WO2024049090A1 - Thermoplastic resin composition and molded product manufactured using same - Google Patents

Abstract

A thermoplastic resin composition is provided. On the basis of 100 parts by weight of a base resin comprising (A) 20-40 wt% of an acrylic rubber-modified graft copolymer, (B) 30-50 wt% of a polymethyl methacrylate resin containing 5 wt% or more of a methyl acrylate-derived component, and (C) 20-40 wt% of an α-methylstyrene-based copolymer, the composition comprises (D) 1-3 parts by weight of an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more, and (E) 1-3 parts by weight of a methyl methacrylate-butyl acrylate block copolymer.

Description

Thermoplastic resin compositions and molded articles made therefrom

The present invention relates to thermoplastic resin compositions and molded articles manufactured therefrom.

Thermoplastic resins, which have recently been widely used in electrical and electronics, automobiles, building materials, and leisure goods, are rapidly replacing existing glass and metal. Accordingly, the demand for thermoplastic resins that can achieve excellent impact resistance, weather resistance, molding processability, and high-quality appearance is increasing.

Acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as ABS resin), which is widely used as a thermoplastic resin, contains chemically unstable double bonds in the rubber component, so the rubber component can be easily aged by ultraviolet rays. Accordingly, ABS resin has poor weather resistance and light resistance, and therefore, when left outdoors for a long time, discoloration and physical properties deteriorate significantly over time, making it unsuitable for outdoor applications exposed to sunlight.

On the other hand, acrylonitrile-styrene-acrylate copolymer resin (hereinafter referred to as ASA resin) uses a chemically stable acrylic rubber polymer instead of butadiene rubber polymer as a rubber component, so it is less prone to aging of the rubber component due to UV rays of ABS resin. It is known as an alternative that can solve the problems of discoloration and deterioration of physical properties. In addition, ASA resin has the advantage of excellent weather resistance and light resistance, as well as moldability, chemical resistance, and thermal stability.

Recently, in accordance with eco-friendly trends, the demand for unpainted thermoplastic resins that can be used without going through a painting process is increasing. Since unpainted thermoplastic resins are used as unpainted molded products, they must have excellent scratch resistance, coloring, impact resistance, and weather resistance. Recently, as the requirements for physical properties have increased, polymethyl methacrylate resin (hereinafter referred to as ASA resin) has been added to ASA resin. Attempts to apply ASA/PMMA alloy resin mixed with PMMA resin are also increasing.

However, ASA/PMMA alloy resin lacks impact resistance and heat resistance compared to ASA resin, and has problems such as bending of large parts and parts exposed to visible light. Accordingly, there are attempts to supplement heat resistance by blending unpainted thermoplastic resin with a polymer with excellent heat resistance (for example, alpha-methylstyrene-based copolymer), but in this case, the continuous phase (matrix) and the dispersed phase are used. Due to the difference in refractive index between domains, the transparency and coloring of the molded product decreases, and the appearance characteristics also deteriorate.

Therefore, research is needed on thermoplastic resin compositions that have excellent heat resistance, coloring, impact resistance, and appearance properties.

One embodiment provides a thermoplastic resin composition having excellent heat resistance, colorability, impact resistance, and appearance properties, and a molded article manufactured therefrom.

According to one embodiment, (A) 20 to 40% by weight of an acrylic rubber-modified graft copolymer; (B) 30 to 50% by weight of polymethyl methacrylate resin containing 5% by weight or more of a methyl acrylate-derived component; and (C) 1 to 3 parts by weight of an aromatic vinyl-cyanide copolymer with a weight average molecular weight of 5,000,000 g/mol or more, based on 100 parts by weight of the base resin containing 20 to 40% by weight of an alpha-methylstyrene-based copolymer. wealth; and (E) 1 to 3 parts by weight of methyl methacrylate-butyl acrylate block copolymer.

The (A) acrylic rubber-modified graft copolymer has a core containing an acrylic rubber polymer, and at least one selected from a (meth)acrylate-based compound, an aromatic vinyl compound, and a vinyl cyanide compound is graft-polymerized to the core. It may include a formed shell.

The average particle diameter of the acrylic rubber polymer may be 100 to 500 nm.

The (A) acrylic rubber-modified graft copolymer may include a butyl acrylate-styrene crosslinked copolymer core and a shell formed by grafting a styrene-acrylonitrile copolymer to the core.

The (B) polymethyl methacrylate resin containing 5% by weight or more of a methyl acrylate-derived component may contain 5 to 10% by weight of a methyl acrylate-derived component.

The (C) alpha-methylstyrene-based copolymer may be a copolymer of a monomer mixture containing 50 to 60% by weight of alpha-methylstyrene, 15 to 35% by weight of a vinyl cyanide compound, and 15 to 35% by weight of an aromatic vinyl compound. there is.

In the (C) alpha-methylstyrene-based copolymer, the aromatic vinyl compound is styrene substituted or unsubstituted with halogen or C1 to C10 alkyl groups (but does not include alpha-methylstyrene), and combinations thereof. The vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

The (C) alpha-methylstyrene-based copolymer may be an alpha-methylstyrene-styrene-acrylonitrile copolymer.

The (D) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g/mol or more.

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

In another embodiment, a molded article manufactured from the thermoplastic resin composition is provided.

The molded product may have a notched Izod impact strength of 8 kgf·cm/cm or more as measured on a 1/8 inch thick specimen according to the ASTM D256 standard.

The molded product may have a Vicat softening temperature (VST) of 100°C or more, measured under B50 conditions according to the ISO 306 standard.

A thermoplastic resin composition with excellent heat resistance, colorability, impact resistance, and appearance properties, and a molded article manufactured therefrom can be provided.

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.

Unless otherwise specified herein, “copolymer” means block copolymerization, random copolymerization, and graft copolymerization, and “copolymer” means block copolymer, random copolymer, and graft copolymer.

Unless specifically mentioned herein, the average particle diameter of the rubbery polymer refers to the volume average diameter and the Z-average particle diameter measured using dynamic light scattering analysis equipment.

Unless specifically mentioned herein, the weight average molecular weight is measured using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) after dissolving the powder sample in an appropriate solvent (the standard sample is Shodex polystyrene). used).

The thermoplastic resin composition according to one embodiment includes (A) 20 to 40% by weight of an acrylic rubber-modified graft copolymer; (B) 30 to 50% by weight of polymethyl methacrylate (PMMA) resin containing 5% by weight or more of a methyl acrylate-derived component; and (C) 1 to 3 parts by weight of an aromatic vinyl-cyanide copolymer with a weight average molecular weight of 5,000,000 g/mol or more, based on 100 parts by weight of the base resin containing 20 to 40% by weight of an alpha-methylstyrene-based copolymer. wealth; and (E) 1 to 3 parts by weight of methyl methacrylate-butyl acrylate block copolymer (MMA-b-BA).

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

(A) Acrylic rubber-modified graft copolymer

The thermoplastic resin composition according to one embodiment includes (A) an acrylic rubber-modified graft copolymer. The (A) acrylic rubber-modified graft copolymer functions to reinforce various physical properties of the thermoplastic resin composition, such as impact resistance, mechanical properties, and appearance properties.

In one embodiment, the (A) acrylic rubber-modified graft copolymer includes a core containing an acrylic rubber polymer, and at least one selected from a (meth)acrylate-based compound, an aromatic vinyl compound, and a vinyl cyanide compound. It may include a shell formed by graft polymerization.

The (A) acrylic rubber-modified graft copolymer can be produced according to any production method known to those skilled in the art.

As the above production method, conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization can be used. To give a non-limiting example, an acrylic rubbery polymer is manufactured, and at least one type selected from a (meth)acrylate compound, an aromatic vinyl compound, and a vinyl cyanide compound is added to a core formed of one or more layers of the acrylic rubbery polymer. It can be produced by graft polymerization to form one or more layers of shell.

The acrylic rubbery polymer may be a crosslinked polymer manufactured using an acrylic compound as a main monomer. The acrylic compound may be, for example, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, hexyl acrylate, or a combination thereof.

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

The average particle diameter of the acrylic rubbery polymer may be 100 to 500 nm, for example, 100 to 400 nm, for example, 100 to 300 nm, but is not limited to these ranges. Within the above average particle size range, the thermoplastic resin composition may have excellent impact resistance, mechanical properties, and coloring properties.

In one embodiment, the (meth)acrylate-based compound included in the shell is methacrylate, acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, and propyl acrylate. It may be one or more types selected from latex, butyl methacrylate, and butyl acrylate, but is not limited thereto.

The aromatic vinyl compound included in the shell may be one or more selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene. , but is not limited to this.

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

In one embodiment, when a monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound is graft polymerized to the core including the acrylic rubber polymer to form a shell, the shell includes the aromatic vinyl compound and the vinyl cyanide compound. It may be a copolymer of a monomer mixture included in a weight ratio of 1:1 to 4:1, for example, 1:1 to 3:1.

In one embodiment, the (A) acrylic rubber-modified graft copolymer may include a butyl acrylate-styrene crosslinked copolymer core and a shell formed by grafting styrene-acrylonitrile copolymer (SAN) to the core. You can.

In one embodiment, the (A) acrylic rubber-modified graft copolymer may be included in an amount of 20 to 40% by weight, for example, 20 to 30% by weight, for example, 30 to 40% by weight, based on 100% by weight of the base resin. there is. Within the above weight % range, the thermoplastic resin composition may have excellent impact resistance, mechanical properties, and coloring properties.

(B) Polymethyl methacrylate resin containing 5% by weight or more of methyl acrylate-derived components

The thermoplastic resin composition according to one embodiment includes (B) a polymethyl methacrylate (PMMA) resin containing 5% by weight or more of a methyl acrylate-derived component, and can impart excellent coloring and appearance characteristics to the thermoplastic resin composition. there is.

The (B) polymethyl methacrylate resin containing 5% by weight or more of the methyl acrylate-derived component is obtained by preparing a monomer mixture containing methyl methacrylate and methyl acrylate using suspension polymerization, bulk polymerization, emulsion polymerization, etc. It can be obtained by polymerization using a known polymerization method.

The thermoplastic resin composition of the present invention can ensure excellent compatibility by comprising a polymethyl methacrylate resin containing 5% by weight or more of the (B) methyl acrylate-derived component, and the methyl acrylate-derived component is specifically It may be included in 5 to 10% by weight. In the above weight range, compatibility between components included in the thermoplastic resin composition may be more excellent, and thus the coloring and appearance characteristics of the thermoplastic resin composition may be more excellent.

The (B) polymethyl methacrylate resin containing 5% by weight or more of the methyl acrylate-derived component may have a glass transition temperature of 100 to 150°C, for example, 110 to 130°C.

The weight average molecular weight of the (B) polymethyl methacrylate resin containing 5% by weight or more of the methyl acrylate-derived component may be 50,000 to 200,000 g/mol, for example, 50,000 to 100,000 g/mol. When the above range is satisfied, the thermoplastic resin composition can exhibit excellent processability and compatibility.

The (B) polymethyl methacrylate resin containing 5% by weight or more of the methyl acrylate-derived component is 30 to 50% by weight, for example, 30 to 40% by weight, for example, 40 to 40% by weight, based on 100% by weight of the base resin. It may be included at 50% by weight. Within the above weight percent range, the coloring and appearance characteristics of the thermoplastic resin composition may be excellent.

(C) Alpha-methylstyrene-based copolymer

The thermoplastic resin composition according to one embodiment may include (C) an alpha-methylstyrene-based copolymer, which may provide excellent heat resistance to the thermoplastic resin composition.

The (C) alpha-methylstyrene-based copolymer can be prepared using conventional manufacturing methods, such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

In one embodiment, the (C) alpha-methylstyrene-based copolymer is a monomer mixture containing 50 to 60% by weight of alpha-methylstyrene, 15 to 35% by weight of a vinyl cyanide compound, and 15 to 35% by weight of an aromatic vinyl compound. It may be a copolymer. Within the above weight range, the thermoplastic resin composition may have excellent compatibility and heat resistance.

In the (C) alpha-methylstyrene-based copolymer, the aromatic vinyl compound is styrene substituted or unsubstituted with halogen or C1 to C10 alkyl groups (but does not include alpha-methylstyrene), and combinations thereof. The vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

In one embodiment, the (C) alpha-methylstyrene-based copolymer may be an alpha-methylstyrene-styrene-acrylonitrile copolymer.

The weight average molecular weight of the (C) alpha-methylstyrene-based copolymer may be 50,000 to 300,000 g/mol, for example, 100,000 to 200,000 g/mol, and when the above range is satisfied, the thermoplastic resin composition containing it has excellent properties. It can exhibit impact resistance and fluidity.

The (C) alpha-methylstyrene-based copolymer may be included in an amount of 20 to 40% by weight, for example, 20 to 30% by weight, for example, 30 to 40% by weight, based on 100% by weight of the base resin. Within the above weight range, the heat resistance and appearance characteristics of the thermoplastic resin composition may be excellent.

(D) Aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more.

In one embodiment, (D) an aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 5,000,000 g/mol or more can improve the appearance characteristics of a thermoplastic resin composition.

The weight average molecular weight of the (D) aromatic vinyl compound-cyanated vinyl compound copolymer is 5,000,000 g/mol or more, for example 5,000,000 to 10,000,000 g/mol, for example 5,000,000 to 9,000,000 g/mol, for example 5,000,000 to 8,000,000. g/mol, for example 5,000,000 to 7,000,000 g/mol.

In one embodiment, the (D) aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 5,000,000 g/mol or more may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g/mol or more.

(D) The aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 5,000,000 g/mol or more according to one embodiment may be included in an amount of 1 to 3 parts by weight, for example, 2 to 3 parts by weight, based on 100 parts by weight of the base resin. You can. Within the above weight parts range, the occurrence of flow marks in the thermoplastic resin composition and molded products manufactured therefrom may be suppressed, thereby providing excellent appearance characteristics.

(E) Methyl methacrylate-butyl acrylate block copolymer

The thermoplastic resin composition according to one embodiment includes (E) methyl methacrylate-butyl acrylate block copolymer (MMA-b-BA), thereby improving compatibility between each component included in the thermoplastic resin composition. can do.

The content of the methyl methacrylate-derived component of the (E) methyl methacrylate-butyl acrylate block copolymer may be 10 to 50 wt%, for example, 30 to 50 wt%.

The weight average molecular weight of the (E) methyl methacrylate-butyl acrylate block copolymer may be 50,000 to 200,000 g/mol, for example, 80,000 to 150,000 g/mol.

(E) Methyl methacrylate-butyl acrylate block copolymer according to one embodiment may be included in an amount of 1 to 3 parts by weight, for example, 2 to 3 parts by weight, based on 100 parts by weight of the base resin. Within the above weight part range, compatibility between components included in the thermoplastic resin composition may be more excellent.

(F) Additives

In addition to the components (A) to (E), the thermoplastic resin composition according to one embodiment includes 1 component as needed to balance each physical property without deteriorating other physical properties, or depending on the final use of the thermoplastic resin composition. It may contain more than one type of additive.

Specifically, the additive may further include at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, dyes, and pigments. .

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 are not limited thereto.

Meanwhile, the thermoplastic resin composition according to one embodiment can also be used by mixing with other resins or other rubber components.

Meanwhile, another embodiment provides a molded article manufactured using the thermoplastic resin composition according to one embodiment. The molded article can be manufactured using the thermoplastic resin composition by various methods known in the art, such as injection molding and extrusion molding.

The molded product has a notched Izod impact strength measured on a 1/8 inch thick specimen according to the ASTM D256 standard of 8 kgf·cm/cm or more, 9 kgf·cm/cm or more, and 10 kgf·cm/ It may be more than cm, or more than 11 kgf·cm/cm.

The molded article may have a Vicat softening temperature (VST) of 100°C or higher, 101°C or higher, 102°C or higher, or 103°C or higher, as measured under B50 conditions according to the ISO 306 standard.

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

Examples 1 to 4 and Comparative Examples 1 to 7

The thermoplastic resin compositions of Examples 1 to 4 and Comparative Examples 1 to 7 were prepared according to the component content ratios shown in Table 1 below.

The components listed in Table 1 and a quinone-based dye mixture expressing black color were dry mixed by adding 0.5 parts by weight based on 100 parts by weight of the total weight of components (A) to (C), and extruded using a twin-screw extruder (L/D). = 29, Φ = 45 mm) was continuously and quantitatively fed into the feed section and melted/kneaded. At this time, the barrel temperature of the twin-screw extruder was set to about 240°C. Next, the thermoplastic resin composition pelletized through a twin-screw extruder was dried at about 80°C for about 4 hours, and then used a 6 oz injection molding machine set at a cylinder temperature of about 240°C and a mold temperature of about 60°C. A specimen for measuring physical properties was prepared. The measured physical properties are shown in Table 2 below.

In Table 1, components (A) to (C) are expressed in weight percent based on the total weight of components (A) to (C), and components (D) and (E) are expressed as weight percent based on the total weight of components (A) to (C). ) is expressed as parts by weight relative to 100 parts by weight of the total weight.

	Example				Comparative example
	One	2	3	4	One	2	3	4	5	6	7
(A)	30	20	40	30	30	30	30	30	30	30	30
(B-1)	40	40	30	50	-	40	40	40	40	60	10
(B-2)	-	-	-	-	40	-	-	-	-	-	-
(C-1)	30	40	30	20	30	-	30	30	30	10	60
(C-2)	-	-	-	-	-	30	-	-	-	-	-
(D)	3	3	3	3	3	3	3	-	-	3	3
(E)	2	2	2	2	2	2	-	2	-	2	2

A description of each component listed in Table 1 above is as follows.

(A) Acrylic rubber-modified graft copolymer

It contains about 50% by weight of a core comprising a butyl acrylate-styrene crosslinked copolymer having an average particle diameter of about 380 nm, and the core contains a styrene-acrylonitrile copolymer (weight ratio of styrene-derived component: acrylonitrile-derived component = about A core-shell type copolymer in which 7:3) was grafted to form a shell was used. (Manufacturer: Lotte Chemical)

(B-1) Polymethyl methacrylate resin

A polymethyl methacrylate resin with a weight average molecular weight of about 60,000 g/mol and a content of methyl acrylate-derived components of about 5% by weight was used (manufacturer: Asahi Kasei).

(B-2) Polymethyl methacrylate resin

A polymethyl methacrylate resin with a weight average molecular weight of about 100,000 g/mol and a content of methyl acrylate-derived components of about 2% by weight was used (manufacturer: Lotte MCC).

(C-1) Alpha-methylstyrene-based copolymer

Alpha-methylstyrene-styrene-acrylonitrile with a weight average molecular weight of about 160,000 g/mol, which is copolymerized with a monomer mixture containing about 19% by weight of styrene, about 27% by weight of acrylonitrile, and about 54% by weight of alpha-methylstyrene. Copolymer was used. (Manufacturer: Lotte Chemical)

(C-2) Alpha-methylstyrene-based copolymer

An alpha-methylstyrene-acrylonitrile copolymer with a weight average molecular weight of about 100,000 g/mol, which is a copolymerization of a monomer mixture containing about 70% by weight of alpha-methylstyrene and about 30% by weight of acrylonitrile, was used. (Manufacturer) : Lotte Chemical)

(D) Aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more.

A styrene-acrylonitrile copolymer with a weight average molecular weight of approximately 5,500,000 g/mol was used (manufacturer: Zibo Huaxing Additives).

(E) Methyl methacrylate-butyl acrylate block copolymer

A methyl methacrylate-butyl acrylate block copolymer containing about 50% by weight of methyl methacrylate-derived components and about 50% by weight of butyl acrylate-derived components was used. (Manufacturer: Kuraray Co.)

Physical property evaluation

The specimens for measuring physical properties according to Examples 1 to 4 and Comparative Examples 1 to 7 were tested for impact resistance, heat resistance, coloring properties, and appearance properties using the following evaluation methods, and the evaluation results are listed in Table 2 below.

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

(2) Heat resistance (unit: ℃): Vicat softening temperature (VST) was measured under B50 conditions according to ISO 306 standards.

(3) Colorability: The brightness (L*) value of a 2.5 mm thick specimen was measured in specular component excluded (SCE) mode according to ASTM E308 using Konica Minolta's CM-3700d. The lower the brightness, the better the black color expression, so it was judged that the coloring properties were excellent.

(4) Appearance characteristics: The degree of flow mark occurrence with the naked eye on a 90 mm x 50 mm x 2 mm specimen that was injection molded at high speed using a pin-point gate structure mold. was observed, and according to the degree of occurrence, it was classified into ○ (occurrence, clearly visible), △ (occurrence, somewhat blurry), and X (not occurrence).

	Example				Comparative example
	One	2	3	4	One	2	3	4	5	6	7
Izod impact strength	10	8	12	9	11	11	7	6	6	7	12
VST	101	102	100	100	105	102	102	102	103	99	103
Brightness (L*)	3.2	2.9	3.4	3.0	4.8	6.8	5.5	5.8	7.1	2.8	4.7
Degree of flow mark occurrence	○	○	○	○	△	△	△	△	X	○	△

From the results in Tables 1 and 2, it can be seen that the thermoplastic resin composition containing the components (A) to (E) and the molded article manufactured therefrom are all excellent in impact resistance, heat resistance, colorability, and appearance characteristics.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can also be made by those skilled in the art using the basic concept of the present invention defined in the appended claims. It falls within the scope of invention rights.

Claims (13)

1. (A) 20 to 40% by weight of acrylic rubber-modified graft copolymer;

   (B) 30 to 50% by weight of polymethyl methacrylate resin containing 5% by weight or more of a methyl acrylate-derived component; and

   (C) With respect to 100 parts by weight of the base resin containing 20 to 40% by weight of alpha-methylstyrene-based copolymer,

   (D) 1 to 3 parts by weight of an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more; and

   (E) A thermoplastic resin composition comprising 1 to 3 parts by weight of methyl methacrylate-butyl acrylate block copolymer.
2. In paragraph 1:

   The (A) acrylic rubber-modified graft copolymer has a core containing an acrylic rubber polymer, and at least one selected from a (meth)acrylate-based compound, an aromatic vinyl compound, and a vinyl cyanide compound is graft-polymerized to the core. A thermoplastic resin composition comprising a formed shell.
3. In paragraph 2,

   A thermoplastic resin composition wherein the acrylic rubber polymer has an average particle diameter of 100 to 500 nm.
4. In any one of paragraphs 1 to 3,

   The (A) acrylic rubber-modified graft copolymer is a thermoplastic resin composition comprising a butyl acrylate-styrene crosslinked copolymer core and a shell formed by grafting a styrene-acrylonitrile copolymer to the core.
5. In any one of paragraphs 1 to 4,

   The (B) polymethyl methacrylate resin containing 5% by weight or more of a methyl acrylate-derived component is a thermoplastic resin composition containing 5 to 10% by weight of a methyl acrylate-derived component.
6. In any one of paragraphs 1 to 5,

   The (C) alpha-methylstyrene-based copolymer is a thermoplastic copolymer of a monomer mixture containing 50 to 60% by weight of alpha-methylstyrene, 15 to 35% by weight of a vinyl cyanide compound, and 15 to 35% by weight of an aromatic vinyl compound. Resin composition.
7. In any one of paragraphs 1 to 6,

   In the (C) alpha-methylstyrene-based copolymer, the aromatic vinyl compound is a group consisting of styrene substituted or unsubstituted with halogen or C1 to C10 alkyl groups (but does not include alpha-methylstyrene) and combinations thereof. , wherein the vinyl cyanide compound is selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
8. In any one of paragraphs 1 to 7,

   The (C) alpha-methylstyrene-based copolymer is an alpha-methylstyrene-styrene-acrylonitrile copolymer, a thermoplastic resin composition.
9. In any one of paragraphs 1 to 8,

   The (D) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 g/mol or more is a styrene-acrylonitrile copolymer having a weight average molecular weight of 5,000,000 g/mol or more.
10. In any one of paragraphs 1 to 9,

    The thermoplastic resin composition further includes at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes. .
11. A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 10.
12. According to clause 11,

    The molded product has a notched Izod impact strength of 8 kgf·cm/cm or more, measured on a 1/8 inch thick specimen according to the ASTM D256 standard.
13. According to claim 11 or 12,

    The molded product has a Vicat softening temperature (VST) of 100°C or more, measured under B50 conditions according to the ISO 306 standard.