KR102566510B1 - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

(A) 50 to 80% by weight of a polycarbonate resin; (B) 10 to 20% by weight of an acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; And (C) based on 100 parts by weight of the base resin containing 10 to 40% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) 2 to 6 parts by weight of the (a)-(b)-(a) type block copolymer wherein (a) is a methacrylate-based polymer block, and (b) is an acrylate-based polymer block.

Description

Thermoplastic resin composition and molded product using the same {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT USING THE SAME}

The present invention relates to a thermoplastic resin composition and a molded article using the same.

Polycarbonate (PC) resin is one of engineering plastics and is widely used in the plastics industry.

Polycarbonate resin has a glass transition temperature (Tg) of about 150 ° C due to its bulky molecular structure, such as bisphenol-A, and thus exhibits high heat resistance and has excellent transparency as an amorphous polymer.

In addition, it has excellent impact resistance and compatibility with other resins, but polycarbonate resin has a disadvantage of low fluidity, so it is widely used in the form of an alloy with various resins to supplement moldability and post-processing. .

Acrylate-styrene-acrylonitrile (ASA) resin has excellent weather resistance and light resistance, and is widely used in outdoor building materials and automotive interior/exterior materials. However, since ASA resin has poor impact resistance, the acrylic rubber polymer content of ASA resin must be increased in order to be applied to applications requiring high impact strength. There is a limit to its application to applications requiring high heat resistance, such as exterior materials.

Accordingly, a method of securing excellent heat resistance, impact resistance, weather resistance, and light resistance by alloying the above-mentioned polycarbonate resin and ASA resin has been proposed, and this PC/ASA resin is applied to various automobile interior/exterior materials. can

However, these PC / ASA resins have problems in appearance and color coloring properties in general due to the difference in refractive index between the acrylic rubber polymer and the PC resin. In order to solve this problem, attempts have been made to minimize the difference in refractive index between the dispersed phase ASA resin and the continuous phase PC resin by introducing a high refractive index monomer into the acrylic rubber polymer and to maximize the dispersibility of the ASA resin. In this case, the PC/ASA resin There is a problem that the impact resistance of the is lowered.

Therefore, there is a need to develop a thermoplastic resin composition having excellent impact resistance, heat resistance, appearance, and colorability.

One embodiment provides a thermoplastic resin composition capable of implementing excellent impact resistance, heat resistance, appearance characteristics and color coloring properties.

Another embodiment provides a molded article using the thermoplastic resin composition.

According to one embodiment, (A) 50 to 80% by weight of a polycarbonate resin; (B) 10 to 20% by weight of an acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; And (C) based on 100 parts by weight of the base resin containing 10 to 40% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) 2 to 6 parts by weight of the (a)-(b)-(a) type block copolymer wherein (a) is a methacrylate-based polymer block, and (b) is an acrylate-based polymer block.

In the (D) (a)-(b)-(a) type block copolymer, (a) is a C1 to C10 alkyl methacrylate polymer block, and (b) is a C1 to C10 alkyl acrylate polymer block. can be

The (D) (a)-(b)-(a) type block copolymer may be a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer.

The (D) (a)-(b)-(a) type block copolymer may have a weight average molecular weight of 10,000 to 100,000 g/mol.

(D) The (a)-(b)-(a) type block copolymer contains 30 to 70% by weight of the (a) methacrylate-based polymer block and 30 to 70% by weight of the (b) acrylate-based polymer block. can include

The (A) polycarbonate resin is The weight average molecular weight may be 10,000 to 100,000 g/mol.

The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may have an average particle diameter of 100 to 500 nm of the acrylic rubber polymer.

The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer has a shell formed by graft polymerization of a core containing an acrylic rubber polymer and a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound to the core; It may have a core-shell structure including

The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may include 45 to 65% by weight of the acrylic rubber polymer.

The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide 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 80% by weight of an aromatic vinyl compound and 20 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 200,000 g/mol.

The thermoplastic resin composition includes at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, inorganic additives, UV stabilizers, antistatic agents, pigments, and dyes may further include.

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

The invention according to one embodiment provides a thermoplastic resin composition having excellent impact resistance and heat resistance by introducing a (meth)acrylate-based block copolymer and having excellent appearance characteristics and colorability.

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, 'copolymerization' means block copolymerization or random copolymerization, and 'copolymer' means block copolymer or random copolymer.

In the present specification, '(meth)acrylate' means acrylate and/or methacrylate.

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

Unless otherwise specified herein, '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). .

One embodiment provides a thermoplastic resin composition having excellent impact resistance and heat resistance while having excellent appearance characteristics and color coloring properties.

The thermoplastic resin composition is (A) 50 to 80% by weight of a polycarbonate resin; (B) 10 to 20% by weight of an acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; And (C) based on 100 parts by weight of the base resin containing 10 to 40% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) 2 to 6 parts by weight of the (a)-(b)-(a) type block copolymer Including, wherein (a) is a methacrylate-based polymer block, and (b) is characterized in that an acrylate-based polymer block.

(A) polycarbonate resin

Polycarbonate (PC) resin is a polyester having a carbonate bond, and its kind is not particularly limited, and any polycarbonate resin available in the resin composition field may be used.

For example, it may be prepared by reacting a compound selected from the group consisting of diphenols represented by Formula 1 and phosgene, halogen acid esters, carbonic acid esters, and combinations thereof.

[Formula 1]

In Formula 1,

A is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group, a substituted or unsubstituted C1 to C30 haloalkyl A rene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C10 cycloalkylidene group, a substituted or unsubstituted C6 to C30 arylene group , A substituted or unsubstituted C1 to C20 alkoxyylene group, a halogen acid ester group, a carbonic ester group, a linking group selected from the group consisting of CO, S and SO2, R ¹ and R ² are each independently substituted or unsubstituted It is a C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and n1 and n2 are each independently an integer of 0 to 4.

Two or more diphenols represented by Chemical Formula 1 may be combined to constitute a repeating unit of a polycarbonate resin.

Specific examples of the diphenols include 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also referred to as 'bisphenol-A'), 2,4-bis(4- Hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl ) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5 -Dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxy Phenyl) ketone, bis (4-hydroxyphenyl) ether, etc. are mentioned. Among the above diphenols, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, and 2,2-bis(3,5- Dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane may be used. More preferably, 2,2-bis(4-hydroxyphenyl)propane can be used.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.

In addition, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester-carbonate copolymer resin, or the like.

The linear polycarbonate resin may be specifically a bisphenol-A-based polycarbonate resin. A specific example of the branched polycarbonate resin may be a resin prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride or trimellitic acid with diphenols and carbonate. The polyester-carbonate copolymer resin may be prepared by reacting a difunctional carboxylic acid with diphenols and carbonate, and the carbonate used herein may be diaryl carbonate such as diphenyl carbonate or ethylene carbonate.

The polycarbonate resin may be prepared using methods such as interfacial polymerization (also called solvent polymerization or phosgene method) and melt polymerization.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 100,000 g/mol, for example 10,000 to 90,000 g/mol, for example 14,000 to 90,000 g/mol, for example 14,000 to 80,000 g/mol, for example 14,000 to 70,000 g/mol, such as 14,000 to 60,000 g/mol, such as 14,000 to 50,000 g/mol, such as 14,000 to 40,000 g/mol. When the weight average molecular weight of the polycarbonate resin is within the above range, a molded article using the polycarbonate resin may exhibit excellent impact resistance and fluidity.

However, one embodiment is not necessarily limited thereto. For example, the polycarbonate resin may be used by mixing two or more types of polycarbonate resins having different weight average molecular weights. By mixing and using polycarbonate resins having different weight average molecular weights, it is easy to adjust the thermoplastic resin composition to have desired fluidity.

The polycarbonate resin may be included in 50 to 80% by weight, for example, 50 to 75% by weight, for example, 50 to 70% by weight, based on 100% by weight of the base resin. When the polycarbonate resin is less than 50% by weight, the mechanical strength of a molded article manufactured from the thermoplastic resin composition containing the polycarbonate resin is not good, and when it exceeds 80% by weight, the moldability of the thermoplastic resin composition containing the polycarbonate resin may be deteriorated.

(B) Acrylic rubber modified aromatic vinyl-vinyl cyanide graft copolymer

In one embodiment, the acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer serves to enhance impact resistance, weather resistance, and light resistance of the thermoplastic resin composition.

In one embodiment, the acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer has a core containing an acrylic rubber polymer, and a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound graft polymerization to the core It may be a core-shell structure including a formed shell.

The acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be prepared according to any method known to those skilled in the art.

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

The acrylic rubber polymer may be prepared by 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 1 to 30% by weight, for example 1 to 25% 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, p-t-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 present in an amount of 45 to 65% by weight, for example, 50 to 65% by weight based on 100% by weight of the acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer.

In the shell layer, the component derived from the aromatic vinyl compound may be 60 to 80% by weight, for example, 65 to 75% by weight based on the total weight of the shell layer, and the component derived from the cyanide vinyl compound of the shell layer 20 to 40% by weight, for example 25 to 35% by weight, based on the total weight.

In one embodiment, the acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-styrene-acrylate graft copolymer.

As a non-limiting example, the acrylonitrile-styrene-acrylate graft copolymer is a monomer containing acrylonitrile and styrene in a two or more layer acrylic rubber polymer core containing a rubbery polymer in which butyl acrylate and styrene are copolymerized. It may be a core-shell acrylonitrile-styrene-acrylate graft copolymer prepared by graft polymerization of the mixture through emulsion polymerization.

In one embodiment, the acrylic rubber-modified aromatic vinyl-vinyl cyanide 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, for example 250 nm or less, for example 200 nm or less, for example 180 nm or less, for example 160 nm or less, for example 100 to 300 nm, for example 100 to 250 nm, such as 100 to 200 nm, such as 110 to 180 nm, such as 110 to 160 nm.

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

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 including the same may be deteriorated, and the appearance characteristics of a molded product manufactured therefrom may be deteriorated (eg, For example, weld line, bronze phenomenon, halo phenomenon, etc.).

The acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be included in an amount of 10 to 20% by weight, for example, 10 to 19% by weight, for example 10 to 18% by weight, based on 100% by weight of the base resin. eg 10 to 17% by weight, eg 10 to 16% by weight, eg 10 to 15% by weight, eg 11 to 20% by weight, eg 12 to 20% by weight, eg 13 to 20% by weight % by weight, for example 14 to 20% by weight, for example 15 to 20% by weight.

When the amount of the acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is less than 10% by weight, the impact resistance of the thermoplastic resin composition containing the same may deteriorate, and when it exceeds 20% by weight, the mechanical properties of the thermoplastic resin composition including the same There is a possibility that physical properties (tensile strength, flexural strength, etc.) and colorability may be deteriorated.

(C) Aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer serves to maintain compatibility between components of the thermoplastic resin composition at a certain level or higher.

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 may be prepared according to any method known to those skilled in the art.

As the preparation method, conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and the like can be used.

The aromatic vinyl-vinyl cyanide copolymer may have 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, and for example 200,000 g/mol or less, for example For example, it may be 150,000 g/mol or less, for example 80,000 to 200,000 g/mol, for example 80,000 to 150,000 g/mol.

When the aromatic vinyl-vinyl cyanide copolymer satisfies the aforementioned weight average molecular weight range, a thermoplastic resin composition containing the copolymer may exhibit excellent fluidity, and a molded product manufactured therefrom may exhibit excellent appearance characteristics.

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).

In one embodiment, based on 100% by weight of the aromatic vinyl-vinyl cyanide copolymer, the component derived from the vinyl cyanide compound is included at 20% by weight or more, for example, 25% by weight or more, for example, 30% by weight or more. It may be, for example, 40% by weight or less, such as 35% by weight or less, such as 20 to 40% by weight, such as 25 to 40% by weight, such as 25 to 35% by weight. .

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be included in an amount of 10 to 40% by weight based on 100% by weight of the base resin, for example, 10 to 35% by weight, for example 15 to 40% by weight, For example, it may be included in 15 to 35% by weight.

When the amount of the aromatic vinyl-vinyl cyanide copolymer is less than 10% by weight, there is a concern that the impact resistance and heat resistance of the thermoplastic resin composition containing the same may decrease, and when the amount exceeds 40% by weight, the impact resistance and weather resistance of the thermoplastic resin composition containing the same may be deteriorated. There is a risk of this deterioration.

(D) (a)-(b)-(a) type block copolymer

The thermoplastic resin composition according to one embodiment is a base resin including the above-described (A) polycarbonate resin, (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer, and (C) aromatic vinyl-vinyl cyanide copolymer , (a) is a methacrylate-based polymer block, (b) is an acrylate-based polymer block, (D) (a)-(b)-(a) type block copolymer by further including impact resistance, appearance and Colorability can be improved.

In the (D) (a)-(b)-(a) type block copolymer, (a) is a C1 to C10 alkyl methacrylate polymer block, and (b) is a C1 to C10 alkyl acrylate polymer. may be a block. The (a) alkyl methacrylate polymer block and (b) alkyl acrylate polymer block within the range in which the (D) (a)-(b)-(a) type block copolymer is compatible with the base resin. The number of carbon atoms in the carbon chain of is not particularly limited.

Alkyl (meth)acrylates that may be included in the (a) or (b) polymer block include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl ( meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2,2-dimethylpropyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, or vinyl (meth)acrylate, but is not limited thereto.

More specifically, the (D) (a)-(b)-(a) type block copolymer may be a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer.

The (D) (a)-(b)-(a) type block copolymer comprises 30 to 70% by weight of the (a) methacrylate-based polymer block and 30 to 70% by weight of the (b) acrylate-based polymer block can include

The (D) (a)-(b)-(a) type block copolymer preferably has a weight average molecular weight of 10,000 to 100,000 g/mol, for example, 10,000 to 90,000 g/mol, e.g. eg 10,000 to 80,000 g/mol, eg 10,000 to 70,000 g/mol, eg 10,000 to 60,000 g/mol, eg 20,000 to 100,000 g/mol, eg 30,000 to 100,000 g/mol, eg For example, it is effective to use 40,000 to 100,000 g/mol, for example 50,000 to 100,000 g/mol. If the weight average molecular weight of the (D) (a)-(b)-(a) type block copolymer is less than 10,000 g/mol, there is a concern that the impact resistance of the thermoplastic resin composition according to an embodiment may be lowered, (D) If the weight average molecular weight of the (a)-(b)-(a) type block copolymer exceeds 100,000 g/mol, there is a concern that the colorability of the thermoplastic resin composition according to one embodiment may be reduced.

In one embodiment, (D) (a)-(b)-(a) type block copolymer is 2 parts by weight or more, 2.5 parts by weight based on 100 parts by weight of the base resin containing the (A) to (C) parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, or 4 parts by weight or more and 6 parts by weight or less, 5.5 parts by weight or less, 5 parts by weight or less, or 4.5 parts by weight or less. When the (D) (a)-(b)-(a) type block copolymer is included in less than 2 parts by weight with respect to 100 parts by weight of the base resin, the effect of improving the impact resistance of the thermoplastic resin composition containing it may be insignificant. And, when the (D) (a)-(b)-(a) type block copolymer exceeds 6 parts by weight with respect to 100 parts by weight of the base resin, there is a concern that the appearance characteristics may be deteriorated.

(E) additives

In addition to the components (A) to (D), the thermoplastic resin composition according to an embodiment does not cause degradation of other physical properties, and conditions that can also prevent degradation of physical properties due to hydrolysis of polycarbonate resin during processing or use In order to balance each physical property under or according to the final use of the thermoplastic resin composition, one or more additives may be further included.

Specifically, as the additives, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, inorganic additives, UV stabilizers, antistatic agents, pigments, dyes, etc. can be used These may be used alone or in combination of two or more.

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 the base resin, but is not limited thereto.

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

Meanwhile, another embodiment provides a molded article manufactured using 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.

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 explanation and are not intended to limit the present invention.

Examples 1 to 4

Each of the components shown in Table 1 was mixed in the amount shown in Table 1, and 0.5 parts by weight of carbon black, 0.2 parts by weight of a heat stabilizer, and 0.3 parts by weight of a lubricant were added as additives common to all examples, respectively, and then melted after mixing. And by extrusion to prepare a thermoplastic resin composition in the form of pellets according to Examples 1 to 4. The extrusion was performed using a twin-screw extruder with L/D = 29 and a diameter of 45 mm, and the barrel temperature was set at 270 °C.

Comparative Examples 1 to 5

Thermoplastic resin compositions according to Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except for using the components and amounts shown in Table 1 below.

ingredient unit Example comparative example One 2 3 4 One 2 3 4 5 base resin (A) weight% 50 50 50 70 50 50 30 50 100 (B) weight% 15 15 20 15 15 15 15 15 - (C) weight% 35 35 30 15 35 35 55 35 - (D) parts by weight 3 5 3 3 - 8 3 - 3 (E) parts by weight - - - - - - - 3 -

(Parts by weight: parts by weight relative to 100 parts by weight of the base resin ((A) + (B) + (C))

(A) polycarbonate resin

Bisphenol-A polycarbonate having a weight average molecular weight of about 21,000 g/mol (Lotte Chemical Co.)

(B) Acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer

It contains about 60% by weight of an acrylic rubbery polymer core of a double core structure composed of an inner core copolymerized with butyl acrylate and styrene and an outer core made of a butyl acrylate rubbery polymer, and contains about 33% by weight of an acrylonitrile-derived component and styrene Copolymer having a core-shell structure including a styrene-acrylonitrile copolymer shell containing about 67% by weight of derived components, and having an average particle diameter of about 160 nm of the acrylic rubbery polymer core (Lotte Chemical Co.)

(C) Aromatic vinyl-vinyl cyanide copolymer

A styrene-acrylonitrile copolymer (Lotte Chemical Co., Ltd.) having a weight average molecular weight of about 120,000 g/mol, including about 68% by weight of a styrene-derived component and about 32% by weight of an acrylonitrile-derived component

(D) (a)-(b)-(a) type block copolymer

Methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer (LA2250, Kuraray Co.) comprising (a) about 50% by weight of a methyl methacrylate block and (b) about 50% by weight of a butyl acrylate block

(E) phenyl methacrylate-methyl methacrylate copolymer

Copolymer containing about 30% by weight of phenyl methacrylate-derived components, about 70% by weight of methyl methacrylate-derived components, and a weight average molecular weight of about 13,000 g/mol (Lotte Chemical Co., Ltd.)

evaluation

After drying the thermoplastic resin composition in the form of pellets prepared according to Examples 1 to 4 and Comparative Examples 1 to 5 at 80 ° C. for 4 hours, a 6 oz injection molding machine was used to set the cylinder temperature to 270 ° C. and the mold temperature to 60 ° C. Specimens for physical property tests were prepared, and impact resistance, heat resistance, appearance characteristics, and coloration properties were measured or observed for each specimen as follows, and the results are summarized in Table 2.

(1) Impact resistance: Notched Izod impact strength was measured for 1/8” thick specimens according to ASTM D256 (unit: kgf cm/cm).

(2) Heat resistance: Vicat softening temperature (VST) was measured according to ISO 306 (unit: °C).

(3) Appearance characteristics: After injection molding of a 10 cm X 10 cm X 0.2 cm specimen at a constant injection speed, the degree of appearance defects such as flow marks, discoloration, and pearl luster on the surface of the specimen is evaluated as follows Evaluated according to the criteria.

<Evaluation Criteria>

- ◎: Less than 1 specimen with poor appearance out of 10 specimens

- ○: 2 to 3 specimens with poor appearance out of 10 specimens

- △: 4 to 5 specimens with poor appearance out of 10 specimens

- X: 6 or more specimens with poor appearance out of 10 specimens

(4) Colorability: The brightness (L) value was measured in the SCE (specular component excluded) mode using a Konica Minolta CM-3700D. Since carbon black was used as an additive, all specimens according to Examples and Comparative Examples showed a black color, and accordingly, the lower the brightness value, the higher the black color, so it was judged that the color coloring property was excellent.

division Example comparative example One 2 3 4 One 2 3 4 5 Izod impact strength 60 63 68 65 48 62 42 40 72 VST 117 115 111 126 120 113 102 112 138 Degree of appearance defects ◎ ◎ ◎ ◎ X △ △ ◎ △ Lightness (L) value 5.8 5.4 6.0 4.8 10.2 6.8 7.2 5.5 6.8

From Table 2, the thermoplastic resin composition according to Examples 1 to 4 includes the components according to one embodiment in an optimal content, and thus has excellent impact resistance, heat resistance, appearance characteristics and color coloring compared to Comparative Examples 1 to 5 It can be confirmed that it has Simple modifications or changes of the present invention can be easily performed by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (15)

(A) 50 to 60% by weight of a polycarbonate resin;
(B) 10 to 20% by weight of an acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; and
(C) 30 to 40% by weight of an aromatic vinyl-vinyl cyanide copolymer
Regarding 100 parts by weight of the base resin containing,
(D) 2 to 6 parts by weight of (a)-(b)-(a) type block copolymer
A thermoplastic resin composition comprising a, wherein (a) is a methacrylate-based polymer block, and (b) is an acrylate-based polymer block.
In paragraph 1,
In the (D) (a)-(b)-(a) type block copolymer, (a) is a C1 to C10 alkyl methacrylate polymer block, and (b) is a C1 to C10 alkyl acrylate polymer. A block-in thermoplastic resin composition.
In paragraph 1,
The (D) (a)-(b)-(a) type block copolymer is a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer thermoplastic resin composition.
In paragraph 1,
The (D) (a)-(b)-(a) type block copolymer has a weight average molecular weight of 10,000 to 100,000 g / mol thermoplastic resin composition.
In paragraph 1,
The (D) (a)-(b)-(a) type block copolymer comprises 30 to 70% by weight of the (a) methacrylate-based polymer block and 30 to 70% by weight of the (b) acrylate-based polymer block A thermoplastic resin composition comprising a.
In paragraph 1,
The (A) polycarbonate resin is A thermoplastic resin composition having a weight average molecular weight of 10,000 to 100,000 g/mol.
In paragraph 1,
The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a thermoplastic resin composition having an average particle diameter of 100 to 500 nm of the acrylic rubber polymer.
In paragraph 1,
The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer has a shell formed by graft polymerization of a core containing an acrylic rubber polymer and a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound to the core; A core-shell structure comprising a thermoplastic resin composition.
In paragraph 8,
The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a thermoplastic resin composition comprising 45 to 65% by weight of the acrylic rubber polymer.
In paragraph 1,
The (B) acrylic rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is an acrylonitrile-styrene-acrylate graft copolymer.
In paragraph 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition of a monomer mixture containing 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound.
In paragraph 1,
The (C) aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of 80,000 to 200,000 g / mol thermoplastic resin composition.
In paragraph 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a styrene-acrylonitrile copolymer thermoplastic resin composition.
In paragraph 1,
The thermoplastic resin composition includes at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, inorganic additives, UV stabilizers, antistatic agents, pigments, and dyes A thermoplastic resin composition further comprising a.
A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 14.