KR101486565B1 - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition and a molded article using the same. More specifically, it relates to (A) a rubber-modified vinyl-based graft copolymer; (B) a copolymer of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound; (C) N- (substituted) maleimide copolymers; And (D) a polyalkyl (meth) acrylate.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition and a molded article using the thermoplastic resin composition.

A thermoplastic resin composition and a molded article using the same.

The acrylonitrile-butadiene-styrene (ABS) resin is excellent in impact resistance and processability, and has good mechanical strength, heat distortion temperature and gloss, and is widely used in electric / electronic parts and office equipment. However, when it is used in a housing for high-grade household appliances such as LCD, PDP TV, audio and the like, scratches easily occur during injection molding or use, and it is difficult to develop high-quality color.

To solve this problem, ABS resin has been coated with urethane or the like on the surface of the article of the ABS resin and coated with acrylic resin having excellent scratch characteristics. However, such an operation is accompanied by a problem that the productivity is lowered due to the complexity of the work and an increase of the defect rate, and the environmental pollution due to the painting due to the additional post-processing.

ABS / PMMA resin, which is excellent in coloring property and scratch resistance, has been widely used since it can realize a high-grade design of household appliances. However, due to the difference in refractive index between ABS and PMMA, the scratch property is excellent, but transparency of a certain level or more is not realized and it is impossible to perform coloring. In addition, there is a problem in that a high heat resistance It is limited to be used for a required automobile interior material. Accordingly, development of an ABS / PMMA resin having high coloring resistance and scratch resistance as well as high heat resistance has been demanded.
On the other hand, the prior art documents related to the present invention include Published Patent Application No. 10-2006-0131483 (2006.12.20.) And Published Patent Application No. 10-2010-0067176 (June 22, 2010).

An embodiment of the present invention provides a thermoplastic resin composition excellent in high coloring property, scratch resistance and heat resistance.

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

According to one embodiment of the present invention, there is provided a rubber composition comprising (A) a rubber-modified vinyl-based graft copolymer; (B) a copolymer of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound; (C) an N- (substituted) maleimide copolymer; And (D) a polyalkyl (meth) acrylate.

Wherein the thermoplastic resin composition is a copolymer of 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the copolymer (B) of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound, And 1 to 20 parts by weight of (substituted) maleimide copolymer (C).

Wherein the thermoplastic resin composition comprises 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the copolymer (B) of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound, And 40 to 65 parts by weight of alkyl (meth) acrylate (D).

The thermoplastic resin composition may contain the N- (substituted) maleimide copolymer (C) and the polyalkyl (meth) acrylate (D) in a weight ratio of 1:10 to 1: 2.

The copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound may be an? -Methylstyrene-acrylonitrile copolymer.

The N- (substituted) maleimide copolymer (C) may comprise 20 to 60% by weight of maleic anhydride and N- (substituted) maleimide monomer and 40 to 80% by weight of an aromatic vinyl compound and a vinyl cyanide compound .

The rubber-modified vinyl-based graft copolymer (A) may contain 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer which is an unsaturated nitrile monomer, an acrylic monomer which is different from the acrylic monomer, a heterocyclic monomer which is different from the above-mentioned heterocyclic monomer, or a combination thereof, 5 to 95% by weight of at least one member selected from the group consisting of a butadiene rubber, an acrylic rubber, an ethylene / propylene rubber, a styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an isoprene rubber, a terpolymer of ethylene- / Polyalkyl (meth) acrylate rubber composite, or a combination thereof, in an amount of 5 to 95% by weight.

The polyalkyl (meth) acrylate (D) may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, And polymers polymerized from monomers selected from combinations thereof.

The thermoplastic resin composition may further include additives selected from dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, release agents, and combinations thereof.

Another embodiment of the present invention provides a molded article produced using the above-mentioned thermoplastic resin composition.

The thermoplastic resin composition is excellent in coloring property, scratch resistance and heat resistance.

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.

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.

Unless otherwise specified in the present specification, the "substitution" means that a hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, C3 to C30 cycloalkenyl groups, C3 to C30 cycloalkynyl groups, or combinations thereof, substituted with a substituent selected from the group consisting of a halogen atom, a C1 to C20 alkoxy group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, .

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.

The thermoplastic resin composition according to one embodiment of the present invention comprises (A) a rubber-modified vinyl-based graft copolymer; (B) a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound copolymer; (C) N- (substituted) maleimide copolymers; And (D) polyalkyl (meth) acrylate. The thermoplastic resin composition comprises (B) a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound copolymer which contain a rubber-modified vinyl-based graft copolymer (A) excellent in transparency and contribute to realizing high heat resistance (C) N- (substituted) maleimide copolymers. Also, (D) contains polyalkyl (meth) acrylate, so that it is excellent in scratch resistance, and the thermoplastic resin composition is used for automobile unpainted interior materials requiring a high heat resistance and scratch resistance, or housings for household appliances .

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

(A) Rubber degeneration Vinyl-based Graft  Copolymer

The rubber-modified vinyl-based graft copolymer is a copolymer in which 5 to 95% by weight of a vinyl-based polymer is grafted to 5 to 95% by weight of a rubbery polymer.

Wherein the vinyl polymer comprises 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer which is an unsaturated nitrile monomer, an acrylic monomer which is different from the acrylic monomer, a heterocyclic monomer which is different from the heterocyclic monomer, or a combination thereof . Here, the " heterogeneous " means different kinds.

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

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Methacrylate may be used.

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

As the unsaturated nitrile monomer, acrylonitrile, methacrylonitrile or a combination thereof may be used.

The rubbery polymer may be at least one selected from the group consisting of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (Meth) acrylate rubber composite, or a combination thereof.

The particle diameter of the rubber particles in the production of the rubber-modified vinyl-based graft copolymer may be 0.05 to 4 탆 in order to improve the impact resistance and the surface characteristics of the molded article. When the particle diameter of the rubber particles is 0.05 to 4 탆, .

The rubber-modified vinyl-based graft copolymer may be used singly or in the form of a mixture of two or more thereof.

Specific examples of the rubber-modified vinyl-based graft copolymer include graft-copolymerized styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture in butadiene rubber, acrylic rubber or styrene / butadiene rubber have.

Specific examples of the rubber-modified vinyl-based graft copolymer include graft-copolymerized methyl (meth) acrylate with butadiene rubber, acrylic rubber or styrene / butadiene rubber.

More specific examples of the rubber-modified graft copolymer include an acrylonitrile-butadiene-styrene graft copolymer.

The method for producing the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used, For example, the aforementioned aromatic vinyl monomer may be added in the presence of a rubbery polymer and emulsion polymerization or bulk polymerization may be carried out using a polymerization initiator.

The rubber-modified vinyl-based graft copolymer may be contained in an amount of 10 to 40% by weight based on the total amount of the thermoplastic resin composition, specifically 20 to 30% by weight. When the rubber-modified vinyl-based graft copolymer is contained in the above range, excellent mechanical strength, impact strength and heat resistance of the thermoplastic resin molded article can be secured.

(B) C1  To C10 Alkyl  Substituted aromatic Vinyl-based  Compound and cyanide Vinyl-based  Compound copolymer

The C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and have a weight average molecular weight of 15,000 to 400,000 g / mol Can be used. The C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer improve the heat resistance of the thermoplastic resin.

As the aromatic vinyl compound of the C1 to C10 alkyl-substituted aromatic vinyl compound, styrene, toluene, naphthalene or a combination thereof may be used. Specifically, C1 to C10 alkyl substituted styrene may be used.

Specific examples of the C1 to C10 alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene, .

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

Specific examples of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer include a copolymer of? -Methylstyrene and acrylonitrile, or a copolymer of styrene,? -Methylstyrene and acrylonitrile , And copolymers of? -Methylstyrene and acrylonitrile are preferable.

In addition, the copolymer may be polymerized by further including a (meth) acrylic acid alkyl ester compound together with a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound.

The (meth) acrylic acid alkyl ester compound is preferably a (meth) acrylic acid alkyl ester having a C1 to C10 alkyl group. For example, there may be mentioned methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, Propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, ethylhexyl acrylate, and the like, or a combination thereof may be used, but is not limited thereto.

For example, the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer may contain 50 to 90% by weight of the C1 to C10 alkyl-substituted aromatic vinyl compound and 10 to 50% by weight of the vinyl cyanide compound Or 60 to 80% by weight of a C1 to C10 alkyl substituted aromatic vinyl compound, 20 to 30% by weight of a vinyl cyanide compound and 0 to 10% by weight of a (meth) acrylic acid alkyl ester compound are polymerized Lt; / RTI > Specifically, it may be a copolymer formed by polymerizing 60 to 80% by weight of the C1 to C10 alkyl-substituted aromatic vinyl compound and 20 to 40% by weight of the vinyl cyanide compound.

The C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer may be contained in an amount of 40 to 60% by weight, for example, 40 to 50% by weight based on the total amount of the thermoplastic resin composition. When the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer are contained within the above range, not only the compatibility is excellent but also the impact resistance and heat resistance can be realized while realizing high coloring property.

(C) N- (substituted) Maleimide  Copolymer

The N- (substituted) maleimide copolymer of the present invention is a copolymer of maleic anhydride, N- (substituted) maleimide monomer, and aromatic vinyl compound. In this case, a vinyl cyanide compound may further be used. In this case, the N- (substituted) maleimide copolymer may be a copolymer of maleic anhydride, N- (substituted) maleimide monomer, vinyl cyanide compound, and aromatic vinyl compound to be.

In this case, in the copolymer, the content of the maleic anhydride and the N- (substituted) maleimide monomer is 20 to 60% by weight, the content of the aromatic vinyl compound and optionally the vinyl cyanide compound is 40 to 80% % Is preferable.

In the mixture of maleic anhydride and N- (substituted) maleimide monomer, the content of maleic anhydride is preferably 0.01 to 20% by weight, and the content of N- (substituted) maleimide is preferably 80 to 99.99% by weight. The content of the vinyl cyanide compound in the mixture of the vinyl cyanide compound and the aromatic vinyl compound is preferably 0 to 20% by weight, and the content of the aromatic vinyl compound is preferably 80 to 100% by weight.

The N- (substituted) maleimide copolymer of the present invention is preferably used in view of compatibility with the rubber-modified vinyl-based graft copolymer (A) and the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer And contributes to realizing high heat resistance of the thermoplastic resin composition.

The N- (substituted) maleimide monomer may be selected from the group consisting of N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and mixtures thereof.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and these may be used alone or in combination. Examples of the aromatic vinyl compound include styrene, halogen-substituted styrene, and alkyl-substituted styrene such as? -Methylstyrene, which may be used alone or in combination.

The N- (substituted) maleimide copolymer is preferably used in an amount of 100 parts by weight or more per 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer , 1 to 20 parts by weight, and may be included in the thermoplastic resin, for example, 5 to 20 parts by weight. A molded article using the thermoplastic resin containing the N- (substituted) maleimide copolymer (C) in the above numerical range has high coloring property and excellent heat resistance.

The weight ratio of the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) described below may be from 1:10 to 1: 2, for example, from 1: 7 to 1: 3 Lt; / RTI > When the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) are used in the above-mentioned numerical ranges, the resin is not easily broken due to an increase in the fluidity of the thermoplastic resin, and heat resistance and scratch resistance This is preferable.

(D) Polyalkyl ( Meta ) Acrylate

The polyalkyl (meth) acrylate is resistant to hydrolysis and can improve the scratch resistance of the thermoplastic resin composition.

The polyalkyl (meth) acrylate can be obtained by polymerizing a starting monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization or emulsion polymerization.

The alkyl (meth) acrylate is a compound having an alkyl group of C1 to C10 and is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (Meth) acrylate, and the like.

At this time, the alkyl (meth) acrylate may be included in an amount of about 3% by weight or more, specifically about 3 to about 10% by weight based on the total amount of the polyalkyl (meth) acrylate.

The polyalkyl (meth) acrylate is added to 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer (B) , 40 to 65 parts by weight, and may be contained in the thermoplastic resin composition, for example, 50 to 60 parts by weight. The rubber-modified vinyl-based graft copolymer (A) and the C 1 to C 10 alkyl-substituted (meth) acrylate-based graft copolymer (A) may be added to the thermoplastic resin in an amount sufficient to improve the scratch resistance of the thermoplastic resin, The intermolecular interaction between the aromatic vinyl compound and the vinyl cyanide compound copolymer (B) is increased, and the hydrolysis resistance and scratch resistance are improved.

The starting monomer constituting the polyalkyl (meth) acrylate may further include a vinyl-based monomer in addition to the alkyl (meth) acrylate. Examples of the vinyl-based monomer include aromatic vinyl monomers such as styrene,? -Methylstyrene,? -Methylstyrene, and the like; And unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile. These monomers may be used singly or in combination.

The polyalkyl (meth) acrylate may have a weight average molecular weight ranging from 10,000 to 200,000 g / mol, and specifically from 15,000 to 150,000 g / mol. When the weight average molecular weight of the polyalkyl (meth) acrylate is within the above range, the rubber-modified vinyl-based graft copolymer (A) and the C1 to C10 alkyl-substituted aromatic vinyl compound and the cyanide vinyl compound copolymer (B) And is excellent in hydrolysis resistance, scratch resistance, processability, and the like.

The balance of the scratch resistance and heat resistance of the polyalkyl (meth) acrylate can be controlled while maintaining the coloring property of the molded article prepared by controlling the content ratio of the polyalkyl (meth) acrylate with the N- (substituted) maleimide copolymer (C). The weight ratio of the N- (substituted) maleimide copolymer (C) and the polyalkyl (meth) acrylate may be from 1:10 to 1: 2, for example, from 1: 7 to 1: 3 have.

(E) Other additives

The thermoplastic resin composition may further include additional additives for further imparting injection moldability, physical properties, and the like.

For example, the thermoplastic resin composition may further contain additives such as a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, and a release agent, and these may be used alone or in combination.

The additive may be appropriately contained within a range that does not impair the physical properties of the thermoplastic resin composition. Specifically, the additive may be included in an amount of 40 parts by weight or less based on 100 parts by weight of the rubber-modified vinyl-based graft copolymer (A) And more specifically 0.1 to 30 parts by weight.

The constituent components of the thermoplastic resin composition have been described and exemplary contents of the constituent components have been described. However, depending on the physical properties of the thermoplastic resin composition to be finally obtained, the intrinsic inherent characteristics of the constituent components are considered And the thermoplastic resin composition can be embodied in an appropriate amount.

The 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.

According to another embodiment, there is provided a molded article produced by molding the above-mentioned thermoplastic resin composition. The molded article may be a molded article having a large or complex size or a thin thickness which is required to have mechanical properties, thermal properties and formability, and more specifically, an automotive exterior material.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

( Example )

Each component used in the production of the thermoplastic resin composition of the following examples is as follows.

(A) Acrylonitrile-butadiene-styrene copolymer (Cheil Industries)

Butadiene 58% by weight and 42% by weight shell, and the shell is composed of 31.5% and 10.5% by weight of styrene and acrylonitrile, respectively.

(B) alpha methyl styrene-acrylonitrile copolymer

SAN resin having a weight average molecular weight of about 120,000 g / mol.

(B-1) acrylonitrile-styrene copolymer

A SAN resin having an acrylonitrile content of 20 wt%, a styrene content of 80 wt% and a weight average molecular weight of about 100,000 g / mol.

(C) N- (substituted) maleimide copolymer

The sum of the maleic anhydride and the N- (substituted) maleimide monomer is 30 wt%, and the sum of the vinyl cyanide compound and the aromatic vinyl compound is 70 wt%.

(D) Polymethyl methacrylate

Methyl methacrylate as a monomer copolymerized with 5% by weight of methyl acrylate and having a molecular weight of 90,000 g / mol.

Example  1 to 4 and Comparative Example  1 to 4

Using the above-mentioned components, the thermoplastic resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared with the compositions shown in Table 1 below.

Example Comparative Example One 2 3 4 One 2 3 4 (A) Acrylonitrile-butadiene-styrene copolymer 11 11 11 11 11 11 11 11 (B) alpha methyl styrene-acrylonitrile copolymer 49 44 49 49 54 - - - (B-1) acrylonitrile-styrene copolymer - - - - - - 54 54 (C) N- (substituted) maleimide copolymer 5 10 10 2 - 5 - 5 (D) PMMA 35 35 30 38 35 84 35 30 (A) + (B) or (A) + (B-1) (100 parts by weight) 100 100 100 100 100 100 100 100 The content of C in (A) + (B) or (A) + (B-1) 8.3 18.2 16.7 3.3 - 45.5 0 7.7 The content of D relative to (A) + (B) or (A) + (B-1) 58.3 63.6 50.0 63.3 53.8 763.6 53.8 46.2

Other additives were added to each thermoplastic resin composition having the composition shown in Table 1 and extruded / processed to prepare a thermoplastic resin in the form of a pellet. 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 230 ° C. The dried pellets were dried at 80 DEG C for 2 hours, and then set at a cylinder temperature of 240 DEG C and a mold temperature of 60 DEG C using a 6 oz injection molding machine to obtain physical properties specimens, scratch resistance of 9 cm x 5 cm x 0.2 cm, A specimen for measurement was prepared.

Test Example  1: Measurement of mechanical properties

The physical properties of the prepared physical specimens were measured by the following methods, and the results are shown in Table 2 below.

(1) HDT: Measurement according to ASTM D648 standard (unit, ° C)

(2) VST: Measured according to ISO R306 (unit, ℃)

(3) BSP width (ball type scratch profile width): Using a tungsten carbide stylus having a diameter of 0.7 mm and a spherical shape according to the Cheil method, a load of 300 g, 500 g and 1000 g was applied, And the scratch width and the scratch width were measured by using a surface profiler. At this time, scratch resistance is increased as the measured scratch width is decreased.

(4) Pencil hardness: The hardness value (pencil and pencil hardness measured in accordance with JIS K5401) when no scratch was caused by pushing a pencil 5 times at a rate of 10 mm / s by raising a weight of 500 g with a pencil according to hardness was measured.

(5) L value: For preparing the specimen, 0.1 to 0.2 parts by weight (based on the total amount of the thermoplastic resin composition) of carbon black was added to each of the thermoplastic resin compositions having the composition shown in Table 1, followed by coloring and extrusion / A specimen of 900mm x 500mm x 25mm is prepared. The L (CCM) values of the specimens were compared using a colorimeter. The higher the measured L value, the greater the brightness of the specimen. The larger the L value, the deeper the black feeling can not be achieved. In general, if the L value is less than 22.0, the color of the piano black can be realized.

Example Comparative Example One 2 3 4 One 2 3 4 HDT (° C) 100 101 103 98 93 90 90 90 VST (캜) 110 112 114 106 102 98 100 96 BSP width 258 261 266 255 259 230 255 261 Pencil hardness H H H H H 2H H H L (CCM) 21.9 22.0 22.1 21.7 21.5 21.0 21.2 21.3

Examples 1 to 4 include the acrylonitrile-butadiene-styrene copolymer (A) and the alphamethylstyrene-acrylonitrile copolymer (B). The acrylonitrile-butadiene-styrene copolymer (A) 18.2, 16.7 and 3.3 parts by weight of the N- (substituted) maleimide copolymer (C) relative to 100 parts by weight of the total of the styrene-acrylonitrile copolymer (B) (D) of 58.3, 63.6, 50.0 and 63.3 parts by weight, respectively. On the other hand, Comparative Examples 1 and 2 do not include the N- (substituted) maleimide copolymer (C) and the alpha methyl styrene-acrylonitrile copolymer (B), and Comparative Examples 3 and 4 are alpha methyl styrene- Styrene copolymer instead of an acrylonitrile-styrene copolymer and a nitrile copolymer.

As a result of the test, Comparative Example 1 which did not contain the N- (substituted) maleimide copolymer (C) had a low strain temperature (HDT) and a softening point (VST) and was poor in heat resistance. On the other hand, Comparative Example 2 contains the N- (substituted) maleimide copolymer (C) but does not contain the alpha methyl styrene-acrylonitrile copolymer (B) HDT) and a softening point (VST).

Further, in Comparative Example 3 and Comparative Example 4, it was confirmed that heat resistance was significantly lowered in Examples 1 to 3 when an acrylonitrile-styrene copolymer was used in place of the alpha methyl styrene-acrylonitrile copolymer.

On the other hand, a composition comprising an acrylonitrile-butadiene-styrene copolymer (A), an alpha methyl styrene-acrylonitrile copolymer (B), an N- (substituted) maleimide copolymer (C) The molded products of the molded products of Examples 1 to 3 had an HDT of 100 ° C or more and a VST of 110 ° C or more, which were excellent in heat resistance. It was confirmed that BSP width and pencil hardness test also had high scratch resistance and that the color tone of the resin was small and the black feeling was excellent and high coloring property was realized.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (11)

(A) a rubber-modified vinyl-based graft copolymer;
(B) a copolymer of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound;
(C) N- (substituted) maleimide copolymers; And
(D) a polyalkyl (meth) acrylate,
Based on 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the copolymer (B) of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound, 1 to 20 parts by weight of the copolymer (C)
Based on 100 parts by weight of the total of the rubber-modified vinyl-based graft copolymer (A) and the copolymer (B) of a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound, the polyalkyl (meth) acrylate And 40 to 65 parts by weight of the thermoplastic resin (D). delete delete The method according to claim 1,
Wherein the weight ratio of the N- (substituted) maleimide copolymer (C) to the polyalkyl (meth) acrylate (D) is from 1:10 to 1: 2. The method according to claim 1,
The copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound is an? -Methylstyrene-acrylonitrile copolymer. The method according to claim 1,
The copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound preferably comprises 60 to 80% by weight of the C1 to C10 alkyl-substituted aromatic vinyl compound and 20 to 40% by weight of the vinyl cyanide compound Wherein the thermoplastic resin composition is a copolymer formed by polymerization. The method according to claim 1,
The N- (substituted) maleimide copolymer (C) comprises 20 to 60% by weight of maleic anhydride and N- (substituted) maleimide monomer, and 40 to 80% by weight of an aromatic vinyl compound and a vinyl cyanide compound Wherein the thermoplastic resin composition is a thermoplastic resin composition. The method according to claim 1,
The rubber-modified vinyl-based graft copolymer (A) may contain 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer which is an unsaturated nitrile monomer, an acrylic monomer which is different from the acrylic monomer, a heterocyclic monomer which is different from the above-mentioned heterocyclic monomer, or a combination thereof, 5 to 95% by weight,
Butadiene rubber, isoprene rubber, an ethylene-propylene-diene terpolymer (EPDM) rubber, a polyorganosiloxane / polyalkyl (meth) acrylate, a styrene / butadiene rubber, Late rubber composite or a combination thereof. ≪ RTI ID = 0.0 > 5. < / RTI > The method according to claim 1,
The polyalkyl (meth) acrylate (D) may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, And a polymer polymerized from a monomer selected from a combination of these. The method according to claim 1,
Wherein the thermoplastic resin composition further comprises an additive selected from a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a release agent, and a combination thereof. A molded article produced by using the thermoplastic resin composition of any one of claims 1 to 10.