KR101466148B1 - Acryl based thermoplastic resin composition and molded product using the same - Google Patents

Abstract

(A) an acrylic copolymer of a core-shell structure comprising a rubber core containing an acrylic compound; And (B) an impact modifier having a core-shell structure formed by grafting a shell containing a rubber core comprising a silicone compound and an alkyl acrylate compound and containing a methacrylic acid alkyl ester compound, an aromatic vinyl compound and an unsaturated nitrile compound Based thermoplastic resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to an acrylic thermoplastic resin composition,

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

ASA (acrylate-styrene-acrylonitrile) resin is widely used in the production of molded articles such as electric and electronic products, automobile exterior parts, and construction materials because of its excellent weather resistance, light resistance, chemical resistance and heat resistance.

However, the ASA resin is poor in coloring property as compared with ABS (acrylonitrile-butadiene-styrene) resin, and thus has limited application to molded articles requiring color development.

In order to overcome this problem, a large amount of dyes and pigments are mainly added. In this case, basic properties of the ASA resin such as weather resistance are deteriorated.

An aspect of the present invention is to provide an acrylic thermoplastic resin composition excellent in color balance, impact resistance and weather resistance.

Another aspect of the present invention is to provide a molded article using the acrylic thermoplastic resin composition.

One aspect of the present invention relates to a rubber composition comprising (A) an acrylic copolymer having a core-shell structure including a rubber core containing an acrylic compound; And (B) an impact modifier having a core-shell structure formed by grafting a shell containing a rubber core comprising a silicone compound and an alkyl acrylate compound and containing a methacrylic acid alkyl ester compound, an aromatic vinyl compound and an unsaturated nitrile compound Wherein the rubber core of the impact modifier (B) has an average particle diameter of 0.07 to 0.13 m and a weight ratio of the silicone compound and the acrylic acid alkyl ester compound in the rubber core of the impact modifier (B) is from 2:98 to 10: 90 < / RTI >

The rubber core included in the acrylic copolymer (A) may have a structure including a single layer, a double layer, or a combination thereof.

When the rubber core is a double layer, it may include an inner layer comprising the acrylic acid alkyl ester compound and the aromatic vinyl compound, and an outer layer including the acrylic acid alkyl ester compound.

The weight ratio of the acrylic acid alkyl ester compound and the aromatic vinyl compound in the inner layer may be 95: 5 to 80:20.

The weight ratio of the inner and outer layers may be from 30:70 to 70:30.

The acrylic copolymer (A) may be grafted with a shell containing an aromatic vinyl compound and a vinyl cyanide compound to the rubber core.

The acrylic copolymer (A) may comprise 30 to 70% by weight of the rubber core and 70 to 30% by weight of the shell.

The weight ratio of the silicone compound and the alkyl acrylate compound in the rubber core of the impact modifier (B) may be from 2:98 to 10:90.

The shell of the impact modifier (B) may contain a ratio of the sum of the content of the methacrylic acid alkyl ester compound and the content of the aromatic vinyl compound and the unsaturated nitrile compound in a weight ratio of 0: 100 to 50: 50.

The impact modifier (B) may comprise 30 to 70% by weight of the rubber core and 70 to 30% by weight of the shell.

The impact modifier (B) may be included in an amount of 10 to 900 parts by weight based on 100 parts by weight of the acrylic copolymer (A).

The acryl-based thermoplastic resin composition may contain at least one selected from the group consisting of a polystyrene resin (PS resin), an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a rubber modified polystyrene resin (HIPS), an acrylonitrile- Styrene copolymer resin (SAN resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate (PC), polyphenylene ether resin (PPE), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyvinyl chloride resin (PMMA), polyamide (PA) based resin, alpha methyl styrene based resin (AMS) and polymaleimide based resin (PMI). Containing or above (C) may further include a thermoplastic resin.

The acrylic thermoplastic resin composition may be contained at a content ratio of 10 to 900 parts by weight of the thermoplastic resin (C) relative to 100 parts by weight of the acrylic copolymer (A).

Another aspect of the invention provides a molded article produced using the acrylic thermoplastic resin composition.

Other aspects of the present invention are included in the following detailed description.

Since the acrylic thermoplastic resin composition is excellent in balance of physical properties such as coloring property, impact resistance and weather resistance, the acrylic thermoplastic resin composition can be effectively applied to various molded articles, especially plastic exterior articles such as electric and electronic parts and automobile parts.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. "(Meth) acrylic acid ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" can be used. It means that it is possible.

(A) an acrylic copolymer of a core-shell structure comprising a rubber core containing an acrylic compound; And (B) an impact modifier having a core-shell structure formed by grafting a shell containing a rubber core comprising a silicone compound and an alkyl acrylate compound and containing a methacrylic acid alkyl ester compound, an aromatic vinyl compound and an unsaturated nitrile compound Based thermoplastic resin composition.

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

(A) an acrylic copolymer having a core-shell structure

The acrylic copolymer may have a structure in which a shell is grafted to a rubber core containing an acrylic compound.

The acrylic compound may be (meth) acrylic acid alkyl ester, (meth) acrylic acid ester or a combination thereof. Wherein the alkyl may be C1 to C10 alkyl. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Examples of the (meth) acrylic acid esters include (meth) And the like, but are not limited thereto.

The rubber core comprising the acrylic compound may have a structure including a single layer, a double layer, or a combination thereof, and preferably a double layer structure.

Specifically, the acrylic copolymer may include a single-layer rubber core containing the acrylic compound. Alternatively, the acrylic copolymer may include a double-layered rubber core including an inner layer containing the acrylic compound and an aromatic vinyl compound, and an outer layer containing the acrylic compound. Among them, an acrylic copolymer including the rubber core of the double layer may be used. By using the double-layered rubber core, it is possible to further improve colorability and gloss while maintaining weather resistance, impact resistance and the like.

The double-layered rubber core may comprise an inner layer and an outer layer.

In one embodiment, the inner layer comprises an acrylic acid alkyl ester compound and an aromatic vinyl compound, and the outer layer comprises an acrylic acid alkyl ester compound.

The acrylic acid alkyl ester compound may be a C1 to C10 alkyl acrylate, for example, methyl acrylate, butyl acrylate, or a combination thereof.

The aromatic vinyl compound may be styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene or a combination thereof. Examples of the alkyl-substituted styrene include, but are not limited to, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

The inner layer may be specifically a copolymer of the acrylic acid alkyl ester compound and the aromatic vinyl compound. The weight ratio of the acrylic acid alkyl ester compound and the aromatic vinyl compound in the inner layer may be from 95: 5 to 80:20, and when it is contained in the weight ratio within this range, the weather resistance, impact resistance, Side performance combination can be obtained.

In other embodiments, the weight ratio of the inner and outer layers may be between 30:70 and 70:30. When the weight ratio is in the above range, it is possible to obtain a physical property balance suitable for use as a predetermined use.

The acrylic copolymer may be used by mixing an acrylic copolymer including the single-layer rubber core and an acrylic copolymer including the double-layer rubber core. At this time, the acrylic copolymer including the single-layer rubber core and the acrylic copolymer including the double-layer rubber core may be mixed at a weight ratio of 20:80 to 80:20, specifically 25:75 to 75: 25 by weight. When the mixing ratio is within the above range, the acrylic thermoplastic resin composition is excellent in coloring property.

The average particle diameter of the rubber may be 0.07 to 0.13 mu m.

The shell grafted to the rubber core comprises an unsaturated compound.

The unsaturated compound may be an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a combination thereof. Of these, a mixture or copolymer of an aromatic vinyl compound and a vinyl cyanide compound may be preferably used. The aromatic vinyl compound and the vinyl cyanide compound may be 90 to 10 wt% and 60 to 40 wt%, respectively.

As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene or a combination thereof may be used. Examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.

As the heterocyclic compound, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.

In another embodiment, the acrylic copolymer may comprise from 70 to 30% by weight of the rubber core and from 30 to 70% by weight of the shell, and more specifically from 60 to 40% by weight of the rubber core and from 40 to 60% % ≪ / RTI > by weight. When the ratio is within the above range, the acrylic thermoplastic resin composition is excellent in colorability.

(B) Impact modifier of core-shell structure

The impact modifier has a structure in which a shell is grafted to a rubber core containing a silicone compound and an alkyl ester compound, and the shell includes a methacrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated nitrile compound.

The silicon-based compound may be a 3-membered ring or higher, preferably a 3- to 6-membered cyclic siloxane compound. Examples of the cyclosiloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, But are not limited to, cyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, or combinations thereof. If necessary, siloxane-containing siloxane functional group-containing crosslinking agent peroxosiloxane vinyl polymer may also be added. At this time, a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane or tetraethoxysilane may be used.

The acrylic acid alkyl ester compound may be a C1 to C10 alkyl acrylate, for example, methyl acrylate, butyl acrylate, or a combination thereof.

The rubber core may be specifically a copolymer of the silicone compound and the alkyl ester compound.

In another embodiment, the weight ratio of the silicone compound and the acrylic alkyl ester compound in the rubber core of the impact modifier (B) may be from 2:98 to 10:90.

The average particle diameter of the rubber core may be 0.07 to 0.13 mu m. When the average particle diameter is within the above range, desired physical properties balance of impact resistance, color tone development and gloss can be obtained.

The shell grafted to the rubber core includes a compound of a methacrylic acid alkyl ester compound, an aromatic vinyl compound and an unsaturated nitrile compound.

The unsaturated compound may further include, in addition to the methacrylic acid alkyl ester compound, the aromatic vinyl compound and the unsaturated nitrile compound, a heterocyclic compound and the like, or a combination thereof may be used together.

The methacrylic acid alkyl ester compound may be a C1 to C10 alkyl methacrylate, for example, methyl methacrylate, butyl methacrylate, ethyl acrylate, 2-ethylhexyl methacrylate, or a combination thereof. Can be used.

As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene or a combination thereof may be used. Examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.

As the heterocyclic compound, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.

The unsaturated compound may specifically be a polymer of a methacrylic acid alkyl ester and a styrene-acrylonitrile polymer.

In another embodiment, the ratio of the content of the methacrylic acid alkyl ester compound to the content of the aromatic vinyl compound and the unsaturated nitrile compound in the shell of the impact modifier may be from 0: 100 to 50: 50. When the shell of the impact modifier is constituted by the content ratio within the above range, it can be suitably applied to a predetermined use in terms of physical property balance such as color tone.

In another embodiment, the impact modifier may have a weight ratio of the rubber core to the shell of from 70:30 to 30:70.

The impact modifier may be included in an amount of 10 to 900 parts by weight based on 100 parts by weight of the acrylic copolymer (A), and specifically 30 to 350 parts by weight. When the impact modifier is included in the above content range, the acrylic thermoplastic resin composition is excellent in balance of physical properties such as impact resistance, colorability and weatherability.

(C) Thermoplastic resin

The acrylic thermoplastic resin composition according to another embodiment may further comprise a thermoplastic resin (C) other than the acrylic copolymer (A).

Specific examples of the thermoplastic resin include polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene- Styrene copolymer resin (AES resin), acrylonitrile-styrene copolymer resin (SAN resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) (PC), a polyphenylene ether resin (PPE), a polyethylene resin (PE), a polypropylene resin (PP), a polyethylene terephthalate resin (PET), a polybutylene terephthalate resin (PBT) (PMMA), a polyamide (PA) based resin, an alpha methyl styrene based resin (AMS), a polymaleimide based resin (PMI), and the like. Mixtures may be used on.

In another embodiment, the thermoplastic resin is an alpha methyl styrene resin (AMS) and / or a polymaleimide resin (PMI).

The thermoplastic resin may be included in an amount of 10 to 900 parts by weight based on 100 parts by weight of the acrylic copolymer (A), and specifically 30 to 800 parts by weight. When the thermoplastic resin is contained in the above content range, the acrylic thermoplastic resin composition is excellent in coloring property, impact resistance and weather resistance.

(D) Other additives

The acrylic thermoplastic resin composition may contain at least one selected from the group consisting of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, , A nucleating agent, an adhesion promoter, a pressure-sensitive adhesive, or a combination thereof.

As the antioxidant, phenol type, phosphite type, thioether type or amine type antioxidant may be used. Examples of the releasing agent include fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid, , A montanic ester wax or a polyethylene wax can be used. Further, benzophenone type or amine type endurance agent can be used as the weathering agent, and a dye or pigment can be used as the coloring agent. Titanium dioxide (TiO ₂ ) or carbon black can be used as the ultraviolet ray blocking agent. As the nucleating agent, talc or clay may be used.

The additive may be appropriately contained within a range that does not impair the physical properties of the acrylic thermoplastic resin composition and may be specifically included in an amount of 40 parts by weight or less based on 100 parts by weight of the acrylic thermoplastic resin composition, 30 parts by weight.

The above-mentioned acrylic thermoplastic resin composition can be produced by a known method for producing a resin composition. For example, the components and other additives according to one embodiment may be simultaneously mixed and then melt-extruded in an extruder and produced in the form of pellets.

In another embodiment, there is provided a molded article produced by molding the above acrylic thermoplastic resin composition. That is, the acrylic thermoplastic resin composition can be used to produce a molded article by various processes such as injection molding, blow molding, extrusion molding, and thermoforming. Particularly, it can be effectively applied to molded articles requiring coloring property, impact resistance and weather resistance, especially plastic exterior products such as electric and electronic parts and automobile parts.

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

( Example )

The constituent components used in the production of the acrylic thermoplastic resin composition of the following examples and comparative examples are as follows.

(A) an acrylic copolymer resin

ASA-1, ASA-2 and ASA-3 consisting of a core layer having the composition shown in the following Table 1 and a shell layer having the composition shown in the following Table 2 were prepared. The weight ratio of the core layer to the shell layer in each of ASA-1, ASA-2 and ASA-3 is 50:50.

(Unit: parts by weight) ASA-1 ASA-2 ASA-3 Core layer

Inner layer
Butyl acrylate rubber 95 85 85 Styrene 5 15 15 Outer layer Butyl acrylate rubber 100 100 100 Rubber particle size (탆) 0.15 0.15 0.1

(Unit: parts by weight) ASA-1 ASA-2 ASA-3 Shell layer
Styrene 70 70 70 Acrylonitrile 30 30 30

(B) a silicone-acrylate resin

Composite rubber a, composite rubber b, composite rubber c, composite rubber d, composite rubber e and composite rubber f composed of a core layer having the composition shown in the following Table 3 and a shell layer having the composition shown in Table 4 below were prepared. The weight ratio of the core layer to the shell layer in each of the composite rubber a, composite rubber b, composite rubber c, composite rubber d, composite rubber e and composite rubber f is 50:50.

The silicone rubber in Table 3 is hexamethylcyclotrisiloxane.

(Unit: parts by weight) Composite rubber a Composite rubber b Composite rubber c Composite rubber d Composite rubber e Composite rubber f Core layer Silicone rubber 5 10 5 5 5 15 Butyl acrylate 95 90 95 95 95 85 Rubber particle size (탆) 0.1 0.1 0.1 0.25 0.4 0.1

(Unit: parts by weight) Composite rubber a Composite rubber b Composite rubber c Composite rubber d Composite rubber e Composite rubber f Shell layer
Styrene 30 30 - 30 30 30 Acrylonitrile 70 70 - 70 70 70 Methyl methacrylate - - 100 - - -

(C1) g-ABS resin

60 parts by weight of a core layer made of butadiene rubber, 40 parts by weight of a monomer mixture composed of 70% by weight of acrylonitrile and 30% by weight of styrene was subjected to graft-emulsion polymerization to obtain a core-shell type graft ABS resin having a rubber particle size of about 0.25 [

(C2) SAN resin

The acrylonitrile content was 32% by weight, the styrene content was 68% by weight,

SAN Resin with self-volume of about 120,000

(C3) AMS resin

The content of acrylonitrile was 20.5% by weight, the content of alpha-methylstyrene was 79.5% by weight

AMS resin having a weight average molecular weight of about 130,000

(C4) PMI resin

A PMI resin having an acrylonitrile content of 15% by weight, a styrene content of 55% by weight, an N-phenylmaleimide content of 30% by weight and a weight average molecular weight of about 150,000

Example  1 to 7

Using the above-mentioned components, the thermoplastic resin compositions of Examples 1 to 7 were prepared with the compositions shown in Table 5 below.

As a production method thereof, the composition shown in the following Table 1 is mixed, melted, kneaded and extruded to produce pellets. A twin-screw extruder having an L / D of 29 and a diameter of 45 mm is used for the extrusion, and the barrel temperature is set to 220 占 폚. The pellets were dried at 80 ° C for 2 hours, and then set at a cylinder temperature of 250 ° C and a mold temperature of 40 ° C using a 6 Oz injection molding machine. The pellets were tested for physical properties and a 9 cm × 5 cm × 0.2 cm coloring, A specimen is prepared.

(Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 The acrylic copolymer resin (A) ASA-1 30 - - - - - - ASA-2 - 30 10 10 10 30 - ASA-3 - - - - - - 30 The silicone-acrylate resin (B) Composite rubber a 10 10 30 30 20 - 10 Composite rubber b - - - - - 10 - Composite rubber c - - - - - - - Composite rubber d - - - - - - - Composite rubber e - - - - - - - Composite rubber f - - - - - - - g-ABS resin (C1) - - - - 5 - - SAN resin (C2) 60 60 60 10 25 60 60 AMS resin (C3) - - - 50 - - - PMI resin (C4) - - - - 40 - -

Comparative Example  1 to 6

Using the above-mentioned components, the thermoplastic resin compositions of Comparative Examples 1 to 6 were prepared in the same manner as in the above Examples, with the compositions shown in Table 6 below.

(Unit: parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 The acrylic copolymer resin (A) ASA-1 30 30 30 30 10 10 ASA-2 - - - - - - ASA-3 - - - - - - The silicone-acrylate resin (B) Composite rubber a - - - - - - Composite rubber b - - - - - - Composite rubber c 10 - - - 20 - Composite rubber d - 10 - - - - Composite rubber e - - 10 - - - Composite rubber f - - - 10 - - g-ABS resin (C1) - - - - 5 30 SAN resin (C2) 60 60 60 10 25 60 AMS resin (C3) - - - 50 - - PMI resin (C4) - - - - 40 -

(Test Example)

The pellets prepared in the above Examples and Comparative Examples were dried at 80 DEG C for 2 hours and then set at a cylinder temperature of 210 DEG C and a mold temperature of 60 DEG C by using an injection molding machine having an injection capability of 6 oz and the ASTM dumbbell d ㎛ b-bell) specimens. The physical properties of the prepared physical specimens were measured by the following methods, and the results are shown in Tables 7 and 8 below.

1) Notch IZOD Impact strength: Measure according to ASTM D256 (specimen thickness 1/8 ", 23 ° C, kgf · cm / cm).

2) Weatherability: Measurement is made according to SAE J 1960 (3,000 hours, ΔE) using a specimen of 9 cm × 5 cm × 0.2 cm.

3) Colorability: Measure the brightness value (L ^* ) of the black color using a Minolta CM-2500C colorimeter with a sample of 9 cm × 5 cm × 0.2 cm size.

4) Glossiness: Suga tester Digital brightness gauge (UGV-6P) Measuring angle 20 ° -20 °

Item unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Notch Izod
Impact strength (1/8) kgf · cm / cm 22 19 22 20 24 21 18 Weatherability ΔE 2.5 2.6 2.4 2.3 2.6 2.6 2.7 Colorability L ^* 28.33 28.12 28.02 29.27 28.47 28.37 27.77 Glossiness % 82 83 82 81 80 82 84

Item unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Notch Izod
Impact strength (1/8) kgf · cm / cm 15 21 19 25 17 26 Weatherability ΔE 2.5 2.7 2.7 2.7 2.6 6.9 Colorability L ^* 28.77 29.48 30.18 29.88 28.99 28.92 Glossiness % 78 75 72 79 78 76

It can be confirmed that the results of Examples 1 to 7 of Table 7 are excellent in balance of physical properties of impact resistance, weather resistance, coloring property and glossiness as compared with the results of Comparative Examples 1 to 6 of Table 8 above.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

(A) an acrylic copolymer of a core-shell structure comprising a rubber core containing an acrylic compound; And
(B) an impact modifier having a core-shell structure formed by grafting a shell containing an aromatic vinyl compound and an unsaturated nitrile compound and a rubber core containing a silicone compound and an alkyl acrylate compound
Lt; / RTI >
Wherein the rubber core of the impact modifier (B) has an average particle diameter of 0.07 to 0.13 탆,
Wherein the weight ratio of the silicone compound to the acrylic alkyl ester compound in the rubber core of the impact modifier (B) is from 2:98 to 10:90. The method according to claim 1,
Wherein the rubber core contained in the acrylic copolymer (A) has a structure comprising a single layer, a double layer, or a combination thereof. The method according to claim 1,
Wherein the rubber core contained in the acrylic copolymer (A) has a structure comprising a double layer. 3. The method of claim 2,
Wherein the double-layered rubber core comprises an inner layer comprising an acrylic acid alkyl ester compound and an aromatic vinyl compound, and an outer layer comprising an acrylic acid alkyl ester compound. 5. The method of claim 4,
Wherein the weight ratio of the acrylic acid alkyl ester compound to the aromatic vinyl compound in the inner layer is 95: 5 to 80:20. 5. The method of claim 4,
Wherein the weight ratio of the inner layer to the outer layer is from 30:70 to 70:30. The method according to claim 1,
Wherein the acrylic copolymer (A) is obtained by grafting a shell containing an aromatic vinyl compound and a vinyl cyanide compound onto the rubber core. The method according to claim 1,
The acrylic thermoplastic resin composition (A) comprises 70 to 30% by weight of the rubber core and 30 to 70% by weight of the shell. delete The method according to claim 1,
The impact modifier (B) comprises 70 to 30% by weight of the rubber core and 30 to 70% by weight of the shell. The method according to claim 1,
Wherein the impact modifier (B) is contained in an amount of 10 to 900 parts by weight based on 100 parts by weight of the acrylic copolymer (A). The method according to claim 1,
The acryl-based thermoplastic resin composition may contain at least one selected from the group consisting of a polystyrene resin (PS resin), an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a rubber modified polystyrene resin (HIPS), an acrylonitrile- Styrene copolymer resin (SAN resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate (PC), polyphenylene ether resin (PPE), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyvinyl chloride resin (PMMA), polyamide (PA) based resin, alpha methyl styrene based resin (AMS) and polymaleimide based resin (PMI). An acrylic thermoplastic resin composition (C) in the thermoplastic resin containing the above and further comprising. 13. The method of claim 12,
The thermoplastic resin (C) is an alphamethylstyrene resin (AMS), a polymaleimide resin (PMI), or a combination of at least one of them. 13. The method of claim 12,
Wherein the acrylic thermoplastic resin composition further comprises 10 to 900 parts by weight of the thermoplastic resin (C) relative to 100 parts by weight of the acrylic copolymer (A). A molded article produced by using the acrylic thermoplastic resin composition of any one of claims 1 to 8 and 10 to 14.