KR102400671B1 - Antifugal polymer composition comprising a polymer compound in which the cationic monomer is graft-polymerized in a fluorine-based copolymer - Google Patents

Abstract

Disclosed is an antibacterial polymer composition comprising a polymer compound obtained by graft polymerization of a cationic monomer including a vinyl group and a quaternary ammonium group to polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE).

Description

Antibacterial polymer composition comprising a polymer compound in which the cationic monomer is graft-polymerized in a fluorine-based copolymer

It relates to an antimicrobial polymer composition comprising a polymer compound obtained by graft polymerization of a cationic monomer to a fluorine-based copolymer.

As sanitary life is actively required in daily life, antibacterial agents are being used in various fields. Many products with antibacterial function have been developed, so it is necessary to prevent bacterial contamination in industries and environments such as storage containers for food, beverages, cosmetics, toothbrushes, stationery, home appliances, bedding, and building materials. It is applied in various fields. If the interior materials of public telephones, public toilets, subways, buses, etc. that are used by multiple people from all daily necessities related to human food, clothing, and shelter are made of easy-to-process high-molecular antibacterial materials, the living environment can become more sanitary and safer. There is a need for an antibacterial polymer material for a coating material having excellent processability.

Generally known antibacterial polymer materials maintain an antifouling function and present a level of performance that inhibits the growth of bacteria.

On the other hand, quaternary ammonium salts, pyridine compounds, organic halogen compounds, thiazoline compounds, phenols, etc. are known as organic antibacterial agents which generally exhibit antibacterial properties. Compounds exhibiting cationic properties in combination with these functional groups may exhibit antibacterial properties. As a conventional document on an antibacterial agent exhibiting such antibacterial properties, there is Korean Patent Registration No. 10-0379774.

An object of one aspect of the present invention is to provide an antibacterial polymer composition having excellent antibacterial properties, in particular, functionality capable of killing bacteria.

In addition, an object of another aspect of the present invention is to provide a polymer composition for an antibacterial coating material having hydrophilicity, stability in an aquatic environment, excellent antibacterial performance, and excellent physical properties.

In order to achieve the above object, in one aspect of the present invention

There is provided an antimicrobial polymer composition comprising a polymer compound obtained by graft polymerization of a cationic monomer including a vinyl group and a quaternary ammonium group to polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE).

In addition, in another aspect of the present invention

To prepare a polymerization solution containing polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE), a cationic monomer containing a vinyl group and a quaternary ammonium group, a metal catalyst, a ligand and a non-polar organic solvent step; and

There is provided a method for producing an antimicrobial polymer composition comprising; preparing a polymer compound in which a cationic monomer is graft polymerized by polymerization using the polymerization solution.

Furthermore, in another aspect of the present invention

Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) is provided with a coating material comprising a polymer compound in which a cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized.

Furthermore, in another aspect of the present invention

There is provided a filter comprising a polymer compound obtained by graft polymerization of a cationic monomer including a vinyl group and a quaternary ammonium group to polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE).

The antibacterial polymer composition provided in one aspect of the present invention can effectively exhibit antibacterial performance because the side chain exposed to the outside has a positive charge, and particularly has excellent properties of killing bacteria, and exhibits hydrophilicity because it has a fluorine polymer main chain, but It is stable in the environment, and it is easy to mix with other fluorine-based polymers in solution, so it has excellent processability. Moreover, the coating material or coating film formed through the antibacterial polymer composition contains vinylidene fluoride and thus has excellent physical properties, and by including a chloride group through chlorotrifluoroethylene, processability is also excellent.

1 is a graph analyzing the polymer compounds prepared in Examples 1 and 2 by nuclear magnetic resonance spectroscopy (NMR);
FIG. 2 is a graph analyzing the polymer compound prepared in Example 3 by nuclear magnetic resonance spectroscopy (NMR);
3 is a graph of the polymer compounds prepared in Examples 1 to 3 analyzed by thermogravimetric analysis (TGA);
4 is a graph showing the antimicrobial activity test results of the polymer compounds prepared in Examples 1 and 3;
Figure 5 shows a photograph taken of the free-standing film prepared in Examples 4 to 7;
6 shows the stress-strain curve graphs of the free-standing films prepared in Examples 4 to 7;
7 is a graph showing the maximum stress value and the maximum strain value by observing the stress-strain curves of the free-standing films prepared in Examples 4 to 7;
8 is a graph showing the results of X-ray rotation analysis of the free-standing films prepared in Examples 4 to 7;
9 is a graph showing the antimicrobial activity test results of the free-standing films prepared in Examples 4 to 7;
10 is a graph showing the biocompatibility evaluation results of the free-standing films prepared in Examples 4 to 7;

In one aspect of the invention

There is provided an antimicrobial polymer composition comprising a polymer compound obtained by graft polymerization of a cationic monomer including a vinyl group and a quaternary ammonium group to polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE).

Hereinafter, the antimicrobial polymer composition provided in one aspect of the present invention will be described in detail.

The antibacterial polymer composition provided in one aspect of the present invention contains a graft polymer compound using a monomer having a positive charge in a polyvinylidene fluoride-based copolymer, so that the side chain exposed to the outside has a positive charge. Because it has a fluorine polymer main chain, it exhibits hydrophilicity, but is stable in an aquatic environment, and has the property of mixing well with other fluorine polymers in solution.

The antimicrobial polymer composition includes a polymer compound obtained by graft polymerization of a cationic monomer including a vinyl group and a quaternary ammonium group to PVDF-co-CTFE, and the PVDF-co-CTFE may be represented by the following formula (1) .

<Formula 1>

(In Formula 1 above

x is 73 to 98;

y is 2 to 27.)

The content of chlorotrifluoroethylene (CTFE) in the polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) is preferably 4 wt% to 40 wt%, and 9 wt% to 31 wt% It is more preferably % by weight, and most preferably 13% to 20) % by weight. If the content of CTFE in the PVDF-co-CTFE is less than 4% by weight, the graft rate of the cationic polymer is low and the antibacterial property is lowered, and there is a problem in that the processability of the coating material is deteriorated due to the low chloride group, and it exceeds 40% by weight. In this case, there is a problem in that the physical properties of the material formed of the polymer composition are insufficient.

The cationic monomer is a monomer including a graft-polymerizable vinyl group and a quaternary ammonium group, and the quaternary ammonium group may be a quaternary alkylammonium group, a pyridinium group, an imidazolium group, or the like.

The cationic monomer may be a monomer prepared by quaternary ammonation of at least one of 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl methacrylate, 2-vinylpyridine and 4-vinylpyridine. Preferably, 2-dimethylaminoethyl methacrylate monomer is 2-methacryloyloxy ethyl trimethylammonium chloride prepared by the quaternary ammoniumization reaction (2-methacryloyloxy ethyl trimethylammonium chloride) or 2-methacryloyl oxide ethyl trimethylammonium iodide (2-methacryloyloxy ethyl trimethylammonium iodide).

For example, the cationic monomer may be a compound of Formula 2 or Formula 3 below.

<Formula 2>

(In Formula 2,

R ₁ to R ₃ are each independently an alkyl group having 1 to 4 carbon atoms,

X is Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ -, (CF ₃ SO ₂ ) ₂ N ^- ,(CF ₃ SO ₂ ) ₃ C ^- ,AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- or (CF ₃ SO ₂ )(CF ₃ CO)N ^- ,

n is 1 to 3.)

<Formula 3>

(In Formula 3,

R ₄ is an alkyl group having 1 to 4 carbon atoms,

X is Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ -, (CF ₃ SO ₂ ) ₂ N ^- ,(CF ₃ SO ₂ ) ₃ C ^- ,AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- or (CF ₃ SO ₂ )(CF ₃ CO)N ^- )

As a specific example, the polymer compound may be a compound represented by the following formula (4).

<Formula 4>

(In Formula 4,

R is a cationic monomer comprising a vinyl group and a quaternary ammonium group is graft polymerization,

x is 73 to 98;

y is 2 to 10,

z is 17 to 25.)

As a specific example, R may be represented by the following formula (5).

<Formula 5>

(In Formula 3 above

R ₁ to R ₃ are each independently an alkyl group having 1 to 4 carbon atoms,

Wherein n is 2 to 1000,

wherein m is 1 to 3.)

In addition, the graft rate of the polymer compound is the content of the cationic monomer graft-polymerized in the polymer compound, preferably 10 wt% to 70 wt%, more preferably 20 wt% to 65 wt%, 25 wt% % to 60% by weight is most preferred. By grafting the cationic monomer at a graft rate in the above range, excellent antibacterial properties may be exhibited, and in particular, it may exhibit a killing property against bacteria.

Furthermore, the content of the graft-polymerized cationic monomer in the polymer compound is preferably 35 wt% to 55 wt%, and more preferably 37 wt% to 50 wt%.

In addition, in another aspect of the present invention

To prepare a polymerization solution containing polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE), a cationic monomer containing a vinyl group and a quaternary ammonium group, a metal catalyst, a ligand and a non-polar organic solvent step; and

There is provided a method for producing an antimicrobial polymer composition comprising; preparing a polymer compound in which a cationic monomer is graft polymerized by polymerization using the polymerization solution.

Hereinafter, each step will be described in detail with respect to the manufacturing method of the antimicrobial polymer composition provided in another aspect of the present invention.

First, the method for preparing the antimicrobial polymer composition provided in another aspect of the present invention is a cationic monomer comprising polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE), a vinyl group and a quaternary ammonium group , preparing a polymerization solution comprising a metal catalyst, a ligand, and a non-polar organic solvent.

In the above step, a polymerization solution containing PVDF-co-CTFE used as a macroinitiator, a cationic monomer for imparting functionality, a metal catalyst, a ligand, and a non-polar organic solvent capable of dissolving the same is prepared.

Since the PVDF-co-CTFE and the cationic monomer are the same as those described in the antimicrobial polymer composition, a detailed description thereof will be omitted below. However, the cationic monomer can be directly prepared and used, for example, a non-polar organic solvent (dimethyl sulfoxide, N-methyl 2-pyrroly) that has polarity and is well mixed with the monomer and can dissolve PVDF-co-CTFE Don, dimethylformamide, etc.) 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl methacrylate, a monomer having a vinyl group that can be modified through the Menschkin reaction because there is nitrogen with a lone pair in 30 ml. Late, 2-vinylpyridine, 4-vinylpyridine, etc. are mixed through stirring, and this is mixed with one halogen substituted halide (methane iodide, ethane bromide, 1-chlorinated hexane, etc.) in a hydrocarbon under a nitrogen atmosphere as a monomer. By adding a molar equivalent, a positively charged monomer can be prepared and used.

It is preferable to use a monovalent copper metal catalyst as the metal catalyst, and monovalent copper chloride or monovalent copper bromide may be used, and monovalent copper chloride is preferably used.

In addition, as the ligand, 2,2-bipyridine, pentamethyldiethylenetriamine, 4,4-dimethyldipyridyl, etc., which can form a mixture with monovalent copper ions, can be used, and pentamethyldiethylenetriamine is used. It is preferable to do

Furthermore, it is preferable to use dimethyl sulfoxide, N-methyl 2-pyrrolidone and dimethylformamide as the non-polar organic solvent.

In addition, the content of PVDF-co-CTFE in the polymerization solution is preferably 2 wt% to 5 wt%, and the content of the cationic monomer is preferably 8 wt% to 15 wt%.

Next, the method for preparing the antimicrobial polymer composition provided in another aspect of the present invention includes the step of preparing a polymer compound in which a cationic monomer is graft-polymerized by polymerization using the polymerization solution.

In the above step, the polymerization reaction is performed using the polymerization solution prepared in the previous step.

As a specific example, the polymerization reaction is carried out under an inert atmosphere in a temperature range of 60 °C to 120 °C, a temperature range of 70 °C to 110 °C, a stirring speed of 300 rpm to 600 rpm in a temperature range of 80 °C to 100 °C, 350 rpm to It can be carried out at a stirring speed of 500 rpm.

Furthermore, in another aspect of the present invention

Cationic monomer comprising at least one selected from the group consisting of a vinyl group and a tertiary alkylamino group, a pyridine group and an imidazole group in polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) Provided is a coating material comprising a polymer compound that is graft polymerized.

The coating material including the polymer compound provided in the present invention exhibits excellent antibacterial properties only by the polymer compound itself, and thus can be applied as an antibacterial coating material requiring high performance and stability.

The coating material is polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) with a cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized with a polymer compound and a fluorine-based polymer. It may be in the form of a blend. As the fluorine-based polymer, polyvinylidene fluoride (PVDF) or a polyvinylidene fluoride-based copolymer (PVDF-CTFE, PVDF-HFP, PVDF-TrFE, etc.) may be used. By blending the polymer compound and the fluorine-based polymer, it can be applied as a fluorine-based polymer blend having antibacterial properties.

In addition, a coating solution prepared by dissolving the polymer compound and the fluorine-based polymer using a solvent may be used. The polymer compound may be applied as an additive, and the content of the polymer compound applied as the additive may be 1 wt% to 20 wt%, 3 wt% to 10 wt%, and the content of the fluorine-based polymer is 80 wt% % to 99% by weight, and may be from 90% to 97% by weight. When the content of the polymer compound is less than 1% by weight, there is a problem in that antibacterial performance is difficult to be expressed normally, and when it exceeds 20% by weight, there is a problem in that the surface stability is deteriorated.

The solvent may be used without limitation as long as it is a solvent capable of dissolving both the polymer compound and the fluorine-based polymer. For example, dimethyl sulfoxide, N-methyl 2-pyrrolidone, dimethylformamide, dimethylacetamide, triethyl phosphate etc. can be used. The concentration of the coating solution may be greater than 0% by weight and less than or equal to 18% by weight of the polymer in the solution.

In addition, in another aspect of the present invention

Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) a free-standing film comprising a polymer compound in which a cationic monomer containing a vinyl group and a quaternary ammonium group is graft-polymerized, or

write; And polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) coated on the substrate and a cationic monomer containing a vinyl group and a quaternary ammonium group is graft polymerized antibacterial comprising a polymer compound A film is provided.

The coating material or the coating material of the blend type may be coated on a substrate to be applied in the form of a film. The substrate can be used without particular limitation as long as it is a material capable of coating the hydrophobic film, but it is preferable to use paper, fiber, filter, pattern surface, glass, metal, fiber, plastic, ceramic, etc., and metal, glass, plastic surface It is preferable to use, etc. In addition, the coating can be used without any particular limitation as long as it is a method capable of coating the hydrophobic film on the substrate according to the present invention, but spin coating, dip coating, roll coating, solution coating, spray coating, etc. are preferable.

In addition, the coated substrate may be used as an antibacterial coating by itself, and the film may be removed from the substrate to be used as a free-standing film.

Furthermore, polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) containing at least one selected from the group consisting of a vinyl group and a tertiary alkylamino group, a pyridine group and an imidazole group. The polymer compound obtained by graft polymerization of the polymeric monomer can be applied in various fields such as filters and medical devices, and since it is based on polyvinylidene fluoride, it can be applied as a separator additive or a resin additive.

Hereinafter, the present invention will be described in detail through Examples and Experimental Examples.

However, the following examples and experimental examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples and experimental examples.

<Example 1> Preparation of antimicrobial polymer composition-1

Step 1: Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) 1.5 g, 2-methacryloyloxy ethyl trimethylammonium iodide 9.4 g, monovalent copper chloride 0.4 g, penta A polymerization solution was prepared by mixing 0.84 ml of methyldiethylenetriamine with 60 ml of dimethyl sulfoxide.

Step 2: The polymerization solution prepared in step 1 was subjected to a polymerization reaction under a nitrogen atmosphere at a temperature of 90° C. and a stirring speed of 350 to 500 rpm to prepare a polymer compound.

<Example 2> Preparation of antimicrobial polymer composition-2

Step 1: Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) 1.5 g, 2-methacryloyloxy ethyl trimethylammonium iodide 9.4 g, monovalent copper chloride 0.12 g, penta A polymerization solution was prepared by mixing 0.24 ml of methyldiethylenetriamine with 60 ml of dimethyl sulfoxide.

Step 2: The polymerization solution prepared in step 1 was subjected to a polymerization reaction under a nitrogen atmosphere at a temperature of 90° C. and a stirring speed of 350 to 500 rpm to prepare a polymer compound.

<Example 3> Preparation of antimicrobial polymer composition-3

Step 1: Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) 1.5 g, 1-methyl-4-vinylpyridinium iodide 9.4 g, monovalent copper chloride 0.11 g, pentamethyl A polymerization solution was prepared by mixing 0.24 ml of diethylenetriamine with 60 ml of dimethyl sulfoxide.

Step 2: The polymerization solution prepared in step 1 was subjected to a polymerization reaction under a nitrogen atmosphere at a temperature of 90° C. and a stirring speed of 350 to 500 rpm to prepare a polymer compound.

<Example 4> Preparation of free-standing film-1

Using the polymer compound prepared in Example 1 as an additive, and using polyvinylidene fluoride (PVDF) as a polymer resin to form a fluorine-based polymer blend, the OHP film is coated with a solution and then peeled off to prepare a free standing film The content of the additive and the polymer resin and the concentration of the solution are shown in Table 1 below, and the sample name is shown as Blend-QDMA-1.

<Example 5> Preparation of free-standing film-2

Using the polymer compound prepared in Example 1 as an additive, and using polyvinylidene fluoride (PVDF) as a polymer resin to form a fluorine-based polymer blend, the OHP film is coated with a solution and then peeled off to prepare a free standing film The content of the additive and the polymer resin and the concentration of the solution are shown in Table 1 below, and the sample name is shown as Blend-QDMA-5.

<Example 6> Preparation of free-standing film-3

Using the polymer compound prepared in Example 3 as an additive, and using polyvinylidene fluoride (PVDF) as a polymer resin to form a fluorine-based polymer blend, after coating the solution on the OHP film and peeling it off to prepare a free standing film The content of the additive and the polymer resin and the concentration of the solution are shown in Table 1 below, and the sample name is shown as Blend-Q4VP-1.

<Example 7> Preparation of free-standing film-4

Using the polymer compound prepared in Example 1 as an additive, and using polyvinylidene fluoride (PVDF) as a polymer resin to form a fluorine-based polymer blend, the OHP film is coated with a solution and then peeled off to prepare a free standing film The content of the additive and the polymer resin and the concentration of the solution are shown in Table 1 below, and the sample name is shown as Blend-Q4VP-5.

sample name Additive type Polymer resin:
additive solution concentration Example 4 Blend-QDMA-1 Example 1 99 : 1 (wt%) 10% by weight Example 5 Blend-QDMA-5 Example 1 99 : 5 (wt%) 10% by weight Example 6 Blend-Q4VP-1 Example 3 99 : 1 (wt%) 10% by weight Example 7 Blend-Q4VP-5 Example 3 99 : 5 (wt%) 10% by weight

<Experimental Example 1> Analysis of polymer compounds

In order to confirm the structure of the polymer compound prepared in Examples 1 to 3, nuclear magnetic resonance spectroscopy (NMR) and thermogravimetric analysis (TGA) were performed, and the results are shown in FIGS. 1 to 3 .

1 and 2, as a result of confirming the polymer compounds prepared in Examples 1 to 3, detailed peaks from the cationic monomer graft polymerized to the PVDF-co-CTFE fluorine-based copolymer were confirmed.

As shown in FIG. 3, as a result of the thermogravimetric analysis experiment of Examples 1 to 3, in the case of PVDF-g-CTFE used as the main chain, it was confirmed that decomposition occurred near 420 ° C. In the case of cationic monomers, it is confirmed that all of them are decomposed around 420°C. Through this, at 420 ° C., it is 61.5 wt% in Example 1, 53 wt% in Example 2, and 60 wt% in Example 3, the weight of PVDF-g-CTFE as the main chain in each polymer compound. It can be confirmed, and it can be confirmed that the content of the graft-polymerized cationic monomer is very high as 38.5 wt% in Example 1, 47 wt% in Example 2, and 40 wt% in Example 3.

<Experimental Example 2> Antimicrobial analysis

A polymer solution was prepared by dissolving 2 wt% of the polymer compound of Examples 1 and 3 in a dimethyl sulfoxide solvent. Then, the prepared solution was applied to a glass plate having a size of 5 cm × 5 cm (width × length) and spin-coated at 1000 rpm and 60 seconds. The glass plate coated with the polymer compound was stored overnight in an oven at 80° C., and the glass plate used as a control was wiped clean with a solvent and stored.

As test strains, Staphylcococcus aureus ATCC 6538, Escherichi coli ATCC 8739, and Candida albicans ATCC 10231 were used. In the case of Staphylococcus aureus and Escherichia coli, inoculate on a nutrient medium (Nutrient agar, NA) and in the case of Candida on potato glucose agar, pre-cultivate at 35℃ for 1-2 days, and then dilute in sterile physiological saline for 10 ⁵ /ml ~ 10 ⁷ /ml A bacterial solution was prepared.

After attaching the specimen cut to 5 cm × 5 cm (width × length) to the bottom of the Petri dish, 0.4 mL of each bacterial solution was inoculated. A sterile film cut to 4 cm × 4 cm (width × length) was covered thereon, and then cultured at 35° C. for 24 hours. In the test using the control group, a sterile film was also used for the film attached to the floor. After incubation, the film inoculated with Staphylococcus aureus and E. coli was GPLP medium, and for the film inoculated with Candida bacteria 10 mL of SDLPA medium was dispensed and homogenized, and the number of bacteria was measured.

The results of the antibacterial activity test are summarized in FIG. 4 . When the polymer compound of Examples 1 and 3 was coated on a glass substrate, no bacteria were detected. This means that the number of viable cells is 10/ml, which means that more than 99.99% of the bacteria are killed compared to the glass plate used as a control, suggesting that the synthesized polymer has excellent antibacterial properties.

The antibacterial polymer composition provided in one aspect of the present invention can effectively exhibit antibacterial performance because the side chain exposed to the outside has a positive charge, and particularly has excellent properties of killing bacteria, and exhibits hydrophilicity because it has a fluorine polymer main chain, but It is stable in the environment, and it is easy to mix with other fluorine-based polymers in solution, so it has excellent processability. Moreover, the coating material or coating film formed through the antibacterial polymer composition contains vinylidene fluoride and thus has excellent physical properties, and by including a chloride group through chlorotrifluoroethylene, processability is also excellent.

<Experimental Example 3> Analysis of shape and physical properties of free-standing film

In order to confirm the shape of the free-standing film prepared in Examples 4 to 7 and its physical properties, the prepared free-standing film was photographed and shown in FIG. 5 . In addition, the stress-strain curve was observed through a material tester to analyze the maximum stress value and the maximum strain value, and the results are shown in FIGS. 6 and 7 . Furthermore, X-ray diffraction analysis was performed and the results are shown in FIG. 8 .

As shown in Figure 5, it can be confirmed that a free-standing film is formed by a simple solution preparation method (in Figure 5, the first film on the left is Example 4, and Examples 5, 6 and 7 are located in order to the right), Since it is made of a polyvinylidene fluoride-based fluorine-based polymer, it has properties that can be practically applied.

In addition, as shown in FIGS. 6 and 7, the free-standing film according to the present invention containing additives compared to the polyvinylidene fluoride film used in the prior art exhibited an excellent maximum stress value, and even in the case of the maximum strain value. There was no significant difference or the value was higher than that. This means that the use of cationic additives has the property of improving the physical properties of the film.

Furthermore, as shown in FIG. 8, the film containing the additive did not show a significant difference in peak compared to the conventional polyvinylidene fluoride film. This means that the use of cationic additives does not adversely affect the microstructural properties of the film.

<Experimental Example 4> Evaluation of antibacterial properties of free-standing films

In order to confirm the antimicrobial properties of the free-standing films prepared in Examples 4 to 7, the results of the antibacterial activity test of the prepared free-standing films are shown in FIG. 9 .

As shown in FIG. 9 , it was found that the free-standing films prepared in Examples 4 to 7 showed excellent antibacterial properties compared to polyvinylidene, and when the additive was contained in 5% by weight than when it contained 1% by weight. It was observed that the antibacterial properties were significantly increased.

<Experimental Example 5> Evaluation of biocompatibility of free-standing films

In order to confirm the biocompatibility of the free-standing film prepared in Examples 4 to 7, the biocompatibility evaluation result of the prepared free-standing film is shown in FIG. 10 .

In the cell survival/death ratio and metabolic activity marker results using a confocal microscope, it was found that all of the free-standing films prepared in Examples 4 to 7 showed excellent biocompatibility of 99.5% or more compared to the control group. This suggests that this polymer has potential as a biomaterial.

The graft polymer using a monomer having a positive charge in the polyvinylidene fluoride-based copolymer presented in the technology of the present invention has great antibacterial properties in itself as a result of the test. Therefore, it has the potential to be used in fields requiring antibacterial power, such as antibacterial coatings, filters, and medical materials. In addition, since the main chain is based on polyvinylidene fluoride, this synthetic polymer is sufficiently applicable as a separator additive or a resin additive.

When the antimicrobial polymer composition provided in one aspect of the present invention is used as a resin additive, it has excellent properties of killing bacteria and fungi even when only 5 wt% is used, and exhibits hydrophilicity because it has a fluorine polymer main chain, but water and humidity It is stable in a high environment and has excellent processability because it is easy to mix with other fluorine-based polymers in solution. Moreover, the use of additives improves physical properties compared to the originally used fluorine-based polymer film, and also has excellent biocompatibility, so the possibility as a biomaterial cannot be ignored.

Claims (15)

A polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized into a polymer compound, wherein the polyvinylidene fluoride The content of chlorotrifluoroethylene in -co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20 wt% to 65 wt% %, the antimicrobial polymer composition.
According to claim 1,
The quaternary ammonium group is at least one antimicrobial polymer composition selected from the group consisting of a quaternary alkylammonium group, a pyridinium group and an imidazolium group.
According to claim 1,
The cationic monomer is an antimicrobial polymer composition in which a monomer comprising at least one selected from the group consisting of a vinyl group and a tertiary alkylamino group, a pyridine group and an imidazole group is a monomer prepared by a quaternary ammonation reaction.
According to claim 1,
The cationic monomer is at least one monomer selected from the group consisting of 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl methacrylate, 2-vinylpyridine and 4-vinylpyridine by a quaternary ammonation reaction. An antimicrobial polymer composition that is a prepared monomer.
delete delete To prepare a polymerization solution containing polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE), a cationic monomer containing a vinyl group and a quaternary ammonium group, a metal catalyst, a ligand and a non-polar organic solvent step; and
Including; a polymerization reaction using the polymerization solution to prepare a polymer compound in which a cationic monomer is graft-polymerized;
The content of chlorotrifluoroethylene in the polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20% by weight to 65% by weight of the method for producing an antimicrobial polymer composition.
8. The method of claim 7,
The metal catalyst is monovalent copper chloride or monovalent copper bromide method for producing an antimicrobial polymer composition.
8. The method of claim 7,
The ligand is 2,2-bipyridine, pentamethyldiethylenetriamine and 4,4-dimethyldipyridyl is one selected from the group consisting of a method for producing an antimicrobial polymer composition.
8. The method of claim 7,
The non-polar organic solvent is dimethyl sulfoxide, N-methyl 2-pyrrolidone and dimethylformamide at least one selected from the group consisting of a method for producing an antimicrobial polymer composition.
Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) and a cationic monomer containing a vinyl group and a quaternary ammonium group comprising a polymer compound graft polymerization, the polyvinylidene fluoride The content of chlorotrifluoroethylene in -co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20 wt% to 65 wt% % phosphorus, coating material.
12. The method of claim 11,
The coating material is polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) with a cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized with a polymer compound and a fluorine-based polymer. A coating material in the form of a blend.
A polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized into a polymer compound, wherein the polyvinylidene fluoride The content of chlorotrifluoroethylene in -co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20 wt% to 65 wt% % phosphorus, free-standing film.
write;
Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) coated on the substrate includes a polymer compound in which a cationic monomer including a vinyl group and a quaternary ammonium group is graft-polymerized,
The content of chlorotrifluoroethylene in the polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20% to 65% by weight of the antimicrobial film.
Polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) and a cationic monomer containing a vinyl group and a quaternary ammonium group comprising a polymer compound graft polymerization, the polyvinylidene fluoride The content of chlorotrifluoroethylene in -co-chlorotrifluoroethylene (PVDF-co-CTFE) is 4 wt% to 40 wt%, and the content of the cationic monomer in the polymer compound is 20 wt% to 65 wt% %, filter.

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