KR20130062779A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to have excellent heat resistance, high scratch resistance, and excellent blackness, thereby providing a molded product with high colorability. CONSTITUTION: A thermoplastic resin composition comprises a rubber-modified vinyl-based graft copolymer; a copolymer of C1-10 alkyl-substituted aromatic vinyl-based compound and cyanate vinyl-based compound; N-(substituted) maleimide copolymer; and polyalkyl(meth)acrylate. The amount of the N-(substituted)maleimide copolymer is 1-20 parts by weight based on 100.0 parts by weight of the sum of the rubber rubber-modified vinyl-based graft copolymer and the copolymer of C1-10 alkyl-substituted aromatic vinyl-based compound and cyanate vinyl-based compound.

Description

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

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

Acrylonitrile-butadiene-styrene (ABS) resins are widely used in electrical and electronic parts and office equipment because of their excellent impact resistance and workability, and good mechanical strength, heat deformation temperature and glossiness. However, when used in high-end consumer housings, such as LCD, PDP TV, audio, etc., there is a problem that the product value is low due to the easy generation of scratches during injection molding or use and difficult to express the color of the high-quality texture.

In order to solve this problem, the surface of the injection molded product of ABS resin has been coated with urethane, UV coating treatment or acrylic resin having excellent scratch characteristics. However, such work is accompanied by the problem of productivity degradation such as the complexity of the work and the increase of the defective rate by the addition of additional post-processing process and the environmental pollution problem due to the painting.

ABS / PMMA resin, which has excellent colorability and scratch resistance, has been widely used for high quality design of home appliances. However, due to the difference in refractive index between ABS and PMMA, the scratch characteristics are excellent, but transparency above a certain level is not realized, and high coloring is impossible.High heat resistance is required to withstand the conditions of home appliances or heat sinks requiring heat resistance. There is a limit to use in the required automotive interior materials. Accordingly, development of ABS / PMMA resins having high colorability and scratch resistance and also high heat resistance is required.

One embodiment of the present invention provides a thermoplastic resin composition excellent in high colorability, 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 invention, (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 copolymer; And (D) a polyalkyl (meth) acrylate.

The thermoplastic resin composition is based on the total of 100 parts by weight of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound, wherein N- (Substituted) may contain 1 to 20 parts by weight of the maleimide copolymer (C).

The thermoplastic resin composition is based on 100 parts by weight of the total of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound. 40 to 65 parts by weight of alkyl (meth) acrylate (D) may be included.

The thermoplastic resin composition may include 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 α-methylstyrene-acrylonitrile copolymer.

The α-methylstyrene-acrylonitrile copolymer may include 15 to 25% by weight of acrylonitrile and 75 to 85% by weight of styrene.

The N- (substituted) maleimide copolymer (C) may include 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 cyan compound.

The rubber-modified vinyl-based graft copolymer (A) is 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer or a combination thereof; And a vinyl polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof. 5 to 95% by weight of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane It may be a copolymer grafted to 5 to 95% by weight of the rubbery polymer of the / polyalkyl (meth) acrylate rubber composite or a combination thereof.

The polyalkyl (meth) acrylate (D) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate And it may be a polymer comprising a monomer selected from these combinations.

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

In another embodiment of the present invention, there is provided a molded article manufactured using the above-mentioned thermoplastic resin composition.

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

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, Hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxy Substituted with a substituent of a C1 to C20 alkoxy group, C6 to C30 aryl group, C6 to C30 aryloxy group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C3 to C30 cycloalkynyl group, or a combination thereof Means that.

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.

Thermoplastic resin composition according to an embodiment of the present invention (A) rubber modified vinyl-based graft copolymer; (B) C1 to C10 alkyl substituted aromatic vinyl compound and vinyl cyanide compound copolymer; (C) N- (substituted) maleimide copolymer; And (D) polyalkyl (meth) acrylates. The thermoplastic resin composition includes a rubber-modified vinyl graft copolymer (A) having excellent transparency and (B) a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound copolymer that contribute to high heat resistance. (C) N- (substituted) maleimide copolymer. In addition, since (D) polyalkyl (meth) acrylate is included together, it is excellent in scratch resistance, and the thermoplastic resin composition is used for automotive unpainted interior materials or housings of home appliances requiring high heat resistance and scratch resistance. It is suitable to be.

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

(A) rubber modification Vinyl-based Graft  Copolymer

The rubber-modified vinyl graft copolymer is a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the 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 a polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof. Can be. In this case, the “heterologous” 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 esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Meta) acrylates 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, ethacrylonitrile, or a combination thereof may be used.

The rubbery polymers include 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 composites or combinations thereof may be used.

The rubber particle size of the rubber-modified vinyl graft copolymer may be 0.05 to 4 μm in order to improve impact resistance and surface properties of the molded product. When the rubber particle size is 0.05 to 4 μm, the impact strength is excellent. Can be secured.

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

Specific examples of the rubber-modified vinyl graft copolymers include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of 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 copolymers include acrylonitrile-butadiene-styrene graft copolymers.

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

(B) C1  To C10 Alkyl  Substituted aromatics Vinyl-based  Compound and Cyanide Vinyl-based  Compound copolymer

The vinyl cyanide compound copolymer including the C1 to C10 alkyl-substituted aromatic vinyl compound may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and has a weight average molecular weight of 15,000 kPa to 400,000 g / mol. Can be used. The 1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer improve heat resistance of the thermoplastic resin.

Styrene, toluene, naphthalene or a combination thereof may be used as the aromatic vinyl compound of the C1 to C10 alkyl substituted aromatic vinyl compound, and specifically, C1 to C10 alkyl substituted styrene may be used.

Specific examples of the alkyl substituted styrene of C1 to C10 include α-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, pt-butyl styrene, 2,4-dimethyl styrene, and the like. It can be mentioned .

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

Specific examples of the C1 to C10 alkyl-substituted aromatic vinyl compound and vinyl cyanide compound copolymer include copolymers of α-methylstyrene and acrylonitrile, or copolymers of styrene, α-methylstyrene and acrylonitrile. These are mentioned, Preferably, the copolymer of (alpha) -methylstyrene and acrylonitrile is mentioned.

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

It is preferable that the said (meth) acrylic-acid alkyl ester compound is the (meth) acrylic-acid alkyl ester which has a C1-C10 alkyl group. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acryl Laterate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, ethyl hexyl acrylate, and the like or a combination thereof may be used, but is not necessarily limited thereto.

For example, the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer are polymerized with 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. 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 It may be coalescing. Specifically, the copolymer may be formed by polymerization of 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 included in an amount of 40 to 60 wt% based on the total amount of the thermoplastic resin composition, for example, 40 to 50 wt%. When the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer are included in the above range, not only the compatibility is excellent, but also the impact resistance and heat resistance may be realized while implementing high colorability.

(C) N- (substituted) Maleimide  Copolymer

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

At this time, in the copolymer, the mixed content of the maleic anhydride and N- (substituted) maleimide monomer is 20 to 60 parts by weight, the mixed content of the aromatic vinyl compound, optionally vinyl cyan compound is preferably 40 to 80 parts by weight. Do. When the mixed content of the maleic anhydride and the N- (substituted) maleimide monomer and the mixed content of the vinyl cyan compound and the aromatic vinyl compound are included in the above range, it is preferable in compatibility between the nylon-based thermoplastic resin and the vinyl-based copolymer resin. .

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

The N- (substituted) maleimide copolymer of the present invention is compatible with rubber modified vinyl graft copolymers (A) and C1 to C10 alkyl substituted aromatic vinyl compounds and vinyl cyanide compound copolymers (B). It is preferable, and contributes to realizing the high heat resistance of the thermoplastic resin composition.

The N- (substituted) maleimide monomer may be selected from the group consisting of N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide and mixtures thereof.

Acrylonitrile, methacrylonitrile, etc. are mentioned as said vinyl cyan compound, These can be used individually or in mixture. As said aromatic vinyl type compound, alkyl substituted styrene, such as styrene, halogen substituted styrene, (alpha) -methylstyrene, etc. are mentioned, These can be used individually or in mixture.

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

In addition, the weight ratio of the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) to be described below may be 1:10 to 1: 2, for example 1: 7 to 1: 3 Can be. When the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) are used in the numerical range, the fluidity of the thermoplastic resin is increased so that the resin is not easily broken, and the heat resistance and scratch resistance This is preferable and good.

(D) Polyalkyl ( Meta ) Acrylate

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

The said polyalkyl (meth) acrylate can be obtained by superposing | polymerizing the raw material monomer containing alkyl (meth) acrylate by well-known polymerization methods, such as suspension polymerization method, block polymerization method, and emulsion polymerization method.

The alkyl (meth) acrylate has an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (Meth) acrylate etc. are mentioned.

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

The polyalkyl (meth) acrylate is based on a total of 100 parts by weight of the rubber-modified vinyl 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 may be included in the thermoplastic resin composition, for example, 50 to 60 parts by weight may be included. When included in the content can improve the scratch resistance of the thermoplastic resin within a range that does not lower the heat resistance of the obtained molded article, the rubber-modified vinyl-based graft copolymer (A) and C1 to C10 alkyl substituted Since the intermolecular interaction with the aromatic vinyl compound and the vinyl cyanide compound copolymer (B) is increased, hydrolysis resistance and scratch resistance are improved.

The raw material monomer constituting the polyalkyl (meth) acrylate may further include a vinyl monomer in addition to the alkyl (meth) acrylate. As said vinylic monomer, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (rho) -methylstyrene; Unsaturated nitrile monomers, such as acrylonitrile and methacrylonitrile, etc. can be used, These can be used individually or in mixture.

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 above-described rubber-modified vinyl graft copolymer (A) and C1 to C10 alkyl substituted aromatic vinyl compound and vinyl cyanide compound copolymer (B) It is excellent in compatibility with hydrolysis resistance, scratch resistance, workability and so on.

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

(E) Other additives

The thermoplastic resin composition may further include additional additives to further impart injection moldability and physical property balance.

For example, the thermoplastic resin composition may further include additives such as dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, and release agents, and these may be used alone or in combination of two or more thereof.

The additive may be appropriately included within the range of not impairing the physical properties of the thermoplastic resin composition, specifically, may be included in 40 parts by weight or less relative to 100 parts by weight of the rubber-modified vinyl-based graft copolymer (A), More specifically, it may be included in 0.1 to 30 parts by weight.

As described above, each component contained in the thermoplastic resin composition has been described, and exemplary contents of each component have been described, but inherent inherent characteristics of each component are considered in accordance with the properties of the thermoplastic resin composition to be finally implemented. By using a properly added content can be implemented a thermoplastic resin composition.

The said thermoplastic resin composition can be manufactured by a well-known method of manufacturing a resin composition. For example, the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

According to another embodiment, a molded article manufactured by molding the aforementioned thermoplastic resin composition is provided. Specifically, the molded article may include a molded article having a large size, a complicated structure, or a thin thickness, in which mechanical properties, thermal properties, and moldability are required, and more specifically, an automotive exterior material, and the like.

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 for manufacture of the thermoplastic resin composition of the following Example is as follows.

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

It consists of a core made of 58% by weight of butadiene and a shell of 42% by weight, the shell consisting of 31.5 and 10.5% by weight of styrene and acrylonitrile, respectively.

(B) alphamethylstyrene-acrylonitrile copolymer

SAN resin having an acrylonitrile content of 27% by weight, an alphamethylstyrene content of 54% by weight and a weight average molecular weight of about 120,000.

(B-1) Acrylonitrile-styrene copolymer

SAN resin having an acrylonitrile content of 20% by weight, a styrene content of 80% by weight and a weight average molecular weight of about 100,000.

(C) N- (substituted) maleimide copolymer

30% by weight of maleic anhydride and N- (substituted) maleimide monomer, and 70% by weight of vinyl cyanide compound and aromatic vinyl compound.

(D) polymethyl methacrylate

Methyl methacrylate is copolymerized with 5% methyl acrylate and has a molecular weight of 900,000.

Example  1 to 4 and Comparative example  1 to 4

The thermoplastic resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 were prepared using the above-mentioned components 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) alphamethylstyrene-acrylonitrile copolymer 49 44 49 49 54 - - - (B-1) Acrylonitrile-styrene copolymer - - - - - - 54 51 (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 C content for (A) + (B) or (A) + (B-1) 8.3 18.2 16.7 3.3 - 45.5 0 7.7 Content of D for (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 to extrude / process to prepare a thermoplastic resin in pellet form. 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. After drying the prepared pellets at 80 ℃ for 2 hours, set the cylinder temperature to 240 ℃ and mold temperature to 60 ℃ using 6oz injection molding machine. A specimen for measuring weatherability was prepared.

Test Example  1: Mechanical property measurement

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

(1) HDT: measured according to ASTM D648 standard (unit, ℃)

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

(3) BSP width (ball type scratch profile width): According to the Cheil method, using a tungsten carbide stylus, the tip of which is 0.7 mm in diameter, is given a load of 300 g, 500 g and 1000 g, respectively, and 75 mm / min. After scratching the specimen at a speed of, the surface roughness was measured using a surface profiler and the scratch width was measured. At this time, the scratch resistance increases as the measured scratch width decreases.

(4) Pencil hardness: The hardness value (pencil and pencil hardness determined in JIS K5401) when the scratch does not occur by pushing the pencil five times at a speed of 10mm / s by lifting the weight of 500g with a pencil according to the hardness.

(5) L value: For the specimen preparation, 900-mm x 500-mm x 25-mm specimens are prepared using pellets extruded / processed by carbon black 0.1 to 0.2%. The specimens were compared for L (CCM) values using a color difference meter. The higher the measured L value, the higher the brightness of the specimen. The higher the L value, the deeper the Black. In general, if the L value is 22.0 or less, the piano black color 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 (℃) 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 1-4 comprise acrylonitrile-butadiene-styrene copolymer (A), alphamethylstyrene-acrylonitrile copolymer (B) and said acrylonitrile-butadiene-styrene copolymer (A), alphamethyl Polyalkyl (meth) acryl containing 8.3, 18.2, 16.7 and 3.3 parts by weight of N- (substituted) maleimide copolymer (C), respectively, based on 100 parts by weight of the total of styrene-acrylonitrile copolymer (B). It relates to a thermoplastic resin composition comprising 58.3, 63.6, 50.0 and 63.3 parts by weight of the rate (D), respectively. On the other hand, Comparative Examples 1 and 2 do not contain N- (substituted) maleimide copolymer (C), alpha methyl styrene- acrylonitrile copolymer (B), respectively, Comparative Examples 3 and 4 to alpha methyl styrene-acrylic A thermoplastic resin composition using an acrylonitrile-styrene copolymer instead of a nitrile copolymer.

As a result, the comparative example 1 which does not contain the N- (substituted) maleimide copolymer (C) had low deformation temperature (HDT) and softening point (VST), and was bad in heat resistance. On the other hand, Comparative Example 2 is a composition containing an N- (substituted) maleimide copolymer (C), but does not contain an alphamethylstyrene-acrylonitrile copolymer (B), as in Comparative Example 1 has a low deformation temperature ( HDT) and softening point (VST).

In addition, Comparative Example 3 and Comparative Example 4 in the case of using the acrylonitrile-styrene copolymer instead of the alpha methyl styrene- acrylonitrile copolymer, it was confirmed that the heat resistance is significantly reduced compared to Examples 1 to 3.

On the other hand, with a composition comprising acrylonitrile-butadiene-styrene copolymer (A), alphamethylstyrene-acrylonitrile copolymer (B), N- (substituted) maleimide copolymer (C) and PMMA (D) The molded articles of Examples 1 to 3 had a HDT of 100 ° C. or more and a VST of 110 ° C. or more. In the BSP width and pencil hardness test, it had high scratch resistance, and the resin had a high blackness, such as a small color L value.

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) rubber modified vinyl graft copolymers;
(B) a copolymer of a C1 to C10 alkyl substituted aromatic vinyl compound and a vinyl cyanide compound;
(C) N- (substituted) maleimide copolymer; And
(D) A thermoplastic resin composition containing polyalkyl (meth) acrylate. The method of claim 1,
The N- (substituted) maleimide based on a total of 100 parts by weight of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound. Thermoplastic resin containing 1 to 20 parts by weight of copolymer (C). The method of claim 1,
The polyalkyl (meth) acrylate based on a total of 100 parts by weight of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of a C1 to C10 alkyl substituted aromatic vinyl compound and a vinyl cyanide compound. Thermoplastic resin containing 40 to 65 parts by weight of (D). The method of claim 1,
The thermoplastic resin composition whose weight ratio of the said N- (substituted) maleimide copolymer (C) and the said polyalkyl (meth) acrylate (D) is 1: 10-1: 2. The method of claim 1,
The copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound is an α-methylstyrene-acrylonitrile copolymer. The method of claim 5,
The α-methylstyrene-acrylonitrile copolymer is a thermoplastic resin composition comprising 15 to 25% by weight of acrylonitrile and 75 to 85% by weight of styrene. The method of claim 1,
The N- (substituted) maleimide copolymer (C) is a thermoplastic containing 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 cyan compound Resin composition. The method of claim 1,
The rubber-modified vinyl graft copolymer (A) may include 50 to 95 wt% of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a vinyl polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof. 5 to 95% by weight,
Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (meth) acrylic Polycarbonate-based thermoplastic resin composition which is a copolymer grafted to 5 to 95% by weight of the rubbery polymer of the rate rubber composite or a combination thereof. The method of claim 1,
The polyalkyl (meth) acrylate (D) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate And a polymer comprising a monomer selected from these combinations. The method of claim 1,
The thermoplastic resin composition further comprises an additive selected from dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, mold release agents and combinations thereof. The molded article manufactured using the thermoplastic resin composition of any one of Claims 1-10.