KR102196034B1 - Method of surface modification and antibacterial coating of polymer material and antibacterial coating oral medicla device using the same - Google Patents

Abstract

An embodiment of the present invention provides a method for modifying the surface of a polymer substrate, an antibacterial coating method for a polymer substrate using the same, and an antibacterial coated medical device for oral use, wherein the method for modifying the surface of a polymer substrate comprises the steps of: (a1) supporting a polymer substrate in an acid solution; (a2) supporting the polymer substrate in a base solution; and (b) treating the polymer substrate with hydrogen peroxide, wherein the steps (a1) and (a2) are each alternately performed one or more times before the step (b), and the order of the steps (a1) and (a2) may be mutually changed. The acid solution is at least one selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrogen bromide, chloric acid, perchloric acid, citric acid and formic acid, and the base solution is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, gallium hydroxide, and ammonia solution.

Description

Surface modification and antimicrobial coating method of polymeric substrates, and antimicrobial coating oral medical devices using the same TECHNICAL AND ANTIBACTERIAL COATING ORAL MEDICLA DEVICE USING THE SAME}

The present invention relates to a surface modification and antibacterial coating, and more particularly, to a surface modification and antibacterial coating of a polymeric substrate and an antibacterial coating using the same for oral medical devices.

Infection in the use of medical devices is a serious problem that can lead to side effects and failure of surgery and procedures. Bacteria adhering to the surface of medical devices secrete and proliferate extracellular multimeric substances to form a biofilm, and bacteria present in the biofilm have resistance to antibiotics 10 times less than those in suspended state, up to 1,000. It has a characteristic that it is more than twice as high and is difficult to remove. Therefore, research and development on antibacterial surface technology that can suppress the adhesion of bacteria and the formation of biofilms on the surface of medical devices is required to prevent infection. In the case of oral medical devices such as mouthpieces, orthodontic devices, and snoring prevention devices, biofilms are formed on the surface of the device and teeth during the wearing period, which causes oral diseases such as tooth decay and periodontal disease and bad breath. In the case of oral medical devices, since they are repeatedly used for a long period of time and physical stimulation is continuously applied to the surface, strong durability and continuous antibacterial ability are required to apply the antibacterial coating technology.

The present invention is to solve the problems of the prior art described above, an object of the present invention is to provide a simple and durable surface modification and antibacterial coating method and an antibacterial coated oral medical device applying the same.

One aspect of the present invention is the step of (a1) supporting a polymer substrate in an acid solution; (a2) supporting the polymer substrate in a base solution; And (b) treating the polymer substrate with hydrogen peroxide, wherein step (a1) and step (a2) are performed alternately at least once before step (b), respectively, and step (a1) and The order of step (a2) is interchangeable, and the acid solution is at least one selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrogen bromide, chloric acid, perchloric acid, citric acid and formic acid, and the base solution is hydroxide It provides a method for modifying a surface of a polymer substrate, which is at least one selected from the group consisting of sodium, potassium hydroxide, calcium hydroxide, gallium hydroxide, and aqueous ammonia.

In one embodiment, the polymeric substrate may be at least one selected from the group consisting of polyethylene, polycarbonate, polyethylene terephthalate, glycol-modified polyethylene terephthalate, and polyurethane.

In one embodiment, the concentration of the acid solution may be 0.01 ~ 5 N.

In one embodiment, step (a1) and step (a2) may be performed for 0.1 to 5 minutes each time.

In one embodiment, the concentration of hydrogen peroxide may be 1 to 20%.

Another aspect of the present invention, (A) the step of surface modification of the polymer substrate according to the surface modification method described above; (B) forming a radical on at least part of the surface of the polymer substrate; And (C) reacting the radical with the antimicrobial substance.

In one embodiment, the step (B) may be heat treatment of the polymer substrate at 50°C or higher.

In one embodiment, the step (B) may be to react the polymer substrate with an oxidation-reduction agent.

In one embodiment, the redox agent is sulfuric acid, nitric acid, potassium permanganate, potassium dichromate, sodium nitride, ferrous chloride, cobalt sulfate, formaldehyde, polyvinylpyrrolidone, aqueous ammonia, ethylenediamine, ethylenediaminetetraacetic acid, and benzotria It may be at least one selected from the group consisting of sol.

In one embodiment, step (C) may be performed by coating an antimicrobial material on the surface of the polymer substrate.

In one embodiment, the antimicrobial material is polyethylene glycol, polyvinylamine, polyarylamine, polyethyleneimine, diethylenetriamine, piperazine, dimethylpiperazine, diphenylamine, polyhexamethylenebiguanidine, polyvinylpyridine, At least one selected from the group consisting of tannic acid, gallic acid, urushiol, flavonoids, chitosan, benzalkonium chloride, quaternary ammonium compounds, silver compounds, inorganic metal compounds, sulfonium compounds, phosphonium compounds, zwitterionic polymers and fatty acid ester compounds Can be

Another aspect of the present invention is a polymer substrate; It provides an antibacterial coated oral medical device comprising a coating layer having a thickness of 1 nm to 500 μm formed by covalently bonding an antimicrobial material to oxygen on at least a portion of the surface of the substrate.

According to an aspect of the present invention, it is possible to provide a method for surface modification and antibacterial coating of a polymer substrate having excellent durability in a simple manner.

According to another aspect of the present invention, it is possible to manufacture an antibacterial coated oral medical device having excellent durability and antibacterial persistence.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram of a surface modification process according to an embodiment of the present invention;
2 is a schematic diagram of an antibacterial coating process according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

When a range of numerical values is described herein, the value has the precision of significant figures provided according to the standard rules in chemistry for significant figures, unless a specific range thereof is stated otherwise. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Surface modification method of polymer substrate

A method for modifying a surface of a polymeric substrate according to an aspect of the present invention includes the steps of: (a1) supporting the polymeric substrate in an acid solution; (a2) supporting the polymer substrate in a base solution; And (b) treating the polymer substrate with hydrogen peroxide, wherein step (a1) and step (a2) are performed alternately at least once before step (b), respectively, and step (a1) and The order of step (a2) is interchangeable, and the acid solution is at least one selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrogen bromide, chloric acid, perchloric acid, citric acid and formic acid, and the base solution is hydroxide It may be at least one selected from the group consisting of sodium, potassium hydroxide, calcium hydroxide, gallium hydroxide, and aqueous ammonia.

The surface modification method can effectively and economically modify the surface of a polymer substrate by using a polymer material sensitively to a change in pH.

Conventionally, a method of plasma treatment of a polymer has been used to modify the hydrophilic surface of a polymer substrate, but when the surface is modified in this way, the period of offsetting of the functional groups is short, so coating must be performed immediately after plasma treatment, and the surface modification and coating are insufficient. There is a problem being performed.

On the other hand, according to the surface modification method according to an aspect of the present invention, it is possible to easily modify the surface of the polymer substrate by chemically thermally modifying the crystal form of the polymer through a simple process of cross-supporting in an acid and base solution. Due to its high stability, workability and efficiency can be excellent.

The surface modification method can be applied to various polymer substrates, for example, the polymer substrate may be at least one selected from the group consisting of polyethylene, polycarbonate, polyethylene terephthalate, glycol-modified polyethylene terephthalate, and polyurethane, It is not limited thereto.

The surface modification method may include the step (a) of chemically thermally modifying the crystal form of the polymer substrate and the step (b) of forming a hydrophilic functional group. The step (a) may include a step (a1) of supporting the polymer substrate in an acid solution and a step (a2) of supporting the polymer substrate in a base solution. In step (a), step (a1) and step (a2) may be performed one or more times regardless of the preceding and following steps. For example, the (a2) step may be performed after the (a1) step, or the (a1) step may be performed after the (a2) step, in the order of (a1), (a2), (a1). Or (a2), (a1), (a2), (a1), (a2), (a1), (a2), (a2), (a1), ( Each of the steps (a1) and (a2) is performed in the order of a2), (a1), and so on, at least once, for example, 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 Times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times or more can be performed crossover, the above It may be excellent in terms of efficiency that steps (a1) and (a2) are each performed three times, but are not limited thereto.

The concentration of the acid solution used in step (a1) is 0.01 to 5 N, for example, 0.01 N, 0.1 N, 0.5 N, 1.0 N, 1.5 N, 2.0 N, 2.5 N, 3.0 N, 3.5 N, 4.0 N, 4.5 N, 5.0 N, or two or more of these values may be in between, but is not limited thereto. When the concentration of the acid solution is excessively low, the surface modification effect may be insufficient, and when excessively high, the physical properties of the final product may be unnecessarily deteriorated due to the denaturation of the polymer substrate.

The step (a1) and step (a2) may be performed for 0.1 to 5 minutes each time. For example, the step (a1) is 0.1 minutes, 0.2 minutes, 0.3 minutes, 0.4 minutes, 0.5 minutes, 0.6 minutes, 0.7 minutes, 0.8 minutes, 0.9 minutes, 1.0 minutes, 1.1 minutes, 1.2 minutes, 1.3 minutes, 1.4 Minutes, 1.5 minutes, 1.6 minutes, 1.7 minutes, 1.8 minutes, 1.9 minutes, 2.0 minutes, 2.1 minutes, 2.2 minutes, 2.3 minutes, 2.4 minutes, 2.5 minutes, 2.6 minutes, 2.7 minutes, 2.8 minutes, 2.9 minutes, 3.0 minutes, 3.1 minutes, 3.2 minutes, 3.3 minutes, 3.4 minutes, 3.5 minutes, 3.6 minutes, 3.7 minutes, 3.8 minutes, 3.9 minutes, 4.0 minutes, 4.1 minutes, 4.2 minutes, 4.3 minutes, 4.4 minutes, 4.5 minutes, 4.6 minutes, 4.7 minutes , 4.8 minutes, 4.9 minutes, 5.0 minutes, or two or more of these are performed for a period of time, independently of which step (a2) is 0.1 minutes, 0.2 minutes, 0.3 minutes, 0.4 minutes, 0.5 minutes, 0.6 minutes , 0.7 minutes, 0.8 minutes, 0.9 minutes, 1.0 minutes, 1.1 minutes, 1.2 minutes, 1.3 minutes, 1.4 minutes, 1.5 minutes, 1.6 minutes, 1.7 minutes, 1.8 minutes, 1.9 minutes, 2.0 minutes, 2.1 minutes, 2.2 minutes, 2.3 Minutes, 2.4 minutes, 2.5 minutes, 2.6 minutes, 2.7 minutes, 2.8 minutes, 2.9 minutes, 3.0 minutes, 3.1 minutes, 3.2 minutes, 3.3 minutes, 3.4 minutes, 3.5 minutes, 3.6 minutes, 3.7 minutes, 3.8 minutes, 3.9 minutes, It may be performed for 4.0 minutes, 4.1 minutes, 4.2 minutes, 4.3 minutes, 4.4 minutes, 4.5 minutes, 4.6 minutes, 4.7 minutes, 4.8 minutes, 4.9 minutes, 5.0 minutes, or for a period of time between two or more of these. It is not limited. If the step (a1) or (a2) is performed one or more times, it may be performed for the same or different time, respectively. If the execution time of each step is excessively short, the chemical thermal transformation process may be insufficient, and if it is excessively long, the polymer substrate may be denatured or unnecessarily time consuming, resulting in a decrease in process efficiency.

The (b) step is a step of introducing a hydrophilic functional group to the surface of the polymer substrate chemically modified in the step (a), for example, a hydroxyl group (ROH) or a hydroperoxide group (ROOH), etc. Can be formed.

The concentration of hydrogen peroxide may be 1 to 20%. For example, the concentration of hydrogen peroxide is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% , 15%, 16%, 17%, 18%, 19%, 20%, or between two or more of these values, but is not limited thereto. If the concentration is less than 1%, the hydrophilic functional group may be insufficiently introduced, and if the concentration is more than 20%, the increase in the amount of the hydrophilic functional group introduced may be insignificant.

Antibacterial coating method for polymer substrates

An antimicrobial coating method for a polymer substrate according to another aspect of the present invention includes the steps of: (A) surface-modifying the polymer substrate according to the above-described surface modification method; (B) forming a radical on at least part of the surface of the polymer substrate; And (C) reacting the radical with the antimicrobial material.

The antimicrobial coating method can effectively and economically perform antimicrobial coating by using the hydrophilic functional group of the polymer material surface-modified by the above-described method sensitively reacting to temperature, pH change, and redox compounds.

The description of step (A) is the same as described above.

In the step (B), oxygen radicals may be formed by decomposing O-O bonds of peroxide functional groups formed on at least a portion of the surface of the polymer substrate.

In one embodiment, the (B) step is the polymer substrate at least 50 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, The heat treatment may be performed at 95°C, 100°C or higher temperature conditions, but is not limited thereto. Since the O-O bond of the peroxide functional group has a relatively weak bonding force, it can be easily decomposed by heat to form oxygen radicals.

In another embodiment, step (B) may be to react the polymer substrate with an oxidation-reduction agent. For example, the redox agents include sulfuric acid, nitric acid, potassium permanganate, potassium dichromate, sodium nitride, and other oxidizing agents, ferrous chloride, cobalt sulfate, formaldehyde, polyvinylpyrrolidone, aqueous ammonia, ethylenediamine, ethylenediaminetetraacetic acid, A reducing agent such as benzotriazole may be used, but is not limited thereto.

The step (C) may be fixing by reacting the highly reactive radical formed in step (B) with an antibacterial material. For example, step (C) may be performed by coating an antimicrobial material on the surface of the polymer substrate, and techniques such as spin coating, dip coating, and spray coating may be used, but the method is not limited thereto. . In step (C), a thin coating layer containing an antibacterial material may be formed on the surface of the polymer substrate.

The antimicrobial substances are polyethylene glycol, polyvinylamine, polyarylamine, polyethyleneimine, diethylenetriamine, piperazine, dimethylpiperazine, diphenylamine, polyhexamethylenebiguanidine, polyvinylpyridine, tannic acid, gallic acid, urushiol, Flavonoids, chitosan, benzalkonium chloride, quaternary ammonium compounds, silver compounds, inorganic metal compounds, sulfonium compounds, phosphonium compounds, zwitterionic polymers, and may be at least one selected from the group consisting of fatty acid ester compounds, but limited thereto. It does not become.

Antibacterial coating oral medical device

An antimicrobial coated oral medical device according to another aspect of the present invention, a polymer substrate; A coating layer having a thickness of 1 nm to 500 μm may be formed by covalently bonding an antimicrobial material with oxygen on at least a portion of the surface of the substrate.

The antimicrobial coated oral medical device may be manufactured by the above-described surface modification method and antibacterial coating method.

The coating layer is covalently bonded to the polymer substrate with oxygen, so that it can easily withstand physical external forces generated during use of the oral medical device, thereby maintaining the antibacterial effect for a longer period of time. As a result, the oral medical device can prevent the formation of a biofilm due to bacterial adhesion.

The oral medical device may be, for example, a mouthpiece, an orthodontic device, a snoring device, etc., but is not limited thereto.

The coating layer may be formed to a thickness of several nanometers to 500 μm, but is not limited thereto. If the thickness of the coating layer exceeds 500 μm, it may cause inconvenience when wearing the oral medical device.

Hereinafter, embodiments of the present invention will be described in more detail. However, the following experimental results are only representative of the above examples, and cannot be interpreted as the scope and content of the present invention are reduced or limited by examples. Effects of each of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

Example 1

The outline of the surface modification process performed in an embodiment of the present invention is schematically shown in FIG. 1.

Polymer specimens made of polyethylene (PE), polycarbonate (PC), polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), and polyurethane (polyurethane (PU)) Each was prepared.

After immersing the specimen in 0.05-3N phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid or sulfuric acid for 1 to 4 minutes, the process of immersing the specimen in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide or aqueous ammonia solution for 1 to 4 minutes is performed. The polymer crystal form of the specimen was chemically thermally modified by repeating it twice.

The specimen was washed in 10% hydrogen peroxide to produce a hydrophilic functional group on the surface to prepare a surface-modified specimen. Hydroperoxide groups (R-O-O-H) and hydroxyl groups (R-OH) were formed on the surface of the specimen.

Example 2

The outline of the antibacterial coating process performed in an embodiment of the present invention is schematically shown in FIG. 2.

The surface-modified specimen of Example 1 was heated to a temperature of 50°C or higher, or an oxidation-reduction reaction was induced with an oxidation-reduction agent such as ferrous chloride to generate radicals. Antibacterial substances such as polyethylene glycol (PEG), polyvinylamine, polyarylamine, polyethyleneimine, diethylenetriamine, piperazine, dimethylpiperazine, diphenylamine, polyhexamethylenebiguanidine, poly Vinylpyridine, tannic acid, gallic acid, urushiol, flavonoids, chitosan, benzalkonium chloride, quaternary ammonium compounds, silver compounds, inorganic metal compounds, sulfonium compounds, phosphonium compounds, zwitterionic polymers, fatty acid ester compounds, respectively, are spin-coated. , By reacting with the radicals generated by dip coating or spray coating to prepare an antibacterial coating specimen.

The surface of the specimen was washed with water or a solvent in which the antibacterial substance was dissolved. Benzene, toluene, xylene, etc. were used as the solvent according to the type of the antibacterial substance.

Each feature of the antimicrobial coated specimen prepared in the above example was compared with a specimen surface-modified by a conventional plasma treatment and a specimen without a separate surface treatment. The coating layer on the surface of the specimen was formed to a thickness of 1 nm to 500 μm. The coating layer had remarkably excellent physical durability compared to the plasma-treated specimen by covalently bonding an antimicrobial material to the polymer surface of the specimen. In addition, the coating layer was able to suppress the formation of the biofilm by the antibacterial material.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (12)

(a1) supporting the polymer substrate in an acid solution;
(a2) supporting the polymer substrate in a base solution; And
(b) comprising the step of treating the polymer substrate with hydrogen peroxide in a concentration of 1 to 20% by weight,
The step (a1) and step (a2) are each alternately performed three or more times prior to step (b),
The order of step (a1) and step (a2) can be mutually changed,
The (a1) step and the (a2) step are each performed for 0.1 to 5 minutes per time,
The acid solution is at least one selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrogen bromide, chloric acid, perchloric acid, citric acid and formic acid,
The base solution is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, gallium hydroxide, and aqueous ammonia. The method of claim 1,
The polymer substrate is at least one selected from the group consisting of polyethylene, polycarbonate, polyethylene terephthalate, glycol-modified polyethylene terephthalate, and polyurethane. The method of claim 1,
The concentration of the acid solution is 0.01 ~ 5 N, the method of modifying the surface of the polymer substrate. delete delete (A) surface-modifying the polymer substrate according to claim 1;
(B) decomposing OO bonds of hydroperoxide functional groups formed on at least a portion of the surface of the polymer substrate to form oxygen radicals; And
(C) comprising the step of reacting the oxygen radical and the antimicrobial material, antibacterial coating method of a polymer substrate. The method of claim 6,
In the step (B), the polymer substrate is heat-treated under conditions of 50° C. or higher. The method of claim 6,
The step (B) is to react the polymer substrate with an oxidation-reduction agent, the antimicrobial coating method of the polymer substrate. The method of claim 8,
The redox agent is at least selected from the group consisting of sulfuric acid, nitric acid, potassium permanganate, potassium dichromate, sodium nitride, ferrous chloride, cobalt sulfate, formaldehyde, polyvinylpyrrolidone, aqueous ammonia, ethylenediamine, ethylenediaminetetraacetic acid and benzotriazole. One, antibacterial coating method of a polymer substrate. The method of claim 6,
The step (C) is performed by coating an antimicrobial material on the surface of the polymer substrate. The method of claim 6,
The antimicrobial substances are polyethylene glycol, polyvinylamine, polyarylamine, polyethyleneimine, diethylenetriamine, piperazine, dimethylpiperazine, diphenylamine, polyhexamethylenebiguanidine, polyvinylpyridine, tannic acid, gallic acid, urushiol, Flavonoids, chitosan, benzalkonium chloride, quaternary ammonium compounds, silver compounds, inorganic metal compounds, sulfonium compounds, phosphonium compounds, zwitterionic polymers, and at least one selected from the group consisting of fatty acid ester compounds Coating method. The polymer substrate surface-modified according to claim 1;
An antimicrobial coated oral medical device comprising a coating layer having a thickness of 1 nm to 500 μm formed by covalently bonding an antimicrobial material with oxygen on at least a portion of the surface of the substrate.

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