KR20210026651A - Thermoplastic resin composition and article including same - Google Patents

Abstract

Provided are a thermoplastic resin composition and a molded article manufactured therefrom, wherein the thermoplastic resin composition comprises: (A) 50 to 85 wt% of a polycarbonate resin; (B) 5 to 25 wt% of an acrylic graft copolymer; (C) 5 to 30 wt% of an aromatic vinyl-vinyl cyanide copolymer; and (D) 0.7 to 7 wt% of a core-shell copolymer having an acrylic rubbery polymer core-(meth)acrylate polymer shell structure. The thermoplastic resin composition has excellent mechanical properties and fluidity.

Description

Thermoplastic resin composition and molded article containing the same {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE INCLUDING SAME}

It relates to a thermoplastic resin composition and a molded article comprising the same.

Recently, advanced countries are establishing various environmental protection policies to protect their own environment. For example, in the fields of architecture and automobiles, research is being made on ways to minimize various environmental hazards that occur in the process.

Among them, the painting and/or plating process is a process that discharges various harmful substances in the process, so in most countries, including Europe and the United States, the expansion of uncoated resins that can omit the painting process for reasons such as environmental protection and cost reduction. Are actively reviewing. In the case of such a non-coated resin product, it may be discolored due to external environmental changes such as ultraviolet rays, humidity, and heat, and therefore, it is necessary to introduce a thermoplastic resin that minimizes weather resistance to external environmental conditions.

Acrylonitrile-styrene-acrylate (ASA) resin has excellent weather resistance, so it is suitable for application to electrical and electronic parts used outdoors, building materials, sports goods, automobile interior/exterior parts, for example. It is suitable for use as the above-described non-painting resin. However, in order to apply the ASA resin to applications that require high impact strength due to poor impact resistance, etc., the content of the acrylic rubber polymer of the ASA resin must be increased. However, if the content of the acrylic rubber polymer is increased, heat resistance, etc. There is a limit to application to applications requiring high heat resistance, such as interior/exterior materials.

As an alternative to this, a method of supplementing heat resistance and impact resistance by using a PC/ASA resin alloyed with ASA resin and polycarbonate (PC) resin having excellent heat resistance has been proposed.

However, when the PC/ASA resin is applied to various electric and electronic parts, building materials, sports goods, automobile interior/exterior parts, and the like, for example, the above-described non-coating resin, appearance characteristics are very important. Representative examples of appearance defects that can describe appearance characteristics include flow marks, weld lines, bronze phenomenon, halo phenomena, and the like, where'halo phenomenon' The term refers to a ring-shaped color bleeding phenomenon that prominently appears near the point where the vertical and horizontal axes of the grid meet, for example, when a molded product molded using a resin has a complex shape such as a grid pattern.

Therefore, there is a need for a method capable of improving appearance characteristics while having excellent basic physical properties of PC/ASA resin.

It provides a thermoplastic resin composition with improved appearance properties while having excellent mechanical properties and fluidity.

Another embodiment provides a molded article manufactured from the thermoplastic resin composition.

According to one embodiment, (A) 50 to 85% by weight of a polycarbonate resin; (B) 5 to 25% by weight of an acrylic graft copolymer; (C) 5 to 30% by weight of an aromatic vinyl-vinyl cyanide copolymer; And (D) 0.7 to 7% by weight of a core-shell copolymer having an acrylic rubbery polymer core-(meth)acrylate polymer shell structure.

The (D) acrylic rubber polymer core-(meth)acrylate polymer shell structure core-shell copolymer may have a shell by graft copolymerization of polymethyl methacrylate to the acrylic rubber polymer core.

The thermoplastic resin composition may further include a core-shell copolymer having a core-(meth)acrylate polymer shell structure including (E) a silicone rubber polymer.

The (A) polycarbonate resin may have a melt flow index of 3 to 20 g/10min measured under conditions of 250°C and 10 kg load.

The (B) acrylic graft copolymer may have an average particle diameter of 100 to 300 nm of the acrylic rubber polymer.

The (B) acrylic graft copolymer may be obtained by graft polymerization of a mixture of an aromatic vinyl compound and a vinyl cyanide compound in 40 to 60% by weight of an acrylic rubber polymer.

The (B) acrylic graft copolymer may be an acrylonitrile-styrene-acrylate graft copolymer.

The (C) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture including 60 to 85% by weight of an aromatic vinyl compound and 15 to 40% by weight of a vinyl cyanide compound.

The (C) aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 80,000 to 300,000 g/mol.

The (C) aromatic vinyl-vinyl cyanide copolymer may have a melt flow index of 1 g/10min or more, measured under conditions of 200°C and 5 kg load.

The thermoplastic resin composition may further include at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye.

Meanwhile, according to another embodiment, a molded article manufactured from the above-described thermoplastic resin composition may be provided.

While having excellent mechanical properties and fluidity, it is possible to provide a thermoplastic resin composition having significantly improved appearance properties (especially halo phenomenon).

1 is an image photographing the appearance of a specimen for evaluation of appearance prepared from the thermoplastic resin composition according to Example 1 in which the degree of occurrence of the halo phenomenon is 1 grade,
2 is an image photographing the appearance of a specimen for evaluation of appearance prepared from the thermoplastic resin composition according to Comparative Example 1 in which the degree of occurrence of the halo phenomenon is 5 grade.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In the present specification, unless otherwise specified, the average particle diameter refers to a volume average diameter, and refers to a Z-average mean particle diameter measured using a dynamic light scattering analyzer.

One embodiment provides a thermoplastic resin composition having excellent mechanical properties and fluidity while having significantly improved appearance properties, in particular, a halo phenomenon.

The thermoplastic resin composition comprises (A) 50 to 85% by weight of a polycarbonate resin; (B) 5 to 25% by weight of an acrylic graft copolymer; (C) 5 to 30% by weight of an aromatic vinyl-vinyl cyanide copolymer; And (D) 0.7 to 7% by weight of a core-shell copolymer different from the component (B) of the acrylic rubbery polymer core-(meth)acrylate polymer shell structure.

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

(A) Polycarbonate resin

The polycarbonate resin is a polyester having a carbonate bond, and its kind is not particularly limited, and any polycarbonate resin available in the field of resin compositions may be used.

The polycarbonate resin may be prepared using an interfacial polymerization method (also called a solvent method or a phosgene method) or a melt polymerization method, but is not limited thereto. In one embodiment, the polycarbonate resin may include a melt polymerization method. Meanwhile, in one embodiment, the polycarbonate resin may be manufactured by melt polymerization.

When preparing a polycarbonate resin through a melt polymerization method, for example, a process of synthesizing a polycarbonate by separating phenol using a transesterification reaction between an aromatic diol compound and a diaryl carbonate compound may be included.

Examples of the aromatic diol compound include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane , 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and the like. Preferably 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4 -Hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and the like, more preferably 2,2-bis-(4-hydroxyphenyl) called "bisphenol A" Propane is mentioned.

Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and the like. Alternatively, two or more types may be used, and for example, diphenyl carbonate may be used.

The polycarbonate resin may have a weight average molecular weight of 5,000 　 to 200,000 　g/mol, and specifically 5,000 　 to 40,000 　g/mol for mechanical properties and fluidity.

The polycarbonate resin has a melt flow index of 3 to 20 g/10min, for example 3 to 18 g/10min, for example 3 to 16 g/10min, measured under a load condition of 250°C and 10 kg. , For example, it may be 8 to 16 g/10min, for example 9 to 16 g/10min, for example 10 to 16 g/10min, for example 11 to 15 g/10min.

When the weight average molecular weight and/or melt flow index of the polycarbonate resin is within the above range, excellent impact resistance and fluidity can be obtained. In addition, in one embodiment, two or more polycarbonate resins having different weight average molecular weight ranges may be mixed and used in order to meet desired fluidity.

The polycarbonate resin is at least 50% by weight or more, such as 60% by weight or more, such as 70% by weight or more, such as 72% by weight, based on the total 100% by weight of the components (A) to (D) It may be included more than, for example, 85% by weight or less, such as 80% or less, such as 78% by weight or less, such as 76% by weight or less, may be included, for example, 50 to 85% by weight, for example For example, it may be included in 60 to 85% by weight, for example 70 to 85% by weight, for example 70 to 80% by weight, for example 70 to 78% by weight, for example 70 to 76% by weight.

When the polycarbonate resin is contained in an amount of less than 50% by weight in the thermoplastic resin composition, there is a concern that the heat resistance of the thermoplastic resin composition is deteriorated, and when it exceeds 85% by weight, there is a concern that the fluidity is reduced.

(B) Acrylic Graft Copolymer

In one embodiment, the acrylic graft copolymer performs a function of enhancing the weather resistance and impact resistance of the thermoplastic resin composition.

In one embodiment, the acrylic graft copolymer may be prepared by graft polymerization of a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound on an acrylic rubber polymer.

The acrylic graft copolymer may be prepared according to any manufacturing method known to a person skilled in the art.

As the production method, conventional polymerization methods, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be used. As a non-limiting example, an acrylic rubber polymer is prepared, and a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized on a core formed with one or more layers of the acrylic rubber polymer to form one or more shell layers. It can be manufactured by a method.

The acrylic rubber polymer may be prepared using an acrylic monomer as a main monomer. The acrylic monomer may be one or more selected from the group consisting of ethyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate, but is not limited thereto.

The acrylic monomer may be copolymerized with one or more radically polymerizable other monomers. When copolymerized, the amount of the one or more radically polymerizable other monomers may be 5 to 30% by weight, specifically 10 to 20% by weight, based on the total weight of the acrylic rubber polymer.

The aromatic vinyl compound included in the shell layer may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene. However, it is not limited thereto.

The vinyl cyanide compound included in the shell layer may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile, but is not limited thereto.

The acrylic rubber polymer may be 30 to 70% by weight, for example, 40 to 60% by weight, based on 100% by weight of the acrylic graft copolymer.

In a shell layer formed by graft polymerization of a monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound on the acrylic rubber polymer core, the aromatic vinyl compound-derived component is 60 to 80% by weight based on the total weight of the shell layer , Specifically, it is 65 to 75% by weight, and the component derived from the vinyl cyanide compound may be 20 to 40% by weight, specifically 25 to 35% by weight, based on the total weight of the shell layer.

In one embodiment, the acrylic graft copolymer may be an acrylate-styrene-acrylonitrile graft copolymer.

As a non-limiting example, the acrylate-styrene-acrylonitrile graft copolymer includes acrylonitrile and styrene in two or more layers of butyl acrylate rubbery polymer core including a rubbery polymer core in which butyl acrylate and styrene are copolymerized. It may be a core-shell type acrylate-styrene-acrylonitrile graft copolymer prepared by graft polymerization through an emulsion polymerization method.

In one embodiment, the acrylic graft copolymer has an average particle diameter of the acrylic rubber polymer of 100 nm or more, such as 110 nm or more, such as 120 nm or more, such as 130 nm or more, for example 300 nm or less, such as 250 nm or less, such as 200 nm or less, such as 180 nm or less, such as 160 nm or less, such as 100 to 300 nm, such as 100 to 250 nm, such as For example, it may be 100 to 200 nm, for example 110 to 180 nm, for example 110 to 160 nm.

When the average particle diameter of the acrylic rubber polymer is less than 100 nm, there is a concern that the thermoplastic resin composition including the same may deteriorate overall mechanical properties such as impact resistance, tensile strength, and flexural strength.

On the other hand, when the average particle diameter of the acrylic rubber polymer exceeds 300 nm, there is a concern that the fluidity and colorability of the thermoplastic resin composition containing the same may be deteriorated, and the molded article manufactured therefrom may exhibit heat appearance characteristics (e.g. For example, there are weld lines, bronze phenomenon, halo phenomenon, etc.).

The acrylic graft copolymer may contain 5% by weight or more, for example 6% by weight or more, based on the total 100% by weight of the components (A) to (D), for example, 25% by weight or less, for example For example, it may be included in an amount of 20% by weight or less, for example, 13% by weight or less, and may be included in an amount of, for example, 5 to 25% by weight, for example, 5 to 20% by weight, for example, 5 to 15% by weight.

If the acrylic graft copolymer is less than 5% by weight, the impact resistance of the thermoplastic resin composition may be deteriorated, and if it exceeds 25% by weight, the mechanical properties (tensile strength, flexural strength, etc.) and colorability of the thermoplastic resin composition may decrease. There is a concern.

(C) aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer performs a function of improving the fluidity of the thermoplastic resin composition and maintaining compatibility between components at a certain level.

In one embodiment, the aromatic vinyl-cyanide vinyl copolymer may be a copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The aromatic vinyl-cyanide vinyl copolymer has a weight average molecular weight of 80,000 g/mol or more, such as 85,000 g/mol or more, such as 90,000 g/mol or more, for example 300,000 g/mol or less, for example 250,000 g/mol or less, such as 200,000 g/mol or less, such as 150,000 g/mol or less, such as 80,000 to 300,000 g/mol, such as 80,000 to 250,000 g/mol, such as 80,000 to 200,000 g/mol, for example, 80,000 to 150,000 g/mol may be used.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer has a melt flow index of 1 g/10min or more, 2 g/10min or more, 3 g/10min or more, 4 It may be g/10min or more, such as 5 g/10min or more, 6 g/10min or more, 7 g/10min or more, such as 8 g/10min or more.

In the present invention, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (column is Shodex's LF-804). , Standard sample is Shodex's polystyrene).

When the aromatic vinyl-vinyl cyanide copolymer satisfies the above-described weight average molecular weight and/or melt flow index range, the thermoplastic resin composition according to an embodiment may exhibit excellent fluidity, and the molded article manufactured therefrom exhibits excellent appearance characteristics. Can be indicated.

The aromatic vinyl compound may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene.

The vinyl cyanide compound may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 80,000 to 300,000 g/mol.

In one embodiment, based on 100% by weight of the aromatic vinyl-vinyl cyanide copolymer, 10% by weight or more of the component derived from the vinyl cyanide compound may be included, for example, 15% by weight or more, for example, 20% by weight or more, For example, it may be included in an amount of 50% by weight or less, for example, 40% by weight or less, and may be included in an amount of, for example, 10 to 50% by weight, such as 15 to 40% by weight, for example, 20 to 40% by weight. .

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer is 5% by weight or more, such as 8% by weight or more, such as 10% by weight or more, based on the total 100% by weight of the components (A) to (D). , For example 11% by weight or more, such as 12% by weight or more, may be included, for example 30% by weight or less, such as 25% by weight or less, such as 20% by weight or less, such as 18% by weight It may be included below, for example 5 to 30% by weight, such as 10 to 30% by weight, such as 10 to 25% by weight, such as 10 to 20% by weight, such as 10 to 18% by weight , For example, it may be included in 12 to 18% by weight.

If the aromatic vinyl-vinyl cyanide copolymer is contained in an amount of less than 5% by weight, the mechanical properties and heat resistance of the thermoplastic resin composition may be deteriorated, and if it exceeds 30% by weight, the impact resistance and weather resistance of the thermoplastic resin composition may be deteriorated. There is.

(D) acrylic rubber polymer core-(meth)acrylate polymer-shell structured core-shell copolymer

The thermoplastic resin composition according to an embodiment includes a core-shell copolymer having an acrylic rubbery polymer core-(meth)acrylate polymer shell structure. The core-shell copolymer performs a function of reinforcing various physical properties of the thermoplastic resin composition, such as impact resistance, mechanical properties, and appearance properties.

In one embodiment, the core-shell copolymer may form a shell by graft copolymerization of a (meth)acrylate polymer to an acrylic rubber polymer core.

The monomer components constituting the acrylic rubber polymer include C1 to C20 linear or C1 to C20 branched alkyl acrylates such as ethyl acrylate and butyl acrylate, C3 to C20 cyclic acrylate, methacrylate, C1 to C20 linear or C2 to C20 branched alkyl methacrylate, C3 to C20 cyclic alkyl methacrylate, and the like, and two or more of these may be used to constitute an acrylic rubber polymer.

The (meth)acrylate polymer shell is a homopolymer of C1 to C20 alkyl (meth)acrylate, or the C1 to C20 alkyl (meth)acrylate and copolymer with one or more monomers capable of radical polymerization such as styrene. It can also be composed of coalescence.

In one embodiment, the core-shell copolymer may form a shell by graft copolymerization of polymethyl methacrylate on an acrylic rubber polymer core.

In one embodiment, the core-shell copolymer reinforces the heat resistance, impact resistance, and weather resistance of the thermoplastic resin composition, while the molded article manufactured therefrom may be adjusted to exhibit excellent appearance characteristics (especially, the halo phenomenon is greatly improved). I can.

In one embodiment, the core-shell copolymer may contain 0.7% by weight or more, for example, 1% by weight or more, based on the total 100% by weight of components (A) to (D), for example 7% by weight. Below, for example, 6% by weight or less, for example, 5% by weight or less, may be included, for example, 0.7 to 7% by weight, such as 0.7 to 6% by weight, for example, may be included in 1 to 5% by weight have.

When the core-shell copolymer is contained in an amount of less than 0.7% by weight, there is a concern that the impact resistance of the thermoplastic resin composition may be deteriorated, and there is a concern that a number of halo phenomena may occur in the molded article manufactured therefrom. On the other hand, when the core-shell copolymer exceeds 7% by weight, there is a concern that the mechanical stiffness (tensile strength, flexural strength, etc.) of the thermoplastic resin composition may decrease.

(E) Core-(meth)acrylate polymer shell structure core-shell copolymer containing silicone rubber polymer

The thermoplastic resin composition according to the embodiment includes a core-(meth)acrylate polymer shell structure including a silicone rubber polymer in addition to the core-shell copolymer having the above-described acrylic rubber polymer core-(meth)acrylate polymer shell structure. It may further include a core-shell copolymer. When the core-shell copolymer of the core-(meth)acrylate polymer shell structure containing the silicone rubber polymer is used together with the core-shell copolymer of the acrylic rubber polymer core-(meth)acrylate polymer shell structure, the thermoplastic resin composition It is possible to reinforce the low-temperature impact resistance of the product, adjust the impact resistance and weather resistance to a target level, and improve the halo phenomenon of the manufactured molded product.

In one embodiment, the core-shell copolymer having a core-(meth)acrylate polymer shell structure including a silicone-based rubber polymer is composed of a polymer of a silicone-based monomer and/or a copolymer of a silicone-based monomer and a (meth)acrylate-based monomer. A (meth)acrylate polymer may be graft-copolymerized to the core to have a structure constituting a shell.

Examples of the silicone-based monomers that can be used as the core include siloxanes containing an alkyl group such as dimethylsiloxane, and the (meth)acrylate-based monomers copolymerizable with the silicone-based monomers include methyl (meth)acrylate, butyl (meth) ) Acrylate, 2-ethylhexyl (meth)acrylate, etc. are mentioned.

The (meth)acrylate polymer shell is a homopolymer of C1 to C20 alkyl (meth)acrylate, or the C1 to C20 alkyl (meth)acrylate and copolymer with one or more monomers capable of radical polymerization such as styrene. It can also be composed of coalescence.

Meanwhile, the core-shell copolymer of the core-(meth)acrylate polymer shell structure including the silicone rubber polymer may be included in an amount of 0 to 3% by weight based on 100% by weight of the total components (A) to (E). have.

(F) additive

In addition to the components (A) to (E), the thermoplastic resin composition according to an embodiment is capable of exhibiting excellent appearance characteristics, and in order to balance the physical properties under conditions that do not deteriorate other physical properties, or the thermoplastic resin It may further include one or more additives required depending on the final use of the composition.

Specifically, as the additive, a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye, etc. may be used, and these may be used alone or in combination of two or more. Can be used.

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on a total of 100 parts by weight of components (A) to (D), but is limited thereto. It does not become.

Meanwhile, the thermoplastic resin composition according to an embodiment may be mixed with other resins or other rubber components and used together.

On the other hand, another embodiment provides a molded article including the thermoplastic resin composition according to the embodiment. The molded article may be manufactured by various methods known in the art, such as injection molding and extrusion molding, using the thermoplastic resin composition.

The molded article has excellent mechanical properties such as fluidity, impact resistance, tensile strength, heat resistance, and weather resistance, while greatly improving its appearance characteristics to provide various electrical and electronic parts used outdoors, building materials, sports goods, interior/exterior of automobiles. It can be advantageously used for parts, in particular unpainted products.

Specifically, even when the molded products are applied to a product having a complex shape such as a grid pattern, such as an automobile radiator grill, the halo phenomenon is minimized, and thus excellent appearance characteristics may be exhibited. However, the use of the molded product is not necessarily limited thereto, and can be applied to products in various industrial fields regardless of painting/unpainted.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited by the following examples.

Example

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples, but the following Examples and Comparative Examples are for the purpose of description and are not intended to limit the present invention.

Examples 1 to 6

Each of the components shown in Table 1 below was mixed in the amount shown in Table 1, and 0.5 parts by weight of carbon black (Orion engineered carbon, Hiblack 50L) and hindered phenolic based on 100 parts by weight of components (A) to (E) After adding 0.1 parts by weight of a thermal stabilizer (BASF, Irganox 1076) as an additive, it was melted and extruded to prepare a thermoplastic resin composition in the form of a pellet. For the extrusion, a twin-screw extruder having L/D=44 and a diameter of 35 mm was used, and the barrel temperature was set to about 260°C.

Comparative Examples 1 to 5

Except for using the components and amounts shown in Table 2 below, the same additives as in Example 1 were added in the same amount, and a thermoplastic resin composition in the form of pellets was prepared in the same manner.

ingredient Example One 2 3 4 5 6 (A) 73 73 73 75 73 73 (B) 7 9 11 8 8 8 (B') 0 0 0 0 0 0 (C) 15 15 15 15 15 15 (C') 0 0 0 0 0 0 (D) 5 3 One 2 2 One (E) 0 0 0 0 2 3

ingredient Comparative example One 2 3 4 5 (A) 73 73 73 73 73 (B) 12 11.5 2 0 12 (B') 0 0 0 12 0 (C) 15 15 15 15 0 (C') 0 0 0 0 15 (D) 0 0.5 10 0 0 (E) 0 0 0 0 0

(A) Polycarbonate resin

Polycarbonate resin with a Melt Flow Index of about 13 g/10min measured under 250℃, 10 kg load condition (manufacturer: Lotte Advanced Materials)

(B) acrylic graft copolymer

Acrylonitrile-styrene-acrylate graft copolymer obtained by graft copolymerization of styrene and acrylonitrile in a weight ratio of 75:25 to 50% by weight of a butyl acrylate rubber polymer having an average particle diameter of about 135 nm (manufacturer: Lotte Advanced Materials )

(B') acrylic graft copolymer

Acrylonitrile-styrene-acrylate graft copolymer obtained by graft copolymerization of styrene and acrylonitrile in a weight ratio of 75:25 to 50% by weight of a butyl acrylate rubber polymer having an average particle diameter of about 320 nm (manufacturer: Lotte Advanced Materials )

(C) aromatic vinyl-vinyl cyanide copolymer

The weight average molecular weight measured by gel permeation chromatography (GPC) is about 95,000 g/mol, the content of the acrylonitrile-derived component is about 28% by weight, and the melt flow index (Melt Flow) measured under conditions of 200°C and 5 kg load. Styrene-acrylonitrile copolymer with an Index) of about 8 g/10min (manufacturer: Lotte Advanced Materials)

(C') aromatic vinyl-vinyl cyanide copolymer

The weight average molecular weight measured by gel permeation chromatography (GPC) is about 230,000 g/mol, the content of the acrylonitrile-derived component is about 27% by weight, and the melt flow index measured at 200°C and 5 kg load condition. Styrene-acrylonitrile copolymer with an Index) of about 0.5 g/10min (manufacturer: Lotte Advanced Materials)

(D) acrylic rubber polymer core-(meth)acrylate polymer-shell structured core-shell copolymer

A core-shell copolymer in which polymethyl methacrylate is graft-copolymerized to a butyl acrylate rubbery polymer core to form a shell (manufacturer: Kaneka, product name: Kane Ace M-577)

(E) Core-(meth)acrylate polymer shell structure core-shell copolymer containing silicone rubber polymer

A core-shell copolymer that forms a shell by graft copolymerization of polymethyl methacrylate on a silicone-butyl acrylate composite rubber core (manufacturer: Mitsubishi Rayon, product name: Metablen S-2001)

Property evaluation

After drying the pellets prepared in Examples 1 to 6 and Comparative Examples 1 to 5 at 80° C. for 6 hours, a cylinder temperature of about 260° C. and a mold temperature of 60° C. were used in a 6 oz injection molding machine, as shown in the specimens and drawings. A specimen for evaluating the appearance of the shape was prepared, and impact resistance, fluidity, tensile strength, flexural strength, and halo phenomenon occurrence degree were measured for each specimen as follows, and the results are shown in Table 3 (Examples 1 to 6) and Table 4 (Comparative Examples 1 to 5), respectively.

(1) Impact resistance (unit: kgf·cm/cm): Notched Izod impact strength was measured for each of 1/8" and 1/4" thick specimens according to ASTM D256.

(2) Flowability (unit: g/10min): The melt flow index (MI) was measured at 250° C. and 10 kg load condition according to ASTM D1238.

(3) Tensile strength (unit: kgf/cm ² ): Tensile strength was measured at a measurement speed of 50 mm/min according to ASTM D638.

(4) Flexural strength (unit: kgf/cm ² ): The flexural strength was measured at a measurement speed of 2.8 mm/min according to ASTM D638.

(5) Halo development: The manufactured specimen for appearance evaluation was set up at 45 degrees in a light box applied to ASTM D1729, and the number of white lines (halo circles) exposed between the grid patterns was determined with the inside of the grid. They were divided into external and summed up, and classified into grades 1 to 5 as follows.

*1st grade: The number of white lines between the grids due to the halo phenomenon is less than 2, and the number of white lines spreading out of the grid is 0.

*2 Grade: The number of white lines between the grids caused by the halo phenomenon is 6 or less, and the number of white lines spreading out of the grid is 0.

*3 grade: The number of white lines between the grids caused by the halo phenomenon is less than 10 and the number of white lines spreading out of the grid is less than 5

*4 Grade: The number of white lines between the grids caused by the halo phenomenon is less than 20, and the number of white lines spreading out of the grid is less than 10.

*5 Grade: The number of white lines between the grids caused by the halo phenomenon is more than 30, and the number of white lines spreading out of the grid is more than 10.

Meanwhile, examples of appearances according to grades 1 and 5 are shown in FIGS. 1 and 2, respectively.

FIG. 1 is an image photographing the appearance of a specimen for evaluation of appearance prepared from the thermoplastic resin composition according to Example 1 in which the degree of occurrence of the halo phenomenon is grade 1, and FIG. 2 is according to Comparative Example 1 in which the degree of occurrence of the halo phenomenon is grade 5. This is an image photographing the appearance of a specimen for appearance evaluation prepared from a thermoplastic resin composition. In FIG. 2, some of the areas where the halo phenomenon has occurred are shown by emphasizing white circles.

Properties Example One 2 3 4 5 6 Impact strength
(kgf cm/cm) 1/8" 57.6 55.9 49.5 50.9 56.3 54.8 1/4" 26.7 23.8 19.4 22.2 24.5 24.0 Melt flow index
(g/10min) 41.0 41.3 39.4 40.1 39.8 38.8 The tensile strength
(kgf/cm ² ) 648 664 678 668 637 631 Flexural strength (kgf/cm ² ) 908 926 959 940 910 906 Halo phenomenon (grade) One One 2 One One One

Properties Comparative example One 2 3 4 5 Impact strength
(kgf cm/cm) 1/8" 48.3 48.2 69.5 59.4 51.9 1/4" 17.1 18.0 63.4 31.2 17.8 Melt flow index
(g/10min) 40.5 38.9 25.6 37.2 5.3 The tensile strength
(kgf/cm ² ) 681 675 578 622 693 Flexural strength (kgf/cm ² ) 948 943 820 898 961 Halo phenomenon (grade) 5 4 One 5 5

From Tables 1 to 4, in the case of the specimens made of the thermoplastic resin composition of the examples, while exhibiting excellent mechanical properties (impact resistance, tensile strength, flexural strength) and fluidity, excellent appearance properties, especially the halo phenomenon, will be greatly improved Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and those skilled in the art using the basic concept of the present invention defined in the appended claims. Various modifications and improvements also belong to the scope of the present invention.

Claims (12)

(A) 50 to 85% by weight of a polycarbonate resin;
(B) 5 to 25% by weight of an acrylic graft copolymer;
(C) 5 to 30% by weight of an aromatic vinyl-vinyl cyanide copolymer; And
(D) 0.7 to 7% by weight of a core-shell copolymer of an acrylic rubber polymer core-(meth)acrylate polymer shell structure
Thermoplastic resin composition comprising a. In claim 1,
The (D) acrylic rubber polymer core-(meth)acrylate polymer shell structure of the core-shell copolymer is a thermoplastic resin composition in which polymethyl methacrylate is graft-copolymerized to an acrylic rubber polymer core to form a shell. In claim 1,
(E) A thermoplastic resin composition further comprising a core-shell copolymer having a core-(meth)acrylate polymer shell structure comprising a silicone rubber polymer. In claim 1,
The (A) polycarbonate resin is a thermoplastic resin composition having a melt flow index of 3 to 20 g/10min measured under conditions of 250°C and 10 kg load. In claim 1,
The (B) acrylic graft copolymer is a thermoplastic resin composition having an average particle diameter of an acrylic rubber polymer of 100 nm to 300 nm. In claim 1,
The (B) acrylic graft copolymer is a thermoplastic resin composition in which a mixture of an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized in 40 to 60% by weight of an acrylic rubber polymer. In claim 1,
The (B) acrylic graft copolymer is an acrylonitrile-styrene-acrylate graft copolymer. In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition that is a copolymer of a monomer mixture containing 60 to 85% by weight of an aromatic vinyl compound and 15 to 40% by weight of a vinyl cyanide compound. In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of 80,000 g/mol to 300,000 g/mol of a thermoplastic resin composition. In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition having a melt flow index of 1 g/10min or more measured under conditions of 200°C and 5 kg load. The method of claim 1,
A thermoplastic resin composition further comprising at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye. A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 11.

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