KR20160072961A - Thermoplastic resin composition and molded article prepared therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a molded foam prepared therefrom. More particularly, the present invention relates to a thermoplastic resin composition and a molded foam prepared therefrom, the composition including: 100 parts by weight of a base resin having: a) 10 to 40 wt% of a core-shell structured acrylate-styrene-acrylonitrile-based copolymer; b) 25 to 55 wt% of a (meth)acrylic alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer; c) 0 to 10 wt% of a maleimide-based copolymer; d) 5 to 45 wt% of an α-methylstyrene-based polymer; and e) 1 to 20 wt% of a core-shell structured silicone-acrylate copolymer; and f) 0.5 to 5 parts by weight of a siloxane polymer master batch including a siloxane polymer having viscosity of 1,000,000 to 3,000,000 cst. According to the present invention, the present invention provides a thermoplastic resin composition having para-heat resistance properties, and excellent weatherproof, scratch resistant properties, gloss, and fluidity, and a molded foam prepared therefrom.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article produced from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom, and more particularly to a thermoplastic resin composition having a quasi heat resistance characteristic and excellent weather resistance, scratch resistance, glossiness and fluidity, and a molded article produced therefrom.

Recently, there has been an increasing demand from consumers for the upgrading of automobile appearance and unpainted trends. However, the acrylonitrile-butadiene-styrene resin used as a material thereof has poor scratch resistance, coloring property and weather resistance, There was a limit to meet.

In order to improve the scratch resistance, coloring property, weather resistance, etc. of such acrylonitrile-butadiene-styrene resin, coating or coating treatment is generally carried out, but a post-processing step accompanies the complication of the work, It happens.

Polymethyl methacrylate having excellent weatherability, coloring property and glossiness can be considered as another automobile appearance material, but it has a problem that impact resistance and injection moldability are poor.

In addition, the methyl methacrylate-acrylonitrile-butadiene-styrene resin which can be used for exterior appearance of a vehicle has good colorability, gloss and impact resistance, but has a problem of poor scratch resistance and heat resistance. , A transparent acrylonitrile-styrene resin and a siloxane-polyester copolymer have been applied. However, even in this case, there is a limit in improving the scratch resistance, and there is a problem that weather resistance and heat resistance are lowered.

In addition, although a silicone acrylate copolymer having an acrylic rubber, a polymethyl methacrylate, a siloxane-polyester copolymer and a core shell structure is applied, there is a problem that fluidity and gloss decrease.

Another acrylonitrile-styrene-acrylonitrile copolymer having excellent weatherability is used as an exterior material of automobile, and it is advantageous that coating or coating treatment is not necessary, but on the other hand, since no post-processing is carried out, scratch resistance, coloring property and glossiness There is an insufficient problem.

Korea Patent Publication No. 2010-0022160 (published on Mar. 2, 2010)

In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a thermoplastic resin composition having a quasi-heat resistant property and excellent weather resistance, scratch resistance, glossiness and fluidity, and a molded article produced therefrom.

The present invention also aims to provide an automobile exterior material as the above molded article.

These and other objects of the present disclosure can be achieved by all of the present invention described below.

In order to achieve the above object, the present invention relates to a resin composition comprising a) 10 to 40% by weight of an acrylate-styrene-acrylonitrile copolymer having a core-shell structure; b) 25 to 55% by weight of a (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer; c) 0 to 10% by weight of a maleimide-based copolymer; d) 5 to 45% by weight of the? -methylstyrene-based polymer; And e) 1 to 20% by weight of a core-shell structured silicone-acrylate copolymer; and f) a siloxane polymer masterbatch comprising a siloxane polymer having a viscosity of 1,000,000 to 3,000,000 cst, And a molded article produced from the thermoplastic resin composition.

According to the present invention, there is provided an effect of providing a thermoplastic resin composition having a quasi heat resistance characteristic without being subjected to a coating step and having excellent weather resistance, scratch resistance, gloss and fluidity, and a molded article produced therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention comprises: a) 10 to 40% by weight of an acrylate-styrene-acrylonitrile-based copolymer having a core-shell structure; b) 25 to 55% by weight of a (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer; c) 0 to 10% by weight of a maleimide-based copolymer; d) 5 to 45% by weight of the? -methylstyrene-based polymer; And e) 1 to 20% by weight of a core-shell structured silicone-acrylate copolymer; and f) a siloxane polymer masterbatch comprising a siloxane polymer having a viscosity of 1,000,000 to 3,000,000 cst, And the like.

As another example, the content of the acrylate-styrene-acrylonitrile-based copolymer in the core-shell structure is 15 to 35% by weight or 20 to 30% by weight based on the base resin.

The acrylate-styrene-acrylonitrile copolymer having a core-shell structure as described above may be a copolymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound on an acrylate rubber. In this case, It is effective.

The acrylate-styrene-acrylonitrile-based copolymer having a core-shell structure as described above may be obtained by copolymerizing 20 to 60% by weight of an acrylate rubber, 10 to 50% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound .

As another example, the acrylate-styrene-acrylonitrile copolymer having a core-shell structure may be prepared by copolymerizing 30 to 50% by weight of an acrylate rubber, 20 to 40% by weight of an aromatic vinyl compound and 3 to 10% by weight of a vinyl cyan compound %. ≪ / RTI >

The acrylate rubber may be at least one selected from the group consisting of acrylate rubber, butyl acrylate rubber, ethyl acrylate rubber and ethylhexyl acrylate rubber. In this case, the acrylate rubber is excellent in heat resistance.

The aromatic vinyl compound may be at least one member selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene and vinyltoluene. In this case, the aromatic vinyl compound is excellent in workability and heat resistance.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The acrylate-styrene-acrylonitrile-based copolymer having a core-shell structure and having an average particle size of 500 to 2,000 angstroms (hereinafter referred to as " acrylate-styrene- (Hereinafter referred to as a large diameter ASA copolymer) and a core-shell acrylate-styrene-acrylonitrile copolymer having an average particle diameter of 2,500 to 6,000 angstrom (hereinafter referred to as a large diameter ASA copolymer).

The small-diameter ASA copolymer may contain 5 to 50% by weight of an acrylate-based rubber, 10 to 50% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound.

The large diameter ASA copolymer may include 10 to 60 wt% of an acrylate rubber, 10 to 40 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyan compound.

The acrylate-styrene-acrylonitrile-based copolymer of the core-shell structure may be prepared by emulsion polymerization including an emulsifier, an initiator, a grafting agent, a crosslinking agent and an electrolyte in an acrylate rubber.

As another example, the amount of the (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer b) relative to the base resin is 30 to 50% by weight or 35 to 45% by weight, And fluidity.

The aromatic vinyl compound-vinyl cyanide copolymer may be, for example, 55 to 85% by weight of a (meth) acrylic acid alkyl ester compound, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 30% by weight of a vinyl cyan compound. 15% by weight.

The (meth) acrylic acid alkyl ester compound is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate and ethyl acrylate.

As another example, the content of the c) maleimide-based copolymer relative to the base resin is 0 to 7% by weight, or 1 to 5% by weight.

The c) maleimide-based copolymer is, for example, an N-phenylmaleimide-aromatic vinyl compound copolymer, an N-phenylmaleimide-aromatic vinyl compound-maleic anhydride copolymer, or a mixture thereof.

As another example, the c) maleimide-based copolymer comprises 40 to 60% by weight of a maleimide-based monomer; 35 to 55% by weight of an aromatic vinyl monomer; And 0.1 to 5% by weight of maleic anhydride or maleic anhydride; and has an excellent balance of heat resistance and physical properties within this range.

The c) maleimide-based copolymer may have a weight average molecular weight of 100,000 to 200,000 g / mol, 120,000 to 180,000 g / mol, or 140,000 to 160,000 g / mol, An excellent balance of physical properties is obtained.

As another example, the content of the d) α-methylstyrene polymer relative to the base resin is 10 to 40% by weight, or 15 to 35% by weight.

The d)? -Methylstyrene polymer may be, for example, an? -Methylstyrene homopolymer or a copolymer of? -Methylstyrene and a comonomer thereof.

The comonomer is at least one selected from the group consisting of an aromatic vinyl compound (except? -Methyl styrene) and a vinyl cyan compound.

As another example, the d) α-methylstyrene polymer may be a copolymer obtained by polymerizing 50 to 90% by weight or 60 to 80% by weight of α-methylstyrene and 10 to 50% by weight or 20 to 40% by weight of vinyl cyan monomer There is an effect of excellent balance of heat resistance and physical properties within this range.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.

As another example, the content of the core-shell structure silicone-acrylate copolymer relative to the base resin is 3 to 15% by weight, or 5 to 10% by weight, and the scratch resistance is improved within the above range .

The core of the core-shell structure silicone-acrylate copolymer (e) may be at least one selected from the group consisting of silicone rubber, silicone-acrylate rubber, and mixtures thereof.

The shell of the core-shell structure silicone-acrylate copolymer of e) may be at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and a (meth) acrylic acid alkyl ester compound.

As another example, the f) siloxane polymer masterbatch for the thermoplastic resin composition is 1 to 4 parts by weight or 1.5 to 3 parts by weight, and the effect of scratch resistance and weather resistance is excellent within this range.

The f) siloxane polymer masterbatch is obtained by dispersing a siloxane polymer having a viscosity of 1,000,000 to 3,000,000 cst in a resin in an amount of 25 to 50%.

The f) siloxane polymer masterbatch may be made, for example, of polydimethylsiloxane, polydiphenylsiloxane, or a combination thereof as a main component.

The resin used in the master batch may be, for example, polymethylmethacrylate (PMMA), epoxy-modified MMA copolymer, or styrene-acrylonitrile copolymer (SAN) In this case, scratch resistance and weather resistance are excellent.

The thermoplastic resin composition may further include at least one additive selected from the group consisting of a heat stabilizer, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, an impact modifier, a pigment, a fluorescent brightener, a light stabilizer, and an inorganic compound.

For example, the thermoplastic resin composition may have a ΔL of 3 or less, 2.5 or less or 2.0 or less by Erichsen test, and has an excellent scratch resistance within this range.

The thermoplastic resin composition is, for example, a grade 4 or higher gray scale according to a fading color standard gray color chart, and has excellent weather resistance within this range.

For example, the thermoplastic resin composition has a flow index of 9 g / 10 min. Measured at a temperature of 220 캜 and a load of 10 Kg. Or more, and excellent workability is obtained within this range.

The molded article of the present invention is characterized by being produced from the thermoplastic resin composition.

The molded article may be, for example, an automobile exterior material. In this case, it is possible to satisfy the demands of consumers for the upgrading of the appearance of automobiles and the unpainted trend in recent years.

The automotive exterior material may be, for example, an automotive side mirror, a filler, or a radiator grill.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

The following materials were used.

a) an acrylate-styrene-acrylonitrile copolymer having a core-shell structure: 20% by weight of a small-diameter ASA copolymer having an average particle diameter of 1000 Å of an acrylate rubber and an average particle diameter of 4,000 to 5,000 And 80 wt% of a large diameter ASA copolymer were used.

b) (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer: A copolymer polymerized with 74% by weight of methyl methacrylate, 19% by weight of styrene and 7% by weight of acrylonitrile was used.

c) maleimide-based copolymer: Polymerized copolymer comprising 52% by weight of phenylmaleimide, 46% by weight of polystyrene and 2% by weight of maleic anhydride was used.

d)? -methylstyrene polymer: A copolymer polymerized with 66% by weight of? -methylstyrene, 6% by weight of styrene and 28% by weight of acrylonitrile was used.

e) An aromatic vinyl compound- (silicone-acrylic rubber) -vinyl cyanide copolymer (SX006, manufactured by MRC Co.) was used as the core-shell structure silicone-acrylate copolymer.

f) Siloxane polymer master batch: CF-1501 (manufactured by Dow Corning) was used.

f ') Other slip agent: Silicone oil (GENIOPLAST PELLET S, manufactured by Wacker) was used.

f ") Other slip agent: Silicone oil (KF54, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

Examples 1 to 6 and Comparative Examples 1 to 8

The respective components were added in the respective amounts as shown in Tables 1 and 2, and the mixture was extruded using a twin-screw extruder under the condition of 240 ° C., and then pelletized and dried to obtain an extruder at an injection temperature of 240 to 250 ° C. To prepare a thermoplastic resin composition specimen.

 [Test Example]

The properties of the thermoplastic resin composition specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 8 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

* Average Particle Diameter: Measured using an intensity Gaussian distribution (Nicomp 380) using a dynamic laser light scattering method.

* Scratch resistance: The value of? L (brightness by CIE1976 L * a * b colorimetric system) was measured based on the Erichsen test.

* Gloss: It is measured with a gloss meter at a 45 degree angle. The higher the gloss value, the better the gloss of the surface.

* Grayscale: The weatherability was evaluated based on a gray scale for evaluating change in color. The larger the value, the better the weather resistance.

* Heat distortion temperature (HDT, ° C): The heat distortion temperature was measured after the specimen was manufactured according to ASTM D648.

Flowability (g / 10 min.): Measured at 220 캜 under a load of 10 Kg for 10 minutes in accordance with ASTM D1238.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 a) (% by weight) 25 30 20 30 25 25 b) (% by weight) 40 40 35 40 35 45 c) (% by weight) - 5 - - - 5 d) (% by weight) 30 20 35 25 30 15 e) (% by weight) 5 5 10 5 10 10 f) (parts by weight) 3 3 2 1.5 1.5 1.5 Scratch resistance ? L <2 ? L <2 ? L <2 ? L <2 ? L <2 ? L <2 Gloss 94 98 94 93 94 97 Heat distortion temperature (HDT) 91 94 93 88 91 92 Gray scale 4th grade 4th grade 4th grade 4th grade 4th grade 4th grade liquidity 12.5 9.4 10.5 11.3 10.6 10.3

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 a) (% by weight) 25 30 30 30 50 25 30 30 b) (% by weight) - 60 40 40 25 40 40 40 c) (% by weight) - - - - 5 - - - d) (% by weight) 70 - 25 30 15 30 25 25 e) (% by weight) 5 10 5 - 5 5 5 5 f) (parts by weight) 3 2 - 3 1.5 10 - - f ') (parts by weight) - - - - - - 3 - f ") (parts by weight) - - - - - - - 3 Scratch resistance ? L = 5 ? L <2 ? L = 6 ? L = 5 ? L = 5 ? L <2 ? L = 5 ? L = 5 Glossiness 93 95 94 93 74 87 92 91 Heat distortion temperature 95 82 89 81 75 85 89 88 Gray scale 4th grade 4th grade 4th grade 4th grade 4th grade Class 3 4th grade 4th grade liquidity 6.3 15.6 12.1 12.7 6.7 11.8 11.2 11.8

As shown in Table 1, it was confirmed that the thermoplastic resin compositions (Examples 1 to 6) of the present invention were excellent in scratch resistance, gloss, heat resistance, gray scale and fluidity.

However, Comparative Examples 3, 4, 7 and 8, which did not contain e) core-shell structure silicone-acrylate copolymer or f) polysiloxane masterbatch, were very poor in scratch resistance. b) Comparative Example 1 in which the (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer was not contained had decreased flowability and scratch resistance, and d) Comparative Example in which the? -methylstyrene polymer was not included 2 had a lower heat resistance, and Comparative Example 5, in which a) an excess of an acrylate-styrene-acrylonitrile copolymer having a core-shell structure, was excessively contained, exhibited glossiness, fluidity, thermal deformation temperature, fluidity and scratch resistance . Also, in Comparative Example 6 in which f) an excessive amount of the polysiloxane master batch was used, the gloss, the heat distortion temperature and the weather resistance were lowered.

Claims (20)

a) 10 to 40% by weight of an acrylate-styrene-acrylonitrile-based copolymer having a core-shell structure;
b) 25 to 55% by weight of a (meth) acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide copolymer;
c) 0 to 10% by weight of a maleimide-based copolymer;
d) 5 to 45% by weight of the? -methylstyrene-based polymer; And
e) 1 to 20% by weight of a silicone-acrylate copolymer having a core-shell structure;
f) 0.5 to 5 parts by weight of a siloxane polymer masterbatch comprising a siloxane polymer having a viscosity of from 1,000,000 to 3,000,000 cSt
By weight based on the total weight of the thermoplastic resin composition.
The method according to claim 1,
The acrylate-styrene-acrylonitrile copolymer of a) core-shell structure is a copolymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound on an acrylate rubber.
3. The method of claim 2,
Wherein the acrylate rubber is at least one selected from the group consisting of acrylate rubber, butyl acrylate rubber, ethyl acrylate rubber and ethylhexyl acrylate rubber.
3. The method of claim 2,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and vinyltoluene.
3. The method of claim 2,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The method according to claim 1,
The acrylate-styrene-acrylonitrile copolymer having a core-shell structure comprises 20 to 60% by weight of an acrylate rubber, 10 to 50% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound And a thermoplastic resin composition.
The method according to claim 1,
The acrylate-styrene-acrylonitrile copolymer having a core-shell structure and having an average particle size of 500 to 2,000 angstroms and an acrylate-styrene-acrylonitrile copolymer having an average particle size of 2,500 Styrene-acrylonitrile-based copolymer having a core-shell structure having a core-shell structure and a core-shell structure.
The method according to claim 1,
The aromatic vinyl compound-vinyl cyan compound copolymer (b) is obtained by copolymerizing 55 to 85% by weight of a (meth) acrylic acid alkyl ester compound, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 15 By weight based on the total weight of the thermoplastic resin composition.
9. The method of claim 8,
Wherein the (meth) acrylic acid alkyl ester compound is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate and ethyl acrylate. Resin composition.
The method according to claim 1,
Wherein the c) maleimide-based copolymer is a thermoplastic resin composition characterized by being an N-phenylmaleimide-aromatic vinyl compound copolymer, an N-phenylmaleimide-aromatic vinyl compound-maleic anhydride copolymer, or a mixture thereof .
The method according to claim 1,
The above-mentioned d)? -Methylstyrene polymer is an? -Methylstyrene homopolymer or a copolymer of? -Methylstyrene and a comonomer thereof.
12. The method of claim 11,
Wherein the comonomer is at least one selected from the group consisting of an aromatic vinyl compound (except? -Methylstyrene) and a vinyl cyan compound.
The method according to claim 1,
Wherein the core of the core-shell structure silicone-acrylate copolymer is at least one selected from the group consisting of silicone rubber, silicone-acrylate rubber, and mixtures thereof.
The method according to claim 1,
Wherein the shell of the core-shell structure silicone-acrylate copolymer is at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and a (meth) acrylic acid alkyl ester compound.
The method according to claim 1,
Wherein said f) siloxane polymer masterbatch comprises polydimethylsiloxane, polydiphenylsiloxane, or a combination thereof.
The method according to claim 1,
Wherein the thermoplastic resin composition has a? L of 3 or less by Erichsen test.
The method according to claim 1,
Wherein the thermoplastic resin composition has a gray scale of 4 or more according to a discolored standard gray color chart.
The method according to claim 1,
The thermoplastic resin composition has a flow index of 9 g / 10 min. Measured at a temperature of 220 캜 and a load of 10 Kg. Based on the total weight of the thermoplastic resin composition.
A molded article produced from the thermoplastic resin composition of any one of claims 1 to 18.
A molded article produced from the thermoplastic resin composition of any one of claims 1 to 18.