TWI630232B - Thermoplastic resin composition and molding product thereof - Google Patents

Abstract

Thermoplastic resin composition and molded article. The thermoplastic resin composition includes 60 to 90% by weight of polycarbonate, 5 to 30% by weight of styrene-acrylonitrile copolymer, 1 to 15% by weight of acrylonitrile-diene-styrene copolymer, and 0.5 ~ 15wt% acrylate-diene-styrene copolymer. The diene monomer unit of the acrylate-diene-styrene copolymer accounts for 71% to 90% of the weight of the acrylate-diene-styrene copolymer.

Description

Thermoplastic resin composition and molded article

The present invention relates to a thermoplastic resin composition and molded article of a polycarbonate / acrylonitrile-butadiene-styrene copolymer (PC / ABS) alloy, and more particularly to a thermoplastic resin with good mechanical properties. Composition and molding.

Polycarbonate / acrylonitrile-butadiene-styrene copolymer (PC / ABS) alloy is a non-crystalline thermoplastic resin with excellent impact strength, heat resistance, high rigidity and other properties. It is widely used in 3C Home appliances, automobiles, electronics, etc. Because it needs to be used in a variety of special and complex environments, including lower temperature places, the low temperature performance of the material itself must meet higher requirements. Therefore, under these occasions, the PC / ABS alloy needs higher low temperature resistance performance to ensure product performance and safety, especially for helmets, sports equipment, suitcases, etc.

Generally speaking, the high and low temperature impact properties of PC / ABS alloys are mainly achieved by adding tougheners with good low temperature toughness, such as using a maleic anhydride and methyl methacrylate grafted ethylene elastomer toughener To improve the low temperature impact resistance of PC / ABS. However, because of the low temperature toughness modifiers and PC / ABS, There is no good compatibility between them, which greatly reduces its effect. On the other hand, PC / ABS is a multi-phase alloy with PC as the marine phase and ABS as the island phase. The effective binding force between ABS and PC is also an important factor that determines the physical properties of the material. Therefore, how to overcome the above factors and prepare polycarbonate (PC) and ABS alloy blends with advantages such as better impact resistance and mechanical properties has become an urgent research topic in the industry.

The disclosure relates to a thermoplastic resin composition and a molded product thereof, which can have good mechanical properties and compatibility.

According to one concept of the present disclosure, a thermoplastic resin composition is proposed, which includes 60 to 90 wt% polycarbonate, 5 to 30 wt% styrene-acrylonitrile copolymer, and 1 to 15 wt% acrylonitrile- Diene-styrene copolymer and 0.5 to 15% by weight of acrylate-diene-styrene copolymer. The diene monomer unit of the acrylate-diene-styrene copolymer accounts for 71% to 90% of the weight of the acrylate-diene-styrene copolymer.

According to another concept of the present disclosure, a molded article is proposed, which is formed of a thermoplastic resin composition. The thermoplastic resin composition includes 60 to 90% by weight of polycarbonate, 5 to 30% by weight of styrene-acrylonitrile copolymer, 1 to 15% by weight of acrylonitrile-diene-styrene copolymer, and 0.5 ~ 15wt% acrylate-diene-styrene copolymer. The diene monomer unit of the acrylate-diene-styrene copolymer accounts for 71% to 90% of the weight of the acrylate-diene-styrene copolymer.

In order to have a better understanding of the above and other aspects of this disclosure, the preferred embodiments are described below in detail with the accompanying drawings, as follows:

The thermoplastic resin composition includes 60 to 90% by weight of polycarbonate, 5 to 30% by weight of styrene-acrylonitrile copolymer, 1 to 15% by weight of acrylonitrile-diene-styrene copolymer, and 0.5 ~ 15wt% acrylate-diene-styrene copolymer.

In one embodiment, the thermoplastic resin composition may include 65 to 85% by weight of polycarbonate, 8 to 25% by weight of styrene-acrylonitrile copolymer, and 2 to 12% by weight of acrylonitrile-diene-benzene. Ethylene-based copolymer and 1-12% by weight of acrylate-diene-styrene copolymer. In one embodiment, the thermoplastic resin composition may include 70 to 80% by weight of polycarbonate, 10 to 18% by weight of styrene-acrylonitrile copolymer, and 5 to 10% by weight of acrylonitrile-diene-benzene. Ethylene-based copolymers and 2 to 8% by weight of acrylate-diene-styrene copolymers.

In the embodiment, the diene monomer unit of the acrylate-diene-styrene copolymer accounts for 71% to 90% of the weight of the acrylate-diene-styrene copolymer, or 71% ~ 88%, or 73% ~ 88%. In the acrylate-diene-styrene copolymer, the weight ratio of the acrylate monomer unit to the styrene monomer unit (that is, the weight of the acrylate monomer unit divided by the styrene monomer The weight of the unit) may be 1.2 to 5, preferably 1.8 to 5, and more preferably 2 to 5. Acrylate The weight-average particle diameter of the system-diene-styrene copolymer may be 50 nm to 500 nm.

Weight ratio of acrylate-diene-styrene copolymer to acrylonitrile-diene-styrene copolymer (i.e., the weight of acrylate-diene-styrene copolymer divided by The weight of the acrylonitrile-diene-styrene copolymer may be 0.4 to 2, preferably 0.6 to 2, and more preferably 0.7 to 2.

The thermoplastic resin composition containing polycarbonate can make the thermoplastic resin composition have excellent mechanical properties, such as high tensile strength and high impact strength.

The thermoplastic resin composition includes polycarbonate, styrene-acrylonitrile-based copolymer, acrylonitrile-diene-styrene-based copolymer, and acrylate-diene-styrene-based copolymer. The total content is 100 parts by weight, and the content of the polycarbonate may be 60 to 90 parts by weight, preferably 65 to 85 parts by weight, and more preferably 70 to 80 parts by weight.

Polycarbonates can include a variety of polycarbonates with different properties. For example, the polycarbonate may include a first polycarbonate and a second polycarbonate having different properties. In the embodiment, the first polycarbonate may account for 60% to 90% of the weight of the polycarbonate, and the second polycarbonate may account for 10% to 40% of the weight of the polycarbonate. In one embodiment, the first polycarbonate may account for 62% to 88% of the weight of the polycarbonate, and the second polycarbonate may account for 12% to 38% of the weight of the polycarbonate. In one embodiment, the first polycarbonate may account for 64% to 86% of the weight of the polycarbonate, and the second polycarbonate may account for 14% to 36% of the weight of the polycarbonate. In an embodiment, the weight ratio of the second polycarbonate to the first polycarbonate (that is, the weight of the second polycarbonate divided by the weight of the first polycarbonate) may be 0.05 to 1.5, preferably 0.07 to 1.1, more preferably 0.1 to 0.8. In one embodiment, for example In other words, the polycarbonate may be composed of the first polycarbonate and the second polycarbonate, that is, the total weight of the polycarbonate is the sum of the weight of the first polycarbonate and the weight of the second polycarbonate.

The weight average molecular weight (Mw) of the polycarbonate measured by gel permeation chromatography (GPC) may be 5,000 to 100,000, preferably 7,000 to 50,000, and more preferably 10,000 to 35,000. For example, the weight average molecular weight (Mw) of the first polycarbonate may be 24,000 to 30,000, and the weight average molecular weight (Mw) of the second polycarbonate may be 15,000 to 20,000.

In embodiments, the polycarbonate may be any known homopolycarbonates or copolycarbonates. The polycarbonate can be prepared by any known method, such as a phosgene method, a transesterification method, a ring-opening polymerization method, a carbon dioxide polymerization method, and the like. The phosgene method is an interfacial polymerization of a dihydroxyaryl compound dissolved in an alkaline solution and a phosgene (phosgene) dissolved in a solvent (such as dichloromethane) in an homogeneous system or a heterogeneous system with an amine as a catalyst By reaction, aromatic polycarbonate can be obtained. The transesterification method is to perform an ester interchange reaction between a dihydroxyaryl compound and a carbonate compound (such as diphenyl carbonate, dimethyl carbonate) in a molten state to obtain an aromatic polycarbonate. Preferably, the polycarbonate can be prepared by transesterifying a dihydroxyaryl compound with a carbonate compound. The dihydroxyaryl compounds are selected from the group consisting of dihydroxybiphenyl compounds, bis- (hydroxyphenyl) alkane compounds, bis- (hydroxyphenyl) bisalkane compounds, and bis- (hydroxyphenyl)- Sulfides, bis- (hydroxyphenyl) ether compounds, bis- (hydroxyphenyl) ketone compounds, bis- (hydroxyphenyl) fluorene compounds, bis- (hydroxyphenyl) fluorene compounds, alkyl groups A cyclohexylene bisphenol compound, a bis- (hydroxyphenyl) -diisopropylbenzene compound, an alkylated derivative of the compound, a halogenated derivative of the compound, or a combination thereof. Specific examples of the aforementioned dihydroxyaryl compounds include 4,4-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane (2,2-bis (4-hydroxyphenyl) propane, bisphenol A for short) (bisphenol A)), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane (1,1-bis (4-hydroxyphenyl) cyclohexane), α , α -bis- (4-hydroxyphenyl) -diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2 , 2-bis- (3-chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5- Dimethyl-4-hydroxyphenyl) -propane (2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane), bis- (3,5-dimethyl-4-hydroxyphenyl)- Hydrazone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (3,5-dimethyl-4-hydroxybenzene ) -Cyclohexane, α , α-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro 4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane (2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ), Halogenated bisphenol, hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide), bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, homopolymers of the above compounds, the above compounds Copolymer or combination thereof. Preferably, the dihydroxyaryl compound is 2,2-bis- (4-hydroxyphenyl) -propane. The carbonate-based compound includes, but is not limited to, diphenyl carbonate, dimethyl carbonate, diethyl carbonate, or a combination thereof. In addition, the structure of the terminal group of the polycarbonate is not particularly limited. The terminal group includes, but is not limited to, a hydroxyl group, an aromatic hydrocarbon-based carbonate, an alkyl carbonate, and the like. In one embodiment, the polycarbonate may include bisphenol-A (ie, 2,2'-bis- (4-hydroxyphenyl) -propane) in a dihydroxy compound, and a carbonate bond in the compound. Diphenyl carbonate is a polycarbonate compound formed by the transesterification (melt method) reaction polymerization.

The thermoplastic resin composition includes polycarbonate, styrene-acrylonitrile-based copolymer, acrylonitrile-diene-styrene-based copolymer, and acrylate-diene-styrene-based copolymer. The content of the styrene-acrylonitrile copolymer may be 5 to 30 parts by weight, preferably 8 to 25 parts by weight, and more preferably 10 to 18 parts by weight based on the total amount of 100 parts by weight. .

The styrene-acrylonitrile-based copolymer may be polymerized from an acrylonitrile-based monomer, a styrene-based monomer, and other copolymerizable monomers. In one embodiment, the styrene-acrylonitrile copolymer contains 14 wt% to 34 wt% of acrylonitrile monomer units, 66 wt% to 86 wt% of styrene monomer units, and 0 wt% to 15 wt% of other copolymerizable units Polymerized monomer units. In one embodiment, the styrene-acrylonitrile copolymer contains 19% to 29% by weight of acrylonitrile monomer units, 71% by weight to 81% by weight of styrene monomer units, and 0% by weight to 10% by weight of other copolymerizable units. Polymerized monomer units. In one embodiment, the styrene-acrylonitrile copolymer contains 22 wt% to 26 wt% of acrylonitrile monomer units, 74 wt% to 78 wt% of styrene monomer units, and 0 wt% to 4 wt% of other copolymerizable polymers. Composite monomer unit. In one embodiment, the weight of the styrene-acrylonitrile copolymer is the weight of the acrylonitrile-based monomer unit, the styrene-based monomer unit, and other copolymerizable monomer units. In one embodiment, the styrene-acrylonitrile copolymer is a polymer obtained by polymerization of acrylonitrile and styrene, and the weight of the styrene-acrylonitrile copolymer is acrylonitrile (monomer unit) and The weight of styrene (monomer unit) is combined. The weight average molecular weight of the styrene-acrylonitrile-based copolymer may be 60,000 to 400,000, preferably 100,000 to 200,000, and more preferably 120,000 to 150,000.

Styrene-based monomers may include styrene, α-methylstyrene, p-third butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4 -Dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene or bromostyrene, dibromo-styrene, 2,4,6-tribromostyrene, etc., among which styrene Or α-methylstyrene is preferred. These styrene-based monomers may be used alone or in combination.

The acrylonitrile-based monomer may include acrylonitrile, α-methacrylonitrile, methacrylonitrile, malononitrile, and butyronitrile, among which acrylonitrile is preferred. These acrylonitrile-based monomers can be used alone or in combination.

Other copolymerizable monomers may include an acrylate-based monomer and a monofunctional maleimide-based monomer.

Specific examples of the acrylate-based monomer may include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylpentyl acrylate, Octyl acrylate, polyethylene glycol diacrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylic acid Octyl alkyl, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate, neopentyl dimethacrylate (neopentyl dimethacrylate), etc. Preferred are methyl methacrylate, butyl methacrylate, and butyl acrylate.

Specific examples of the monofunctional maleimide-based monomer may include maleimide, N-methylmaleimide, N-isopropylmaleimide, and N-butylmaleimide. Fluorenimine, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide Lyme imine, N-2-methylphenylmaleimide, N-2,3-dimethylphenylmaleimide, N-2,4-dimethylphenylmaleimide Imine, N-2,3-diethylphenylmaleimide, N-2,4-diethylphenylmaleimide, N-2,3-dibutylphenylmaleimide Fluorenimine, N-2,4-dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-2,3-dichlorophenylmaleimide Fluorenimine, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide, or N-2,4-dibromophenylmaleimide Amine, etc. N-phenylmaleimide is preferred.

In addition, other copolymerizable monomers may also include acrylic monomers (e.g. acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous methyl fumaric acid, Fumar Unsaturated carboxylic acid compounds such as fumaric acid, itaconic acid and their esterification monomers (e.g. dimethyl fumarate, dibutyl itaconic acid), ethylene, propylene, 1- Butene, 1-pentene, 4-methyl 1-pentene, chlorine Ethylene, vinyl chloride fork, ethylene tetrafluoride, ethylene chlorotrifluoride, propylene hexafluoride, allylamine, isobutenylamine, vinyl acetate, ethyl vinyl ether, methyl vinyl ketone, triene Propyl isocyanate (triallyl isocyanate) and the like. The above other copolymerizable monomers may be used alone or in combination of several kinds.

The polymerization method of the styrene-acrylonitrile copolymer can be a block polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like. Among them, a block polymerization method or a solution polymerization method is preferred. In addition, the method for producing a styrene-acrylonitrile-based copolymer preferably includes a polymerization reaction using a reactor capable of performing a continuous block or solution polymerization method. The reactor includes: a column flow reactor, a completely mixed reactor (CSTR), or a tube reactor containing a static mixing element, etc., of which a completely mixed reactor is preferred. The number of the reactors may be one, or two or more of them may be used in combination.

In one embodiment, a method for preparing a styrene-acrylonitrile copolymer is performed by a solution polymerization reaction. The solvent used in the solution polymerization reaction is, for example, toluene, ethylbenzene or methyl ethyl ketone. Preferably, the operating temperature range of the solution polymerization reaction is 70 ° C to 140 ° C; more preferably, the operating temperature range of the solution polymerization reaction is 90 ° C to 130 ° C.

In an embodiment, when preparing the styrene-acrylonitrile copolymer, a thermal polymerization method may be adopted or a polymerization initiator may be added to the reaction, wherein the polymerization initiator is, for example, but not limited to, hydrogen peroxide ( Hydroperoxides), for example: tert-butyl hydroperoxide or Isopropylcumyl hydroperoxide; etc .; peroxyketals (Peroxyketal) compounds, such as: 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane (1,1-Di- (tert-butylperoxy) -3,3, 5-trimethylcyclohexane) or 2,2-di (4,4-di (tert-butylperoxy) cyclohexyl) propane (2,2-Di (4,4-di (tert-butylperoxy) cyclohexyl) propane)); Diacyl peroxides compounds, for example: Dilauroyl peroxide, Decanoyl peroxide, Dibenzoyl peroxide (hereinafter referred to as BPO), etc .; Peroxyesters compounds, such as: t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanol peroxidation) Alkane (2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane), etc .; ketal peroxides, for example: 4,4-diperoxy third butyl-valeric acid-n-butyl ester (4 , 4-di-t-butyl peroxy valeric acid-n-butyl ester (referred to as TX-17), etc .; peroxycarbonates compounds, for example: 2-ethylhexyl tert-pentyl peroxycarbonate (tert -Amylperoxy 2-ethylhexyl carbonate), 2-ethylhexyl tert-butyl peroxy Carbonate (tert-Butylperoxy 2-ethylhexyl carbonate) and the like; or an azo compound having a nitro group and the like cyclohexanes. Based on the total amount of the styrene-based monomer, acrylonitrile-based monomer, and other copolymerizable monomers being 100 parts by weight, the addition amount of the polymerization initiator ranges from 0.01 to 2.0 parts by weight, preferably It is 0.01 to 1.0 part by weight.

The grafting rate of the styrene-acrylonitrile copolymer can be controlled by adjusting the conditions of the graft polymerization reaction, such as: polymerization temperature, chemical properties of the rubbery polymer, particle size, monomer addition rate, initiator , Chain transfer agent, milk Factors such as the amount and type of chemical agents will affect the degree of grafting.

For example, the chain transfer agent may include: n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan ) Or tert-dodecyl mercaptan. In one embodiment, the total amount of the monomer mixture is 100 parts by weight, and the use amount of the chain transfer agent ranges from 0.01 to 0.1 parts by weight.

The thermoplastic resin composition includes polycarbonate, styrene-acrylonitrile-based copolymer, acrylonitrile-diene-styrene-based copolymer, and acrylate-diene-styrene-based copolymer. The total content is 100 parts by weight, and the content of the acrylonitrile-diene-styrene copolymer may be 1 to 15 parts by weight, preferably 2 to 12 parts by weight, and more preferably 5 parts by weight To 10 parts by weight.

The acrylonitrile-diene-styrene copolymer can be polymerized from an acrylonitrile-based monomer, a diene-based monomer, a styrene-based monomer, and other copolymerizable monomers. In one embodiment, the acrylonitrile-diene-styrene copolymer may contain 50 wt% to 90 wt% diene monomer units, 1 wt% to 30 wt% acrylonitrile monomer units, and 8 wt% to 45 wt%. % Of styrene-based monomer units and 0% to 20% by weight of other copolymerizable monomer units. In one embodiment, the acrylonitrile-diene-styrene copolymer may contain 55 wt% to 85 wt% diene monomer units, 3 wt% to 25 wt% acrylonitrile monomer units, and 12 wt% to 40 wt%. % Of styrene-based monomer units and 0% to 15% by weight of other copolymerizable monomer units. In one embodiment, the acrylonitrile-diene-styrene copolymer may contain 60 wt% to 80 wt% diene monomer units, 5 wt% to 20 wt% acrylonitrile monomer units, and 15 wt% to 35 wt. % Of styrene series Body units and other copolymerizable monomer units from 0% to 10% by weight.

The type of the acrylonitrile-based monomer described above is the same as the acrylonitrile-based monomer of the aforementioned styrene-acrylonitrile-based copolymer, and will not be repeated here.

The type of the above-mentioned styrene-based monomer is the same as that of the styrene-acrylonitrile-based copolymer of the aforementioned styrene-based copolymer, and will not be repeatedly described here.

The types of other copolymerizable monomers mentioned above are the same as those of other copolymerizable monomers of the aforementioned styrenic-acrylonitrile copolymer, and will not be repeated here.

The diene-based monomer may include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloroprene, 1 1,3-pentadiene, 2-phenylbutadiene, 1,3-hexadiene, 1,3-octadiene, etc., among which 1,3-butadiene, 2-methyl-1,3 -Butadiene, chloroprene or 1,3-pentadiene are preferred. These diene-based monomers may be used alone or in combination.

In one embodiment, the acrylonitrile-diene-styrene copolymer may be a graft copolymer having acrylonitrile monomer units, butadiene monomer units, and styrene monomer units.

In one embodiment, the acrylonitrile-diene-styrene copolymer may be a graft copolymerized by a styrene monomer, an acrylonitrile monomer, and other copolymerizable monomers on a diene rubber. Branch copolymer.

The diene rubber may be a polymer obtained by polymerizing the diene monomers described above, or a copolymer obtained by copolymerizing two or more diene monomers. Among them, polybutadiene is preferred. Diene rubber is also available Copolymers obtained by copolymerizing the above diene monomers with other vinyl-containing monomers, for example, butadiene-styrene copolymers, butadiene-vinyltoluene copolymers, and the like Olefin-styrene copolymer; butadiene-acrylonitrile copolymer, butadiene-methacrylonitrile copolymers such as butadiene-nitrified ethylene-based copolymer; butadiene-methyl acrylate copolymer , Butadiene-ethyl acrylate copolymer, butadiene-butyl acrylate copolymer, butadiene-2-ethyl acrylate copolymer, butadiene-methyl methacrylate copolymer, butadiene-methyl Butadiene- (meth) acrylic acid alkyl ester copolymers and the like. The diene rubber may be a terpolymer having a butadiene content of 50% by weight or more.

In one embodiment, the weight average particle diameter of the acrylonitrile-diene-styrene copolymer may be 50 nm to 800 nm.

In one embodiment, the weight average particle diameter of the acrylonitrile-diene-styrene copolymer may be 200 nm to 400 nm, for example, 300 nm.

The weight average particle diameter of the acrylonitrile-diene-styrene copolymer was measured in a latex state. MASTERSIZER 2000 manufactured by MALVERN Instrument Co., Ltd. was used as a measuring device, and the weight average particle diameter (nm) was measured by a light scattering method.

Acrylonitrile-diene-styrene copolymers can be prepared by individual block, solution, suspension, or emulsion polymerization methods, or by a combination of these polymerizations, such as emulsion-block or block The state-suspension polymerization method is preferably an emulsion polymerization method, a block polymerization method, or a solution polymerization method, and the emulsion polymerization method is the most preferable.

In one embodiment, the method for preparing acrylonitrile-diene-styrene copolymer can be a diene rubber emulsion, and a styrene monomer and propylene are added. Nitrile monomers and other copolymerizable monomers, and optionally adding additives such as emulsifiers, polymerization initiators, or chain transfer agents, are prepared by graft polymerization to obtain graft copolymers. The diene-based rubber emulsion may be prepared by an emulsion polymerization method, or may be further enlarged after the emulsion polymerization reaction.

In one embodiment, the operating temperature range of the aforementioned emulsion polymerization reaction is preferably 90 ° C. or lower; in another embodiment, the operating temperature range of the aforementioned emulsion polymerization reaction is preferably 10 ° C. to 80 ° C.

The graft ratio of acrylonitrile-diene-styrene copolymer can be controlled by adjusting the conditions of the graft polymerization reaction, such as: polymerization temperature, chemical properties of rubbery polymers, particle size, and monomer addition rate Factors such as, amount of initiator, chain transfer agent, emulsifier, etc. all affect the degree of grafting.

In one embodiment, various conventional emulsifying radical polymerization initiators can be used as the aforementioned initiators, such as organic hydrogen peroxides, such as diisopropyl benzene hydroperoxide. Cumene hydroperoxide; peroxides, such as: dibenzoyl peroxide, tert-butyl peroxide; persulfates, such as : Potassium persulfate, etc. Among them, organic hydrogen peroxides are preferred.

In one embodiment, for example, the total amount of the styrene-based monomer, the acrylonitrile-based monomer, and other copolymerizable monomers is 100 parts by weight, and the amount of the initiator used may range from 0.01 to 5.0 weight. Parts, preferably 0.1 to 3.0 parts by weight. Moreover, the aforementioned initiator can be added in increments, which is beneficial to the progress of the graft polymerization reaction.

Moreover, in the aforementioned emulsion polymerization reaction, a chain transfer agent may be optionally added to affect the graft ratio of the acrylonitrile-diene-styrene copolymer. The chain transfer agent can be used alone or in combination, and the chain transfer agent includes but is not limited to n-dodecyl mercaptan (NDM), third-dodecyl mercaptan, TDM for short), n-butyl mercaptan, n-octyl mercaptan, and the like.

In an embodiment, preferably, based on the total amount of the styrene-based monomer, acrylonitrile-based monomer, and other copolymerizable monomers being 100 parts by weight, the range of the amount of the chain transfer agent used is, for example, 0.05 ~ 0.5 parts by weight, preferably 0.1 to 1.0 parts by weight.

In one embodiment, the acrylonitrile-diene-styrene copolymer emulsion after the graft polymerization reaction is completed is further added with an appropriate coagulant for coagulation. Generally, the coagulants used are sulfuric acid and acetic acid. Alkaline earth metal salts, for example: calcium salts of calcium chloride, magnesium chloride, magnesium salts of magnesium sulfate, aluminum salts of aluminum sulfate, of which alkaline earth metal salts are preferred. The coagulated polymer slurry is dehydrated to remove water, and then dried to obtain a powdered acrylonitrile-diene-styrene copolymer.

In an embodiment, preferably, based on 100 parts by weight of the acrylonitrile-diene-styrene copolymer, the use amount of the coagulant is, for example, 0.5 to 5.0 parts by weight, and preferably 1.0 to 3.0 parts by weight.

In the thermoplastic resin composition, polycarbonate, styrene-acrylonitrile-based copolymer, acrylonitrile-diene-styrene-based copolymer, and acrylate The total amount of the system-diene-styrene copolymer is 100 parts by weight, and the content of the acrylate-diene-styrene copolymer may be 0.5 part by weight to 15 parts by weight, and preferably 1 part by weight. Parts to 12 parts by weight, more preferably 2 parts to 8 parts by weight. In one embodiment, when the addition amount of the acrylate-diene-styrene copolymer is more than 2 parts by weight, the low-temperature impact resistance of the thermoplastic resin composition (or its molded article) can be significantly improved. In one embodiment, when the addition amount of the acrylate-diene-styrene copolymer is between 2 and 10 parts by weight, the low-temperature impact resistance of the thermoplastic resin composition (or its molded article) can be significantly improved. , And the cost will not increase significantly.

In one embodiment, the thermoplastic resin composition, wherein the polycarbonate includes a first polycarbonate and a second polycarbonate, and the weight average molecular weight of the first polycarbonate is 24,000 to 30,000. The weight average molecular weight of the second polycarbonate is 15,000 ~ 20,000, wherein the weight ratio of the acrylate-diene-styrene copolymer to the second polycarbonate (that is, the acrylate-diene- The weight of the styrenic copolymer divided by the weight of the second polycarbonate may be 0.08 to 3. In one embodiment, the thermoplastic resin composition, wherein the polycarbonate includes a first polycarbonate and a second polycarbonate, and the weight average molecular weight of the first polycarbonate is 24,000 to 30,000. The weight average molecular weight of the second polycarbonate is 15,000 to 20,000, and a weight ratio of the acrylate-diene-styrene copolymer to the second polycarbonate may be 0.1 to 2. In one embodiment, the thermoplastic resin composition, wherein the polycarbonate includes a first polycarbonate and a second polycarbonate, and the weight average molecular weight of the first polycarbonate is 24,000 to 30,000. The weight average molecular weight of the second polycarbonate is 15,000 ~ 20,000, wherein the propylene The weight ratio of the acid ester-diene-styrene copolymer to the second polycarbonate may be 0.15 to 1.

In one embodiment, the acrylate-diene-styrene copolymer may be a graft copolymer obtained by graft polymerization of an acrylate monomer and a styrene monomer on a diene rubber.

The type of the above-mentioned acrylate monomer is the same as the acrylate monomer in the other copolymerizable monomers of the aforementioned styrene-acrylonitrile copolymer, and will not be repeated here.

The type of the above-mentioned styrene-based monomer is the same as that of the styrene-acrylonitrile-based copolymer of the aforementioned styrene-based copolymer, and will not be repeatedly described here.

The type of the diene rubber is the same as the diene rubber of the acrylonitrile-diene-styrene copolymer described above, and will not be repeated here.

In one embodiment, the weight average particle diameter of the acrylate-diene-styrene copolymer is 50 nm to 500 nm. In one embodiment, the weight average particle diameter of the acrylate-diene-styrene copolymer may be 70 nm to 300 nm, for example, 150 nm. When the weight average particle diameter of the acrylate-diene-styrene copolymer is more than 50 nm, a resin having high impact resistance can be obtained. If the weight average particle diameter of the acrylate-diene-styrene copolymer is less than 500 nm, the gloss of the resin can be improved or maintained.

The weight average particle diameter of the acrylate-diene-styrene copolymer was measured in a latex state. MASTERSIZER 2000 manufactured by MALVERN Instrument Co., Ltd. was used as a measuring device, and the weight was measured by a light scattering method. Average particle size (nm). In one embodiment, a method for synthesizing an acrylate-diene-styrene copolymer includes the following steps: firstly synthesize a diene rubber emulsion (BR emulsion) with a small particle diameter of 50 to 150 nm, wherein The content of diene (for example, butadiene) is 80 to 95%, and the content of styrene (for example, styrene) is 5 to 20%. Then, a diene rubber emulsion (BR emulsion) was subjected to graft polymerization. For example, styrene-based (such as styrene) and acrylate-based (such as methyl methacrylate) are added in a continuous addition manner to obtain an acrylate-diene-styrene resin emulsion. This acrylate-diene-styrene resin emulsion is coagulated, washed, and dried to obtain an acrylate-diene-styrene copolymer. In one embodiment, the acrylate-diene-styrene copolymer is methyl methacrylate-butadiene-styrene copolymer (MBS).

The thermoplastic resin composition may also include other materials, such as antioxidants, lubricants, or other additives used according to actual needs.

In one embodiment, the total amount of the thermoplastic resin composition is 100 parts by weight, and the amount of the antioxidant used is 2 parts by weight or less.

The antioxidant may include a phenol-based antioxidant, a thioether-based antioxidant, a phosphorus-based antioxidant, or other types of antioxidants, or a combination thereof.

Phenolic antioxidants such as, but not limited to, 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenylpropanoic acid octadecyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid octadecyl ester, model: antioxidant IX-1076), triethylene glycol bis [3- (3-third-butyl-5-methyl-4-hydroxyphenyl) propionate], tetra [Methenyl-3- (3,5-bis-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy -6-A Phenylbenzyl) -4-methylphenylacrylate, 2,2'-methylidene-bis (4-methyl-6-third butylphenol) (2,2'-methylenebis (4-methyl -6-tert-butylphenol), Model: Antioxidant 2246), 2,2'-thiobis (4-methyl-6-third butylphenol), 2,2'-thio-diethylene- Bis [3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate], or 2,2'-ethylenediamine-bis [ethyl-3- (3,5-bis -Third butyl-4-hydroxyphenyl) propionate] and the like.

The thioether-based antioxidant can be used alone or in combination. Sulfide-based antioxidants such as, but not limited to, distearyl thiodipropionate, dipalmitine thiodipropionate, pentaerythritol-tetra- (β-dodecylmethyl thiopropionate), or Dioctadecyl sulfide and the like.

The phosphorus-based antioxidant may be used alone or in combination. The phosphorus-based antioxidant may include a phosphite-containing phosphorus-based antioxidant, a phosphate-containing phosphorus-based antioxidant, or a combination thereof. Examples of the phosphite-containing phosphorus-based antioxidant include, but are not limited to, tris (nonylphenyl) phosphite, dodecyl phosphite, 4,4′-butylenebis (3-methyl-6-th Tributylphenyl-bistridecyl phosphite), tris (2,4-third butylphenyl) phosphite, and the like. The phosphate-containing phosphorus-based antioxidant is, for example, but not limited to, tetra (2,4-third butylphenyl) -4,4'-biphenylphenyl phosphate, or 9,10-dihydro-9-oxyl -10-Phenanthrene-10-oxophosphate and so on.

The lubricant can be used alone or in combination. Lubricants such as, but not limited to, metal soaps such as calcium stearate, magnesium stearate, lithium stearate, ethylene bis-stearamide (EBA), methylene distearylamine, Ammonium palmitate, butyl stearate, palmityl stearate, pentaerythritol tetrafatty acid ester, polypropionate tristearate, compounds such as behenic acid, stearic acid, polyethylene wax, Octacosanoic acid wax, carnuba wax, petroleum wax and the like. In one embodiment, the The total amount of the thermoplastic resin composition is 100 parts by weight, and the amount of the lubricant used is in the range of 2 parts by weight or less.

Additives may include flame retardant aids, heat stabilizers, release agents, processing aids, coupling agents, antistatic agents, dispersants (dispersant), weather resistant agents, ultraviolet absorbers, colorants such as pigments or dyes, and inorganic fillers and the like. Additives are not limited to being added during the polymerization reaction, after the polymerization reaction, before coagulation, or during extruding and kneading.

In order to make the above-mentioned objects, features, and advantages of this disclosure more comprehensible, the preferred embodiments are described below in detail with the accompanying drawings, as follows:

<Polycarbonate (A)>

Polycarbonate, which is commercially available from Chi Mei Corporation, is used as the first polycarbonate and PC-175 as the second polycarbonate. The polycarbonate contains 100 parts by weight of polycarbonate and 0.05 parts by weight or less of toner and antioxidant. , Lubricant, weathering agent, etc. The weight average molecular weight (Mw) of PC-110 was 27,000, and the weight average molecular weight (Mw) of PC-175 was 17,000.

<Preparation of styrene-acrylonitrile copolymer (B)>

76 parts by weight of styrene, 24 parts by weight of acrylonitrile, and 8 parts by weight of ethylbenzene were mixed, and then 0.01 parts by weight of tertiary-dodecyl mercaptan was mixed, and the flow rate was continuous at 35 kg / hr. It was supplied into a completely mixed continuous reactor, wherein the volume of the reactor was 40 liters, the internal temperature was maintained at 145 ° C, the pressure was maintained at 4 kg / cm ² , and the overall conversion rate was about 50%.

After the polymerization is completed, the obtained copolymer solution is heated in a preheater, and volatile substances such as unreacted monomers and solvents are removed in a reduced pressure degassing tank. Next, the obtained polymer melt was extruded and granulated to obtain a styrene-acrylonitrile copolymer (AS) having a weight average molecular weight (Mw) of 140,000 and a styrene monomer unit content of 76% and an acrylonitrile monomer. The unit content is 24%.

<Preparation of acrylonitrile-butadiene-styrene copolymer (C)>

95 parts by weight of 1,3-butadiene, 5.0 parts by weight of acrylonitrile, 15 parts by weight of potassium persulfate solution (1% by weight), 2.3 parts by weight of rosin soap as an emulsifier, 140.0 parts by weight of distilled water, and 0.2 parts by weight of a third-dodecyl mercaptan as a chain transfer agent was reacted at a temperature of 65 ° C. for 12 hours to obtain a butadiene rubber containing a conversion rate of about 94%, a solid content of about 40%, and an average particle diameter of 100 nm. Emulsion.

Using 3.3 parts by weight (dry weight) of the polymer coagulant, the particle size of the rubber particles in 100 parts by weight (dry weight) of the 100 nm butadiene rubber emulsion was increased to obtain a one-particle enlarged butadiene rubber. Emulsion.

100.0 parts by weight of the aforementioned enlarged butadiene rubber emulsion (dry weight), 25 parts by weight of styrene, 8.3 parts by weight of acrylonitrile, 0.2 parts by weight of tertiary-dodecyl mercaptan, and 0.5 parts by weight Cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2% by weight), 3.0 parts by weight of formaldehyde sodium bisulfite solution (concentration 10% by weight), 20.0 parts by weight of ethylenediamine tetraacetic acid solution (Concentration: 0.25% by weight), 1.1 parts by weight of rosin soap, and 200.0 parts by weight of distilled water were mixed and reacted. Among them, styrene and acrylonitrile were continuously added to the reaction system for polymerization within 5 hours. After coagulation with calcium chloride (CaCl ₂ ), dehydration, and drying to a moisture content of 2% or less, the acrylonitrile-butadiene-styrene copolymer required in this embodiment can be obtained. The acrylonitrile-butadiene-styrene copolymer has a weight average particle diameter of 300 nm and the acrylonitrile monomer unit content is 7.5%, the styrene monomer unit content is 17.5%, and the butadiene monomer unit content is 75% .

<Preparation of methyl methacrylate-butadiene-styrene copolymer (D)>

The preparation steps of the methyl methacrylate-butadiene-styrene copolymer in this preparation example (including the first methyl methacrylate-butadiene-styrene copolymer (D-1), the second methacrylic acid The methyl ester-butadiene-styrene copolymer (D-2) was prepared as follows: 95 parts by weight of 1,3-butadiene, 5.0 parts by weight of styrene, and 15 parts by weight of a potassium persulfate solution ( 1% by weight), 2.3 parts by weight of rosin soap as an emulsifier, 140.0 parts by weight of distilled water, and 0.2 parts by weight of a third-dodecyl mercaptan as a chain transfer agent were reacted at a temperature of 65 ° C for 12 hours to obtain conversion A butadiene rubber emulsion having a rate of about 94%, a solid content of about 40%, and a weight average particle diameter of 100 nm.

《The First Methyl Methacrylate-Butadiene-Styrene Copolymer (D-1)》

100.0 parts by weight of the above-mentioned butadiene rubber emulsion (dry weight) having an average particle diameter of 100 nm, 22 parts by weight of methyl methacrylate, 6.3 parts by weight of styrene, and 0.2 parts by weight of tertiary-dodecyl group Thiol, 0.5 parts by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration 0.2% by weight), 3.0 parts by weight of a formaldehyde sodium bisulfite solution (concentration 10% by weight), 20.0 parts by weight An ethylenediamine tetraacetic acid solution (concentration: 0.25% by weight) and 200.0 parts by weight of distilled water were mixed and reacted. Among them, methyl methacrylate and styrene were added to the reaction system for polymerization within 5 hours by continuous addition. Finally, the salt solution is coagulated, dehydrated, and then dried to a moisture content of less than 2% to obtain the first methyl methacrylate-butadiene-styrene copolymer required in this embodiment.

Determination of monomer composition of methyl methacrylate-butadiene-styrene copolymer: The measurement is to dissolve methyl methacrylate-butadiene-styrene copolymer in CDCl ₃ deuterated solvent at room temperature It was performed under conditions such as a nuclear magnetic resonance spectrometer (manufactured by Bruker Co., Ltd., model AV 400, NMR spectrometer) with a total of 24 times. Tetra-Methyl Silane (TMS) is used as a zero-point reference material for the chemical shift δ value. Based on the chemical shift in the NMR spectrum, 3.4 ~ 3.6ppm is the characteristic signal of -OCH ₃ group in (meth) acrylate, 5.5 ~ 6.5ppm is the characteristic signal of -C = CH group in butadiene and 7.0 ~ 7.5ppm It is a characteristic signal of styrene Ar-H, and the respective composition of the methyl methacrylate-butadiene-styrene copolymer is calculated from its signal strength. The unit is% by weight.

The first methyl methacrylate-butadiene-styrene copolymer (D-1) was According to a nuclear magnetic resonance spectrometer (NMR spectrometer) analysis, the proportion of each monomer unit was 17% of methyl methacrylate monomer units, 78% of butadiene monomer units, and 5% of styrene monomer units. The particle size is 150 nm. In Table 1, the methyl methacrylate monomer unit is represented by the symbol MMA, the butadiene monomer unit is represented by the symbol BD, and the styrene monomer unit is represented by the symbol SM. In the first methyl methacrylate-butadiene-styrene copolymer (D-1), the weight ratio of the methyl methacrylate monomer unit (MMA) to the styrene monomer unit (SM) was 3.4 ( (D), the weight ratio of MMA / SM).

《Second methyl methacrylate-butadiene-styrene copolymer (D-2)》

100.0 parts by weight of the aforementioned butadiene rubber emulsion (dry weight) having an average particle size of 100 nm, 29 parts by weight of methyl methacrylate, 24 parts by weight of styrene, and 0.2 parts by weight of tertiary-dodecyl Thiol, 0.5 parts by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration 0.2% by weight), 3.0 parts by weight of a formaldehyde sodium bisulfite solution (concentration 10% by weight), 20.0 parts by weight An ethylenediamine tetraacetic acid solution (concentration: 0.25% by weight) and 200.0 parts by weight of distilled water were mixed and reacted. Among them, methyl methacrylate and styrene were added to the reaction system for polymerization within 5 hours by continuous addition. Finally, the salt solution is coagulated, dehydrated, and then dried to a moisture content of less than 2% to obtain the second methyl methacrylate-butadiene-styrene copolymer required in this embodiment.

The second methyl methacrylate-butadiene-styrene copolymer (D-2) was analyzed by a nuclear magnetic resonance spectrometer (NMR spectrometer), and the proportion of each monomer unit was composed. They are 19% of methyl methacrylate monomer units, 65% of butadiene monomer units, and 16% of styrene monomer units, and their weight average particle diameters are 150 nm. In the second methyl methacrylate-butadiene-styrene copolymer (D-2), the weight ratio of the methyl methacrylate monomer unit (MMA) to the styrene monomer unit (SM) was 1.18 ( (D), the weight ratio of MMA / SM).

<Thermoplastic resin composition>

Table 1 shows the components of the thermoplastic resin composition of the examples and comparative examples. Table 2 shows the physical property test results of molded articles obtained from the thermoplastic resin compositions of Examples and Comparative Examples.

Take Example 1 as an example. The thermoplastic resin composition is 50 parts by weight of the first polycarbonate (PC-1) and 25 parts by weight of the second polycarbonate (PC-2) as the polycarbonate (PC), and 15 parts by weight of benzene Ethylene-acrylonitrile copolymer (B), 7.0 parts by weight of acrylonitrile-butadiene-styrene copolymer (C), and 3.0 parts by weight of first methyl methacrylate-butadiene-styrene copolymer ( D-1), after dry mixing with a Hanschel mixer, a twin-shaft extruder with an exhaust port (made by Zeki Industry Co., Ltd.) with a screw sleeve temperature of 210 to 275 ° C and a die temperature of 270 ° C; Model ZPT-25) can be melted, kneaded and granulated to obtain granular products. Wherein, the weight ratio of the first methyl methacrylate-butadiene-styrene copolymer (D-1) to the acrylonitrile-butadiene-styrene copolymer (C) is 0.43 ((D) / (C ) 'S weight ratio). The first polycarbonate (PC-1) accounts for 67% by weight of the polycarbonate (A) (PC-1 accounts for the weight percentage of (A)). The weight ratio of the second polycarbonate (PC-2) to the first polycarbonate (PC-1) is 0.5 (PC-2 / PC-1 weight ratio). The weight ratio of the first methyl methacrylate-butadiene-styrene copolymer (D-1) to the second polycarbonate (PC-2) was 0.12 ((D) / PC-2 weight ratio).

The thermoplastic resin compositions of Examples 2-6 and Comparative Examples 1-5 were prepared in the same manner as in Example 1. However, the difference is that the components and contents of the thermoplastic resin composition are changed as shown in Table 1.

<Property test>

The properties of the thermoplastic resin composition shown in Table 2 are described below.

Impact strength (IZOD): The thermoplastic resin composition is injection-molded to form a notched 1 / 8-inch-thick molded product test piece. Next, Izod impact strength was measured at 23 ° C / -30 ° C according to ISO 180 at a thickness of 1/8 ". The higher the impact strength, the better the impact resistance (unit: KJ / m ² ).

Tensile strength (TSy): The thermoplastic resin composition is injection-molded to form a 3 mm thick molded product test piece. Next, the tensile strength was measured according to ISO 527 at a 50mm / min stretch rate. Higher tensile strength indicates better mechanical properties (unit: MPa).

Melt flow index (MFR, MI, MVR): The thermoplastic resin composition is tested at a temperature of 260 ° C and a load of 5 kg in accordance with ISO 1133 (unit: cm3 / 10min).

Elongation (EL): injection molding of a thermoplastic resin composition A 3 mm-thick molded product test piece was formed. Next, the tensile strength was measured according to ISO 527 at a 50mm / min stretch rate. A larger elongation value indicates better elongation properties. (unit:%).

Drop-ball impact strength at low temperature: The thermoplastic resin composition is injection molded to form a 107mm × 107mm × 1/8 ”molded product test piece. These test pieces must be placed in a -40 ° C freezer before testing After 24 hours of freezing in accordance with the requirements of ASTM D3763, Dynatup 8250 was used for the measurement. The weight of the falling weight was 23.64 kg, the height of the falling weight was 0.56 meters, and the impact speed was 3.34 m / sec. Appearance evaluation. In Table 2, the symbol "◎" indicates that a hole with a diameter of less than 2cm is caused on the test piece after the impact; the symbol "○" indicates that a hole with a diameter of 2cm to 3cm is caused; the symbol "△" indicates that the diameter is greater than 3cm; The symbol “×” indicates that the diameter of the hole having a diameter greater than 3 cm was caused and the test piece was broken into two pieces, in which the fracture surface passed through the hole. That is, the impact strength of the thermoplastic resin composition is gradually marked as strong in the order of the symbol "×", the symbol "△", the symbol "○", and the symbol "◎".

<Evaluation Results>

Please refer to Table 2. Compared with the thermoplastic resin composition (Comparative Examples 1, 4, and 5) using the second methyl methacrylate-butadiene-styrene copolymer (D-2), The thermoplastic resin composition (Example 1-6) of the methyl acrylate-butadiene-styrene copolymer (D-1) based on elongation (EL) and low-temperature falling ball impact strength are better. This shows the heat content of the first methyl methacrylate-butadiene-styrene copolymer (D-1) The overall mechanical properties of the plastic resin composition are better.

In Examples 1-6, in addition to the better elongation (EL) and low-temperature falling ball impact strength, Examples 1-5 also have good flow characteristics. This shows that when the second polycarbonate (PC-2) is contained, the thermoplastic resin composition not only has good overall mechanical properties, but also has good processing characteristics.

Table 2

In summary, the present invention provides a thermoplastic resin composition. Among them, the thermoplastic resin composition can have good mechanical properties, such as good impact resistance, especially low-temperature falling ball impact strength, and thermoplasticity, by controlling the ratio of the acrylate-diene-styrene copolymer. The resin composition also has good processability. In this way, the thermoplastic resin composition of the present invention has wider applicability, and can better meet industry requirements for the properties of the resin composition.

In summary, although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application.

Claims (10)

A thermoplastic resin composition comprising 60 to 90 wt% polycarbonate, 5 to 30 wt% styrene-acrylonitrile copolymer, and 1 to 15 wt% acrylonitrile-diene-styrene copolymer And 2 to 15 wt% of the acrylate-diene-styrene copolymer, wherein the acrylate-diene-styrene copolymer has a diene monomer unit of the acrylate- 71% to 90% of the weight of the diene-styrene copolymer, wherein in the acrylate-diene-styrene copolymer, the proportion of the acrylate monomer unit to the styrene monomer unit The weight ratio is 1.2 ~ 5. The thermoplastic resin composition according to item 1 of the patent application range, wherein the diene monomer unit of the acrylate-diene-styrene copolymer accounts for the acrylate-diene- 71% to 88% of the weight of the styrenic copolymer. The thermoplastic resin composition according to item 1 of the patent application range, wherein the diene monomer unit of the acrylate-diene-styrene copolymer accounts for the acrylate-diene- 73% to 88% of the weight of the styrenic copolymer. The thermoplastic resin composition according to item 1 of the patent application scope, wherein the polycarbonate comprises a first polycarbonate and a second polycarbonate, and the first polycarbonate is a weight of the polycarbonate 60% ~ 90% of the second polycarbonate is 10% ~ 40% of the weight of the polycarbonate, the weight average molecular weight of the first polycarbonate is 24,000 ~ 30,000, and the second polycarbonate is The weight average molecular weight is 15,000 ~ 20,000. The thermoplastic resin composition according to item 1 of the patent application scope, wherein the polycarbonate comprises a first polycarbonate and a second polycarbonate, and the second polycarbonate has a The weight ratio is 0.05 to 1.5, the weight average molecular weight of the first polycarbonate is 24,000 to 30,000, and the weight average molecular weight of the second polycarbonate is 15,000 to 20,000. The thermoplastic resin composition according to item 1 of the patent application range, wherein the polycarbonate includes a first polycarbonate and a second polycarbonate, and the weight average molecular weight of the first polycarbonate is 24,000 ~ 30,000 The weight average molecular weight of the second polycarbonate is 15,000 ~ 20,000, wherein the weight ratio of the acrylate-diene-styrene copolymer to the second polycarbonate is 0.08 ~ 3. The thermoplastic resin composition according to item 1 of the patent application range, wherein the polycarbonate includes a first polycarbonate and a second polycarbonate, and the weight average molecular weight of the first polycarbonate is 24,000 ~ 30,000 The weight average molecular weight of the second polycarbonate is 15,000 to 20,000, wherein the weight ratio of the acrylate-diene-styrene copolymer to the second polycarbonate is 0.15 to 1. The thermoplastic resin composition according to item 1 of the scope of the patent application, wherein the styrene-acrylonitrile copolymer contains 14% to 34% by weight of acrylonitrile monomer units, and 66% by weight to 86% by weight of the benzene The weight average molecular weight (Mw) of the ethylene-based monomer unit and other copolymerizable monomer units of 0 to 15% by weight of the styrene-acrylonitrile copolymer is 60,000 to 400,000. The thermoplastic resin composition according to item 1 of the scope of the patent application, wherein the acrylonitrile-diene-styrene copolymer contains 50% to 90% by weight of a diene monomer unit, and 1% to 30% by weight. % Acrylonitrile monomer unit and 8 wt% to 45 wt% of the styrene monomer unit and 0 wt% to 20 wt% of other copolymerizable monomer units, the acrylonitrile-diene-styrene copolymer The weight-average particle diameter of the product is 50 nm to 800 nm. A molded article is formed from the thermoplastic resin composition according to any one of claims 1 to 9 of the scope of patent application.