KR20160048331A - Vinyl-aromatic Graft Copolymer Composition with Excellent Anti-blocking Property and Thermoplastic Resin Composition Containing The Same - Google Patents

Abstract

The present invention relates to an aromatic vinyl-based graft copolymer including an aromatic vinyl-based graft copolymer of a core-shell form, which graft-polymerizes aromatic vinyl-vinyl cyanide copolymer in a diene-based rubber polymer and a silicone compound of an emulsion form, and to a thermoplastic resin composition containing the same. Blocking caused by aggregating copolymer particles capable of being generated in storing, transferring, and producing processes of the aromatic vinyl-based graft copolymer is prevented. The thermoplastic resin composition having excellent impact resistance, fluidity, and gloss properties is produced by using the aromatic vinyl-based graft copolymer.

Description

[0001] The present invention relates to an aromatic vinyl-based graft copolymer composition having excellent anti-blocking properties, and a thermoplastic resin composition containing the same. ≪ Desc / Clms Page number 1 >

The present invention relates to an aromatic vinyl-based graft copolymer composition and a thermoplastic resin composition containing the same. More particularly, the present invention relates to an aromatic vinyl-based graft copolymer composition having a high rubber-like polymer content and excellent blocking resistance, and a thermoplastic resin composition capable of realizing excellent impact resistance, will be.

Generally, as a method of imparting impact resistance to a thermoplastic resin, a method of adding a rubber component to a hard thermoplastic resin is widely known. The thermoplastic resin imparted with such impact resistance is an acrylonitrile-butadiene-styrene copolymer (ABS) resin. ABS resin is excellent in physical properties such as impact resistance, mechanical strength and moldability, and is used in electric, electronic parts, office equipment, automobile parts and the like. However, as the properties required for the ABS resin are diversified according to recent product diversification, it is difficult to improve physical properties other than impact resistance and to balance these physical properties in order to satisfy the complex physical properties required by the consumer.

ABS resins are generally produced using emulsion polymerization. Specifically, the ABS resin is prepared by graft-copolymerizing styrene, acrylonitrile, monomers such as acrylate copolymerizable therewith by emulsion polymerization using a butadiene-based rubbery polymer latex as a seed, and then subjecting the latex to coagulation, dehydration and drying A powdery graft copolymer is prepared and melt-kneaded with a styrene-acrylonitrile copolymer (hereinafter referred to as SAN) resin.

The particle size, particle distribution and rubbery polymer latex content of the rubbery polymer are important for the balance of physical properties such as impact resistance, workability and gloss of such ABS resin. Up to now, in order to improve the impact resistance of the ABS resin, a method of using a rubber polymer having a large average particle diameter alone or in combination with a rubber polymer having a small average particle diameter, or a method of increasing the molecular weight of the graft SAN formed at the time of graft copolymerization come. A method of increasing the particle size of the double rubbery polymer or increasing the rubbery polymer content is mainly used. This is because the larger the rubbery polymer particle size is, and the higher the rubbery polymer content is, the better the impact resistance is.

However, when the content of the rubbery polymer is increased or a rubbery polymer having a large particle diameter is used, the particles tend to agglomerate with each other, resulting in a blocking phenomenon during storage, transportation or processing. In order to prevent this, attempts have been made to apply additives such as carbon black, talc and zinc stearate to rubbery polymer latex particles. However, the addition of such an additive complicates the process or is not suitable for some applications. In particular, there is a problem that the physical properties of the resin containing the additive may be lowered or environmental pollution may occur.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide an aromatic vinyl-based graft copolymer composition in which the content of a rubbery polymer is increased or a blocking phenomenon hardly occurs even when a rubbery polymer having a large average particle size is used .

Another object of the present invention is to provide a thermoplastic resin composition capable of realizing excellent impact resistance, fluidity and gloss characteristics by using the aromatic vinyl-based graft copolymer composition.

In order to achieve the above object, the present invention provides a rubber composition comprising a core-shell type aromatic vinyl-based graft copolymer obtained by graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer with a diene rubber- An aromatic vinyl-based graft copolymer composition is provided.

The aromatic vinyl-based graft copolymer composition according to one embodiment of the present invention may contain 0.1 to 2 parts by weight of a silicone-based compound in emulsion form relative to 100 parts by weight of the aromatic vinyl-based graft copolymer.

In the aromatic vinyl-based graft copolymer composition according to one embodiment of the present invention, the emulsion-type silicone compound may have a weight average molecular weight of 1,000 to 100,000 g / mol.

In the aromatic vinyl-based graft copolymer composition according to one embodiment of the present invention, the silicone-based compound in emulsion form may contain an organopolysiloxane.

In the aromatic vinyl-based graft copolymer composition according to one embodiment of the present invention, the aromatic vinyl-based graft copolymer may contain 55 to 80% by weight of the diene-based rubbery polymer.

In the aromatic vinyl-based graft copolymer composition according to one embodiment of the present invention, the diene-based rubbery polymer may have an average particle diameter of 0.1 to 4.0 탆.

The present invention also provides a process for producing a core-shell type aromatic vinyl-based graft copolymer by graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer onto a diene-based rubbery polymer, And stirring the mixture obtained by mixing the emulsion-type silicone compound and the emulsion-type silicone compound.

In the method for producing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the emulsion-type silicone compound may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the aromatic vinyl-based graft copolymer .

In the process for producing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the solid content of the emulsion-type silicone compound may be 10 to 80% by weight.

In the process for preparing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the emulsion-type silicone compound may have a weight average molecular weight of 1,000 to 100,000 g / mol.

In the method for producing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the emulsion-type silicone compound may contain an organopolysiloxane.

In the method for producing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the aromatic vinyl-based graft copolymer may include 55 to 80% by weight of a diene-based rubbery polymer.

In the method for producing an aromatic vinyl-based graft copolymer composition according to an embodiment of the present invention, the diene-based rubbery polymer may have an average particle diameter of 0.1 to 4.0 탆.

The present invention provides a thermoplastic resin composition comprising the above-mentioned aromatic vinyl-based graft copolymer composition.

The thermoplastic resin composition according to one embodiment of the present invention may comprise 10 to 40 parts by weight of an aromatic vinyl graft copolymer composition and 60 to 90 parts by weight of an aromatic vinyl-cyanide vinyl copolymer.

Further, the present invention can provide a molded article produced from the thermoplastic resin composition.

The aromatic vinyl-based graft copolymer composition according to the present invention has an advantage that the content of the rubbery polymer can be remarkably increased, and the blocking phenomenon during storage, movement and processing can be prevented.

In addition, the thermoplastic resin composition containing the aromatic vinyl-based graft copolymer composition according to the present invention can improve the impact resistance, fluidity and gloss properties by using a rubber polymer having a high rubber polymer content or a large average particle diameter, .

1 is a TEM (Transmission Electron Microscopy) photograph showing the dispersibility of an aromatic vinyl-based graft copolymer in the thermoplastic resin composition according to Example 1. Fig.
2 is a TEM photograph showing the dispersibility of the aromatic vinyl-based graft copolymer in the thermoplastic resin composition according to Comparative Example 1. Fig.

Hereinafter, the aromatic vinyl-based graft copolymer composition of the present invention and the thermoplastic resin composition containing the aromatic vinyl-based graft copolymer composition will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.

The aromatic vinyl-based graft copolymer composition of the present invention comprises a core-shell type aromatic vinyl-based graft copolymer obtained by graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer with a diene rubber-like polymer, and an emulsion- Blocking between aromatic vinyl-based graft copolymer particles can be prevented to improve migration and storage stability, and at the same time, a synergistic effect of impact resistance and gloss characteristics of the thermoplastic resin composition containing the aromatic vinyl graft copolymer grains can be realized.

The method for producing an aromatic vinyl-based graft copolymer composition of the present invention comprises the steps of: graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer to a diene rubber-like polymer to prepare an aromatic vinyl-based graft copolymer in the form of a core- And mixing and stirring the prepared aromatic vinyl-based graft copolymer with an emulsion-type silicone compound.

Specifically, the process for producing the aromatic vinyl-based graft copolymer composition includes: introducing ion-exchanged water and an emulsifier into a diene-based rubber-like polymer, adding a monomer mixture composed of an aromatic vinyl monomer and a vinyl cyan monomer and a molecular weight regulator, After the temperature is elevated, a cross-linking agent and an initiator are added to conduct a graft polymerization reaction to prepare a primary aromatic vinyl graft copolymer. An initiator is added in the presence of the primary graft copolymer, and the mixture is stirred. A modifier is added over 2 to 5 hours to conduct a second graft polymerization reaction to prepare an aromatic vinyl graft copolymer in the form of a core-shell, and then the resulting aromatic vinyl graft copolymer is reacted with an emulsion- And mixing and stirring the compound.

Hereinafter, each step of the present invention will be described in more detail.

(1) Production of primary aromatic vinyl-based graft copolymer

Ion exchange water is added to a diene rubber polymer having an average particle diameter of 0.1 to 4.0 占 퐉 in a polymerization reactor, and an emulsifier is added thereto, followed by stirring. A monomer mixture comprising 10 to 20 parts by weight of an aromatic vinyl monomer and 1 to 15 parts by weight of a vinyl cyanide monomer based on 100 parts by weight of the whole diene-based rubbery polymer and the monomer mixture to be added in the production of the aromatic vinyl-based graft copolymer after the stirring, And the mixture is heated for 2 hours to 5 hours while being continuously added and stirred. When the temperature inside the reactor reaches 55 to 65 ° C, 0.05 to 0.5 parts by weight of a crosslinking agent and 0.05 to 0.2 parts by weight of a fat-soluble pyrolysis polymerization initiator are added to initiate a polymerization reaction. After the initiation of the reaction, if the temperature inside the reactor reaches 65 to 75 ° C, the internal temperature of the reactor is maintained in the range of 65 to 75 ° C by using a cooler, and the reaction is continued for 20 to 120 minutes. The primary aromatic vinyl-based graft copolymer is prepared by cooling the reactor and terminating the polymerization at a polymerization conversion rate of 93% or more.

(2) Preparation of Secondary Aromatic Vinyl Graft Copolymer Composition Step

Based on 100 parts by weight of the whole diene-based rubbery polymer and the monomer mixture to be added in the production of the aromatic vinyl-based graft copolymer in the range of 65 to 75 캜 in the presence of the above-prepared primary aromatic vinyl-based graft copolymer, 0.5 part by weight of a monomer mixture composed of 5 to 20 parts by weight of an aromatic vinyl monomer and 2.5 to 10 parts by weight of a vinyl cyanide monomer and 0.01 to 0.5 parts by weight of a molecular weight modifier are added to the reactor so as to participate in the graft reaction at a constant rate And continuously introduced over a period of 2 hours to 5 hours to carry out graft polymerization. When the addition of the monomer is completed, the reactor temperature is maintained at 65 to 75 ° C for 20 to 120 minutes. When the final polymerization conversion rate reaches 93% or more, the polymerization is terminated by forced cooling to prepare the second aromatic vinyl-based graft copolymer do. Thereafter, the secondary aromatic vinyl-based graft copolymer and the emulsion-type silicone compound are mixed and stirred for 30 minutes to 1 hour to prepare a final aromatic vinyl-based graft copolymer composition.

The diene rubber polymer may be selected from among butadiene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) Do not.

The diene-based rubbery polymer is not limited, but preferably has an average particle diameter of 0.1 to 4.0 m. If the average particle diameter of the diene rubber polymer is less than 0.1 占 퐉, the effect of improving the impact resistance is insignificant. If the average particle diameter is more than 4.0 占 퐉, the gloss characteristics may be deteriorated. The diene-based rubbery polymer may have a different average particle diameter from each other. For example, a small particle size and a large particle size, a small particle size, a medium particle size or a medium particle size and a large particle size rubbery polymer may be used.

The diene-based rubbery polymer may have a gel content of 60 to 95% by weight. If the content of the gel is less than 60% by weight, impact resistance may be deteriorated. If the content of the gel is more than 95% by weight, appearance properties may be deteriorated.

The diene rubber-like polymer may have a swelling index of 10 to 30. The swelling index is an index related to the gel content. If the swelling index is less than 10, the impact resistance may be deteriorated. If the swelling index is more than 30, the appearance property may be deteriorated.

The diene rubber-like polymer may be contained in the aromatic vinyl-based graft copolymer composition in an amount of 55 to 80% by weight, more preferably 55 to 70% by weight. In the present invention, by dramatically increasing the content of the diene-based rubbery polymer, not only the impact resistance is maximized, but also the fluidity and surface characteristics can be improved by combining with other components. In particular, the aromatic vinyl-based graft copolymer comprising the diene-based rubber-like polymer is likely to agglomerate with each other due to temperature and pressure, which may cause blocking during lubrication, storage and processing. It is possible to prevent the blocking of the aromatic vinyl-based graft copolymer particles containing a high content of the diene-based rubbery polymer, thereby facilitating handling during production processing.

Examples of the emulsifying agent include metal salts such as potassium rosinate and sodium rosinate, metal salts of fatty acids such as sodium laureate, sodium oleate, potassium oleate, potassium stearate, sodium lauryl sulfate, and the like, but not always limited thereto . Among them, potassium stearate or potassium rosinate can be used singly or in combination. The amount of the emulsifier may be 0.3 to 1.5 parts by weight. When the emulsifier is used in an amount of less than 0.3 part by weight, agglomeration of the rubbery polymer can easily occur. When the amount of the emulsifier is more than 1.5 parts by weight, it is difficult to control physical properties such as graft ratio of the aromatic vinyl graft copolymer, Gas silver streak may occur on the appearance of the molded article during injection molding of the thermoplastic resin composition containing the composition.

The monomer mixture used in preparing the aromatic vinyl-based graft copolymer composition may include an aromatic vinyl monomer and a vinyl cyanide monomer. The aromatic vinyl monomer may be, for example, styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl-substituted styrene. Styrene may be preferably used.

In the present invention, the aromatic vinyl monomer may be used in an amount of 15 to 40 parts by weight based on 100 parts by weight of the entire mixture of the diene-based rubbery polymer and the monomer to be added when preparing the aromatic vinyl-based graft copolymer composition. When the above range is satisfied, the thermoplastic resin composition comprising the aromatic vinyl-based graft copolymer composition is excellent in coloring property and moldability.

The vinyl cyanide monomer may be acrylonitrile, methacrylonitrile or the like, but is not limited thereto. Preferably, acrylonitrile can be used.

In the present invention, the content of the vinyl cyanide monomer may be 3.5 to 25 parts by weight based on 100 parts by weight of the whole diene-based rubbery polymer and the monomer mixture to be added when preparing the aromatic vinyl-based graft copolymer composition. When the above range is satisfied, the chemical resistance can be realized without lowering the physical properties in combination with other components.

Among the monomers used in the aromatic vinyl-based graft copolymer composition, the monomers used in the primary grafting reaction may swell the rubbery polymer particles to allow more monomers to polymerize within the particles, affect. After the completion of the reaction, grafting monomers can continuously maintain the equilibrium state between the grafted monomers by continuously progressing the graft reaction on the surface of the rubbery polymer particles.

The oil-soluble pyrolysis polymerization initiator may be at least one selected from the group consisting of acetylchrohexylsulfonylperoxide, 2-2 'azobis-2,4-dimethylvaleronitrile, 2-2' azobis- (2-amidinopropane) dihydrochloride, Azo-bis-isobutylonitrile, benzoyl peroxide, dimethyl-2,2'-azobisisobutylonitrile, 4,4'-azobis-4-cyanovaleric acid, And a mixture of a polymerization initiator and a polymerization initiator. Preferably, 2-2'-azobisisobutylonitrile having a relatively low decomposition temperature can be used. The content of the oil-soluble pyrolysis polymerization initiator may be 0.05 to 0.2 parts by weight.

Examples of the initiator include water-soluble initiators such as cumene hydroperoxide, benzoyl peroxide, and dicumyl peroxide, and water-soluble initiators such as ammonium persulfate, potassium persulfate, and potassium carbonate. Preferably, cumene hydroperoxide 0.2 to 0.5 parts by weight may be used. The cumene hydroperoxide initiator is formed by introducing a redox catalyst composed of iron sulfate, tetrasodium pyrophosphate, dextrose and the like to form a redox system so that the stability of the rubber polymer in the production of the graft copolymer even at a relatively low temperature And it is easy to control physical properties such as graft rate. The redox catalyst may be used in an amount of 0.0005 to 0.006 parts by weight of ferrous sulfate, 0.01 to 0.15 parts by weight of sodium pyrophosphate, and 0.05 to 0.15 parts by weight of dextrin. When the content is less than the above range, the effect of raising the graft rate is insignificant, and unreacted monomers are increased, so that a large amount of non-graft polymer can be formed. In addition, if it is used in excess of the above range, the amount of the solidification product can be increased by increasing the reaction rate.

The molecular weight modifier may be selected from mercaptans or organic halogen compounds having 8 to 18 carbon atoms and alpha-methylstyrene diester, terpinolene, alpha-terpinene, or a mixture of two or more thereof. The molecular weight regulator may be used in an amount of 0.01 to 0.5 parts by weight. If it is used in an amount less than the above range, the stability of the polymer and the physical properties of the final molded article may be lowered due to excessive grafting reaction. If the amount exceeds the above range, the polymerization rate will be decreased and the productivity will be lowered. . It is preferable that the molecular weight modifier is continuously mixed with the graft monomer.

The primary or secondary graft polymerization reaction can be produced by chain radical polymerization such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

In the present invention, the step of mixing the aromatic vinyl-based graft copolymer and the emulsion-type silicon-based compound may prevent blocking of the aromatic vinyl-based graft copolymer particles that may occur during storage, transportation, and processing . The emulsion-type silicone compound improves the interfacial characteristics of the aromatic vinyl-based graft copolymer particles to increase dispersibility and prevent agglomeration which may easily occur between particles. As a result, the content of the rubbery polymer of the aromatic vinyl-based graft copolymer can be remarkably increased, and when applied to the thermoplastic resin composition, the impact resistance can be remarkably increased, and the fluidity and gloss characteristics can be improved at the same time. Particularly, the structure in which the aromatic vinyl-based graft copolymer and the emulsion-type silicone compound are used at the same time is advantageous in that the addition of a conventionally used lubricant or stabilizer is not required and the degradation of physical properties according to the lubricant or stabilizer can be prevented, So that productivity and economy are excellent.

At this time, the content of the emulsion-type silicone compound may be 0.1 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the total aromatic vinyl-based graft copolymer. If it is less than the above range, the antiblocking effect is insignificant, and if it is out of the above range, the workability may be deteriorated.

The silicone-based compound in the emulsion form may contain an organopolysiloxane, and preferably a polydimethylsiloxane compound may be used. The polydimethylsiloxane compound may be modified by a functional group or not modified.

The emulsion-type silicone compound may have a solid content of 10 to 80% by weight, preferably 50 to 75% by weight, in order to realize a synergistic effect of impact resistance and gloss characteristics. If the solid content is less than 10 wt%, the synergistic effect of the impact resistance and the gloss characteristics is insignificant. If the solid content is more than 80 wt%, the chargeability and moldability may be deteriorated.

In the emulsion type silicone compound, the silicone compound may have a weight average molecular weight of 1,000 to 100,000 g / mol. When the silicone compound having a weight average molecular weight of less than 1,000 g / mol is used, the blocking prevention effect may be insignificant. If a silicone compound having a weight average molecular weight of more than 100,000 g / mol is used, problems of phase separation and coloring may occur. In the present invention, the weight-average molecular weight is measured by dissolving a sample in THF (tetrahydrofuran) and then using Gel Permeation Chromatography (GPC; Agilent Technologies 1200 series). At this time, Shodex LF-804 (8.0.1.D. × 300 mm) was used as a column and polystyrene (Shodex) was used as a standard sample.

The present invention can provide an aromatic vinyl-based graft copolymer composition produced from the above-described process for producing an aromatic vinyl-based graft copolymer composition.

Further, the present invention can provide a thermoplastic resin composition comprising the aromatic vinyl-based graft copolymer composition. The thermoplastic resin composition may include 10 to 40 parts by weight of the aromatic vinyl-based graft copolymer composition and 60 to 90 parts by weight of the aromatic vinyl-cyanide vinyl copolymer.

The thermoplastic resin composition can remarkably improve fluidity and gloss as well as impact resistance.

The present invention can provide a molded article produced using the thermoplastic resin composition.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

(Example 1)

(Step 1) Production of primary graft ABS

60 parts by weight of a polybutadiene rubber having an average particle diameter of 0.25 mu m, a gel content of 80% and a swelling index of 20, and 130 parts by weight of ion-exchanged water were charged in a reactor under a nitrogen atmosphere, and 0.5 part by weight of an emulsifier and 0.1 part by weight of dodecylmercaptan Respectively. Then, 16 parts by weight of styrene and 6 parts by weight of acrylonitrile were continuously added for 60 minutes, and then the mixture was heated to 60 DEG C while stirring. After the temperature of the mixture in the reactor reached 60 占 폚, the mixture was stirred for 10 minutes. Then, 0.5 part by weight of triarylisocyanurate and 0.1 part by weight of 2,2'-azobisisobutyronitrile were fed into the reactor. After 50 minutes, Respectively. When the temperature of the mixture reached 70 ° C, the polymerization was continued for 60 minutes, then the reactor was cooled and the reaction was terminated to prepare the first graft ABS.

(Step 2) Preparation of Secondary Graft ABS Composition

The temperature was maintained at 70 캜 in the presence of the prepared primary graft ABS, and 0.3 part by weight of sodium persulfate was added to the reactor and stirred for 10 minutes. Then, 14 parts by weight of styrene, 4 parts by weight of acrylonitrile and 0.1 part by weight of dodecylmercaptan 0.1 The weight-added monomer mixture was continuously added for 4 hours. When the addition of the monomer was completed, the internal temperature of the reactor was maintained at 70 캜 for 60 minutes, and then the reactor was cooled and the polymerization reaction was terminated. Thereafter, 0.1 part by weight of an emulsion type silicon compound (VTP-100, manufactured by Saishin Silichem Co., Ltd.) having a solid content of 60% by weight was added to the reactor while maintaining the reactor temperature at 60 占 폚 and stirred for 30 minutes to prepare a second graft ABS A final aromatic vinyl graft copolymer composition was prepared.

(Example 2)

The procedure of Example 1 was repeated except that the amount of the silicone compound in emulsion form was changed to 0.5 part by weight in the second step.

(Example 3)

The procedure of Example 1 was repeated except that the amount of the silicone-based compound in emulsion form was changed to 1.0 part by weight in the second step.

(Example 4)

The procedure of Example 1 was repeated except that the amount of the silicone compound in emulsion form was changed to 0.05 part by weight in the second step.

(Example 5)

Except that 2.5 parts by weight of the emulsion type silicone compound was used in the second step.

(Example 6)

Except that 65 parts by weight of polybutadiene rubber, 13 parts by weight of styrene and 6 parts by weight of acrylonitrile were used in the first step and 12 parts by weight of styrene and 4 parts by weight of acrylonitrile were used to change the monomer content in the second step Was carried out in the same manner as in Example 1.

(Example 7)

Except that 70 parts by weight of polybutadiene rubber, 10 parts by weight of styrene and 6 parts by weight of acrylonitrile were used in the first step and 10 parts by weight of styrene and 4 parts by weight of acrylonitrile were used to change the monomer content in the second step Was carried out in the same manner as in Example 1.

(Example 8)

Except that in the first step 55 parts by weight of polybutadiene rubber, 20 parts by weight of styrene and 6 parts by weight of acrylonitrile were used and that the monomer content was changed by using 15 parts by weight of styrene and 4 parts by weight of acrylonitrile in the second step Was carried out in the same manner as in Example 1.

(Comparative Example 1)

The procedure of Example 1 was repeated except that the emulsion-type silicone compound was not added in the second step.

(Comparative Example 2)

The procedure of Example 1 was repeated except that silicone oil (Momentive Co., Ltd., TSF-451) was added in place of the silicone compound in emulsion form in the second step.

(Experimental Example)

22 parts by weight of the aromatic vinyl-based graft copolymer composition prepared in Examples 1 to 8 and Comparative Examples 1 and 2 and 78 parts by weight of SAN resin having a weight average molecular weight of 125,000 g / mol were mixed and then L / D = 29 And extruded (barrel temperature: 230 캜) using a twin-screw extruder having a diameter of 45 mm to prepare a thermoplastic resin composition in the form of a pellet. The prepared pellets were dried at 80 ° C for 2 hours and then injection-molded at a cylinder temperature of 240 ° C and a mold temperature of 60 ° C using a 6 oz injection molding machine to prepare injection molding specimens for measurement of physical properties.

(evaluation)

(1) Whether the powder is blocked (whether or not the lumping phenomenon occurs)

A 10 cm x 10 cm x 10 cm container was filled with an aromatic vinyl graft copolymer composition in the form of a powder, loaded under a load of 10 kg, allowed to stand at 60 DEG C for 24 hours, and then evaluated for powder blocking. The measurement results were evaluated as?: Very severe occurrence,?: Occurring, and X: non-occurrence.

(2) Izod Impact strength (unit: kgf · cm / cm)

A 1/8 "thick Izod impact strength injection molded specimen was measured at room temperature according to the evaluation method specified in ASTM D256 under notched conditions.

(3) Melt-flow Index (unit: g / 10 min)

According to the evaluation method defined in ASTM D1238, the pellets were measured at a temperature of 220 DEG C under a load of 10 kg.

(4) Gloss (unit:%)

A 1/8 "thick injection molded specimen was measured at a 60 ° angle with a Gardner gloss meter according to the evaluation method specified in ASTM D523.

division Example Comparative Example One 2 3 4 5 6 7 8 One 2 Polybutadiene rubber 60 60 60 60 60 65 70 55 60 60 Styrene 30 30 30 30 30 25 20 35 30 30 Acrylonitrile 10 10 10 10 10 10 10 10 10 10 The emulsion type silicone compound 0.1 0.5 1.0 0.05 2.5 0.1 0.1 0.1 - - Silicone oil - - - - - - - - - 0.5 Powder blocking
Occurrence X X X X X X X X ◎ ◎

division Example Comparative Example One 2 3 4 5 6 7 8 One 2 Izod
Impact strength
(kgf · cm / cm) 23 24 24 23 25 26 27 21 20 23 Flow index
(g / 10 min) 3.8 3.7 3.6 3.8 3.4 3.5 3.2 3.7 3.5 3.9 Glossiness
(%) 90.4 90.4 90.5 90.4 90.3 90.5 90.2 90.5 88.3 89.5

In the case of the aromatic vinyl-based graft copolymer compositions according to Examples 1 to 8 of the present invention, the blockage phenomenon of the aromatic vinyl-based graft copolymer composition powder was not generated at all, even though it had a high rubber polymer content, . On the other hand, in Comparative Examples 1 and 2, a blocking phenomenon occurred due to aggregation of the aromatic vinyl-based graft copolymer particles. In addition, as shown in Table 2, in the case of Comparative Example 1 having the same rubbery polymer content as in Example 1, a blocking phenomenon occurred and the impact strength of the aromatic vinyl-based graft copolymer particles due to micro dispersion (FIG. 2) However, it was confirmed that the dispersibility of the aromatic vinyl-based graft copolymer particles in Example 1 according to the present invention was excellent (FIG. 1), and the fluidity and gloss as well as the impact strength were improved as compared with Comparative Example 1.

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 embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (13)

An aromatic vinyl-based graft copolymer composition comprising a core-shell type aromatic vinyl-based graft copolymer obtained by graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer with a diene-based rubbery polymer and an emulsion type silicone compound.
The method according to claim 1,
Wherein the emulsion-type silicone compound is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the aromatic vinyl-based graft copolymer.
The method according to claim 1,
Wherein the emulsion type silicone compound has a weight average molecular weight of 1,000 to 100,000 g / mol.
The method according to claim 1,
Wherein the emulsion type silicone compound comprises an organopolysiloxane.
The method according to claim 1,
Wherein the aromatic vinyl-based graft copolymer comprises 55 to 80% by weight of a diene-based rubbery polymer.
The method according to claim 1,
Wherein the diene-based rubbery polymer has an average particle diameter of 0.1 to 4.0 占 퐉.
Preparing a core-shell type aromatic vinyl-based graft copolymer by graft-polymerizing an aromatic vinyl-cyanide vinyl copolymer onto a diene-based rubbery polymer; and
Mixing and stirring the prepared aromatic vinyl-based graft copolymer with a silicone compound in emulsion form
By weight based on the weight of the aromatic vinyl-based graft copolymer.
8. The method of claim 7,
Wherein the emulsion-type silicon-based compound has a solid content of 10 to 80% by weight.
8. The method of claim 7,
Wherein the emulsion type silicone compound has a weight average molecular weight of 1,000 to 100,000 g / mol.
8. The method of claim 7,
Wherein the emulsion-type silicone-based compound comprises an organopolysiloxane.
A thermoplastic resin composition comprising an aromatic vinyl-based graft copolymer composition according to any one of claims 1 to 6.
12. The method of claim 11,
Wherein the thermoplastic resin composition comprises 10 to 40 parts by weight of an aromatic vinyl graft copolymer composition and 60 to 90 parts by weight of an aromatic vinyl-cyanide vinyl copolymer.
A molded article produced from the thermoplastic resin composition according to any one of claims 11 to 12.

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