KR101061493B1 - Composition of unsaturated polyester resin having antibacterial property, prepreg of antibacterial unsaturated polyester using the same, antibacterial unsaturated polyester glass mat sheets using the prepreg and preparing method thereof - Google Patents

Abstract

The present invention relates to an antimicrobial unsaturated polyester resin composition, an antimicrobial unsaturated polyester prepreg, an antimicrobial unsaturated polyester glass mat sheet and a method for producing the antimicrobial unsaturated polyester glass mat sheet using the same, and more particularly, carbon nanotubes- The present invention relates to an antimicrobial unsaturated polyester resin composition comprising a polymer nanocomposite, an antimicrobial unsaturated polyester prepreg, an antimicrobial unsaturated polyester glass mat sheet and a method for producing the antimicrobial unsaturated polyester glass mat sheet .

Description

An antimicrobial unsaturated polyester resin composition, a prepreg, a sheet molding compound, an antimicrobial unsaturated polyester glass mat sheet using the same, and a method for producing the antimicrobial unsaturated polyester glass mat sheet polyester using the same, Antibacterial unsaturated polyester glass mat sheets using the prepreg and Preparing Method Thereof}

The present invention relates to an antimicrobial unsaturated polyester resin composition, an antimicrobial unsaturated polyester prepreg using the same, an antimicrobial unsaturated polyester glass mat sheet using the antimicrobial unsaturated polyester prepreg, and a method for producing the antimicrobial unsaturated polyester glass mat sheet. More specifically, an antimicrobial unsaturated polyester resin composition simultaneously exhibiting improved antimicrobial activity and enhanced mechanical properties, including a multiwalled carbon nanotube nanocomposite functionalized with a tetravalent ammonium polymer having excellent dispersibility in a polymer resin, The present invention relates to an antibacterial unsaturated polyester prepreg used, an antibacterial unsaturated polyester glass mat sheet using an antibacterial unsaturated polyester prepreg and a method for producing an antibacterial unsaturated polyester glass mat sheet.

Carbon nanotubes are usually carbon materials having a high aspect ratio ranging in diameter from 1 to 100 nanometers (nm) and lengths ranging from several nanometers (nm) to tens of micrometers (μm). Carbon nanotubes have a honeycomb-shaped planar carbon structure in which one carbon atom is bonded to three other carbon atoms to form a tube shape.

In order to utilize the excellent electrical conductivity, thermal stability, and mechanical properties of carbon nanotubes, carbon nanotubes are mixed with a polymer material or a metal material to manufacture and use a hybrid nanocomposite material.

Carbon nanotubes have a high van der Waals force acting between them to cause agglomeration phenomenon, and carbon nanotube nano functionalized as a polymer by covalently bonding carbon nanotubes and polymers in order to improve dispersibility to polymer resins by suppressing them. A method for producing a composite has been proposed.

In addition, carbon nanotubes have an antimicrobial effect showing significant cytotoxicity against bacteria such as Escherichia coli due to the nanoscale size effect of the carbon nanotubes ( Langmuir , 24, 6409-6413 (2008). )) Reported.

However, conventionally, when carbon nanotubes are used as additives in composite materials, the focus was on mechanical, thermal, and electrical properties, and the application of the antimicrobial properties of carbon nanotubes was rare.

An object of the present invention is to provide an antimicrobial unsaturated polyester resin composition that can utilize the antimicrobial properties of carbon nanotubes.

Another object of the present invention is to provide a prepreg obtained by impregnating the antimicrobial unsaturated polyester resin composition on a substrate and an antimicrobial unsaturated polyester glass mat sheet using the same.

It is another object of the present invention to provide a method for producing an antimicrobial unsaturated polyester glass mat sheet.

The present invention provides an antimicrobial unsaturated polyester resin composition comprising a carbon nanotube-polymer nanocomposite, an unsaturated polyester resin and a curing agent to solve the above problems.

The present invention also provides a prepreg obtained by impregnating the substrate with the antimicrobial unsaturated polyester resin composition.

The present invention also provides an antimicrobial unsaturated polyester glass mat sheet using the prepreg and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The antimicrobial unsaturated polyester resin composition according to the present invention is characterized in that it comprises a carbon nanotube-polymer nanocomposite, an unsaturated polyester resin and a curing agent.

In the present invention, the polymer of the carbon nanotube-polymer nanocomposite is poly (2- (dimethylamino ethyl) methacrylate) (poly (2- (dimethylamino ethyl) methacrylate, PDMAEMA)), poly (2-hydroxy Poly (2-hydroxyethyl methacrylate), poly (trimethylammonium 2-hydroxypropylmethacrylate hydrochloride), poly (N, N-dimethylacrylamide) ( poly (N, N-dimethlacrylamide)), and poly (N-vinyl-2-pyrrolidone) (poly (N-vinyl-2-pyrrolidone)).

In the present invention, the carbon nanotube-polymer nanocomposite is characterized in that the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed.

In the tetravalent ammonium group, all hydrogen present in ammonium (NH ₄ ) is substituted with organic molecules, and alkyl ammonium, dialkyl quaternary ammonium, trialkyl quaternary ammonium, aromatic quaternary ammonium or heterocyclic quaternary ammonium It is possible to use, but not limited to.

In general, quaternary ammonium compounds can be used for antimicrobial action simultaneously with surfactant use. The antimicrobial mechanism of the quaternary ammonium compound is first absorbed by the quaternary ammonium compound on the surface of the microbial cell, then the antimicrobial material is diffused through the cell wall and the cytoplasmic membrane is destroyed, releasing K ⁺ ions and cellular components such as DNA and RNA to release microorganisms. It is known to activate.

The tetravalent ammonium polymers may be used in various ways by being fixed to the support by a method such as deterioration fixation, probe or coating, and dealcoholization.

In the present invention, the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed is prepared by using the carbon nanotube-polymer nanocomposite in a suitable solvent, bromomethane, bromoethane, iodomethane ( iodomethane, iodoethane, chloromethane, chloroethane, iodopropane, chloropropane, iodoisopropane, ioisoisopropane, chloroisopropane and Formed by treatment with one or more halogenated alkane compounds selected from the group consisting of combinations thereof.

In the present invention, the antimicrobial unsaturated polyester resin composition is characterized in that it comprises 0.0001 to 1.0% by weight of carbon nanotube-polymer nanocomposites with respect to the weight of the unsaturated polyester resin. When the weight of the carbon nanotube-polymer nanocomposite is less than or equal to the above range, the antimicrobial effect and mechanical properties of the nanocomposite are weakened.

In the present invention, the curing agent is t-butyl perbenzoate (t-butyl perbenzoate, TBPB), di- (2,4-dichlorobenzoyl)-peroxide (di- (2,4-dichlorobenzoyl) -peroxide), Dibenzoyl peroxide, 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-di- (t-butylperoxy) -3,3,5 -trimethylcyclohexane), dicumyl peroxide, di- (2-t-butylperoxyisopropyl) benzene, t-butylcumylperoxide ), 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane (2,5-dimethyl-2,5-di (t-butylperoxy) -hexane), and di-t-butylpearl It is preferably one or more selected from compounds consisting of oxides (di-t-butylperoxide).

The present invention also provides a sheet molding compound composition in which the antimicrobial unsaturated polyester resin composition is reinforced with a cut or continuos glass fiber strand mat.

The sheet molding compound is impregnated with a cut or continuos glass fiber strand mat in a composition consisting of a thermosetting resin, an unsaturated polyester resin, a curing agent and other conventional additives, followed by a hydraulic press. It is manufactured in a sheet form by heating and pressure molding in a furnace, and becomes a material of fiber reinforced plastic.

The antimicrobial unsaturated polyester resin composition according to the present invention can be utilized as an effective sheet molding compound (SMC) mixed with the existing SMC composition and has excellent mechanical properties, corrosion resistance and excellent moldability by heating and pressurizing construction materials, It can be manufactured and used in sheet form in various fields such as interior and exterior panels and water tanks of commercial vehicles.

The sheet molding compound composition according to the present invention may include a composition for sheet molding compound which is generally used conventionally. As is known, existing sheet molding compound compositions are, for example, about 40 parts by weight to about 100 parts by weight of unsaturated polyester resin in low weight, such as polystyrene, polyethylene, polymethyl methacrylate or copolymers thereof. , Release agents such as zinc stearate and calcium stearate, about 5 parts by weight, curing agents such as 3-butylperoxybenzoate and 3-butylperoxy isopropyl carbonate, about 1 part by weight, magnesium oxide and magnesium hydroxide, about 2 parts by weight. Thickeners, and reinforcing agents such as glass fibers of about 150 parts by weight.

The present invention also provides a prepreg obtained by impregnating a substrate with such an antimicrobial unsaturated polyester resin composition.

In the present invention, any one selected from the group consisting of glass, glass paper, and glass fiber mat may be used as the base material, and a double glass fiber mat is preferable. The glass fiber mat is preferably any one selected from E-glass, S-glass, A-glass, and C-glass. Glass fiber mats are widely used as products for products that require strength at the same time as lightweight materials such as bathtubs, water tanks, septic tanks, ships (hull), and reinforcing fibers.

The present invention also relates to an antimicrobial unsaturated polyester glass mat sheet obtained by heating and molding one or more of the prepregs.

Method for producing an antimicrobial unsaturated polyester glass mat sheet of the present invention is shown in Figure 1, looking at this in detail (a) forming a tetravalent ammonium group in the carbon nanotube-polymer nanocomposite; (b) dispersing the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed in an unsaturated polyester resin; (c) adding a curing agent to the dispersed resin; (d) impregnating the mixed solution of step (c) into a substrate to prepare a prepreg; And (e) curing the prepreg to produce an antimicrobial unsaturated polyester glass mat sheet.

The technology of the carbon nanotube-polymer nanocomposite exhibiting improved antimicrobial properties than the antimicrobial properties of the multi-walled carbon nanotubes itself is disclosed in Korean Patent No. 10-2010-0085750 filed in 2010 (patent name: “dispersibility and antibacterial activity Attention is directed to a method for producing such a high carbon nanotube-polymer composite and a carbon nanotube-polymer composite having high dispersibility and antibacterial activity produced by the present invention.

The carbon nanotube-polymer nanocomposite according to the present invention may be prepared according to the applicant's patent, and the contents of the patent may be included in the present invention. The carbon nanotubes included in the nanocomposite of the present invention may be a multi-walled carbon nanotube (MWNT) consisting of two or more walls or a single walled carbon nanotube (SWNT) consisting of a single wall. Can be used.

In addition, the polymer included in the nanocomposite is poly (2- (dimethylamino ethyl) methacrylate) (poly (2- (dimethylamino ethyl) methacrylate, PDMAEMA)), poly (2-hydroxyethyl methacrylate) (poly (2-hydroxyethyl methacrylate), poly (trimethylammonium 2-hydroxypropylmethacrylate hydrochloride), poly (N, N-dimethylacrylamide) (poly (N, N-dimethlacrylamide) ), And poly (N-vinyl-2-pyrrolidone) (poly (N-vinyl-2-pyrrolidone)) is preferably at least one member selected from the group consisting of poly (2- (dimethylamino Most preferred is ethyl) methacrylate) (poly (2- (dimethylamino ethyl) methacrylate, PDMAEMA)).

The polymers exhibit antimicrobial properties, and their applicability is expanding because they are not only maintained for a long time but also environmentally friendly.

In the step (a), bromomethane (bromomethane), bromoethane (bromoethane), iodomethane (iodomethane), iodoethane (iodoethane), chloromethane (chloromethane), chloroethane (chloroethane), iodopropane ( It is characterized in that it is formed by treatment with at least one halogenated alkane compound selected from the group consisting of iodopropane, chloropropane, chloropropane, iodoisopropane, chloroisopropane and combinations thereof.

The carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group according to the present invention is formed has a feature of acting as an excellent antimicrobial agent in the unsaturated polyester glass mat sheet of the present invention.

In the step (b), the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed is preferably dispersed in an amount of 0.0001 to 1.0 wt% of the carbon nanotube-polymer nanocomposite with respect to the weight of the unsaturated polyester resin. If the content of the carbon nanotube-polymer nanocomposites dispersed in the unsaturated polyester resin is less than 0.0001% by weight, the antimicrobial effect and mechanical properties may be weakened due to the inclusion of the carbon nanotubes.

In the step (b) in the present invention, when the unsaturated polyester resin and the carbon nanotube-polymer nanocomposite are mixed, the carbon nanotube-polymer nanocomposite through ultrasonic treatment (Branson Model 450; 60 minutes, Cycle 30, Power 3) It is preferred that the is evenly dispersed in the unsaturated polyester resin.

In step (c), a curing agent is added to the dispersed resin. Specific examples of the curing agent include t-butyl perbenzoate (TBPB), di- (2,4-dichlorobenzoyl) -peroxide (di- (2,4-dichlorobenzoyl) -peroxide), dibenzyl Dibenzoyl peroxide, 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane ), Dicumyl peroxide, di- (2-t-butylperoxyisopropyl) benzene, t-butylcumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane (2,5-dimethyl-2,5-di (t-butylperoxy) -hexane), and di-t-butyl peroxide ( di-t-butylperoxide) is preferably at least one member selected from compounds.

The content of the curing agent is contained in 0.01 ~ 10.0% by weight based on the weight of the unsaturated polyester resin, if the content is less than 0.01% by weight of the curing effect is insufficient, when the content exceeds 10.0% by weight causes excessive curing reaction to workability problem It is not desirable to have. In addition, after the curing agent is added, it is preferable to remove bubbles in the unsaturated polyester resin for 1 hour by connecting to the tube of the aspirator.

In step (d), a prepreg is prepared by impregnating the mixed solution of step (c) on a substrate. The substrate is any one selected from the group consisting of glass, glass paper, and glass fiber mat, and is preferably a glass fiber mat. The glass fiber mat is selected from E-glass, S-glass, A-glass, and C-glass.

The prepreg is prepared by placing several sheets of glass mat of a predetermined size in a mold, and impregnating a composition mixture containing the carbon nanotube-polymer nanocomposite, an unsaturated polyester resin, and a curing agent thereon for 30 minutes. Can be.

Finally, (d) the prepreg can be put in a hot press to cure the unsaturated polyester resin to produce a final unsaturated polyester glass mat sheet. The curing reaction of the prepreg is preferably carried out for 20 to 60 minutes at a temperature of 100 ~ 140 ℃, pressure 30 ~ 70kg / cm ² .

The unsaturated polyester glass mat sheet of the present invention exhibits excellent antimicrobial activity against microorganisms such as Escherichia coli and Staphylococcus aureus because MWNT / PDMAEMA nanocomposites formed with tetravalent ammonium act as antibacterial agents.

In addition, the unsaturated polyester glass mat sheet of the present invention has an effect of improved mechanical properties (impact).

1 is a manufacturing process of an unsaturated polyester glass mat sheet according to an embodiment of the present invention,
2 to 5 show the results of E. coli antibacterial activity test on the surface of the unsaturated polyester glass mat sheet according to Comparative Example 1 and Example 1, FIG. 2 is 100 times dilution rate, FIG. 3 is 1,000 times dilution rate, and FIG. Multiple times 5,000 times, Figure 5 is the result at dilution times 10,000 times,
6 to 7 are the results of the antibacterial activity of Staphylococcus aureus on the surface of the unsaturated polyester glass mat sheet according to Comparative Example 1 and Example 1, Figure 6 is a dilution factor 1 million times, Figure 7 is a dilution factor 10 million times ego,
FIG. 8 is a micrograph (5x magnification) of the Petri-film surface of FIG. 3;
9 to 11 show results of measuring mechanical properties (area 10 cm * 10 cm) of Comparative Example 1 and unsaturated polyester glass mat sheets according to Examples 1 to 3, respectively.

The present invention as described above may be implemented as the following specific synthesis examples and embodiments, but various synthesis examples and embodiments according to the present invention can be modified in various other forms. On the other hand, since the embodiments of the present invention are provided only for the purpose of more fully illustrating the present invention to those skilled in the art, the scope of the present invention is limited to the embodiments described below. It should be understood that it should not be interpreted as being.

Example 1 Preparation of Unsaturated Polyester Glass Mat Sheet Comprising MWNT / PDMAEMA Nanocomposites with Tetraammonium Formed

(1) 1 g of MWNT / PDMAEMA nanocomposite and 10 ml of bromoethane were mixed in 20 ml of acetonitrile as a solvent, followed by stirring at 40 ° C. for 12 hours.

(2) MWNT / PDMAEMA nanocomposite was formed by adding 0.05 g of the tetravalent ammonium-containing MWNT / PDMAEMA nanocomposite to 50 g of unsaturated polyester resin, setting sonifier (Branson Model 450) to Power 3, Cycle 30, and sonicating for 60 minutes. It was dispersed in unsaturated polyester resin.

(3) 0.5 g of a hardener t-butyl perbenzoate (TBPB) was added to an unsaturated polyester resin in which MWNT / PDMAEMA nanocomposites were dispersed, stirred for 5 minutes, and then connected to an aspirator tube for 1 hour to an unsaturated polyester resin. Removed bubbles were removed.

(4) Place 9 sheets (12.5g) of 10cm * 10cm glass mat in a mold, and put a mixed solution containing MWNT / PDMAEMA nanocomposite, unsaturated polyester resin and curing agent on it, and impregnate for 30 minutes to prepreg prepreg).

(5) The mold containing the prepreg was put into a hot press and the temperature was 120 ° C. for 40 minutes, and the pressure was 50 kg / cm 2. After carrying out a curing reaction to prepare an unsaturated polyester glass mat sheet (UPGMS), it was cooled at 0 ° C.

<Example 2>

Except for using 5 ml of iodomethane as a compound for forming tetravalent ammonium in step (1) of <Example 1> and using 25 ml of nitromethane as a solvent, Unsaturated Polyester Glass Mat Sheet (UPGMS) containing MWNT / PDMAEMA nanocomposites in which tetravalent ammonium was formed by performing the same process from Step (2) to Step (5) of <Example 1>. Was prepared.

<Example 3>

Except for using 0.1 g of the MWNT / PDMAEMA nanocomposite used as the antimicrobial agent in step (2) of Example 1, steps (1) and (3) to (5) of <Example 1> By performing the same process to the UPGMS was prepared including the MWNT / PDMAEMA nanocomposites formed with tetravalent ammonium.

Example 4

Except for using 0.01 g of the MWNT / PDMAEMA nanocomposite used as the antimicrobial agent in step (2) of Example 1, from step (1) and step (3) to step (5) of <Example 1> The same procedure was followed to prepare UPGMS comprising MWNT / PDMAEMA nanocomposites with tetravalent ammonium.

Example 5

Step (1), Step (2) and Step (4) of Example 1, except that 0.45 g of dibenzoyl peroxide is used as a curing agent in Step (3) of Example 1. ) And UPGMS comprising MWNT / PDMAEMA nanocomposites in which tetravalent ammonium was formed by following the same procedure as in (5).

Example 6

Except for using 0.55 g of di- (2-t-butylperoxyisopropyl) benzene (di- (2-t-butylperoxyisopropyl) benzene) as a curing agent in step (3) of <Example 1>, The UPGMS containing the MWNT / PDMAEMA nanocomposites in which tetravalent ammonium was formed by performing the same procedure as in Step (1), (2), (4) and (5) of Example 1 was prepared.

Comparative Example 1

An unsaturated polyester resin glass mat resin containing no MWNT / PDMAEMA nanocomposites with tetravalent ammonium was prepared and used as a control for comparison with the examples of the present invention.

Experimental Example 1 Antimicrobial Activity Test against Escherichia Coli on UPGMS Surface

The antimicrobial activity test for Escherichia coli and Staphylococcus aureus on the surface of UPGMS prepared according to Example 1 was carried out as follows according to the film contact method (Japanese Industrial Standard; JIS Z 2801: 2000) It is shown in Figures 2-5.

(1) Escherichia coli ( E. coli ) was cultured in a liquid medium containing bacto yeast 0.5g, bacto trypton 1g, NaCl 0.5g, distilled water 20ml, etc. Prepare.

(2) The surface of the Unsaturated Polyester Glass Mat Sheet (UPGMS) was washed and dried with ethanol to sterilize the surface, and then inoculated thereon with 400 μL of the liquid medium containing E. coli prepared in Step (1). Cover the PE-film of 4cm * 4cm size on it, and incubate for 24 hours at 37 ℃.

(3) Sterilized PE-pack containing a microbial cultured unsaturated polyester glass mat sheet (UPGMS) containing a liquid culture solution containing 1 g of bacto yeast, 2 g of bacto trypton, 1 g of NaCl, and 40 ml of distilled water. E. coli in the PE-film is dissolved in the liquid culture solution, and then the PE-pack is incubated at 37 ° C for 24 hours.

(4) Take about 1ml of E. coli in the cultured PE-pack, dilute it with an appropriate drainage using sterile distilled water, inoculate 1 ml of petri-film (3M), and incubate at 37 ° C for 24 hours. As the number of E. coli strains increases, the color is dark red.

Figure 2 is a result of E. coli antimicrobial activity test 100 times dilution photo, Figure 3 is a result of E. coli antibacterial activity test dilution fold 1,000 times, Figure 4 is a result of E. coli antibacterial activity test dilution fold 5,000 times and Figure 5 is E. coli antibacterial As a result of the activity test, it is a photograph of 10,000-fold dilution. Each result is summarized in Table 1 below.

 <Antibacterial Activity Test on Escherichia Coli of Unsaturated Polyester Glass Mat Sheet> Comparative example
(Coliform bacillus,
 Unit: pcs) Example 1
(Coliform bacillus,
Unit: pcs) Dilution rate 100 times Not measurable 3 Dilution rate 1000 times 1600 2 5000 times dilution 800 0 Dilution rate 10000 times 73 0

As can be seen from the results of Figs. 2 to 5, in the case of unsaturated polyester glass mat sheet (UPGMS) in which MWNT / PDMAEMA nanocomposite in which tetravalent ammonium is formed as an antimicrobial agent acts as an antimicrobial agent, even if the dilution factor is different, It can be seen that little is observed.

However, in the glass mat sheet of the comparative example which does not include the MWNT / PDMAEMA nanocomposite in which tetravalent ammonium was formed according to the present invention, it was found that E. coli increased in a large amount, and the surface color was also observed to have a deep reddish purple color. As a result, it was confirmed that the unsaturated polyester glass mat sheet including the MWNT / PDMAEMA nanocomposite in which the quaternary ammonium group was used in the present invention had excellent antibacterial activity against E. coli.

Experimental Example 2 Antimicrobial Activity Test against Staphylococcus Aureus on the Surface of UPGMS

Antimicrobial experiments against Staphylococcus aureus ( S. aureus ) except adding 0.34 g of bacto tryptone, 0.06 g of bacto soytone, 0.1 g of NaCl, 0.05 g of K ₂ HPO ₄ , and 20 ml of distilled water. In the same manner as in Experimental Procedures (1) to (4) for Escherichia coli of Experimental Example <1> on the surface of UPGMS prepared according to Example 1 above.

The result is shown to the following FIGS. 6-7, and each result was put together in Table 2. FIG. 6 is a photograph of 1 million times dilution as a result of Staphylococcus aureus antibacterial activity test, and FIG. 7 is a photograph of 10 million times of dilution as a result of Staphylococcus aureus antibacterial activity test.

<Antibacterial Activity Test on Staphylococcus Aureus of Unsaturated Polyester Glass Mat Sheet> Comparative Example (Yellow Grape Staphylococcus, Unit: Dogs) Example 1 (yellow staphylococcus aureus, unit: dog) Dilution factor 1 million times 121 14 Dilution factor 10 million times 11 0

As shown in the results of FIGS. 6 to 7 and Table 2, yellow for the unsaturated polyester glass mat sheet (UPGMS) in which the tetravalent ammonium-formed MWNT / PDMAEMA nanocomposite prepared as Example 1 of the present invention acted as an antimicrobial agent. It can be seen that staphylococci are very small or rarely observed. However, in the glass mat sheet of the comparative example which does not contain the MWNT / PDMAEMA nanocomposite in which tetravalent ammonium was formed by this invention, a large amount of Staphylococcus aureus was observed.

Therefore, the tetravalent ammonium-formed MWNT / PDMAEMA nanocomposite used in the present invention properly performs the role of an antimicrobial agent, whereby an unsaturated polyester glass mat sheet prepared using the MWNT / PDMAEMA nanocomposite formed with the tetravalent ammonium (UPGMS ) Showed excellent antibacterial activity against Staphylococcus aureus.

Experimental Example 3 Measurement of Surface Micrograph

The Petri dish surface subjected to the E. coli activity experiment (diluted, 1,000 times) of FIG. 3 was observed under a microscope (5 times magnification), and the results are shown in FIG. 8.

As shown in FIG. 8, the unsaturated polyester glass mat sheet (UPGMS) in which the tetravalent ammonium-containing MWNT / PDMAEMA nanocomposite of the present invention acted as an antimicrobial agent exhibited very clean surface properties in addition to one or two coliforms observed. Was observed.

However, in the glass mat sheet of the comparative example which does not contain the MWNT / PDMAEMA nanocomposite in which tetravalent ammonium was formed, it was observed that countless Escherichia coli is scattered on the surface.

Experimental Example 4 Measurement of Mechanical Properties

Mechanical properties (impact) measurement of the UPGMS in the present invention was prepared by performing the same procedure as in <Example 1> to <Example 3>, except that four glass mats are used to prepare UPGMS, measurement experiment Was carried out according to the following procedure. The results are shown in the following Figures 9-11, Table 3.

(1) Put the manufactured UPGMS on the floor and drop the weight of 500g vertically from 1.5m height on the seat.

(2) In order to photograph the surface of the UPGMS surface damaged in the above step (1), the camera is fixed between the seat and the camera lens by 30 cm intervals and then photographed.

(3) The broken UPGMS fragments are defined as fragments in which the fracture line is surrounded by three or more planes, and the number of fragments appeared within a certain area of 10 cm * 10 cm.The lower the impact strength of UPGMS, the more the number of fragments. Increases.

<Measurement of Mechanical Properties (impact) of Unsaturated Polyester Glass Mat Sheet> Comparative Example Fragments Example Fragment Count (Number of fragments, unit:) (Number of fragments, unit:) 255 For Example 1-95 93 For Example 2-66 135 For Example 3-108

9-11, unsaturated polyester glass mat sheets (UPGMS) comprising MWNT / PDMAEMA nanocomposites formed with tetravalent ammonium prepared in Examples 1 to 3 of the present invention were formed of fragments exhibited within a certain area. The number was found to be significantly lower than that of the glass mat sheet of the comparative example which does not contain the MWNT / PDMAEMA nanocomposite antimicrobial with tetravalent ammonium. That is, it can be confirmed that the impact strength of the manufactured UPGMS is excellent.

This is because the MWNT / PDMAEMA nanocomposite with tetravalent ammonium used in the present invention not only acts as an antimicrobial agent, but also acts as a reinforcing agent, which is unsaturated using a MWNT / PDMAEMA nanocomposite with tetravalent ammonium. Mechanical properties of <Example 1> to <Example 3> using a polyester glass mat sheet were compared with those of <Comparative Example> using an unsaturated polyester glass mat sheet containing no MWNT / PDMAEMA nanocomposite with tetravalent ammonium. It can be seen that improved than the physical properties.

Claims (13)

A carbon nanotube-polymer nanocomposite formed with a tetravalent ammonium group, an unsaturated polyester resin, and a curing agent,
An antimicrobial unsaturated polyester resin composition comprising 0.0001 to 1.0 wt% of the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed, and 0.01 to 10.0 wt% of the curing agent, based on the weight of the unsaturated polyester resin.
The method of claim 1,
The polymer of the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed is poly (2- (dimethylamino ethyl) methacrylate) (poly (2- (dimethylamino ethyl) methacrylate, PDMAEMA)), poly (2-hydroxy) Poly (2-hydroxyethyl methacrylate), poly (trimethylammonium 2-hydroxypropylmethacrylate hydrochloride), poly (N, N-dimethylacrylamide) (poly (N, N-dimethlacrylamide)) and poly (N-vinyl-2-pyrrolidone) (poly (N-vinyl-2-pyrrolidone)).
delete The method of claim 1,
The carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed is selected from the group consisting of carbon nanotube-polymer nanocomposites such as bromomethane, bromoethane, iodomethane, and iodoethane. 1 selected from the group consisting of chloromethane, chloroethane, iodopropane, chloropropane, chloropropane, iodoisopropane, chloroisopropane and combinations thereof An antimicrobial unsaturated polyester resin composition formed by treatment with at least one halogenated alkane compound.
delete The method of claim 1,
The hardener is t-butyl perbenzoate (TBPB), di- (2,4-dichlorobenzoyl) -peroxide (di- (2,4-dichlorobenzoyl) -peroxide), dibenzyl peroxide ( dibenzoyl peroxide), 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane) Wheat peroxide, di- (2-t-butylperoxyisopropyl) benzene, t-butylcumylperoxide, 2,5 -Dimethyl-2,5-di (t-butylperoxy) -hexane (2,5-dimethyl-2,5-di (t-butylperoxy) -hexane), and di-t-butyl peroxide (di-t -butylperoxide) is an antimicrobial unsaturated polyester resin composition selected from at least one compound selected from.
The prepreg obtained by impregnating a base material with the antimicrobial unsaturated polyester resin composition of Claim 1.
The method of claim 7, wherein
The substrate is any one selected from the group consisting of glass, glass paper and glass fiber mat.
The method of claim 8,
The glass fiber mat is a prepreg, characterized in that any one selected from E-glass, S-glass, A-glass and C-glass.
The antimicrobial unsaturated polyester glass mat sheet obtained by heat-press-molding one or more sheets of the prepreg of Claim 7.
A sheet molding compound composition wherein the antimicrobial unsaturated polyester resin composition of claim 1 is reinforced with a cut or continuous glass fiber strand mat.
(a) forming a tetravalent ammonium group in the carbon nanotube-polymer nanocomposite;
(b) dispersing the carbon nanotube-polymer nanocomposite in which the tetravalent ammonium group is formed in an unsaturated polyester resin;
(c) adding a curing agent to the dispersed resin;
(d) impregnating the mixed solution of step (c) into a substrate to prepare a prepreg; And
(e) a method for producing an antimicrobial unsaturated polyester glass mat sheet comprising curing the prepreg.
The method of claim 12,
In the step (a), bromomethane (bromomethane), bromoethane (bromoethane), iodomethane (iodomethane), iodoethane (chloromethane), chloroethane in the carbon nanotube-polymer nanocomposite treated with one or more halogenated alkane compounds selected from the group consisting of (chloroethane), iodopropane, chloropropane, iodoisopropane, chloroisopropane and combinations thereof. A method for producing an antimicrobial unsaturated polyester glass mat sheet, characterized by forming an ammonium group.

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