KR102400080B1 - Thermoplastic resin composition and article including same - Google Patents

Abstract

(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 a core-(meth)acrylate polymer shell structure of an acrylic rubbery polymer, and a molded article prepared therefrom.

Description

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

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

Recently, developed countries are establishing various environmental protection-related policies for their own environment protection. For example, in the field of architecture and automobiles, methods to minimize various environmental harmful factors that occur during the process are being studied.

Among these, the painting and/or plating process is a process that emits various harmful substances, so in most countries, including Europe and the United States, the coating process can be omitted for reasons such as environmental protection and cost reduction. is being actively considered. Such unpainted resin products may be discolored by 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 outdoor electrical and electronic parts, building materials, sporting goods, automobile interior/exterior parts, etc. It is suitable for use as the above-mentioned unpainted resin. However, since the ASA resin has poor impact resistance and the like, in order to be applied to applications requiring high impact strength, the acrylic rubber polymer content of the ASA resin must be increased. There is a limit to its 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 in which an ASA resin and a polycarbonate (PC) resin having excellent heat resistance are alloyed has been proposed.

However, when the PC/ASA resin is applied to various electrical and electronic parts, building materials, sporting goods, automobile interior/exterior parts, etc., for example, the above-mentioned unpainted resin, appearance characteristics are very important. Representative examples of appearance defects that can explain the appearance characteristics include flow marks, weld lines, bronze phenomena, halo phenomena, etc., where the 'halo phenomenon' When the molded article molded using Iranian resin has a complex shape such as a grid pattern, for example, it means a ring-shaped color bleeding phenomenon that appears prominently near the point where the vertical and horizontal axes of the grid meet.

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

Provided is a thermoplastic resin composition having excellent mechanical properties and fluidity while having improved appearance properties.

Another embodiment provides a molded article prepared 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 rubbery polymer core-(meth)acrylate polymer shell structure core-shell copolymer may have a shell formed by graft copolymerization of polymethylmethacrylate onto an acrylic rubbery polymer core.

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

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

In the (B) acrylic graft copolymer, the average particle diameter of the acrylic rubber polymer may be 100 to 300 nm.

The (B) acrylic graft copolymer may be obtained by graft polymerization of a mixture of an aromatic vinyl compound and a vinyl cyanide compound to 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 comprising 60 to 85 wt% of an aromatic vinyl compound and 15 to 40 wt% 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/10 min or more measured at 200° C. and a load of 5 kg.

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 mold release agent, a heat stabilizer, a UV stabilizer, an antistatic agent, a pigment, and a dye.

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

It is possible to provide a thermoplastic resin composition having excellent mechanical properties and fluidity while having greatly improved appearance properties (particularly, halo phenomenon).

1 is an image of 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;
2 is an image of 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 grades.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, 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 is a volume average diameter, and means a Z-average mean particle diameter measured using a dynamic light scattering analyzer.

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

The thermoplastic resin composition is (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 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 the type thereof is not particularly limited, and any polycarbonate resin available in the field of the resin composition 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 one prepared by a melt polymerization method. Meanwhile, in one embodiment, the polycarbonate resin may be prepared by melt polymerization.

When the polycarbonate resin is prepared through melt polymerization, a process of synthesizing polycarbonate by separating phenol using, for example, 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, etc., More preferably 2,2-bis-(4-hydroxyphenyl) called "bisphenol A" and propane.

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

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

The polycarbonate resin has a melt flow index (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 250°C and 10 kg load condition. , for example from 8 to 16 g/10min, for example from 9 to 16 g/10min, for example from 10 to 16 g/10min, for example from 11 to 15 g/10min.

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

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

When the polycarbonate resin in the thermoplastic resin composition is included in an amount of less than 50% by weight, there is a fear that the heat resistance of the thermoplastic resin composition may decrease, and if it exceeds 85% by weight, there is a fear that the fluidity may decrease.

(B) Acrylic graft copolymer

In one embodiment, the acrylic graft copolymer serves to enhance 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 to an acrylic rubber polymer.

The acrylic graft copolymer may be prepared according to any preparation method known to those skilled in the art.

As the preparation method, conventional polymerization methods, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, may be used. As a non-limiting example, preparing an acrylic rubber polymer, graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound to a core formed of 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 rubbery polymer may be prepared using an acrylic monomer as a main monomer. The acrylic monomer may be at least one 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 other radically polymerizable monomers. In the case of copolymerization, 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 rubbery polymer.

The aromatic vinyl compound included in the shell layer may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene. However, the present invention 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.

Based on 100% by weight of the acrylic graft copolymer, the amount of the acrylic rubbery polymer may be 30 to 70% by weight, for example, 40 to 60% by weight.

In the shell layer formed by graft polymerization of a monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound to the acrylic rubbery polymer core, the aromatic vinyl compound-derived component is 60 to 80 wt% based on the total weight of the shell layer , specifically, 65 to 75 wt%, and the component derived from the vinyl cyanide compound may be 20 to 40 wt%, specifically 25 to 35 wt%, 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 is prepared by adding acrylonitrile and styrene to at least two layers of a 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, in the acrylic graft copolymer, the average particle diameter of the acrylic rubber polymer is 100 nm or more, for example 110 nm or more, for example 120 nm or more, for example 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, for example 100 to 300 nm, such as 100 to 250 nm, such as 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, the thermoplastic resin composition including the same may have lower 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 risk that the fluidity, colorability, etc. of the thermoplastic resin composition containing the same may decrease, and the molded article manufactured therefrom may exhibit poor appearance characteristics (for example, For example, there is a weld line, bronze phenomenon, halo phenomenon, etc.).

The acrylic graft copolymer may be included in 5 wt% or more, for example, 6 wt% or more, based on 100 wt% of the total of components (A) to (D), for example, 25 wt% 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, for example, 5 to 25% by weight, for example 5 to 20% by weight, for example 5 to 15% by weight.

When the amount of the acrylic graft copolymer is less than 5% by weight, the impact resistance of the thermoplastic resin composition may decrease, 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 are concerns.

(C) aromatic vinyl-vinyl cyanide copolymer

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

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of 80,000 g/mol or more, for example 85,000 g/mol or more, for example 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/10 min or more, 2 g/10 min or more, 3 g/10 min or more, 4 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 LF-804 from Shodex Corporation). , the standard sample used is Shodex's polystyrene).

When the aromatic vinyl-vinyl cyanide copolymer satisfies the above-mentioned weight average molecular weight and/or melt flow index range, the thermoplastic resin composition according to one embodiment may exhibit excellent fluidity, and the molded article prepared therefrom exhibits excellent appearance characteristics. can indicate

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, for example, 15% by weight or more, for example, 20% by weight or more of the component derived from the cyanide compound may be included, For example, it may be included in an amount of 50% by weight or less, for example, 40% by weight or less, for example, 10 to 50% by weight, for example 15 to 40% by weight, for example, 20 to 40% by weight or less. .

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

When the aromatic vinyl-vinyl cyanide copolymer is included in an amount of less than 5% by weight, there is a risk that the mechanical properties and heat resistance of the thermoplastic resin composition may decrease, and if it exceeds 30% by weight, the impact resistance and weather resistance of the thermoplastic resin composition may decrease there is

(D) Core-shell copolymer of acrylic rubbery polymer core-(meth)acrylate polymer shell structure

The thermoplastic resin composition according to an exemplary 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, in the core-shell copolymer, a (meth)acrylate polymer may be graft-copolymerized onto an acrylic rubbery polymer core to form a shell.

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 acrylates, methacrylates, and C1 to C20 straight chain or C2 to C20 branched chain alkyl methacrylate, and C3 to C20 cyclic alkyl methacrylate, and two or more of these may be used to form the acrylic rubbery polymer.

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

In one embodiment, the core-shell copolymer may have a shell formed by graft copolymerization of polymethyl methacrylate on an acrylic rubbery 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 prepared therefrom can be adjusted to exhibit excellent appearance properties (particularly, greatly improve the halo phenomenon). can

In one embodiment, the core-shell copolymer may be included in an amount of 0.7 wt% or more, for example, 1 wt% or more, for example, 7 wt%, based on 100 wt% of the components (A) to (D). 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, for example 0.7 to 6% by weight, for example 1 to 5% by weight can be included. there is.

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

(E) Core-shell copolymer of a core-(meth)acrylate polymer shell structure comprising a silicone-based rubbery polymer

The thermoplastic resin composition according to one embodiment is a core-(meth)acrylate polymer shell structure comprising a silicone-based rubbery polymer in addition to the core-shell copolymer of the aforementioned acrylic rubbery 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 including the silicone-based rubbery polymer is used together with the core-shell copolymer of the acrylic rubbery polymer core-(meth)acrylate polymer shell structure, the thermoplastic resin composition It can 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 of the core-(meth)acrylate polymer shell structure including the silicone-based rubbery 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. It may have a structure in which a (meth)acrylate polymer is graft-copolymerized on the core to constitute a shell.

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

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

On the other hand, the core-shell copolymer of the core-(meth)acrylate polymer shell structure including the silicone-based rubbery polymer may be included in an amount of 0 to 3% by weight based on 100% by weight of the total of the components (A) to (E). there is.

(F) additives

In addition to the components (A) to (E), the thermoplastic resin composition according to an embodiment may exhibit excellent external properties while balancing the respective physical properties under conditions in which deterioration of other properties does not occur, or the thermoplastic resin According to the end use of the composition, one or more additives may be further included.

Specifically, as the additive, a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, an antibacterial agent, a mold release agent, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye, etc. 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 100 parts by weight of a total of components (A) to (D), but limited thereto. it is not going to be

Meanwhile, the thermoplastic resin composition according to an embodiment may be mixed with other resins or other rubber components to be 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 maintains excellent mechanical properties, such as fluidity, impact resistance, tensile strength, heat resistance, and weather resistance, while greatly improving the appearance characteristics, so that various electrical and electronic parts used outdoors, building materials, sporting goods, automobile interior/exterior exterior It can be advantageously used for parts, in particular unpainted products.

Specifically, the molded articles may exhibit excellent appearance characteristics as the halo phenomenon is minimized even when applied to products having a complex shape, such as a grid pattern, such as a radiator grill for an automobile. However, the use of the molded article is not necessarily limited thereto, and it can be applied to products in various industrial fields regardless of painting/non-painting.

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 illustrative purposes and are not intended to limit the present invention.

Examples 1 to 6

Each of the components shown in Table 1 was mixed in the amounts shown in Table 1 below, 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 heat stabilizer (BASF, Irganox 1076) as an additive, it was melted and extruded to prepare a thermoplastic resin composition in the form of pellets. 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 pellet form 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/10 min measured at 250°C and a load of 10 kg (Manufacturer: Lotte Advanced Materials)

(B) acrylic graft copolymer

An 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

An 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 acrylonitrile-derived components is about 28 wt%, and the melt flow index (Melt Flow) measured at 200°C and under a load of 5 kg Index) of about 8 g/10 min of styrene-acrylonitrile copolymer (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 acrylonitrile-derived components is about 27 wt%, and the melt flow index (Melt Flow) measured at 200°C and under a load of 5 kg Index) of about 0.5 g/10 min of styrene-acrylonitrile copolymer (Manufacturer: Lotte Advanced Materials)

(D) Core-shell copolymer of acrylic rubbery polymer core-(meth)acrylate polymer shell structure

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

(E) Core-shell copolymer of a core-(meth)acrylate polymer shell structure comprising a silicone-based rubbery polymer

A core-shell copolymer in which polymethyl methacrylate is graft-copolymerized onto a silicone-butyl acrylate composite rubber core to form a shell (Manufacturer: Mitsubishi Rayon, Product Name: Metablen S-2001)

Physical property evaluation

After drying the pellets prepared in Examples 1 to 6 and Comparative Examples 1 to 5 at 80 ° C. for 6 hours, using a 6 oz injection molding machine, under the conditions of a cylinder temperature of about 260 ° C and a mold temperature of 60 ° C. After preparing a specimen for evaluating the appearance of the shape, and measuring the impact resistance, fluidity, tensile strength, flexural strength, and the degree of occurrence of the halo phenomenon for each specimen as follows, 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): 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 rate of 50 mm/min according to ASTM D638.

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

(5) Halo phenomenon: Stand the manufactured specimen for appearance evaluation at 45 degrees in a light box applied to ASTM D1729, and measure the number of white lines (Halo circles) by the halo pattern revealed between the grid patterns with the inside of the grid. They were divided into external categories, each summed up, and classified into grades 1 to 5 as follows.

*1 Grade: The number of white lines between the grids due to the halo phenomenon is 2 or less, and the number of white lines spreading outside the grid is 0

*Level 2: The number of white lines between the grids due to the halo effect is 6 or less and the number of white lines spreading outside the grid is 0

* Grade 3: The number of white lines between the grids due to the halo effect is 10 or less and the number of white lines spreading outside the grid is 5 or less

*4 Grade: The number of white lines between the grids due to the halo effect is 20 or less and the number of white lines spreading outside the grid is 10 or less

*Grade 5: The number of white lines between the grids due to the halo effect is 30 or more, and the number of white lines spreading outside the grid is more than 10

On the other hand, examples of the appearance according to grades 1 and 5 are shown in FIGS. 1 and 2 , respectively.

1 is an image of a specimen for appearance evaluation 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. It is an image obtained by photographing the appearance of the specimen for appearance evaluation prepared from the thermoplastic resin composition. In FIG. 2 , some of the portions where the halo phenomenon occurred are highlighted with 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 tensile strength
(kgf/cm ² ) 648 664 678 668 637 631 Flexural strength (kgf/cm ² ) 908 926 959 940 910 906 Halo Phenomenon (Rank) 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 tensile strength
(kgf/cm ² ) 681 675 578 622 693 Flexural strength (kgf/cm ² ) 948 943 820 898 961 Halo Phenomenon (Rank) 5 4 One 5 5

From Tables 1 to 4, in the case of the specimens made of the thermoplastic resin compositions of Examples, excellent mechanical properties (impact resistance, tensile strength, flexural strength) and fluidity are exhibited, and excellent appearance properties, particularly the halo phenomenon, will be greatly improved. Although 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 fall within 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 having an average particle diameter of 100 nm to 200 nm of the acrylic rubbery polymer;
(C) 5 to 30% by weight of an aromatic vinyl-vinyl cyanide copolymer; and
(D) 0.7 to 7 wt% of an acrylic rubbery polymer core-(meth)acrylate polymer shell structure core-shell copolymer
including,
The monomer component constituting the acrylic rubbery polymer of the (D) acrylic rubbery polymer core-(meth)acrylate polymer shell structure of the core-shell copolymer is a C1 to C20 straight chain or C1 to C20 branched chain alkyl acrylate, C3 to C20 cyclic acrylate, methacrylate, C1 to C20 straight chain or C2 to C20 branched chain alkyl methacrylate, C3 to C20 cyclic alkyl methacrylate, the thermoplastic resin composition. In claim 1,
The (D) acrylic rubber polymer core-(meth) acrylate polymer shell structure core-shell copolymer is a thermoplastic resin composition in which polymethyl methacrylate is graft-copolymerized onto 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-based rubbery polymer. In claim 1,
The (A) polycarbonate resin is a thermoplastic resin composition having a melt flow index (Melt Flow Index) of 3 to 20 g/10min measured at 250°C and a load of 10 kg. delete 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 wt% of an acrylic rubber polymer. In claim 1,
The (B) acrylic graft copolymer is an acrylonitrile-styrene-acrylate graft copolymer of a thermoplastic resin composition. In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition that is a copolymer of a monomer mixture comprising 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 (Melt Flow Index) of 1 g/10 min or more measured at 200 °C and a load of 5 kg. 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 mold release agent, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye. A molded article prepared from the thermoplastic resin composition according to any one of claims 1 to 4, and any one of claims 6 to 11.

Images