WO2019132387A1 - Rubber-modified vinyl graft copolymer and thermoplastic resin composition including same - Google Patents

Abstract

A rubber-modified vinyl graft copolymer of the present invention is prepared by graft-polymerizing, in a rubber polymer, a monomer mixture comprising: an aromatic vinyl monomer; a vinyl cyanide monomer; and an acrylic monomer represented by chemical formula 1. The rubber-modified vinyl graft copolymer and the thermoplastic resin composition including the same have an excellent antibacterial property and the like.

Description

Rubber-modified vinyl-based graft copolymer and thermoplastic resin composition containing the same

The present invention relates to a rubber-modified vinyl-based graft copolymer and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a rubber-modified vinyl-based graft copolymer excellent in antibacterial properties, and a thermoplastic resin composition containing the same.

Rubber-modified vinyl copolymer resin and the like are excellent in impact resistance, rigidity, workability and chemical resistance and are widely used in various applications such as automobiles, electric / electronic appliances, office equipment, home appliances, toys and the like.

Such a thermoplastic resin composition is considered to be hardly deteriorated by microorganisms. However, when the additive used in the processing becomes the nutrient of the microorganism or the contaminant attached to the surface of the molded article formed from the thermoplastic resin composition becomes the nutrient of the microorganism, There is a case.

In recent years, consumer interest in environment and health has increased, and markets for household appliances and household goods containing antimicrobial substances have been activated. In response to this, products with antimicrobial properties have been developed in the plastic field, .

In order to prepare such an antimicrobial thermoplastic resin composition, it is necessary to add an antimicrobial agent. The antimicrobial agent can be divided into an inorganic antimicrobial agent and an organic antimicrobial agent. The inorganic antibacterial agent is an antimicrobial agent containing a metal component such as silver or copper and is excellent in thermal stability and is widely used in the production of an antibacterial thermoplastic resin composition (antibacterial resin). However, since the antibacterial agent is insufficient in antibacterial activity, There are disadvantages such as relatively high price, uniform dispersion problem in processing, discoloration due to metal components, and there are many restrictions in use. Organic antimicrobial agents are relatively inexpensive and have good antimicrobial activity in a small amount. However, they sometimes have human toxicity and may be effective only for certain bacteria. have. In addition, there is a disadvantage in that discoloration after processing may cause discoloration and that the antibacterial persistence is short due to the elution problem, and thus the range of the organic antibacterial agent applicable to the antibacterial thermoplastic resin composition is extremely limited.

Therefore, there is a need to develop a rubber-modified vinyl-based graft copolymer and a thermoplastic resin composition containing the rubber-modified vinyl-based graft copolymer excellent in antimicrobial properties without using an additional antimicrobial agent.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2015-0138275.

It is an object of the present invention to provide a rubber-modified vinyl-based graft copolymer excellent in antibacterial properties and the like.

Another object of the present invention is to provide a thermoplastic resin composition comprising 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.

1. One aspect of the present invention relates to rubber-modified vinyl-based graft copolymers. The rubber-modified vinyl-based graft copolymer is obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and an acrylic monomer represented by the following formula (1)

[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms.

In one embodiment, the rubber-modified vinyl-based graft copolymer comprises about 30 to about 70 weight percent of the rubbery polymer, about 15 to about 55 weight percent of the aromatic vinyl monomer, about 1 to about 30 weight percent of a vinyl cyanide monomer %, And about 0.1 to about 10% by weight of an acrylic monomer represented by the formula (1) may be graft-polymerized.

3. In the above-mentioned one or two embodiments, the acrylic monomer represented by the formula (1) is prepared by reacting a compound represented by the following formula (2) prepared by stirring zinc oxide with an aqueous solution of sodium hydroxide and an acrylic monomer represented by the following formula You can get:

(2)

(3)

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

4. Another aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is a rubber-modified vinyl-based graft copolymer according to any one of 1 to 3 above; And an aromatic vinyl-based copolymer resin.

5. In the four embodiments, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

6. The thermoplastic resin composition according to 4 or 5 above, wherein the antibacterial activity value measured after 24 hours is inoculated with a Staphylococcus aureus strain and a Escherichia coli in a 5 cm x 5 cm size specimen according to JIS Z 2801 antibacterial evaluation method From about 3 to about 7.

The present invention has the effect of providing a thermoplastic resin composition comprising a rubber-modified vinyl-based graft copolymer excellent in antibacterial properties and the rubber-modified vinyl-based graft copolymer.

Hereinafter, the present invention will be described in detail.

In the present specification, "a to b" representing numerical ranges are defined as "? A and? B".

The rubber-modified vinyl-based graft copolymer according to the present invention has antimicrobial properties, and is obtained by copolymerizing an aromatic vinyl-based monomer; Vinyl cyanide monomers; And a specific acrylic monomer is graft-polymerized. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing the monomer mixture to a rubbery polymer, and the polymerization can be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. Further, the rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer)-shell (copolymer of a monomer mixture).

Examples of the rubbery polymer include a diene rubber such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), a saturated rubber which is hydrogenated with the diene rubber, an isoprene rubber, A copolymer of an alkyl (meth) acrylate rubber having 2 to 10 carbon atoms, an alkyl (meth) acrylate having 2 to 10 carbon atoms and styrene, and an ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, diene rubber, alkyl (meth) acrylate rubber and the like can be used. Specifically, butadiene rubber, butyl acrylate rubber and the like can be used.

In embodiments, the rubbery polymer (rubber particles) may have an average particle size of from about 0.01 to about 5 microns, such as from about 0.05 to about 3 microns, specifically from about 0.10 to about 2 microns. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state. Specifically, a rubbery polymer latex was smeared on a mesh to remove coagulum formed during the polymerization of the rubbery polymer, and a solution prepared by mixing 0.5 g of latex and 30 ml of distilled water was poured into a 1,000 ml flask and filled with distilled water to prepare a sample , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size analyzer (malvern, nano-zs).

In embodiments, the content of the rubbery polymer may be about 30 to about 70 weight percent, for example about 40 to about 60 weight percent, of 100 weight percent of the total rubber modified vinyl based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, the aromatic vinyl-based monomer may be an aromatic vinyl-based monomer used in a conventional aromatic vinyl-based copolymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p- Methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and mixtures thereof. Specifically, styrene,? -Methylstyrene, a mixture thereof, or the like can be used.

In embodiments, the aromatic vinyl-based monomer may be from about 15 to about 55 weight percent, for example from about 25 to about 45 weight percent, of 100 weight percent of the total rubber-modified vinyl-based graft copolymer. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In the specific examples, the vinyl cyanide monomer may be a vinyl cyanide monomer used in a conventional aromatic vinyl copolymer, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl Acrylonitrile,? -Chloroacrylonitrile, fumaronitrile, mixtures thereof, and the like. Specifically, acrylonitrile, methacrylonitrile and the like can be used.

In an embodiment, the aromatic vinyl monomer may be from about 1 to about 30 weight percent, for example from about 5 to about 20 weight percent, of 100 weight percent of the total rubber modified vinyl based graft copolymer. In the above range, the impact resistance, heat resistance, fluidity and the like of the thermoplastic resin composition can be excellent.

In an embodiment, the acrylic monomer of the present invention is capable of imparting antimicrobial properties to an aromatic vinyl-based copolymer including zinc oxide, and can be represented by the above formula (1).

[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms.

In an embodiment, the acrylic monomer represented by the formula (1) can be obtained by reacting a compound represented by the following formula (2) and an acrylic monomer represented by the following formula (3) prepared by stirring zinc oxide in an aqueous solution of sodium hydroxide.

(2)

(3)

Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

More specifically, about 1 to about 10 parts by weight of zinc oxide (ZnO) is added to about 100 parts by weight of an aqueous solution of sodium hydroxide (NaOH) at a concentration of 0.5 mol / L, and about 50 to about 100 OH for about 1 to about 10 hours to prepare a compound represented by the formula (2) (ZnO-OH), dispersing the compound in a solvent, and reacting the acrylic monomer represented by the above formula (3) in the presence of ammonium hydroxide, And about 1: 1 (Formula 2: Formula 3) at about 50 to about 100 캜 for about 10 to about 36 hours.

Here, the number of -OH bonded to the zinc oxide of the formulas (1) and (2) may be three or more so as to be able to react with -OR ₃ of the formula (3), and is not particularly limited.

In embodiments, the zinc oxide may have an average particle size, as measured by a scanning electron microscope (SEM), of from about 0.02 to about 3 microns, such as from about 0.1 to about 2 microns, and a specific surface area BET of from about 1 to about 50 m ² / g, such as from about 1 to about 40 m ² / g, and the purity may be greater than about 99%. Within the above range, the antimicrobial property, weather resistance, etc. of the aromatic vinyl-based copolymer may be more excellent.

In an embodiment, the zinc oxide has a size ratio (B / A) of peak A in the region of 370 to 390 nm and peak B in the region of 450 to 600 nm in the range of about 0.01 to about 10, For example from about 0.01 to about 1 or from about 1.1 to about 8. Within the above range, the aromatic vinyl-based copolymer may be excellent in low-brittleness, weather resistance, and the like.

In an embodiment of the present invention, the zinc oxide has a peak position 2θ value in the range of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (Full of diffraction peak the crystallite size value calculated by applying Scherrer's equation (Equation 1) based on the width at half maximum may be about 100 to about 2,000 A, for example, about 120 to about 1,800 A. Within the above range, the thermoplastic resin composition may have excellent initial color, weather resistance, antimicrobial properties, and the like.

[Formula 1]

Microcrystalline size (D) =

In Equation 2, K is a shape factor,? Is an X-ray wavelength,? Is a FWHM value, and? Is a peak position degree.

In one embodiment, the zinc oxide is prepared by melting zinc in the form of a metal and then vaporizing it by heating to a temperature of from about 850 to about 1,000 ° C, for example, from about 900 to about 950 ° C, After cooling to 30 DEG C, if necessary, heat treatment is performed at about 700 to about 800 DEG C for about 30 minutes to about 150 minutes while injecting nitrogen / hydrogen gas into the reactor, and then cooled to room temperature (20 to 30 DEG C) .

In another embodiment, the zinc oxide is prepared by dissolving zinc in the form of a metal and then vaporizing it by heating to a temperature of from about 850 to about 1,000 DEG C, for example, from about 900 to about 950 DEG C, Followed by cooling to 30 占 폚 and then heating at about 400 to about 900 占 폚, for example, about 500 to about 800 占 폚 for about 30 to about 150 minutes, such as about 60 to about 120 minutes.

In an embodiment, the acrylic monomer may be excellent in antibacterial properties, heat resistance, mechanical properties, processability and the like.

The aromatic vinyl monomer may be about 0.1 to about 10% by weight, for example about 0.5 to about 5% by weight, based on 100% by weight of the rubber-modified vinyl-based graft copolymer. In the above range, the rubber-modified vinyl-based graft copolymer may have antimicrobial properties, and the thermoplastic resin composition may have excellent antimicrobial activity, mechanical properties, processability, and the like.

In a specific example, the rubber-modified vinyl-based graft copolymer may further include a monomer or the like for imparting processability and heat resistance. Examples of such a monomer include, but are not limited to, (meth) acrylic acid, an ester thereof, maleic anhydride, N-substituted maleimide and the like. When the monomer for imparting processability and heat resistance is used, the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight, based on 100% by weight of the rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.

The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified vinyl-based graft copolymer and (B) an aromatic vinyl-based copolymer resin.

(A) a rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer of the present invention has antimicrobial properties, and a rubber-modified vinyl-based graft copolymer containing the specific acrylic monomer can be used.

In the specific examples, the rubber-modified vinyl-based graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer (g-ABS), an alkyl acrylate-styrene-acrylonitrile graft copolymer (g-ASA) Modified vinyl-based graft copolymer of the present invention, or may be used together.

In embodiments, the rubber-modified vinyl-based graft copolymer may comprise from about 10 to about 50 weight percent, such as from about 15 to about 45 weight percent, of 100 weight percent of the thermoplastic resin composition. In the above range, the thermoplastic resin composition can be excellent in antibacterial properties, impact resistance, molding processability, and the like.

(B) an aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a usual rubber-modified vinyl-based copolymer resin. For example, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

In an embodiment, the aromatic vinyl-based copolymer resin can be obtained by mixing an aromatic vinyl monomer, a vinyl cyanide monomer or the like and then polymerizing the aromatic vinyl monomer, and the polymerization can be carried out by known polymerization such as emulsion polymerization, suspension polymerization, Method. ≪ / RTI >

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example about 30 to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In the specific examples, examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used. The content of the vinyl cyanide monomer may be about 10 to about 80% by weight, for example about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In an embodiment, the aromatic vinyl-based copolymer resin may be a polymer obtained by further comprising a monomer for imparting processability and heat resistance to the monomer mixture. Examples of the monomer for imparting the above processability and heat resistance include (meth) acrylic acid, N-substituted maleimide and the like, but are not limited thereto. When the monomer for imparting processability and heat resistance is used, the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.

In embodiments, the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 300,000 g / mol, such as from about 15,000 to about 150,000 g / . Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

In an embodiment, the aromatic vinyl-based copolymer resin (B) may include about 50 to about 90% by weight, for example about 55 to about 85% by weight, of 100% by weight of the total thermoplastic resin composition. In the above range, the thermoplastic resin composition can be excellent in antibacterial properties, impact resistance, molding processability, and the like.

The thermoplastic resin composition according to one embodiment of the present invention may contain, in addition to the rubber-modified vinyl-based copolymer resin, ordinary thermoplastic resins such as polycarbonate resin, polyester resin, poly (meth) Mixtures, and the like.

In an embodiment, the thermoplastic resin composition may further include conventional additives as required. Examples of the additives include flame retardants, fillers, antioxidants, anti-drop agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, the content thereof may be about 0.001 to about 50 wt% of the total thermoplastic resin composition.

The thermoplastic resin composition according to one embodiment of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, after mixing the above components and other additives as necessary, they may be melt-extruded in an extruder to produce pellets. The produced pellets can 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 to those of ordinary skill in the art to which the present invention pertains. The thermoplastic resin composition is a rubber-modified vinyl-based graft copolymer to which antimicrobial properties are imparted without an antimicrobial agent and solves the problems associated with the use of the antimicrobial agent. The thermoplastic resin composition can be used in various applications such as automobiles, electric / / Can be used in exterior materials and building exterior materials

In a specific example, the thermoplastic resin composition is prepared by inoculating Staphylococcus aureus and Escherichia coli to a 5 cm x 5 cm specimen according to JIS Z 2801 antibacterial evaluation method, and measuring antimicrobial activity values measured after 24 hours from about 3 to about 7 days .

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example

Manufacturing example  1: Preparation of acrylic monomer represented by formula (1)

5 g of zinc oxide (ZnO) was added to 200 ml of an aqueous solution of 0.5 mol / L sodium hydroxide (NaOH) and stirred at 70 ° C for 4 hours to prepare ZnO-OH (Formula 2) 0.5 mol of ammonium hydroxide and 5 g of MPS (3-Methacryloxypropyltrimethoxysilane, Formula 3, R ₁ : methyl group, R ₂ : propylene group, R ₃ : methyl group) were added and dispersed in a 20% aqueous methanol solution. And reacted for 24 hours. After the unreacted MPS was removed by centrifugation, the resultant was washed with isopropyl alcohol and dried in a vacuum oven to obtain an acrylic-based acrylic resin represented by the following formula (1) (R ₁ : methyl group, R ₂ : propylene group) Monomers were prepared.

[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (3), R ₁ is a methyl group, R ₂ is a propylene group, and R ₃ is a methyl group.

Example  1 to 2 and Comparative Example  1 ~ 2: Rubber Modification Vinyl-based Graft  Preparation of Copolymer

(A soap-based compound of rosin acid) and a rubbery polymer (polybutadiene rubber (manufacturer: Lotte Hi-tech Co., average particle size: 0.2 탆) or butyl acrylate rubber (SM) and acrylonitrile (AN) were added thereto, and the mixture was heated to 60 DEG C and stirred. Then, a polymerization initiator (cumene hydroperoxide) was added thereto, ), A mixture of the monomer mixture containing the acrylic monomer (ZnO-MPS) represented by the formula 1 prepared in Preparation Example 1 and a molecular weight modifier (compound name: tert-dodecylmercaptan) was stirred for 1 to 5 hours And graft polymerization was carried out. After completion of the polymerization, dehydration and drying were performed to prepare a rubber-modified vinyl-based graft copolymer in the form of particles.

	Example 1	Example 2	Comparative Example 1	Comparative Example 2
Polybutadiene rubber	50	-	50	-
Butyl acrylate rubber	-	50	-	50
Styrene (wt%)	35.25	35.25	37.5	37.5
Acrylonitrile (% by weight)	11.75	11.75	12.5	12.5
ZnO-MPS (% by weight)	3	3	-	-

Example  3 to 4 and Comparative Example  3 to 4: Preparation of Thermoplastic Resin Composition

As the rubber-modified vinyl-based graft copolymer and the aromatic vinyl-based copolymer resin prepared in Examples 1 and 2 and Comparative Examples 1 and 2, a SAN resin in which 75 wt% of styrene and 25 wt% of acrylonitrile were polymerized Average molecular weight: 130,000 g / mol) in the amounts shown in Table 2, and then extruded at 230 DEG C to prepare pellets. The pellets were extruded at a temperature of 230 ° C. and a mold temperature of 60 ° C. in a 6 Oz extruder at 80 ° C. for 2 hours or more, . The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 2 below.

How to measure property

(1) Antibacterial activity value: Staphylococcus aureus and E. coli were inoculated on a 5 cm × 5 cm specimen according to JIS Z 2801 antibacterial evaluation method, and then cultured at 35 ° C. and RH 90% for 24 hours.

(2) IZOD Impact Strength (Unit: kgf · cm / cm): The notched Izod impact strength of a 1/8 "thick specimen was measured based on the evaluation method specified in ASTM D256.

		Example 3	Example 4	Comparative Example 3	Comparative Example 4
(A1) Example 1 Copolymer (% by weight)		25	-	-	-
(A2) Example 2 Copolymer (% by weight)		-	25	-	-
(A3) Comparative Example 1 Copolymer (% by weight)		-	-	25	-
(A4) Comparative Example 2 Copolymer (% by weight)		-	-	-	25
(B) SAN resin (% by weight)		75	75	75	75
Antimicrobial activity value	Staphylococcus	6.2	6.2	2.1	1.8
	Escherichia coli	6.1	5.8	1.3	0.5
Notch Izod impact strength (kgf · cm / cm)		21.1	10.2	21.3	9.9

From the above results, it can be seen that the thermoplastic resin composition according to the present invention has an antibacterial activity value of 5.8 or more and is excellent in antibacterial activity without deteriorating impact resistance and the like.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. A rubber-modified vinyl-based graft copolymer, which is obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer and an acrylic monomer represented by the following formula (1)

   [Chemical Formula 1]

   

   Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms.
2. The rubber-modified vinyl-based graft copolymer of claim 1, wherein the rubber-modified vinyl-based graft copolymer comprises about 30 to about 70 weight percent of the rubbery polymer, about 15 to about 55 weight percent of the aromatic vinyl monomer, about 1 to about 30 weight percent of a vinyl cyanide monomer %, And about 0.1 to about 10% by weight of an acrylic monomer represented by the general formula (1) is graft-polymerized. The rubber-modified vinyl-based graft copolymer according to claim 1,
3. The acrylic monomer of claim 1 or 2, wherein the acrylic monomer represented by the following formula (2) and the acrylic monomer represented by the following formula (3) are prepared by reacting zinc oxide with an aqueous solution of sodium hydroxide and stirring the resulting mixture, By weight of a rubber-modified vinyl-based graft copolymer:

   (2)

   

   (3)

   

   Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
4. A rubber-modified vinyl-based graft copolymer according to any one of claims 1 to 3; And

   A thermoplastic resin composition comprising an aromatic vinyl-based copolymer resin.
5. The thermoplastic resin composition according to claim 4, wherein the aromatic vinyl-based copolymer resin is a polymer of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
6. 6. The thermoplastic resin composition according to claim 4 or 5, wherein the thermoplastic resin composition is inoculated with a Staphylococcus aureus strain and a Escherichia coli strain in a 5 cm x 5 cm size specimen according to JIS Z 2801 antibacterial evaluation method, Lt; RTI ID = 0.0 > about 3 to about 7. < / RTI >