WO2018124595A1 - Aromatic vinyl-based copolymer and thermoplastic resin composition containing same - Google Patents

Abstract

The present invention relates to an aromatic vinyl-based copolymer. The aromatic vinyl-based copolymer is a polymer of a reaction mixture comprising: an aromatic vinyl-based compound; a cyanovinyl-based compound; and an acrylic compound represented by chemical formula 1. The aromatic vinyl-based copolymer and a thermoplastic resin composition containing the same have an excellent antibacterial property and the like.

Description

Aromatic vinyl copolymer and thermoplastic resin composition comprising the same

The present invention relates to an aromatic vinyl copolymer and a thermoplastic resin composition comprising the same. More specifically, the present invention relates to an aromatic vinyl copolymer having excellent antibacterial properties and the like, and a thermoplastic resin composition including the same.

Thermoplastic resins such as aromatic vinyl copolymers are excellent in impact resistance, rigidity, processability, chemical resistance, and the like, and are widely used in various applications such as automobiles, electrical and electronic equipment, office equipment, home appliances, toys, and the like.

Although these thermoplastic resins are considered to be difficult to deteriorate to microorganisms, additives used in processing become microbial nutrients, or contaminants attached to the surface of molded products formed from thermoplastic resins become microbial nutrients, causing microbial deterioration. have.

Recently, as consumers' interest in the environment and health increases, the market for household appliances and household goods containing antimicrobial substances is activated. In response, products with antimicrobial properties have been developed in the plastic field, and commercial production has increased. Doing.

In order to prepare such an antimicrobial thermoplastic resin composition, the addition of an antimicrobial agent is necessary, and the antimicrobial agent may be divided into inorganic antimicrobial agents and organic antimicrobial agents. Inorganic antibacterial agent is an antimicrobial agent containing metal components such as silver and copper, which has excellent thermal stability, and is widely used in the production of antimicrobial thermoplastic resin compositions (antimicrobial resins). Relatively high price, disadvantages of uniform dispersion during processing, discoloration due to metal components, etc., there are many restrictions on use. Organic antimicrobial agents are relatively inexpensive and have a good antimicrobial effect even with a small amount. However, they are sometimes toxic to humans and may only be effective against specific bacteria. have. In addition, there may be a cause of discoloration after processing, there is a shortage of antimicrobial persistence due to elution problem, the range of organic antimicrobial agent that can be applied to the antimicrobial thermoplastic resin composition is extremely limited.

Therefore, there is a need for development of a thermoplastic resin (aromatic vinyl copolymer) having excellent antibacterial properties even without using an antibacterial agent.

Background art of the present invention is disclosed in the Republic of Korea Patent Publication No. 2015-0138275.

An object of the present invention is to provide an aromatic vinyl copolymer having excellent antibacterial properties.

Another object of the present invention is to provide a thermoplastic resin composition comprising the aromatic vinyl 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 aromatic vinyl based copolymers. The aromatic vinyl copolymer is an aromatic vinyl compound; Vinyl cyanide compounds; And an acrylic compound represented by the following Chemical Formula 1; a polymer of a reaction mixture comprising:

[Formula 1]

In Formula 1, 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.

In an embodiment, the reaction mixture is represented by Formula 1 with respect to about 100 parts by weight of the monomer mixture comprising about 60 to about 90 wt% of the aromatic vinyl compound and about 10 to about 40 wt% of the vinyl cyanide compound. The acrylic compound may include about 0.1 to about 10 parts by weight.

In an embodiment, the acryl-based compound represented by Chemical Formula 1 may be obtained by reacting a compound represented by Chemical Formula 2 and an acryl-based compound represented by Chemical Formula 3 prepared by stirring zinc oxide in an aqueous sodium hydroxide solution:

[Formula 2]

[Formula 3]

In Formula 3, 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.

In some embodiments, the reaction mixture may further include about 10 to about 300 parts by weight of alkyl (meth) acrylate based on about 100 parts by weight of the monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound.

In embodiments, the aromatic vinyl copolymer may have a weight average molecular weight of about 100,000 to about 300,000 g / mol.

In embodiments, the aromatic vinyl copolymer may have a glass transition temperature of about 90 to about 120 ℃.

In one embodiment, the aromatic vinyl copolymer is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm size specimen according to the JIS Z 2801 antimicrobial evaluation method, the antimicrobial activity measured after 24 hours is about 3 to about 7 and about 3 to about 7.

Another aspect of the invention relates to a thermoplastic resin composition. The thermoplastic resin composition is characterized in that it comprises the aromatic vinyl copolymer.

The present invention has the effect of providing an aromatic vinyl copolymer having excellent antimicrobial properties and the like, and a thermoplastic resin composition containing the aromatic vinyl copolymer.

Hereinafter, the present invention will be described in detail.

The aromatic vinyl copolymer according to the present invention includes (A) an aromatic vinyl compound; (B) vinyl cyanide compound; And (C) an acrylic compound.

(A) Aromatic vinyl compound

As the aromatic vinyl compound according to one embodiment of the present invention, an aromatic vinyl monomer used in a conventional aromatic vinyl copolymer may be used without limitation, and for example, styrene, α-methylstyrene, β-methylstyrene , p-methyl styrene, pt-butyl styrene, ethyl styrene, vinyl xylene, monochloro styrene, dichloro styrene, dibromo styrene, vinyl naphthalene, mixtures thereof and the like can be exemplified. Specifically, styrene, (alpha) -methylstyrene, these mixtures, etc. can be used.

In embodiments, the aromatic vinyl compound is about 60 to about 90 in 100% by weight of the monomer mixture (A) + (B) comprising the aromatic vinyl compound (A) and the vinyl cyanide compound (B) Weight percent, such as from about 65 to about 85 weight percent. In the above range, the mechanical properties, processability, and the like of the aromatic vinyl copolymer may be excellent.

(B) Vinyl Cyanide Compound

As the vinyl cyanide compound according to an embodiment of the present invention, a vinyl cyanide monomer used in a conventional aromatic vinyl copolymer may be used without limitation, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile. Nitrile, phenyl acrylonitrile, (alpha)-chloro acrylonitrile, fumaronitrile, a mixture thereof, etc. can be illustrated. Specifically, acrylonitrile, methacrylonitrile and the like can be used.

In an embodiment, the vinyl cyanide compound is about 10 to about 40 in 100% by weight of a monomer mixture (A) + (B) comprising the aromatic vinyl compound (A) and the vinyl cyanide compound (B) Weight percent, such as about 15 to about 35 weight percent. In the above range, the impact resistance, heat resistance and the like of the aromatic vinyl copolymer may be excellent.

(C) acrylic compound

The acryl-based compound used in the present invention is capable of imparting antimicrobial activity to an aromatic vinyl copolymer including zinc oxide, and may be represented by Chemical Formula 1.

[Formula 1]

In Formula 1, 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.

In an embodiment, the acryl-based compound represented by Chemical Formula 1 may be obtained by reacting a compound represented by Chemical Formula 2 and an acryl-based compound represented by Chemical Formula 3 prepared by stirring zinc oxide in an aqueous sodium hydroxide solution.

[Formula 2]

[Formula 3]

In Formula 3, 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, the acryl-based compound represented by Chemical Formula 1 contains about 1 to about 10 parts by weight of zinc oxide (ZnO) in about 100 parts by weight of an aqueous solution of sodium hydroxide (NaOH) at a concentration of about 0.5 mol / L, and about 50 to about Stirring at 100 ° C. for about 1 to about 10 hours to prepare a compound represented by Chemical Formula 2 (ZnO-OH), dispersing it in a solvent, and in the presence of ammonium hydroxide, an acrylic resin represented by Chemical Formula 3 The compound may be prepared by reacting the compound with a weight ratio of about 1: 1 (Formula 2: Formula 3) at about 50 to about 100 ° C. for about 10 to about 36 hours.

In embodiments, the zinc oxide may have an average particle size of about 0.02 to about 3 μm, for example, about 0.1 to about 2 μm, as measured by an electron scanning microscope (SEM), using a nitrogen gas adsorption method, a BET analyzer Specific surface area BET measured by Surface Area and Porosity Analyzer ASAP 2020, Micromeritics Co., Ltd. may be about 1 to about 50 m ² / g, for example about 1 to about 40 m ² / g, purity May be at least about 99%. In the above range, the antibacterial and weather resistance of the aromatic vinyl copolymer may be more excellent.

In embodiments, the zinc oxide has a size ratio (B / A) of peak A in the 370 to 390 nm region and peak B in the 450 to 600 nm region when measured by photo luminescence, eg, about 0.01 to about 10 For example from about 0.01 to about 1 or from about 1.1 to about 8. Low odor, weather resistance and the like of the aromatic vinyl copolymer in the above range may be excellent.

In embodiments, the zinc oxide has a peak position 2θ of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (full of diffraction peaks). The crystallite size value calculated by applying the Scherrer's equation (Equation 1) based on the width at Half Maximum may be about 100 to about 2,000 GPa, for example, about 120 to about 1,800 GPa. In the above range, the initial color of the thermoplastic resin composition, weather resistance, antibacterial and the like can be excellent.

[Equation 1]

Microcrystal size (D) =

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

In an embodiment, the zinc oxide is dissolved in zinc in the form of metal, vaporized by heating to about 850 to about 1,000 ° C., for example, about 900 to about 950 ° C., followed by injection of oxygen gas and about 20 to about 30 After cooling to ℃, if necessary, the heat treatment for about 30 minutes to about 150 minutes at about 700 to about 800 ℃ while injecting nitrogen / hydrogen gas into the reactor, and then cooled to room temperature (20 to 30 ℃) It can manufacture.

In embodiments, the acrylic compound is about 0.1 to about 100 parts by weight based on a monomer mixture (A) + (B) comprising the aromatic vinyl compound (A) and the vinyl cyanide compound (B) 10 parts by weight, for example, about 1 to about 5 parts by weight. In the above range, the antibacterial, heat resistance, mechanical properties, processability, etc. of the aromatic vinyl copolymer may be excellent.

In the aromatic vinyl copolymer according to one embodiment of the present invention, the reaction mixture may further include an alkyl (meth) acrylate in order to improve the transparency, scratch resistance and the like of the aromatic vinyl copolymer. Here, "(meth) acryl" means that both "acryl" and "methacryl" are possible. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

In embodiments, the alkyl (meth) acrylate is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, butyl Ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, etc. can be illustrated. For example, methyl methacrylate can be used.

In an embodiment, the alkyl (meth) acrylate is further from about 10 to about 300 parts by weight, for example from about 100 to about 300 parts by weight, relative to about 100 parts by weight of the monomer mixture ((A) + (B)). May be included. In the above range, the transparency, scratch resistance, and the like of the aromatic vinyl copolymer may be excellent.

The aromatic vinyl copolymer according to one embodiment of the present invention can be prepared using a conventional polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization. For example, suspension polymerization can be used. Specifically, a polymerization initiator and a chain transfer agent may be added to the reaction mixture of the above content to prepare a reaction mixture, and the reaction mixture may be prepared by suspending polymerization by adding a suspension stabilizer or the like into an aqueous solution. The polymerization temperature and the polymerization time can be appropriately adjusted. For example, it may be reacted for about 1 to about 8 hours at a polymerization temperature of about 65 to about 125 ° C, specifically about 70 to about 120 ° C.

The polymerization initiator may be a conventional radical polymerization initiator known in the polymerization art, for example, octanoyl peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichloro Benzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile and azobis- (2,4-dimethyl) -valeronitrile and the like may be used, but is not limited thereto. . The polymerization initiator may be applied alone or by mixing two or more kinds. The polymerization initiator may be included in about 0.01 to about 10 parts by weight, for example, about 0.03 to about 5 parts by weight based on about 100 parts by weight of the reaction mixture, but is not limited thereto.

The chain transfer agent may be used to control the weight average molecular weight of the copolymer and to improve thermal stability. As the chain transfer agent, conventional chain transfer agents known in the polymerization art may be used. For example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, isopropyl Alkyl mercaptans in the form of CH ₃ (CH ₂ ) _n SH (n is an integer from 1 to 20), including mercaptans, n-amyl mercaptans, and the like; Halogen compounds including carbon tetrachloride and the like; And aromatic compounds including alpha methylstyrene dimer or alpha ethylstyrene dimer, and the like, but are not limited thereto. These can be applied individually or in mixture of 2 or more types. The chain transfer agent may be included in an amount of about 0.01 to about 10 parts by weight, for example about 0.02 to about 5 parts by weight, based on about 100 parts by weight of the reaction mixture. In the above range, a copolymer having excellent heat resistance and an appropriate molecular weight can be prepared.

The aromatic vinyl copolymer may be polymerized by introducing the reaction mixture into an aqueous solution containing at least one additive such as a suspension stabilizer, a suspension stabilizer, and an antioxidant. The additive may be included in about 0.001 to about 20 parts by weight based on about 100 parts by weight of the reaction mixture, but is not limited thereto.

Examples of the suspension stabilizer include organic suspension stabilizers including homopolymers or copolymers of acrylic acid or methacrylic acid, polyalkylacrylate-acrylic acid, polyolefin-maleic acid, polyvinyl alcohol, cellulose, and the like; Inorganic suspension stabilizers including tricalcium phosphate; Mixtures thereof and the like can be used, but are not limited thereto. Here, the acrylic acid or methacrylic acid may be in the form of a salt of sodium, potassium or ammonium in order to maintain proper solubility.

As the suspension stabilizing aid, disodium hydrogen phosphate, sodium dihydrogen phosphate, or the like may be used, and sodium sulfate or the like may be added to control solubility characteristics of the water-soluble polymer or monomer.

The antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydrophenyl) propionate, triethylene glycol-bis-3 (3-tert-butylbutyl-4-hydroxy-5- Methylphenyl) propionite, 2,6-di-tert-butyl-4-methyl phenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), tri (2,4-di Tert-butylphenyl) phosphite, normal-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di Tert-butyl-4-hydroxybenzyl) isocyanate, 3-3,5-di-tert-butyl-4-hydroxyphenyl), disterylthiol dipropionate, lauthiol propionate methane and di -Phenyl-isooctyl phosphinate and the like can be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types.

After the polymerization is completed, the aromatic vinyl copolymer in the form of particles may be obtained through cooling, washing, dehydration, and drying.

In embodiments, the aromatic vinyl copolymer may have a weight average molecular weight of about 100,000 to about 300,000 g / mol, for example, about 130,000 to about 200,000 g / mol, as measured by gel permeation chromatography (GPC). It may be excellent in the heat resistance, injection processability, etc. of the aromatic vinyl copolymer in the above range.

In embodiments, the aromatic vinyl copolymer may have a glass transition temperature of about 90 to about 120 ℃, for example about 95 to about 115 ℃. It may be excellent in the heat resistance, injection processability, etc. of the aromatic vinyl copolymer in the above range.

In an embodiment, the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm size specimen, based on JIS Z 2801 antimicrobial evaluation method, and measured after incubation at 35 ° C. and RH 90% for 24 hours. The antimicrobial activity may be about 3 to about 7 and about 3 to about 7, for example about 5 to about 7 and about 5 to about 7.

The thermoplastic resin composition according to the present invention includes the aromatic vinyl copolymer.

In an embodiment, the aromatic vinyl copolymer of the present invention is a conventional aromatic vinyl type such as styrene-acrylonitrile copolymer resin (SAN resin), methyl methacrylate-styrene-acrylonitrile copolymer resin (MSAN resin), and the like. Copolymer resins may be substituted or used together.

In one embodiment, the thermoplastic resin composition, in addition to the aromatic vinyl copolymer, a common thermoplastic resin, for example, rubber-modified aromatic vinyl copolymer resin, polycarbonate resin, poly (meth) acrylate resin, these It may include a thermoplastic resin including a mixture and the like.

In an embodiment, the thermoplastic resin composition may further include conventional additives as necessary. Examples of the additives include 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 may be about 0.001 to about 50% by weight of the total thermoplastic resin composition.

In an embodiment, the thermoplastic resin composition may be prepared by a known thermoplastic resin composition manufacturing method. For example, the components may be mixed with other additives as necessary and then melt-extruded in an extruder to produce pellets. 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 includes an aromatic vinyl copolymer having excellent antimicrobial properties, and solves problems caused by the use of an antimicrobial agent, and includes various applications, for example, interior / exterior materials such as automobiles, electrical / electronic products, and building exterior materials. It can be used in the field of

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: Preparation of Acrylic Compound Represented by Formula 1

5 g of zinc oxide (ZnO) was added to 200 ml of 0.5 mol / L sodium hydroxide (NaOH) aqueous solution, and stirred at 70 ° C. for 4 hours to prepare ZnO-OH (Formula 2), followed by 5 g of ZnO-OH. Was dispersed in a 20% aqueous methanol solution, and 0.5 mol of ammonium hydroxide and 5 g of MPS (3-Methacryloxypropyltrimethoxysilane, Chemical Formula 3, R ₁ : methyl group, R ₂ : propylene group, and R ₃ : methyl group) were added thereto at 70 ° C. The reaction was carried out for 24 hours. After removing the unreacted MPS through centrifugation, washing with isopropyl alcohol (dry), dried in a vacuum oven, the acrylic system represented by the following formula (R ₁ : methyl group, R ₂ : propylene group) The compound was prepared.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 and 3, R ₁ is a methyl group, R ₂ is a propylene group, R ₃ is a methyl group.

Example  1 and 2 and Comparative example  1 to 2: aromatic Vinyl  Preparation of Copolymer

According to the composition and content of Table 1, styrene (SM), acrylonitrile (AN), the acrylic compound represented by Formula 1 prepared in Preparation Example 1 (ZnO-MPS) and methyl methacrylate (MMA) To 100 parts by weight of the reaction mixture, 0.05 part by weight of t-dodecyl mercaptan (TDM) as a chain transfer agent (molecular weight regulator) and 0.2 part by weight of azobisisobutyronitrile (AIBN) as a polymerization initiator were added. In addition, this was added to an aqueous solution (including 0.05 parts by weight of suspension stabilizer (tricalcium phosphate) and 140 parts by weight of deionized water) in which a suspension stabilizer was dissolved, and the suspension polymerization was carried out at 70 ° C. for 4 hours, and after completion of polymerization, dehydration and drying were performed. Aromatic vinyl based copolymers were prepared. The glass transition temperature, weight average molecular weight and antimicrobial activity of the prepared aromatic vinyl copolymer were measured and shown in Table 1 below.

Property measurement method

(1) Glass transition temperature (Tg, unit: ℃): Using TA Instrument's Q2910, first raise the temperature from 20 ℃ to 160 ℃ at a rate of 20 ℃ / min, then cool slowly to maintain equilibrium at 50 ℃ After making the temperature rise again, the temperature was raised to 160 ° C at a rate of 10 ° C / min. The inflection point of the endothermic transition curve was determined by the glass transition temperature.

(2) Weight average molecular weight (Mw, unit: g / mol): measured by ASTM D 5296-05 method using a 515 HPLC pump, 2414 RI detector from Waters, and KF-805L column from Shodex.

(3) Antibacterial activity value: In accordance with JIS Z 2801 antimicrobial evaluation method, 5 cm × 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and measured after culturing for 24 hours at 35 ℃, RH 90% conditions.

		Example 1	Example 2	Comparative Example 1	Comparative Example 2
SM (% by weight)		71	81.6	71	81.6
AN (% by weight)		29	18.4	29	18.4
ZnO-MPS (parts by weight)		1.01	3.75	-	-
MMA (parts by weight)		-	270	-	270
Glass transition temperature (℃)		109	104	110	103
Weight average molecular weight (g / mol)		153,000	151,000	151,000	150,000
Antimicrobial activity	Staphylococcus	6.1	6.1	2.1	1.6
	Escherichia coli	6.1	6.0	1.4	0.5

* Parts by weight: parts by weight based on 100 parts by weight of styrene (SM) and acrylonitrile (AN)

From the above results, it can be seen that the aromatic vinyl copolymer according to the present invention has an antimicrobial activity value of 6 or more, and is excellent in antimicrobial activity without deterioration in heat resistance and processability.

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 (8)

1. Aromatic vinyl compounds;

   Vinyl cyanide compounds; And

   An aromatic vinyl copolymer, characterized in that the polymer of the reaction mixture containing;

   [Formula 1]

   

   In Formula 1, 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.
2. The compound of claim 1, wherein the reaction mixture is about 60 parts by weight to about 100 parts by weight of the aromatic vinyl compound and about 10 parts by weight to about 40% by weight of the vinyl cyanide compound. An aromatic vinyl copolymer comprising about 0.1 to about 10 parts by weight of the acrylic compound to be displayed.
3. According to claim 1, wherein the acrylic compound represented by the formula (1) is obtained by reacting the compound represented by the formula (2) and the acrylic compound represented by the formula (3) prepared by adding zinc oxide in an aqueous sodium hydroxide solution Aromatic vinyl copolymers:

   [Formula 2]

   

   [Formula 3]

   

   In Formula 3, 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. The method of claim 1, wherein the reaction mixture further comprises about 10 to about 300 parts by weight of alkyl (meth) acrylate based on about 100 parts by weight of the monomer mixture comprising the aromatic vinyl compound and the vinyl cyanide compound. An aromatic vinyl copolymer.
5. The aromatic vinyl copolymer of claim 1, wherein the aromatic vinyl copolymer has a weight average molecular weight of about 100,000 to about 300,000 g / mol.
6. The aromatic vinyl copolymer of claim 1, wherein the aromatic vinyl copolymer has a glass transition temperature of about 90 to about 120 ° C.
7. According to claim 1, wherein the aromatic vinyl copolymer is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm × 5 cm size specimen according to the JIS Z 2801 antimicrobial evaluation method, the antimicrobial activity measured after 24 hours is about 3 respectively To about 7 and about 3 to about 7 aromatic vinyl-based copolymers.
8. A thermoplastic resin composition comprising the aromatic vinyl copolymer according to any one of claims 1 to 7.