WO2017105007A1 - Rubber modified vinyl-based graft copolymer, and thermoplastic resin composition containing same - Google Patents

Abstract

A rubber modified vinyl-based graft copolymer of the present invention has a core-shell structure in which a monomer mixture is graft polymerized to a core comprising a rubbery polymer, so as to form a shell, wherein the monomer mixture comprises: an aromatic vinyl-based monomer; a cyanovinyl-based monomer; and a siloxane compound represented by chemical formula 1. A thermoplastic resin composition containing the rubber modified vinyl-based graft copolymer has excellent impact resistance, flowability, appearance characteristics and the like.

Description

Rubber modified vinyl graft copolymer and thermoplastic resin composition comprising same

The present invention relates to a rubber-modified vinyl graft copolymer and a thermoplastic resin composition comprising the same. More specifically, the present invention relates to a rubber-modified vinyl graft copolymer having excellent impact resistance, flowability, appearance characteristics, and the like, a method for preparing the same, and a thermoplastic resin composition including the same.

Generally, impact modifiers are added to compensate for the impact resistance of thermoplastics. As such an impact modifier, a rubber-modified aromatic vinyl copolymer resin having a core-shell structure such as acrylonitrile-butadiene-styrene (ABS) resin is widely used. Here, the reason why the impact modifier has a core-shell structure is to prevent aggregation of core particles, which are rubber components, and to improve compatibility between the core particles and the thermoplastic resin. Factors that determine the physical properties of the impact modifier having a core-shell structure include the size and content of the rubber particles (core), the distance between the rubber particles, the degree of swelling with respect to the solvent, and the graft efficiency of the shell component with respect to the core component.

In addition, in order to further improve the impact resistance of the thermoplastic resin composition, a method of adding a silicone compound or the like as an impact aid together with an impact modifier of a core-shell structure is used. Polydimethylsiloxane (PDMS), a typical silicone impact aid, does not have carbon-carbon double bonds and has a very low glass transition temperature. When added to a resin composition, excellent thermal stability, chemical resistance, and (low temperature) impact resistance Etc. can be implemented.

However, when a thermoplastic resin composition containing a silicone-based compound (impact aid) such as polydimethylsiloxane is applied to a transparent product, low-temperature clouding may occur, and physical properties such as appearance characteristics may be lowered.

Accordingly, there is a demand for development of a rubber-modified vinyl graft copolymer having excellent (low temperature) impact resistance and the like and no thermoplastic resin composition including the same without occurrence of low temperature cloudiness.

Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2008-31219.

An object of the present invention is to provide a rubber-modified vinyl-based graft copolymer and a method for producing the same that can implement excellent (low temperature) impact resistance, fluidity, appearance characteristics.

Another object of the present invention is to provide a thermoplastic resin composition having excellent (low temperature) impact resistance, fluidity, appearance characteristics and the like including the rubber-modified vinyl-based graft copolymer.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to rubber-modified vinyl-based graft copolymers. The rubber-modified vinyl graft copolymer has a core-shell structure in which a monomer mixture is graft-polymerized on a core including a rubbery polymer to form a shell, and the monomer mixture comprises an aromatic vinyl monomer; Vinyl cyanide monomers; And siloxane compounds represented by the following Formula 1;

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 1 to 15 carbon atoms, R ₅ And R ₆ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the average value of n is 50 to 1,000.

In some embodiments, the rubber-modified vinyl graft copolymer may be about 50 parts by weight to about 200 parts by weight of the monomer mixture (shell component) based on about 100 parts by weight of the core.

In some embodiments, the monomer mixture may include about 30 to about 90 weight percent of the aromatic vinyl monomer, about 5 to about 30 weight percent of the vinyl cyanide monomer, and about 0.01 to about 0.4 weight percent of the siloxane compound.

In embodiments, the average particle diameter of the rubbery polymer may be about 0.05 to about 6 μm.

In embodiments, the core may be a polymerized aromatic vinyl monomer and vinyl cyanide monomer in the rubber polymer.

In embodiments, the core is about 10 to about 110 parts by weight of the aromatic vinyl monomer and vinyl cyanide monomer, based on about 100 parts by weight of the rubbery polymer, the core of the aromatic vinyl monomer and the vinyl cyanide monomer The weight ratio may be about 1.5: about 1 to about 5: about 1.

Another aspect of the present invention relates to a method for producing the rubber-modified vinyl graft copolymer. The method includes graft polymerizing a monomer mixture including an aromatic vinyl monomer, a vinyl cyanide monomer, and a siloxane compound represented by Formula 1 on a core including a rubbery polymer.

In an embodiment, the core is prepared by mixing an aromatic vinyl monomer, a vinyl cyanide monomer, and a polymerization initiator with the rubbery polymer, and then adding and stirring an emulsifier, a molecular weight modifier and water, and the aromatic vinyl monomer and vinyl cyanide. The system monomer is swelled into the rubbery polymer; And it may be prepared by polymerization.

Another aspect of the invention relates to a thermoplastic resin composition. The thermoplastic resin composition is the rubber-modified vinyl graft copolymer; And aromatic vinyl copolymer resins.

In some embodiments, the thermoplastic resin composition may include about 10 wt% to about 40 wt% of the rubber-modified vinyl graft copolymer and about 60 wt% to about 90 wt% of the aromatic vinyl copolymer copolymer resin.

In an embodiment, the aromatic vinyl copolymer resin may include a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer.

In an embodiment, the thermoplastic resin composition has a notched Izod impact strength of about 1/8 "thick specimen measured in accordance with ASTM D256 of about 24 to about 40 kgfcm / cm, 200 ° C, 10 kg in accordance with ISO 1133. The melt flow index, measured under load conditions, may be from about 2 to about 5 g / 10 minutes.

The present invention provides a rubber-modified vinyl graft copolymer capable of realizing excellent (low temperature) impact resistance, fluidity, appearance characteristics, and a manufacturing method thereof, and a (low temperature) impact resistance including the rubber-modified vinyl graft copolymer, The invention has the effect of providing a thermoplastic resin composition having excellent fluidity, appearance characteristics and the like.

Hereinafter, the present invention will be described in detail.

The rubber-modified vinyl graft copolymer according to the present invention comprises (a) a core comprising (a) a rubbery polymer, (b) an aromatic vinyl monomer; (c) vinyl cyanide monomers; And (d) a siloxane compound; is a core-shell structural copolymer in which a monomer mixture including (B) is graft polymerized to form a shell.

(A) core

The core according to an embodiment of the present invention may include a rubbery polymer (a1) used in a conventional rubber-modified vinyl-based graft copolymer.

In one embodiment, the rubbery polymer (a1) is a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubber, isoprene rubber, hydrogenated to the diene rubber, Acrylic rubbers such as polybutylacrylic acid, ethylene-propylene-diene monomer terpolymer (EPDM) and the like can be exemplified. These can be applied individually or in mixture of 2 or more types. For example, polybutadiene (PBD, butadiene rubber) etc. can be used.

In embodiments, the average particle diameter (Z-average) of the rubbery polymer may be about 0.05 to about 6 μm, for example about 0.1 to about 2 μm, specifically about 0.1 to about 0.6 μm. It is possible to obtain a rubber-modified vinyl-based graft copolymer that can be excellent in polymerization efficiency during the graft polymerization in the above range, and can exhibit excellent impact resistance, appearance characteristics, and the like.

In one embodiment, the rubber polymer (a1) may be used alone or the (a2) aromatic vinyl monomer (aromatic vinyl monomer) and (a3) vinyl cyanide monomer may be used as the core (A). A swelled and polymerized thing can be used. The core in which the aromatic vinyl monomer and the vinyl cyanide monomer are swelled and polymerized in the rubbery polymer is added to the rubbery polymer, for example, by mixing the aromatic vinyl monomer and the vinyl cyanide monomer with a polymerization initiator, and then adding an emulsifier and a molecular weight. A control agent and water may be added and stirred to allow the aromatic vinyl monomer and the vinyl cyanide monomer to swell into the rubbery polymer, and then polymerized thereto, but is not limited thereto. The method for producing such a core is known and can be easily performed by those skilled in the art.

The aromatic vinyl monomer (a2) is styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, Vinyl naphthalene may be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. For example, styrene can be used.

The vinyl cyanide monomer (a3) may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. For example, acrylonitrile can be used.

In an embodiment, when the core (A) is polymerized by swelling the aromatic vinyl monomer (a2) and the vinyl cyanide monomer (a3) in the rubbery polymer (a1), about 100 parts by weight of the rubbery polymer (a1) The aromatic vinyl monomer (a2) and the vinyl cyanide monomer (a3) may be polymerized to about 10 to about 110 parts by weight, for example, about 15 to about 106 parts by weight. In addition, the weight ratio (a2: a3) of the aromatic vinyl monomer (a2) and the vinyl cyanide monomer (a3) may be about 1.5: about 1 to about 5: about 1, for example, about 2: about 1 to about 4 : May be about 1. It is possible to obtain a rubber-modified vinyl graft copolymer that can implement excellent impact resistance in the above range.

(B) shell

The shell of the present invention is formed by graft polymerization of the monomer mixture comprising (b) an aromatic vinyl monomer, (c) a vinyl cyanide monomer, and (d) a siloxane compound copolymerizable with the core (A). will be. The rubber-modified vinyl graft copolymer of the present invention forms a shell with at least three components (b, c, and d), such that low-temperature clouding occurs when a silicone-based compound such as polydimethylsiloxane is used alone as an impact aid. It is possible to implement excellent (low temperature) impact resistance, fluidity, appearance characteristics, etc. without a problem of deterioration of physical properties.

As the aromatic vinyl monomer (b) of the present invention, an aromatic vinyl monomer used in a conventional rubber-modified vinyl graft copolymer may be used. For example, styrene, α-methylstyrene, α-ethylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl Naphthalene, mixtures thereof and the like can be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. For example, styrene, α-methylstyrene, mixtures thereof, and the like can be used.

In embodiments, the aromatic vinyl monomer (b) may be included in about 30 to about 90% by weight, for example about 35 to about 80% by weight, in 100% by weight of the monomer mixture. It is possible to obtain a rubber-modified vinyl-based graft copolymer that can implement excellent (low temperature) impact resistance, fluidity, appearance characteristics in the above range.

As the vinyl cyanide monomer (c) of the present invention, a vinyl cyanide monomer used in a conventional rubber modified vinyl graft copolymer may be used. For example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile and the like can be used, but are not limited thereto. These can be applied individually or in mixture of 2 or more types. Specifically acrylonitrile or the like can be used.

In an embodiment, the vinyl cyanide monomer (c) may be included in about 5 wt% to about 30 wt%, such as about 10 wt% to about 25 wt% in 100 wt% of the monomer mixture. It is possible to obtain a rubber-modified vinyl graft copolymer capable of realizing excellent (low temperature) impact resistance, fluidity, appearance characteristics, chemical resistance and the like in the above range.

The siloxane compound (d) of the present invention is copolymerizable with the aromatic vinyl monomer and the vinyl cyanide monomer, and is a siloxane compound having two or more unsaturated reactors (such as (meth) acrylate groups). For example, the siloxane compound may be represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 1 to 15 carbon atoms, R ₅ And R ₆ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and an average value of n may be 50 to 1,000, for example, 60 to 300.

In embodiments, the siloxane compound may include a compound represented by the following Formula 1a.

[Formula 1a]

In Formula 1a, the average value of n is as defined in Formula 1.

In an embodiment, the siloxane compound (d) may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 4,000 to about 74,500 g / mol, for example, about 4,780 to about 22,500 g / mol. . It is possible to obtain a rubber-modified vinyl graft copolymer capable of realizing excellent (low temperature) impact resistance and the like in the above range.

In embodiments, the siloxane compound (d) may be included in about 0.01 to about 0.4% by weight, for example from about 0.02 to about 0.3% by weight of 100% by weight of the monomer mixture. In the above range, a rubber-modified vinyl graft copolymer capable of realizing excellent (low temperature) impact resistance, fluidity, appearance characteristics, and the like, without deteriorating physical properties such as low temperature cloudiness caused by a silicone compound can be obtained.

In addition, the siloxane compound (d) may be included in an amount of about 0.05 to about 0.1 parts by weight based on about 100 parts by weight of the core (A), the aromatic vinyl monomer (b), and the vinyl cyanide monomer (c). In the above range, a rubber-modified vinyl graft copolymer capable of realizing excellent (low temperature) impact resistance, fluidity, appearance characteristics, and the like, without deteriorating physical properties such as low temperature turbidity caused by a silicone compound can be obtained.

In an embodiment, the rubber-modified vinyl-based graft copolymer has about 50 to about 200 parts by weight of the shell component (including b, c and d), for example about 60 to about 150, based on about 100 parts by weight of the core. The parts by weight may be graft copolymerized. It is possible to obtain a rubber-modified vinyl-based graft copolymer that can implement excellent (low temperature) impact resistance, fluidity, appearance characteristics in the above range.

Method for producing a rubber-modified vinyl graft copolymer according to an embodiment of the present invention is the aromatic vinyl monomer (b), the vinyl cyanide monomer (c) and the siloxane compound (d) in the core (A) It may comprise the step of graft polymerization of the monomer mixture comprising a. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

In an embodiment, the polymerization is carried out at a temperature of about 45 to about 90 ° C. for about 1 to about 20 hours in the presence of water (ion exchange water, etc.), a polymerization initiator, an emulsifier, a molecular weight regulator, and the like according to a known emulsion polymerization method. , For example, for about 1 to about 10 hours.

Examples of the polymerization initiator include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroxy peroxide, t-butyl peroxylaurate, t-butyl peroxy acetate, t-butyl peroxy Peroxide initiators such as propyl caponate; Redox-based initiators combining a redox agent; Combinations of these and the like may be used, but the present invention is not limited thereto. The amount of the polymerization initiator used may be about 0.1 to about 1 part by weight based on about 100 parts by weight of the core.

The emulsifiers include soap-based compounds of fatty acids, soap-based compounds of rosin acids, acrylate acrylic acid copolymers saponified with sodium hydroxide, sulfate salts of polyoxyethyleneallylglycidylnonylphenylether, alkylarylsulfonates, and alkalimethylalkyl sulfates. , Sulfonated alkyl esters, combinations thereof, and the like can be used, but is not limited thereto. The amount of the emulsifier may be about 0.1 to about 5 parts by weight based on about 100 parts by weight of the core.

As the molecular weight modifier, tert-dodecyl mercaptan, bis (isopropoxythiocarbonyl) disulfide, p-methoxyphenyldiazothio-2-naphthyl ether, combinations thereof, and the like can be used, but are not limited thereto. It doesn't work. The amount of the molecular weight modifier may be about 0.1 to about 2 parts by weight based on about 100 parts by weight of the core.

In an embodiment, when the core (A) is a polymer in which the aromatic vinyl monomer (a2) and the vinyl cyanide monomer (a3) are swelled and polymerized in the rubber polymer (a1), the aromatic vinyl monomer in the rubber polymer (a1) is polymerized. After mixing (a2) and the vinyl cyanide monomer (a3) with a polymerization initiator, the emulsion, the molecular weight modifier, and water are added and stirred to swell the aromatic vinyl monomer and the vinyl cyanide monomer into the rubbery polymer. Then polymerize it (swell polymerization) to produce a core; Here, the monomer mixture (including b, c and d) and, if necessary, a polymerization initiator, a molecular weight regulator, etc. may be added, and graft polymerization of the monomer mixture to the core.

In an embodiment, the rubber-modified vinyl graft copolymer may be added to a sulfuric acid solution or the like to destroy the latex (latex) polymer after completion of the graft polymerization, and then washed with water and dried to obtain a powdery polymer.

The thermoplastic resin composition according to the present invention comprises the rubber-modified vinyl graft copolymer; And aromatic vinyl copolymer resins. In the thermoplastic resin composition, the rubber-modified vinyl graft copolymer may be present in a form dispersed in the aromatic vinyl copolymer resin (matrix resin).

In an embodiment, the aromatic vinyl copolymer resin may be an aromatic vinyl copolymer resin used in a conventional rubber-modified aromatic vinyl copolymer resin. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including a monomer copolymerizable with an aromatic vinyl monomer such as an aromatic vinyl monomer and a vinyl cyanide monomer.

In an embodiment, the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene Vinyl naphthalene may be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In a specific embodiment, as the monomer copolymerizable with the aromatic vinyl monomer, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. Vinyl cyanide monomers, maleimide monomers and the like can be used, and can be used alone or in combination of two or more. The content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 wt% to about 80 wt%, for example, about 20 wt% to about 70 wt% of the total 100 wt% of the aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin comprises about 20 to about 90 weight percent of an aromatic vinyl monomer (b), for example about 30 to about 80 weight percent, and about 10 to about 80 vinyl cyanide monomer (c). Weight percent, such as about 20 to about 70 weight percent of a copolymer. For example, a styrene-acrylonitrile (SAN) copolymer or the like can be used as the aromatic vinyl copolymer resin. In the above range, a thermoplastic resin composition excellent in impact resistance, fluidity (processability), appearance characteristics, and the like can be obtained.

In embodiments, the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 300,000 g / mol, for example, about 15,000 to about 250,000 g / mol Can be. Within the above range, the polymerization stability of the aromatic vinyl copolymer resin may be excellent, and the fluidity of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin is about 10 to about 40 weight percent of the rubber-modified vinyl graft copolymer, for example about 15 to about 35 weight percent and the aromatic vinyl copolymer resin of about 60 to About 90% by weight, for example about 65% to about 85% by weight. Within this range, the (low temperature) impact resistance, fluidity, appearance characteristics, and the like of the thermoplastic resin composition may be excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further include conventional additives as necessary. The additives include, but are not limited to, flame retardants, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like. When using the additive, the content thereof may be about 0.001 to about 20 parts by weight based on about 100 parts by weight of the base resin including the rubber-modified vinyl graft copolymer and the aromatic vinyl copolymer resin, but is not limited thereto.

In an embodiment, the thermoplastic resin composition may be prepared by a known thermoplastic resin composition manufacturing method. For example, the above components and, if necessary, other additives may be mixed and then melt-extruded in an extruder to prepare pellets. In addition, the prepared pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art.

The thermoplastic resin composition according to one embodiment of the present invention has a notched Izod impact strength of about 1/8 "thick specimen measured in accordance with ASTM D256 of about 24 to about 40 kgfcm / cm, for example about 24 to about 35 kgf cm / cm, melt flow index measured at 200 ° C. and 10 kg load conditions in accordance with ISO 1133 for about 2 to about 5 g / 10 minutes, for example about 2.1 to about 4.5 g / 10 minutes Can be.

In an embodiment, the thermoplastic resin composition is excellent in (low temperature) impact resistance, fluidity, appearance characteristics, etc., and thus is useful as an interior / exterior material such as electric / electronic products.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Example

Production Example  1 and 2: rubber modification Vinyl Graft  Preparation of Copolymer

According to the composition and content of Table 1, butadiene rubber (PBD, average particle diameter: 0.3 ㎛), styrene (SM), acrylonitrile (AN), and a siloxane compound represented by the formula (1a) (MPDMS) To 100 parts by weight of the butadiene rubber (core), 0.3 parts by weight of cumene hydroperoxide as a polymerization initiator, 0.5 parts by weight of tert-dodecyl mercaptan as a molecular weight regulator and 1 part by weight of a rosin acid soap-based compound were added as an emulsifier. Then, it was stirred and graft polymerized at 60 to 80 ° C. for 10 hours. After the completion of the polymerization, it was added to the sulfuric acid solution to destroy the polymer in the latex state, and the polymer in the form of powder (rubber-modified vinyl-based graft copolymer of the core-shell structure) through a washing and drying process.

[Formula 1a]

In Formula 1a, n has an average value of 118 (weight average molecular weight: about 9,000 g / mol).

Production Example  3: rubber modification Vinyl Graft  Preparation of Copolymer

According to the composition and content of Table 1, except that the siloxane compound (MPDMS) was not used in the same manner as in Preparation Example 1 of the polymer of the powder form (core-shell structure rubber modified vinyl-based graft copolymer )

Production Example  4: rubber modification Vinyl Graft  Preparation of Copolymer

According to the composition and content of Table 1, except for using the polydimethylsiloxane (PDMS, weight average molecular weight: 9,000 g / mol) instead of the siloxane compound (MPDMS) of the powder form in the same manner as in Preparation Example 1 A polymer (a rubber-modified vinyl graft copolymer having a core-shell structure, a form in which PDMS was not included in the shell but included separately) was obtained.

Production Example One 2 3 4 Core (PBD) (parts by weight) 100 100 100 100 Monomer mixture SM (% by weight) 74.81 74.91 75 74.81 AN (% by weight) 24.94 24.97 25 24.94 MPDMS (% by weight) 0.25 0.12 - - PDMS (wt%) - - - 0.25 Monomer mixture parts by weight 65 65 65 65 yield(%) 99.3 99.25 99.2 99.2

(Parts of monomer mixture: parts by weight based on 100 parts by weight of the core)

Specifications of each component used in the following Examples and Comparative Examples are as follows.

(A) Rubber modified vinyl graft copolymer resin

(A1) The rubber-modified vinyl graft copolymer resin of Production Example 1 was used.

(A2) The rubber-modified vinyl graft copolymer resin of Production Example 2 was used.

(A3) The rubber-modified vinyl graft copolymer resin of Production Example 3 was used.

(A4) The rubber-modified vinyl graft copolymer resin of Production Example 4 was used.

(B) Aromatic Vinyl Copolymer Resin

A styrene-acrylonitrile copolymer resin (SAN) having a weight average molecular weight of 200,000 g / mol prepared by suspension polymerization of 74% by weight of styrene and 26% by weight of acrylonitrile was used.

Example  1 and 2 and Comparative example  1 to 2: Preparation of the thermoplastic resin composition

According to the composition and content of Table 2 below, the components were mixed for 10 minutes by a tumbler mixer, and then added to a twin screw type extruder having a diameter of L / D = 32, 45 mm, and a barrel temperature. Pellets were prepared by melting and extruding at 250 ° C. and 250 rpm conditions. The prepared pellets were dried at 80 ° C. for at least 2 hours, and then injected into an injection machine (manufacturer: LG Cable, product name: LGH-140N) at a cylinder temperature of 230 ° C. to prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 2 below.

Property measurement method

(1) Notched Izod Impact Strength (unit: kgf · cm / cm): Notched Izod impact strength of a 1/8 "thick specimen was measured according to the evaluation method specified in ASTM D256.

(2) Melt-flow index (MI, unit: g / 10 min): measured under load conditions of 220 ° C. and 10 kg based on the evaluation method specified in ISO 1133.

(3) The L value of the specimen was measured using a Minolta (CM-2500C) color difference meter, and the transparency of the initial specimen was confirmed.

(4) Whether low-temperature clouding occurred: The specimen was placed in a sub-zero 30 ° C chamber and left for 2 hours to visually check whether the clouding phenomenon occurred.

Example Comparative example One 2 One 2 (A) (% by weight) (A1) 22 - - - (A2) - 22 - - (A3) - - 22 - (A4) - - - 22 (B) (% by weight) 78 78 78 78 Notch Izod Impact Strength 28 24 19 22 Melt flow index 2.2 2.1 2.0 2.1 L 4.8 4.9 5.0 4.8 Low temperature clouding × × × ○

From the above results, it can be seen that the thermoplastic resin composition comprising the rubber-modified vinyl graft copolymer (Preparation Examples 1 to 2) according to the present invention is excellent in impact resistance, fluidity (molding processability), appearance characteristics, and the like.

On the other hand, in the case of the thermoplastic resin composition (Comparative Example 1) including the rubber-modified vinyl-based graft copolymer (Preparation Example 3) that does not contain MPDMS as a shell component, it can be seen that the impact resistance is lowered. In the case of the thermoplastic resin composition (Comparative Example 2) including the rubber-modified vinyl-based graft copolymer (Comparative Example 4) that does not include PDMS and separately includes PDMS, low-temperature clouding occurs to reduce appearance characteristics. have.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

A monomer mixture is grafted to a core comprising a rubbery polymer to have a core-shell structure in which a shell is formed, The monomer mixture is an aromatic vinyl monomer; Vinyl cyanide monomers; And a siloxane compound represented by the following Formula 1; rubber-modified vinyl graft copolymer comprising: [Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ₃ and R ₄ are each independently an alkylene group having 1 to 15 carbon atoms, R ₅ And R ₆ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the average value of n is 50 to 1,000. The rubber-modified vinyl graft copolymer according to claim 1, wherein the rubber-modified vinyl graft copolymer has about 50 to about 200 parts by weight of the monomer mixture graft-polymerized based on about 100 parts by weight of the core. coalescence. The method of claim 1, wherein the monomer mixture comprises about 30 to about 90 weight percent of the aromatic vinyl monomer, about 5 to about 30 weight percent of the vinyl cyanide monomer, and about 0.01 to about 0.4 weight percent of the siloxane compound. Rubber modified vinyl graft copolymer characterized in that. The rubber-modified vinyl graft copolymer according to claim 1, wherein the rubber polymer has an average particle diameter of about 0.05 to about 6 mu m. The rubber-modified vinyl graft copolymer according to claim 1, wherein the core is polymerized with an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer. The method of claim 5, wherein the core is about 10 parts by weight to about 110 parts by weight of the aromatic vinyl monomer and vinyl cyanide monomer, based on about 100 parts by weight of the rubbery polymer, and the aromatic vinyl monomer and the vinyl cyanide monomer. A rubber modified vinyl graft copolymer, characterized in that the weight ratio of monomers is about 1.5: about 1 to about 5: about 1. A rubber-modified vinyl graft aerial comprising graft polymerizing a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and a siloxane compound represented by Formula 1 on a core including a rubbery polymer Process for the preparation of coalescing. The method of claim 7, wherein the core is mixed with an aromatic vinyl monomer, a vinyl cyanide monomer and a polymerization initiator to the rubbery polymer, and then added with an emulsifier, a molecular weight modifier and water and stirred, and the aromatic vinyl monomer and Allowing the vinyl cyanide monomer to swell into the rubbery polymer; And a method of producing a rubber-modified vinyl graft copolymer, characterized in that it is prepared by polymerization. Rubber modified vinyl graft copolymer according to any one of claims 1 to 8; And A thermoplastic resin composition comprising an aromatic vinyl copolymer resin. The thermoplastic resin composition of claim 9, wherein the thermoplastic resin composition comprises about 10 wt% to about 40 wt% of the rubber-modified vinyl graft copolymer and about 60 wt% to about 90 wt% of the aromatic vinyl copolymer copolymer resin. Resin composition. The thermoplastic resin composition of claim 9, wherein the aromatic vinyl copolymer resin comprises a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer. The method according to claim 9, wherein the thermoplastic resin composition has a notched Izod impact strength of 1/8 "thick specimen measured according to ASTM D256 of about 24 to about 40 kgfcm / cm, 200 ℃, according to ISO 1133 A thermoplastic resin composition, characterized in that the melt flow index measured at 10 kg load conditions is about 2 to about 5 g / 10 minutes.