being contained relative to the total weight of the thermoplastic resin composition, so that the thermoplastic resin composition has excellent impact resistance, fluidity, and heat resistance, and can display a deep black color while providing economic advantages due to no increase in processing cost.

Description

[Technical Field][1] [Cross-Reference to Related Applications][2] This application claims priority to Korean PatentApplication No. 10-2020-0078393, filed on June 26, 2020, andKorean Patent Application No. 10-2021-0025196, re-filed onFebruary 25, 2021, based on the priority of the above patent,in the Korean Intellectual Property Office, the disclosuresof each of which are incorporated herein by reference.[3] The present invention relates to a thermoplasticresin composition and a molded article including the same.More particularly, the present invention relates to athermoplastic resin composition having excellent impactresistance, fluidity, and heat resistance; and providing aneconomic advantage by not increasing processing cost; andimplementing a deep black color, and a molded articleincluding the thermoplastic resin composition.[Background Art][4] To overcome the drawbacks of conventionalacrylonitrile-butadiene-styrene (ABS) resins, such as poorweather resistance and chemical resistance, acrylonitrilestyrene-acrylate (ASA) resins having excellent weatherresistance and chemical resistance have been used. Inaddition to weather resistance and chemical resistance, theASA resins have excellent impact resistance, fluidity, heatresistance, and the like, and thus have been used in variousfields such as automobiles, electric and electronic devices,office equipment, home appliances, toys, and stationery.[5] In recent years, in the automotive field, a paintingprocess can be omitted by using ASA resins having excellentimpact resistance, fluidity, heat resistance, weatherresistance, and chemical resistance, thereby improving pricecompetitiveness through cost reduction. In addition, tomanufacture a molded article having a luxurious feeling,attempts to implement an ASA resin exhibiting a deep blackcolor are being conducted.[6] However, conventional heat-resistant ASA resins usedfor automotive exterior materials have a limitation inrealizing a deep black color due to poor compatibility withdyes.[7] Therefore, demand for an ASA resin exhibiting a deepblack color and having excellent impact resistance, fluidity,and heat resistance is increasing in the automotive field.[8] [Related Art Documents][9] [Patent Documents]

[10] KR 2015-0123709 A[Disclosure][Technical Problem]

[11] Therefore, the present invention has been made inview of the above problems, and it is one object of thepresent invention to provide a thermoplastic resincomposition having excellent impact resistance, fluidity,and heat resistance; providing an economic advantage bysuppressing increase in processing cost; and implementing adeep black color and a molded article including thethermoplastic resin composition.

[12] The above and other objects can be accomplished bythe present invention described below.[Technical Solution]

[13] In accordance with one aspect of the presentinvention, provided is a thermoplastic resin compositionincluding two or more types of acrylic graft resins (A)having different average particle diameters; a firstcopolymer (B) including an alkyl-substituted styrene, a(meth)acrylate, and a vinyl cyanide compound; a secondcopolymer (C) including an alkyl-unsubstituted styrene, a(meth)acrylate, and a vinyl cyanide compound; and a(meth)acrylate polymer (D), wherein the (meth)acrylate isincluded in an amount of 40 to 59 % by weight based on atotal weight of the thermoplastic resin composition.

[14] In accordance with another aspect of the presentinvention, provided is a molded article including thethermoplastic resin composition.[Advantageous effects]

[15] According to the present invention, a thermoplasticresin composition having excellent impact resistance,fluidity, and heat resistance; providing an economicadvantage by not increasing the processing cost; andimplementing a deep black color and a molded articleincluding the thermoplastic resin composition can beprovided.[Best mode]

[16] Hereinafter, a thermoplastic resin composition and amolded article including the same will be described indetail.

[17] The present inventors made much effort to develop anASA resin having a high degree of blackness. As a result,when an alkyl-substituted styrene-(meth)acrylate-vinylcyanide compound copolymer and an alkyl-unsubstitutedstyrene-(meth)acrylate-vinyl cyanide compound copolymer wereadded to a composition including an ASA resin and apolymethyl methacrylate resin (hereinafter referred to as"PMMA resin"), heat resistance and fluidity were improved.In particular, when reducing the content of the PMMA resinand increasing the total weight of the (meth)acrylate in thecomposition, heat resistance, impact resistance, fluidity,and blackness were improved. Consequently, the presentinventors confirmed that the resin composition of thepresent invention could provide a product having a luxuriousfeeling and high quality to industrial fields requiring highheat resistance and impact resistance, such as automotiveexterior materials. Based on these results, the presentinventors conducted further studies to complete the presentinvention.

[18]

[19] The thermoplastic resin composition of the presentinvention includes two or more types of acrylic graft resins(A) having different average particle diameters; a firstcopolymer (B) including an alkyl-substituted styrene, a(meth)acrylate, and a vinyl cyanide compound; a secondcopolymer (C) including an alkyl-unsubstituted styrene, a(meth)acrylate, and a vinyl cyanide compound; and a(meth)acrylate polymer (D). In this case, based on a totalweight of the thermoplastic resin composition, the(meth)acrylate is included in an amount of 40 to 59 % byweight. In this case, impact resistance, fluidity, and heatresistance may be excellent, an economic advantage may beobtained by suppressing increase in processing cost, and adeep black color may be implemented.

[20]

[21] Hereinafter, each component of the thermoplasticresin composition of the present invention will be describedin detail.

[22]

[23] (A) Acrylic graft resins

[24] For example, the acrylic graft resins (A) of thepresent invention may include two or more types of acrylicgraft resins having different average particle diameters.In this case, compared to a case of including one type ofacrylic graft resin, impact resistance, colorability,elongation and heat resistance may be improved. Inparticular, blackness and impact resistance may be improvedat the same time.

[25] In this specification, unless defined otherwise, theacrylic graft resin may refer to a resin obtained by graftpolymerizingacrylate monomers.

[26] Two or more types of acrylic graft resins describedabove mean two or more acrylic graft resins having differentaverage particle diameters.

[27] As a specific example, the acrylic graft resins (A)may include a first acrylic graft resin having an averageparticle diameter of 400 to 650 nm and a second acrylicgraft resin having an average particle diameter of 50 to 160nm. In this case, blackness may be improved whilemaintaining impact resistance, fluidity, and heat resistanceat a high level.

[28] For example, the first acrylic graft resin may havean average particle diameter of 300 to 650 nm, preferably350 to 550 nm, more preferably 400 to 500 nm, still morepreferably 450 to 500 nm. Within this range, in addition toexcellent impact resistance, fluidity, and heat resistance,a high level of blackness may be implemented, enablingproduction of high-quality products that may be applied toautomotive exterior materials.

[29] For example, the second acrylic graft resin may havean average particle diameter of 30 to 250 nm, preferably 40to 200 nm, more preferably 50 to 150 nm, still morepreferably 80 to 130 nm. Within this range, in addition toexcellent impact resistance, fluidity, and heat resistance,a high level of blackness may be implemented, enablingproduction of high-quality products that may be applied toautomotive exterior materials.

[30] In this specification, average particle diameter maybe measured by dynamic light scattering, and specifically,may be measured as an intensity value using a Nicomp 380 HPLparticle analyzer in a Gaussian mode.

[31] In addition, in this specification, average particlediameter may mean an arithmetic average particle diameter,i.e., an average particle diameter of an intensitydistribution, in a particle size distribution measured bydynamic light scattering. As a specific measurement example,a sample is prepared by diluting 0.1 g of latex (TSC: 35 to50 wt%) 1,000 to 5,000 times with distilled water, and theaverage particle diameter of the sample is measured using aflow cell in auto-dilution in a measurement mode of dynamiclight scattering / intensity 300 kHz / intensity-weight Gaussiananalysis. At this time, setting values are as follows:temperature: 23 °C; measurement wavelength: 632.8 nm; andchannel width: 10 μsec.

[32] For example, the acrylic graft resins (A) mayinclude the first acrylic graft resin and the second acrylicgraft resin in a weight ratio of 1:1 to 1:30, preferably1:1.5 to 1:20, more preferably 1:2 to 1:18. Within thisrange, blackness may be significantly improved whilemaintaining impact resistance, fluidity, and heat resistanceat a high level.

[33] In this specification, the weight ratio of the firstacrylic graft resin to the second acrylic graft resin refersto the weight ratio of the first acrylic graft resin : thesecond acrylic graft resin.

[34] For example, based on 100 % by weight of thethermoplastic resin composition, the acrylic graft resins (A)may be included in an amount of 20 to 45 % by weight,preferably 25 to 40 % by weight, more preferably 31 to 38 %by weight. Within this range, in addition to excellentimpact resistance, colorability, elongation, fluidity, andheat resistance, a high level of blackness may beimplemented.

[35] For example, the acrylic graft resins (A) may beprepared by graft-copolymerizing an aromatic vinyl compoundand a vinyl cyanide compound onto acrylate rubber.

[36] For example, the acrylate rubber may have an averageparticle diameter of 400 to 600 nm, preferably 450 to 500 nm.Within this range, in addition to excellent impactresistance, fluidity, and heat resistance, a high level ofblackness may be implemented.

[37] As another example, the acrylate rubber may have anaverage particle diameter of 50 to 250 nm, preferably 70 to150 nm. Within this range, in addition to excellent impactresistance, fluidity, and heat resistance, a high level ofblackness may be implemented.

[38] Here, the average particle diameter of the acrylaterubber is smaller than the average particle diameters of theacrylic graft resins.

[39] For example, the acrylic graft resins (A) mayinclude 40 to 60 % by weight of acrylate rubber, 20 to 50 %by weight of an aromatic vinyl compound, and 10 to 20 % byweight of a vinyl cyanide compound. Within this range,impact resistance, fluidity, heat resistance, and blacknessmay be excellent.

[40] As a preferred example, the acrylic graft resins (A)may include 45 to 55 % by weight of acrylate rubber, 30 to40 % by weight of an aromatic vinyl compound, and 12 to 17 %by weight of a vinyl cyanide compound. Within this range,blackness may be further improved while maintaining impactresistance, fluidity, and heat resistance at a high level.

[41] In this specification, a resin comprising a certaincompound refers to a polymer prepared by polymerizing thecompound. In this case, a unit of the polymer is derivedfrom the compounds.

[42] For example, the acrylate rubber may be an alkylacrylate rubber.

[43] For example, the alkyl acrylate may be an acrylatehaving an alkyl group containing 1 to 10 carbon atoms,preferably alkyl acrylate having an alkyl group containing 4to 10 carbon atoms, more preferably butyl acrylate. In thiscase, intrinsic physical properties such as weatherresistance and chemical resistance may be excellent, and ahigh level of blackness may be implemented.

[44] For example, the aromatic vinyl compound may includeone or more selected from the group consisting of styrene,α-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, tbutylstyrene,and chlorostyrene, preferably styrene. Inthis case, fluidity and mechanical properties may beexcellent.

[45] For example, the vinyl cyanide compound may includeone or more selected from the group consisting ofacrylonitrile, methacrylonitrile, and ethacrylonitrile,preferably acrylonitrile.

[46] For example, the acrylic graft resins (A) may beacrylate-aromatic vinyl compound-vinyl cyanide compoundgraft copolymers, preferably butyl acrylate-styreneacrylonitrilegraft copolymers.

[47]

[48] (B) First copolymer

[49] For example, the first copolymer (B) of the presentinvention may include an alkyl-substituted styrene, a(meth)acrylate, and a vinyl cyanide compound. In this case,blackness may be greatly improved.

[50] As a specific example, the first copolymer (B) maybe a copolymer of a monomer mixture including an alkylsubstitutedstyrene, a (meth)acrylate, and a vinyl cyanidecompound.

[51] The alkyl-substituted styrene is obtained bysubstituting at least one hydrogen of styrene with an alkylgroup, and the alkyl group is preferably an alkyl groupcontaining 1 to 20 carbon atoms.

[52] For example, the alkyl-substituted styrene mayinclude one or more selected from the group consisting of α-methylstyrene, p-methylstyrene, and 2,4-dimethylstyrene,preferably α-methylstyrene. In this case, the desiredeffects of the present invention may be effectively achieved.

[53] For example, the (meth)acrylate may be an alkyl(meth)acrylate, preferably methyl methacrylate. In thiscase, the stability of the composition of the presentinvention may be improved, and as a result, impactresistance, fluidity, heat resistance, and blackness may beexcellent.

[54] For example, the vinyl cyanide compound may includeone or more selected from the group consisting ofacrylonitrile, methacrylonitrile, ethacrylonitrile, and 2-chloroacrylonitrile. In this case, the desired effects ofthe present invention may be effectively achieved.

[55] For example, in the first copolymer (B), the alkylsubstitutedstyrene may be included in an amount of 25 to50 % by weight, preferably 30 to 45 % by weight, morepreferably 30 to 40 % by weight, still more preferably 35 to40 % by weight based on 100 % by weight of the firstcopolymer. Within this range, impact resistance, fluidity,heat resistance, and blackness may be excellent.

[56] For example, in the first copolymer (B), the(meth)acrylate may be included in an amount of 40 to 60 % byweight, preferably 40 to 55 % by weight, more preferably 40to 50 % by weight based on 100 % by weight of the firstcopolymer. Within this range, impact resistance, fluidity,and heat resistance may be excellent, an economic advantagemay be obtained by suppressing increase in processing cost,and a deep black color may be implemented.

[57] In this specification, unless defined otherwise, theprocessing cost may mean a cost used in a process formanufacturing a thermoplastic resin composition, such as apainting process.

[58] For example, in the first copolymer (B), the vinylcyanide compound may be included in an amount of 10 to 30 %by weight, preferably 15 to 30 % by weight, more preferably17 to 22 % by weight based on 100 % by weight of the firstcopolymer. Within this range, impact resistance, fluidity,heat resistance, and blackness may be excellent.

[59] For example, based on 100 % by weight of thethermoplastic resin composition, the first copolymer (B) maybe included in an amount of 10 to 30 % by weight, preferably15 to 22 % by weight. Within this range, impact resistance,fluidity, heat resistance, and blackness may be excellent.

[60] As the most preferred example, the first copolymer(B) may be an α-methylstyrene-methyl methacrylateacrylonitrilecopolymer. In this case, the desired effectsof the present invention may be effectively achieved.

[61] For example, the first copolymer (B) may have aglass transition temperature of 90 to 130 °C, preferably 100to 125 °C, more preferably 110 to 122 °C. Within this range,the resin composition of the present invention may haveexcellent heat resistance, and thus the resin compositionmay be applied to manufacture products requiring high heatresistance, such as automotive exterior materials.

[62] In this specification, the glass transitiontemperature (Tg) may be measured using a differentialscanning calorimeter (DSC), as a specific example, adifferential scanning calorimeter manufactured by the TAInstrument company.

[63] For example, the first copolymer (B) may have aweight average molecular weight of 70,000 to 150,000 g / mol,preferably 70,000 to 120,000 g / mol, more preferably 85,000to 120,000 g / mol, still more preferably 90,000 to 110,000g / mol. Within this range, impact resistance, fluidity, heatresistance, and blackness may be excellent.

[64] In this specification, weight average molecularweight may be measured using tetrahydrofuran (THF) as aneluate through gel permeation chromatography. In this case,weight average molecular weight is obtained as a relativevalue to a polystyrene standard (PS) specimen. Specificmeasurement conditions are as follows: solvent: THF, columntemperature: 40 °C, flow rate: 0.3 ml / min, sampleconcentration: 20 mg / ml, injection amount: 5 μl, columnmodel: 1xPLgel 10 μm MiniMix-B (250x4.6 mm) + 1xPLgel 10 μmMiniMix-B (250x4.6 mm) + 1xPLgel 10 μm MiniMix-B Guard(50x4.6 mm), equipment name: Agilent 1200 series system,refractive index detector: Agilent G1362 RID, RI temperature:35 °C, data processing: Agilent ChemStation S / W, and testmethod (Mn, Mw and PDI): OECD TG 118.

[65] For example, the first copolymer (B) may have arefractive index of 1.50 to 1.57, preferably 1.52 to 1.55.Within this range, heat resistance and blackness may beexcellent.

[66] In this specification, refractive index may bemeasured at 25 °C using an Abbe refractometer according toASTM D542.

[67] The first copolymer (B) of the present invention isa ternary copolymer including the alkyl-substituted styrene,the (meth)acrylate, and the vinyl cyanide compound, and isdifferent from a binary copolymer including two componentsamong the three components. Since the thermoplastic resincomposition of the present invention includes the firstcopolymer, which is a ternary copolymer, blackness may begreatly improved while maintaining impact resistance,fluidity, and heat resistance at a high level.

[68] In addition, the thermoplastic resin composition ofthe present invention does not include a binary copolymer,and the binary copolymer may be, for example, an alkylsubstitutedstyrene-acrylonitrile copolymer.

[69]

[70] (C) Second copolymer

[71] For example, the second copolymer (C) of the presentinvention may include an alkyl-unsubstituted styrene, a(meth)acrylate, and a vinyl cyanide compound. In this case,blackness may be greatly improved.

[72] The alkyl-unsubstituted styrene means that nohydrogen of styrene is substituted with an alkyl group. Inthis case, substituents other than alkyl groups may beincluded.

[73] For example, the alkyl-unsubstituted styrene mayinclude one or more selected from the group consisting ofstyrene, p-bromostyrene, o-bromostyrene, and p-chlorostyrene,preferably styrene.

[74] The (meth)acrylate and the vinyl cyanide compoundincluded in the second copolymer (C) may be the same as the(meth)acrylate and the vinyl cyanide compound included inthe first copolymer (B) of the present invention.

[75] For example, the second copolymer (C) may include 15to 30 % by weight of the alkyl-unsubstituted styrene, 60 to80 % by weight of the (meth)acrylate, and 3 to 15 % byweight of the vinyl cyanide compound. Within this range,impact resistance, fluidity, heat resistance, and blacknessmay be excellent.

[76] For example, in the second copolymer (C), the alkylunsubstitutedstyrene may be included in an amount of 15 to30 % by weight, preferably 17 to 26 % by weight, morepreferably 20 to 25 % by weight based on 100 % by weight ofthe second copolymer. Within this range, fluidity andblackness may be excellent.

[77] For example, in the second copolymer (C), the(meth)acrylate may be included in an amount of 60 to 80 % byweight, preferably 63 to 78 % by weight, more preferably 65to 75 % by weight based on 100 % by weight of the secondcopolymer. Within this range, colorability may be improvedwithout deterioration in impact resistance.

[78] For example, in the second copolymer (C), the vinylcyanide compound may be included in an amount of 3 to 15 %by weight, preferably 5 to 15 % by weight, more preferably 6to 11 % by weight based on 100 % by weight of the secondcopolymer. Within this range, excellent chemical resistanceand rigidity may be obtained.

[79] For example, the second copolymer (C) may beincluded in an amount of 5 to 25 % by weight, preferably 5to 20 % by weight based on 100 % by weight of thethermoplastic resin composition. Within this range,fluidity may be excellent, and impact resistance, heatresistance, and blackness may be improved.

[80] As the most preferred example, the second copolymer(C) may be a methyl methacrylate-styrene-acrylonitrilecopolymer. In this case, the desired effects of the presentinvention may be effectively achieved.

[81] For example, the second copolymer (C) may have aglass transition temperature of 80 to 120 °C, preferably 90to 110 °C. Within this range, the resin composition of thepresent invention may have excellent heat resistance, andthus the resin composition may be applied to manufactureproducts requiring high heat resistance, such as automotiveexterior materials.

[82] For example, the second copolymer (C) may have aweight average molecular weight of 80,000 to 200,000 g / mol,preferably 100,000 to 170,000 g / mol, more preferably 120,000to 155,000 g / mol. Within this range, impact resistance,fluidity, heat resistance, and blackness may be excellent.

[83] For example, the second copolymer (C) may have arefractive index of 1.45 to 1.55, preferably 1.50 to 1.53.Within this range, blackness may be excellent.

[84]

[85] (D) (Meth)acrylate polymer

[86] For example, the (meth)acrylate polymer (D) of thepresent invention may include 70 % by weight or more of amethacrylate compound, preferably a polymethyl methacrylateresin including 100 % by weight of a methacrylate compound.In this case, impact resistance, fluidity, heat resistance,and blackness may be excellent.

[87] For example, based on 100 % by weight of thethermoplastic resin composition, the (meth)acrylate polymer(D) may be included in an amount of 25 to 45 % by weight,preferably 30 to 40 % by weight. Within this range,colorability, scratch resistance, and weather resistance maybe excellent, and blackness may be improved.

[88] For example, the (meth)acrylate polymer (D) may havea glass transition temperature of 80 to 130 °C, preferably95 to 120 °C. Within this range, heat resistance may beexcellent.

[89] For example, the (meth)acrylate polymer (D) may havea weight average molecular weight of 60,000 to 120,000 g / mol,preferably 85,000 to 120,000 g / mol, more preferably 80,000to 100,000 g / mol. Within this range, blackness may beexcellent.

[90] For example, the (meth)acrylate polymer (D) may havea refractive index of 1.40 to 1.55, preferably 1.45 to 1.52.Within this range, blackness may be excellent.

[91]

[92] Thermoplastic resin composition

[93] For example, based on 100 % by weight of thethermoplastic resin composition, the thermoplastic resincomposition may include the (meth)acrylate in an amount of40 to 59 % by weight, preferably 45 to 59 % by weight, morepreferably 48 to 53 % by weight. Within this range, impactresistance and blackness may be improved while maintainingheat resistance and fluidity at a high level.

[94] In addition, when the (meth)acrylate is included inan amount less than the above range, a deep black color maybe difficult to implement. When the (meth)acrylate isincluded in an amount exceeding the above range, impactresistance, fluidity, and heat resistance may be degraded.Thus, the content of the (meth)acrylate is preferablyadjusted within the above range.

[95] For example, the thermoplastic resin composition mayfurther include a silicon compound. In this case, fluidityand impact resistance may be improved.

[96] For example, the silicon compound may be apolyester-modified siloxane. In this case, fluidity andimpact resistance may be improved, and a deep black colormay be implemented.

[97] The polyester-modified siloxane may mean a siloxanemodified with a polyester.

[98] For example, based on 100 parts by weight in totalof the thermoplastic resin composition, the silicon compoundmay be included in an amount of 0.5 to 3 parts by weight,preferably 0.7 to 2 parts by weight, more preferably 0.8 to1.2 parts by weight.

[99] For example, the thermoplastic resin composition mayfurther include one or more additives selected from thegroup consisting of a colorant, a lubricant, an antioxidant,a fluorescent brightening agent, a chain extender, a releaseagent, a pigment, a dye, an antibacterial agent, aprocessing aid, a metal deactivator, a smoke inhibitor, aninorganic filler, glass fiber, an anti-friction agent, ananti-wear agent, a heat stabilizer, and a UV stabilizer. Inthis case, compatibility may be excellent, and the desiredeffects of the present invention may be effectively achieved.

[100] For example, based on 100 parts by weight in totalof the thermoplastic resin composition, the additives may beincluded in an amount of 0.01 to 10 parts by weight,preferably 0.1 to 7 parts by weight, more preferably 1 to 5parts by weight. Within this range, the desired effects ofthe present invention may be effectively achieved withoutdeterioration in the intrinsic physical properties of thethermoplastic resin composition of the present invention.

[101] For example, the colorant may be an anthraquinonebaseddye, as a preferred example, a black organic dyecontaining 50 % by weight or more of 1,4-bis(ptolylamino)anthraquinone. The black organic dye is a greentoneblack organic dye and has excellent compatibility withthe composition of the present invention, thereby enablingeasy expression of a deep black color.

[102] For example, based on 100 parts by weight in totalof the thermoplastic resin composition, the colorant may beincluded in an amount of 0.1 to 1.5 parts by weight,preferably 0.3 to 1.0 part by weight. Within this range,blackness may be excellent.

[103] For example, the lubricant may include one or moreselected from the group consisting of an ester-basedlubricant, a metal salt-based lubricant, a carboxylic acid15based lubricant, a hydrocarbon-based lubricant, and anamide-based lubricant, preferably an amide-based lubricant,more preferably a stearamide-based lubricant, still morepreferably alkylene bis(stearamide) containing alkylenehaving 1 to 10 carbon atoms. In this case, the intrinsiceffects of a lubricant may be efficiently expressed withoutdeterioration in the mechanical properties and thermalstability of a resin.

[104] The stearamide-based lubricant may includestearamide and a stearamide substituent in which one or morehydrogens thereof are substituted with other substituents.

[105] Ester-based lubricants, metal salt-based lubricants,carboxylic acid-based lubricants, hydrocarbon-basedlubricants, and amide-based lubricants commonly used in theart may be used in the present invention without particularlimit.

[106] For example, based on 100 parts by weight in totalof the thermoplastic resin composition, the lubricant may beincluded in an amount of 0.1 to 3 parts by weight,preferably 0.5 to 1.5 parts by weight. Within this range,the wettability of the composition of the present inventionmay be improved, and the composition of the presentinvention may have excellent impact resistance.

[107]

[108] For example, the thermoplastic resin composition mayhave a Charpy impact strength (thickness: 4.0 mm, widthafter notched: 8 mm, 23 °C) of 5 kJ / m2 or more, preferably 6to 12 kJ / m2 as measured according to ISO 179-1. Within thisrange, the thermoplastic resin composition of the presentinvention may have excellent impact resistance.

[109] For example, the thermoplastic resin composition mayhave a flow index of 4 to 20 g / 10 min, preferably 5 to 15g / 10 min, more preferably 5 to 10 g / 10 min as measured underconditions of 220 °C and 10 kgf according to ISO 1133-1.Within this range, due to excellent fluidity thereof, thethermoplastic resin composition may be easily injectionmoldedinto products of various shapes.

[110] For example, the thermoplastic resin composition mayhave a heat deflection temperature of 70 to 100 °C,preferably 75 to 85 °C as measured according to ISO 75.Within this range, physical property balance may beexcellent, and heat resistance may be improved.

[111] For example, the thermoplastic resin composition mayhave a Vicat softening temperature (VST) of 90 to 120 °C,preferably 94 to 110 °C as measured according to ISO 306.Within this range, physical property balance may beexcellent, and heat resistance may be improved.

[112] For example, the thermoplastic resin composition mayhave a blackness (L) of 4 or less, preferably 1 to 3.5, morepreferably 1 to 2.5 as measured in an SCE mode. Within thisrange, a deep black color may be implemented, therebyproviding a product having a luxurious feeling.

[113]

[114] Hereinafter, a method of preparing the thermoplasticresin composition of the present invention and a moldedarticle including the thermoplastic resin composition willbe described. In description of the method of preparing thethermoplastic resin composition and the molded articleincluding the thermoplastic resin composition, all thecontents of the thermoplastic resin composition of thepresent invention are included.

[115]

[116] Method of preparing thermoplastic resin composition

[117] For example, the method of preparing thethermoplastic resin composition of the present inventionincludes a step of kneading and extruding two or more typesof acrylic graft resins (A) having different averageparticle diameters; a first copolymer (B) including analkyl-substituted styrene, a (meth)acrylate, and a vinylcyanide compound; a second copolymer (C) including an alkylunsubstitutedstyrene, a (meth)a crylate, and a vinyl cyanidecompound; and a (meth)acrylate polymer (D). In this case,based on a total weight of the thermoplastic resincomposition, the (meth)acrylate is included in an amount of40 to 59 % by weight. In this case, impact resistance,fluidity, and heat resistance may be excellent, an economicadvantage may be obtained by suppressing increase inprocessing cost, and a deep black color may be implemented.

[118] In this specification, unless defined otherwise,"comprising ~" includes the meaning of "prepared bypolymerizing ~".

[119] For example, the step of kneading and extruding maybe performed using a single-screw extruder, a twin-screwextruder, or a Banbury mixer. In this case, since thecomposition is uniformly dispersed, compatibility may beexcellent.

[120] For example, the step of kneading and extruding maybe performed at a processing temperature of 200 to 300 °C,preferably 220 to 270 °C. In this case, throughput per unittime may be appropriate, and melting and kneading may besufficiently performed. In addition, occurrence of problemssuch as thermal decomposition of a resin component may beprevented.

[121] For example, the kneading and extruding may beperformed at a screw rotation rate of 100 to 500 rpm, 150 to400 rpm, 100 to 350 rpm, 200 to 310 rpm, preferably 250 to350 rpm. In this case, throughput per unit time may beappropriate, and thus process efficiency may be excellent.In addition, excessive cutting may be prevented.

[122]

[123] Molded article

[124] For example, the molded article of the presentinvention may include the thermoplastic resin composition ofthe present invention. Since the molded article hasexcellent heat resistance and impact resistance, deformationdue to external environments may be very small, and a highlevel of blackness may be implemented, thereby providing aluxurious feeling.

[125] For example, the molded article may be an automotiveexterior material. In this case, since the molded articleincludes the thermoplastic resin composition of the presentinvention, the molded article may satisfy all of heatresistance, impact resistance, fluidity, a deep black color,and economics required by the market, thereby providing ahigh-quality automotive exterior material.

[126] For example, the automotive exterior material may bea side mirror housing, a radiator grill, a filler, or agarnish. Compared to conventional cases, cost may bereduced, thereby providing an economic advantage. Inaddition, the automotive exterior material may satisfyconsumer needs such as heat resistance, impact resistance,and a deep black color.

[127]

[128] In description of the thermoplastic resincomposition of the present invention and the molded articleincluding the same, other conditions or equipment notexplicitly described herein may be appropriately selectedwithin the range commonly practiced in the art, withoutparticular limit.

[129]

[130] Hereinafter, the present invention will be describedin more detail with reference to the following preferredexamples. However, these examples are provided forillustrative purposes only and should not be construed aslimiting the scope and spirit of the present invention. Inaddition, it will be apparent to those skilled in the artthat various changes and modifications may be made withoutdeparting from the spirit and scope of the present invention,and such changes and modifications are also within the scopeof the appended claims.

[131]

[132] [Examples]

[133] Materials used in Examples and Comparative Examplesbelow are as follows.

[134] (A1) First acrylic graft resin: an ASA resin havingan average particle diameter of 450 to 500 nm prepared bygraft-polymerizing styrene and acrylonitrile onto a butylacrylate rubber

[135] (A2) Second acrylic graft resin: an ASA resin havingan average particle diameter of 300 to 350 nm prepared bygraft-polymerizing styrene and acrylonitrile onto a butylacrylate rubber

[136] (A3) Third acrylic graft resin: an ASA resin havingan average particle diameter of 80 to 130 nm prepared bygraft-polymerizing styrene and acrylonitrile onto a butylacrylate rubber

[137] (B1) AMS-MMA-AN ternary copolymer including 30 to40 % by weight of α-methylstyrene (AMS), 40 to 50 % byweight of methyl methacrylate (MMA), and 15 to 30 % byweight of acrylonitrile (AN) and having a glass transitiontemperature of about 120 °C, a weight average molecularweight of 85,000 to 120,000 g / mol, and a refractive index of1.5336

[138] (B2) AMS-AN copolymer including 65 to 75 % by weightof α-methylstyrene and 25 to 35 % by weight of acrylonitrileand having a glass transition temperature of about 123 °C, aweight average molecular weight of 85,000 to 120,000 g / mol,and a refractive index of 1.5695

[139] (C1) MMA-SM-AN copolymer including 65 to 75 % byweight of methyl methacrylate, 20 to 25 % by weight ofstyrene (SM), and 5 to 15 % by weight of acrylonitrile andhaving a glass transition temperature of about 102 °C, aweight average molecular weight of 100,000 to 170,000 g / mol,and a refractive index of 1.515

[140] (D1) Polymethyl methacrylate having a glasstransition temperature of about 113 °C, a weight averagemolecular weight of 85,000 to 120,000 g / mol, and arefractive index of 1.49

[141] (E1) Polyester-modified silicon compound (TEGOMER6441P, EVONIK Co.) (melting point (Tm): about 54 °C)

[142] (F1) Colorant containing 1,4-bis(ptolylamino)anthraquinone as a main component

[143]

[144] Examples 1 to 6, Comparative Examples 1 to 9, andReference Examples 1 and 2

[145] The above-described components were mixed andstirred according to the contents shown in Table 1 below toprepare thermoplastic resin compositions.

[146]

[147] [Table 1]ClassificationExamples Comparative ExamplesReferenceExamples1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 1 2(A1) ASAresin3 - - 2 4 - - - 10 10 2 - 2 3 2 20 30(A2) ASAresin- 10 7 - - 4 10 - - - - 10 - - - - -(A3) ASAresin30 23 26 35 29 32 23 33 23 23 35 23 35 30 35 13 3(B1) AMSMMA-ANcopolymer18 20 18 21 18 21 - 18 - - - 7 30 - 28 18 18(B2) AMS-ANcopolymer- - - - - - - - - - - - - 18 - - -(C1) MMASM-ANcopolymer15 15 15 7 15 7 - 15 - 30 28 10 23 15 - 15 15(D1) PMMA 34 32 34 35 34 36 67 34 67 33 35 55 5 34 35 34 34(E1)Siliconcompound1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0(F1)Colorant0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6Totalweight ofMMA[wt%]51~5450~5351~5448~5151~5449~5267 51~5467 53~5653~5664~6632~3744~4546~4951~5451~54

[148] In Table 1, the content of each of (A1), (A2), (A3),(B1), (B2), (C1), and (D1) is given in % by weight based onthe total weight thereof, and the content of each of (E1)and (F1) is given in parts by weight based on 100 parts byweight in total of (A1), (A2), (A3), (B1), (B2), (C1), and(D1). In addition, in Table 1, the total weight of MMA isthe total weight of MMA included in components (B1), (B2),(C1), and (D1), and is calculated based on 100 % by weightin total of (A1), (A2), (A3), (B1), (B2), (C1), and (D1).

[149] [Test Examples]

[150] The thermoplastic resin compositions prepared inExamples 1 to 6, Comparative Examples 1 to 9, and ReferenceExamples 1 and 2 were fed into an extrusion kneader(processing temperature: 240 °C) and extruded to preparepellets. The prepared pellets were injected using a 120 MTinjection machine (processing temperature: 240 °C) accordingto ISO standard to obtain specimens. The properties of thespecimens were measured using the following methods, and theresults are shown in Table 2 below. For reference,specimens for measuring blackness were prepared as squarehigh-gloss specimens having a size of 3 mm (thickness) x 10cm (width) x 10 cm (length). The high-gloss specimens had agloss of 85 to 95 as measured at 60° using a GLOSS meter.

[151] (1) Charpy impact strength (kJ / m2, notched,thickness: 4.0 mm, width after notched: 8 mm): Charpy impactstrength was measured at 23 °C using an IMPACT TESTER(Tinius Olsen Co.) according to ISO 179-1. Here, as themeasurement value increases, impact resistance increases.

[152] (2) Flow index (g / 10 min): Weight was measured at atemperature of 220 °C under a load of 10 kg for 10 minutesusing an MI-4 (GOTTFERT Co.) according to ISO 1133-1. Here,as the measurement value increases, fluidity becomes better.

[153] (3) Heat deflection temperature (°C): Heatdeflection temperature was measured using an auto HDT Tester6A-2 (TOYOSEIKI Co.) according to ISO 75. Here, as themeasurement value increases, heat resistance increases.

[154] (4) Vicat softening temperature (°C): Vicatsoftening temperature was measured using a devicemanufactured by the TOYOSEIKI corporation according to ISO306. Here, as the measurement value increases, heatresistance increases.

[155] (5) Blackness (L): An L value was measured in an SCEmode using a Ci7800 (X-rite Co.). Here, the L value is avalue for determining white to black values in the L*a*b*color system. As the L value decreases, blackness becomesbetter.

[156]

[157] [Table 2]ClassificationExamples Comparative ExamplesReferenceExamples1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 1 2Charpyimpactstrength[kJ / m2]8 9 8 9.1 8.3 8.4 8 5.9 8.6 8 8.2 6 8.6 8 9.2 9.8 11.8Flowindex(MI)[g / 10min]6.7 6 6.5 5.2 6.3 5.7 4.4 6.8 3.8 5.5 4.8 4.5 5.8 5.8 5.8 5.8 5.3Heatdeflectiontemperature(HDT)[°C]78 80 78 80 80 80 78 77 78 76 77 78 79 79 81 78 78Vicatsofteningtemperature(VST)[°C]96 97 96 97 97 97 96 95 96 94 94 95 97 96 98 96 96Blackness(L)2.1 3.2 3.0 2.0 2.0 2.4 4.7 2.2 5.7 4.8 4.9 3.1 4.2 6 5.3 4.4 4.7

[158] As shown in Table 2, it can be confirmed that thethermoplastic resin compositions of Examples 1 to 6according to the present invention have heat resistance andfluidity equal or superior to those of the thermoplasticresin compositions of Comparative Examples 1 to 9, whereasthe impact resistance and blackness of the thermoplasticresin compositions of Examples 1 to 6 are very much improvedcompared to Comparative Examples 1 to 9. In particular,since the thermoplastic resin composition of the presentinvention includes two types of acrylic graft resins havingdifferent average particle diameters in a specific weightratio, the thermoplastic resin composition of the presentinvention has excellent impact resistance, fluidity, andheat resistance and implements a high level of blackness,thereby providing a luxurious feeling.

[159] In addition, it can be confirmed that, compared toComparative Examples 1 and 3 not including (B1) and (C1),the fluidity and blackness of the thermoplastic resincomposition of the present invention are significantlyimproved. In addition, it can be confirmed that, comparedto Comparative Examples 4 and 5 not including (B1), theblackness of the thermoplastic resin composition of thepresent invention is significantly improved.

[160] In addition, it can be confirmed that, compared toComparative Example 2 in which one type of ASA resin is used,the thermoplastic resin composition of the present inventionhas excellent impact resistance while maintaining fluidity,heat resistance, and blackness equal or superior to those ofthe thermoplastic resin composition of Comparative Example 2.The composition having reduced impact resistance accordingto Comparative Example 2 is difficult to apply to productsrequiring high impact resistance, such as automotiveexterior materials.

[161] In addition, it can be confirmed that, compared toComparative Example 6 in which (A), (B), (C), and (D) areincluded but the (meth)acrylate is included in an amountexceeding the weight range of the present invention,Examples 1 to 6, in which (A), (B), (C), and (D) areincluded and the (meth)acrylate is included within theweight range of the present invention, have excellent impactresistance, fluidity, and heat resistance.

[162] In addition, it can be confirmed that, compared toComparative Example 7 in which the (meth)acrylate isincluded in an amount less than the weight range of thepresent invention, Examples 1 to 6 in which the(meth)acrylate is included within the weight range of thepresent invention have excellent blackness.

[163] In addition, it can be confirmed that, compared toExamples 1 to 6, in the case of Comparative Example 8including the binary copolymer (B2) consisting of the alkylsubstitutedstyrene and the vinyl cyanide compound insteadof the ternary copolymer (B 1) consisting of the alkylsubstitutedstyrene, the (meth)acrylate, and the vinylcyanide compound, blackness is significantly deteriorated,and thus the desired effect of the present invention, i.e.,a deep black color, is not implemented.

[164] In addition, it can be confirmed that, compared toExamples 1 to 6, in the case of Comparative Example 9 thatdoes not just include (C1), blackness is significantlydeteriorated.

Claims

1. A thermoplastic resin composition, comprising: two or more types of acrylic graft resins (A) having different average particle diameters; a first copolymer (B) comprising an alkyl-substituted styrene, a (meth)acrylate, and a vinyl cyanide compound; a second copolymer (C) comprising an alkyl10 unsubstituted styrene, a (meth)acrylate, and a vinyl cyanide compound; and a (meth)acrylate polymer (D), wherein the (meth)acrylate is comprised in an amount of 40 to 59 % by weight based on a total weight of the thermoplastic resin composition.

2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 20 to 45 % by weight of the acrylic graft resins (A); 10 to 30 % by weight of the first copolymer (B); 5 to 25 % by weight of the second copolymer (C); and 25 to 45 % by weight of the (meth)acrylate polymer (D).

3. The thermoplastic resin composition according to claim 1, wherein the acrylic graft resins (A) comprise a first acrylic graft resin having an average particle diameter of 400 to 650 nm and a second acrylic graft resin having an average particle diameter of 50 to 160 nm.

4. The thermoplastic resin composition according to claim 3, wherein the acrylic graft resins (A) comprise the first acrylic graft resin and the second acrylic graft resin in a weight ratio of 1:1 to 1:30.

5. The thermoplastic resin composition according to claim 1, wherein the first copolymer (B) comprises 25 to 50 % by weight of the alkyl-substituted styrene, 40 to 60 % by weight of the (meth)acrylate, and 10 to 30 % by weight of the vinyl cyanide compound.

6. The thermoplastic resin composition according to claim 1, wherein the second copolymer (C) comprises 15 to 30 % by weight of the alkyl-unsubstituted styrene, 60 to 80 % by weight of the (meth)acrylate, and 3 to 15 % by weight of the vinyl cyanide compound.

7. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a blackness (L) of 4 or less as measured in an SCE mode.

8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flow index of 4 to 20 g / 10min as measured under conditions of 220 °C and 10 kgf according to ISO 1133-1.

9. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a Charpy impact strength of 5 kJ / m2 or more as measured under conditions of 4.0 mm thickness, 8 mm width after notched and 23 °C according to ISO 179-1.

10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises a silicon compound.

11. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises one or more additives selected from the group consisting of a colorant, a lubricant, an antioxidant, a fluorescent brightening agent, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke inhibitor, an inorganic filler, glass fiber, an anti-friction agent, an anti-wear agent, a heat stabilizer, and a UV stabilizer.

12. A molded article, comprising the thermoplastic resin composition of any one of claims 1 to 11.

13. The molded article according to claim 12, wherein the molded article is an automotive exterior material.