KR20140143295A - Dental implant including antibiotic coating layer and surface treatment method thereof - Google Patents

Abstract

The present invention relates to a dental implant including an abutment having a nitrogen-doped titania nanotube coating layer and a method for treating the surface of the same. By means of the dental implant of the present invention, the elution time and elution amount of an antibiotic having an antibacterial activity can be regulated, so that the surroundings of the implant can be prevented from microbism even after the implant is implanted in the gum. Also, alveolar bone reduction and implant loss caused by microbism can be prevented. Moreover, when the method for treating the surface of the dental implant of the present invention is used, the elution time and elution amount of drugs can be effectively regulated, and drugs can be effectively transferred to a target region. Accordingly, the side effects of the antibiotic can be minimized, and microbism can be effectively prevented during implant treatment. A nitrogen-doped titania nanotube is formed on the surface of the implant, so that an optical catalyst can be induced also by visible rays and side effects such as mucosal damage caused by ultraviolet rays can be resolved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental implant and an antimicrobial coating layer,

The present invention relates to a dental implant including an abutment having a nitrogen-doped titania nanotube coating layer and a surface treatment method thereof.

Implant is a biomedical device that is implanted in a living body and exhibits a desired function. A dental implant is used to support a prosthesis for restoration of a missing tooth. The implant is placed in or on the jawbone (embedded in the gums and gums) Is a fixed body.

The implant is largely composed of a fixture, an abutment, and a crown portion. The fixture serves as a root of a tooth. The implant is mainly made of titanium. The abutment includes a crown The crown corresponds to the head of the tooth in the natural tooth due to the upper prosthesis of the implant. In consideration of the position and condition of the tooth, the crown corresponds to the neck of the natural tooth, .

Because implants are required to meet the conditions related to biocompatibility and chemical compatibility such as bone adhesion, research on implants has been conducted mainly on fixtures corresponding to roots. Particularly, since titanium or titanium alloy having excellent biocompatibility is mainly used as the fixture, researches for promotion of bonding or stress dispersion of titanium material and bone, for example, surface treatment using titania (TiO ₂ ) nanotubes Technology, and so on.

However, since the implant using such an implant has a possibility of bacterial infection due to a surgical operation, the bone surrounding the implant may melt due to the bacterial infection, resulting in loss of the implant, side effects such as pain, inflammation or edema, This leads to greater problems in implant treatment.

The most ideal method to solve the bacterial infection is to administer the antibiotic for about two months after the implant treatment, but the research on the antibiotic delivery method which can continuously deliver the useful amount of the antibiotic in the oral cavity during the period has been limited to be.

The antibiotic delivery method generally includes an intramuscular administration method, an intravenous administration method, an intramuscular administration method, and a local administration method. Among the above antibiotic delivery methods, there is a problem that an unintended side effect is generally caused in an infusion administration method.

Therefore, in recent years, various antibiotic delivery methods have been under study to increase the effectiveness of antibiotics administered at the site of implant treatment. As an example, an antibiotic delivery device for solving the side effects of the infiltrative administration method has been proposed. Since the antibiotic delivery device can control the amount of the antibiotic dissolved in the active site, it is possible to reduce side effects of the infusion administration method due to excessive antibiotic administration. However, the disadvantage that the initiation or termination of drug release can not be controlled have.

The photocatalytic effect, that is, the method of using light irradiation as a stimulus, is a method of controlling dissolution of antibiotics including the modification or termination of the drug elution, and it is advantageous that both complications and side effects can be minimized. Specifically, a method using titania is provided as a method of controlling the dissolution of antibiotics using the light irradiation as a stimulus.

The above-mentioned titania (TiO ₂ ) is characterized in that the material on the surface is separated when irradiated with ultraviolet rays according to the photocatalytic effect. The previously reported titania has a characteristic that a photocatalytic effect is generated only by ultraviolet rays.

In the case of the titania photocatalytic activity, since it is stimulated only by ultraviolet rays in spite of sterilization in the oral cavity, there is a problem that damage to the oral mucosa may occur due to the ultraviolet rays to be irradiated. Therefore, if the photocatalytic effect can be induced by the visible ray region which is mainly used in daily life without damaging the skin such as the mucous membrane, it can be usefully used for the drug delivery. Therefore, various studies are being conducted to make the photocatalytic activity of titania nanotubes possible in the visible light region.

For example, it has been reported that nanotubes prepared by doping iron (Fe) with titania exhibit better photocatalytic activity than pure titania nanotubes in the visible region.

As described above, in relation to the control of the dissolution of antibiotics using the photocatalytic effect, the photocatalytic effect is also induced by light irradiation in the visible light region, thereby minimizing adverse effects due to ultraviolet rays and improving the effect of controlling the amount of drug release Research is needed to develop technology.

KR 10-2011-0082658 A KR 10-2012-0129270 A

An object of the present invention is to provide a surface treatment method for forming a dental implant and a nitrogen-doped titania nanotube coating layer including an abutment having a nitrogen-doped nanotube coating layer containing an antibiotic in a nanotube .

According to an aspect of the present invention, there is provided a dental implant including an abutment portion having a dental implant, specifically, a nitrogen-doped titania nanotube coating layer.

The dental implant includes an abutment portion having a nitrogen-doped titania nanotube coating layer, and the nitrogen-doped titania nanotube includes an antibiotic and a mixture of polylactic acid.

The nitrogen-doped titania nanotube coating layer may be formed of anodizing electrolyte solution for nitrogen doping containing 0.01 M to 0.15 M of diethanolamine.

The anodizing electrolyte solution for nitrogen doping may include hydrofluoric acid in a mixture of water and acetic acid. The content of the dispersion may be 0.4 to 0.6% by weight (w / w) based on the weight of the hydrofluoric acid based on the total weight of the electrolytic solution. The mixing ratio of the water and the acetic acid mixture may be 6: 1 (water: acetic acid) to 8: 1 (water: acetic acid) based on the volume ratio.

The antibiotic may be any one selected from the group consisting of tetracycline, chlorhexidine, and combinations thereof.

The mixing ratio of the antibiotic and the polylactic acid mixture may be 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid) based on the weight ratio.

The present invention also relates to a method of surface treatment of a dental implant.

The surface treatment method of the dental implant includes preparing an anodized electrolyte solution for nitrogen doping by mixing 0.01 M to 0.15 M of diethanolamine (DEA) in an anodic oxidation electrolyte solution, preparing an anodized electrolyte solution for nitrogen doping Doped titania nanotube gating layer on the titanium by anodic oxidation at an applied voltage of 5 to 25 V for 20 to 50 minutes, and a step of immersing the dental implant in which the nitrogen-doped titania nanotube coating layer is formed with antibiotics and polylactic acid polylacticacid) to form the mixture in the nanotube coating layer.

In the surface treatment method, the anodic electrolytic solution may include hydrofluoric acid in a mixture of water and acetic acid. The content of hydrofluoric acid may be 0.4 to 0.6 wt% (w / w) based on the weight of the hydrofluoric acid with respect to the total weight of the electrolytic solution. The mixing ratio of the water and the acetic acid mixture may be 6: 1 (water: acetic acid) to 8: 1 (water: acetic acid) based on the volume ratio.

In the surface treatment method, the mixing ratio of the antibiotic and the polylactic acid mixture may be 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid) based on the weight ratio.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention have been studying a method of preventing bacterial infection in the vicinity of an implant and implanting an effective antibiotic for preventing bacterial infection even after implantation of the implant into the gum in order to increase the success rate of the implant treatment, The present inventors completed the present invention by confirming that it is possible to continuously prevent bacterial infection in the vicinity of the implant by forming a coating layer capable of controlling the release timing and elution amount of the antibiotic having antimicrobial activity to the abutment of the implant. In order to solve the side effect of ultraviolet rays related to the activity of the coating layer, when nitrogen-doped titania is applied, the antibiotic contained in the nanotube coating layer is eluted by the photocatalytic effect of visible light, The present invention has been accomplished by confirming that alveolar bone loss and implant loss can be prevented by preventing bacterial infection.

In particular, in the case of an implant including an abutment having a nitrogen-doped titania nanotube coating layer containing the antibiotic of the present invention, dissolution of the drug by the photocatalyst occurs even when visible light is irradiated, The timing and amount of elution can be controlled, and the delivery of the drug can be performed more effectively.

The present invention relates to a dental implant. The dental implant includes an abutment having a nitrogen-doped titania nanotube coating layer, wherein the implant comprises an antibiotic and a mixture of polylactic acid in a nitrogen-doped titania nanotube coating layer.

The implant implies a biomedical medical device which is implanted in a living body and exhibits a desired function. The dental implant is used for supporting a prosthesis for restoration of a missing tooth. The implant is placed in or on the jawbone (between the gum and the gum ) ≪ / RTI >

The implant generally consists of a fixture, an abutment and a crown or upper crown portion. In the present invention, the implant may be a concept or an abutment alone, including a fixture, abutment, and crown.

The fixture serves as a root of the tooth. The fixture is a threaded portion below the portion indicated by yellow in Fig. 8, and in the case of the fixture portion, it is intended to allow bone and adhesion to occur well through biocompatibility. The risk of bacterial infection is low.

The abutment serves to connect the crown and the fixture, and shows a yellow portion in FIG. The material of the abutment may be any material conventionally used, and titanium is preferably used, although not limited thereto. When titanium is used as the material of the abutment, the nitrogen-doped titania nanotube coating layer can be formed more effectively.

The titanium may preferably have a flatness of 5 nm or less. When the electrolytic polishing is performed so that the titanium can satisfy the flatness, contaminants and debris present on the surface can be removed, so that inflammation caused by the contaminants or debris can be prevented .

In the case of the above abutment, the risk of bacterial infection is high because it is exposed to the outside of the gum in the oral cavity, and when the peripheral region of the implant is infected with bacteria, osteointefration fails due to reduction of the alveolar bone, In the case of the abutment having the titania nanotube coating layer containing the antibiotic, when the stimulation is obtained by the light irradiation, when the photocatalytic reaction of the antibiotic contained in the nanotube coating layer occurs, And the antibacterial action against the bacteria in the surrounding tissues of the implants can be solved. Therefore, problems such as failure of adhesion of implants due to bacterial infection can be solved.

When the titania nanotube coating layer is a nitrogen-doped titania nanotube coating layer, a photocatalytic action is also caused by visible light, so that side effects such as mucosal damage due to irradiation in the oral cavity do not occur.

The crown is an upper prosthesis of the implant, which corresponds to the head of a tooth in natural teeth, and is generally formed above the portion indicated by yellow in FIG.

The nitrogen-doped titania nanotube coating layer may be formed of an anodic oxidation electrolyte solution for nitrogen doping including diethanolamine.

The surface treatment method for forming the titania nanotube coating layer on the surface of the dental implant can be carried out by a surface treatment method commonly used in the technical field of the present invention and preferably a surface treatment method by an anodic oxidation method But is not limited thereto.

The nitrogen-doped titania nanotube coating layer may be formed by an anodic oxidation treatment method. The anodic oxidation surface treatment method can be carried out by a conventional method in the field of the present invention. For example, the anode may be used as the abutment of the present invention, and the anode may be made of any one selected from the group consisting of platinum, tungsten and silver And an electrochemical reaction is performed using an electrolyte solution for 30 minutes to 2 hours to form a nanotube coating layer on the surface of the anode substrate.

The formed nitrogen-doped titania nanotubes may be anatase-type nanotubes.

The electrolytic solution may include hydrofluoric acid in a mixture of diethanolamine, water and acetic acid.

The mixture of water and acetic acid may preferably be prepared by mixing water and acetic acid in a volume ratio of 6: 1 to 8: 1. If the electrolyte solution does not satisfy the above range, The length of the generated nanotubes becomes excessively long, and the surface nanotubes may be damaged during the implantation.

The hydrofluoric acid may be contained in an amount of 0.1 wt% (w / w) to 0.9 wt% (w / w) based on the weight of the hydrofluoric acid, preferably 0.4 wt% % (w / w). If the concentration of hydrofluoric acid in the electrolyte solution is too low, it is difficult to form the nanotubes. If the concentration of hydrofluoric acid is too high, the nanotubes may be dissolved by hydrofluoric acid during the formation of the nanotubes. Is appropriate.

The diethanolamine may be contained in an amount of less than 0.2 M, preferably 0.01 M to 0.15 M. When the electrolyte solution contains less than 0.01 M of diethanolamine, the effect of nitrogen doping on the nanotubes is insignificant, so that a photocatalyst due to visible light may not be induced. When the electrolyte solution contains more than 0.15 M of diethanolamine There arises a problem that nitrogen-doped titania nanotubes are not formed.

The nitrogen-doped titania nanotube electrolyte solution was added to a mixture of water and acetic acid mixed with 6: 1 (water: acetic acid) to 8: 1 (water: acetic acid) based on the volume ratio of 0.4 To 0.6% by weight (w / w) of hydrofluoric acid, and the diethanolamine may be 0.01M to 0.15M. The nanotube coating layer formed by the nitrogen-doped titania nanotube electrolyte solution satisfying the above range is suitable because the diameter of the nanotube includes an antibiotic and a mixture of polylactic acid. Thus, it is possible to effectively control the one-time elution amount of the drug, Induction is also higher than that of conventional titania nanotubes, so that the drug contained in the nanotubes can be effectively eluted even in the visible light region.

The nitrogen-doped titania nanotubes include an antibiotic and a mixture of polylactic acid in the nanotube.

The antibiotics are, for example, small amounts produced by microorganisms. These antibiotics are substances that inhibit the growth or life of other microorganisms. Examples of such antibiotics include penicillins, cephalosporins, aminoglycosides, And may be any one selected from the group consisting of tetracycline, chloramphenicol, polypeptide antibiotics and quinolone antibiotics. Examples of the antibiotic include tetracycline,

 Chlorhexidine, and a combination thereof. However, the antibiotic can be selected and used by the user of the present invention as needed, but is not limited thereto.

The polylactic acid is one of the thermoplastic aliphatic polyesters extracted from corn starch, tapioca roots or sugar cane using a renewable raw material and is a biodegradable polymer and has already been proved to be harmless to the human body.

When the mixture of antibiotics and polylactic acid is included in the inside of the nitrogen-doped titania nanotube, it is hardly eluted during normal operation. However, when the drug present in the titania nanotube elutes due to the photocatalytic action, Antibiotic toxicity can more effectively prevent harmful side effects. In addition, since polylactic acid is coated with antibiotics, the antibacterial activity of the surrounding area of the implant can be continuously prevented because the antibacterial activity of the eluted antibiotic is slowed and the antibacterial activity is maintained while staying in the periphery of the implant during the time of decomposition of polylactic acid.

The mixing ratio of the antibiotic and the polylactic acid mixture is 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid), preferably 9: 1 to 11: 1, May be 10: 1.

 When the antibiotic and the polylactic acid are mixed in the above range, it is possible to effectively exhibit the antimicrobial activity only around the implant after being eluted from the nanotube, thereby reducing side effects and effectively controlling the amount of antibiotic leaching.

The present invention also relates to a method for surface treatment of a dental implant. The dental implant may be an abutment included in the implant.

The surface treatment method of the dental implant may include preparing an anodized electrolyte solution for nitrogen doping, forming a nanotube coating layer, and incorporating the mixture into the nanotube. The dental implant may be an abutment included in the implant.

The step of preparing the anodic oxidation electrolyte solution for nitrogen doping may be performed by mixing diethanolamine with an anodic oxidation electrolyte solution.

The anodic oxidation electrolyte solution is meant to include all electrolytic solutions commonly used in anodization, preferably hydrofluoric acid, water and acetic acid, more preferably water and acetic acid in a volume ratio of 6: 1 (W / w) to 0.9 wt% (w / w), or 0.4 wt% (w / w) to 0.6 wt%, based on the weight of the hydrofluoric acid, (W / w). ≪ / RTI >

The anodizing electrolyte solution for nitrogen doping may further include diethanolamine in the anodizing electrolyte solution. The diethanolamine may be contained in an amount of less than 0.2 M, preferably 0.01 M to 0.15 M.

When the surface treatment is carried out using a nitrogen-doped anodic oxidation electrolyte solution containing less than 0.01 M of diethanolamine, the effect of nitrogen doping on the nanotubes may be insufficient, so that a photocatalyst due to visible light may not be induced. When the surface treatment is performed using the nitrogen-doped anodic oxidation electrolyte solution containing more than 0.15M, there arises a problem that nitrogen-doped titania nanotubes are not formed.

The step of forming the nanotube coating layer may include anodizing the anodic oxidation electrolyte solution for nitrogen doping at an applied voltage of 5 V to 25 V for 20 to 50 minutes to form a nitrogen-doped titania nanotube coating layer on the surface of the dental implant . ≪ / RTI >

The applied voltage may preferably be in the range of 10 V to 25 V. When the applied voltage is lowered, the diameters of the generated nanotubes may be reduced to effectively contain antibiotics, It is preferable to form the nitrogen-doped titania nanotube coating layer on the surface of the dental implant by anodic oxidation.

The nitrogen-doped titania nanotubes formed by the above method may be preferably anatase-type nanotubes.

The step of incorporating the mixture in the nanotubes is performed by immersing the dental implant in which the nitrogen-doped titania nanotube coating layer is formed in an antibiotic and a polylactic acid mixture, and the mixture is contained in the nanotubes. The method of incorporating the mixture into the nanotubes can be carried out by a conventional method in the field of the present invention. For example, the dental implant having the nitrogen-doped titania nanotube coating layer may be immersed in the mixture and stirred for 10 minutes to 60 minutes.

The method for surface treatment of an implant may further include washing the dried implant after the step of adding the mixture to the nanotube, and performing heat treatment at 400 ° C to 600 ° C for 1 hour to 3 hours.

The antibiotics are, for example, small amounts produced by microorganisms. These antibiotics are substances that inhibit the growth or life of other microorganisms. Examples of such antibiotics include penicillins, cephalosporins, aminoglycosides, And may be any one selected from the group consisting of tetracycline, chloramphenicol, polypeptide antibiotic and quinolone antibiotics. Examples of the antibiotic include tetracycline, chlorhexidine, And a combination thereof. However, the antibiotic can be selected and used by the user of the present invention as needed, but is not limited thereto.

The polylactic acid is one of the thermoplastic aliphatic polyesters extracted from corn starch, tapioca roots or sugar cane using a renewable raw material and is a biodegradable polymer and has already been proved to be harmless to the human body.

When the mixture of the antibiotic and the polylactic acid is contained in the inside of the nitrogen-doped titania nanotube, when the drug of the titania nanotube is eluted by the photocatalytic action, a large amount of the drug elutes in the early stage and the cells in the oral cavity are damaged by the antibiotic toxicity It is possible to prevent the adverse side effect more effectively. In addition, since polylactic acid is coated with antibiotics, the antibacterial activity of the surrounding area of the implant can be continuously prevented because the antibacterial activity of the eluted antibiotic is slowed and the antibacterial activity is maintained while staying in the periphery of the implant during the time of decomposition of polylactic acid.

The mixing ratio of the antibiotic and the polylactic acid mixture is 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid), preferably 9: 1 to 11: 1, more preferably 10: 1 < / RTI > When the antibiotic and the polylactic acid are mixed in the above range, it is possible to effectively exhibit the antimicrobial activity only around the implant after being eluted from the nanotube, thereby reducing side effects and effectively controlling the amount of antibiotic leaching.

The dental implant surface treatment method may further include a surface planarization step of the implant before the surface treatment. The implant surface planarization step may be performed by polishing the implant.

The polishing may preferably be performed by an electrolysis method, more preferably 4% to 8% perchloric acid (Sigma, USA), 30% to 40% butoxy ethylene glycol (Junsei I, Japan) And 50 to 70% methanol (methanol, Sigma, USA).

In order to planarize the surface of the implant before forming the nitrogen-doped titania nanotubes on the implant, contaminants and debris present on the surface may be removed when electrolytic polishing is performed, Or inflammation induced by debridement can be prevented.

According to the dental implant of the present invention, it is possible to control the elution timing and elution amount of the antibiotic having antimicrobial activity, so that it is possible to prevent the bacterial infection in the vicinity of the implant even after the implant is placed in the gum, and the alveolar bone loss, Can be prevented. In addition, according to the surface treatment method of the dental implant of the present invention, it is possible to effectively control the elution time and elution amount of the drug and effectively deliver the drug to the target site, thereby minimizing the side effect on the antibiotic, By forming nitrogen-doped titania nanotubes on the surface of the implant, the photocatalyst can be induced by visible light, and the side effects such as damage to the mucous membrane due to ultraviolet rays can be solved.

FIG. 1 is a FE-SEM (field emission scanning electron microscopic) photograph showing the formation of nitrogen-doped titania nanotubes according to the concentration of diethanolamine of the present invention. FIG. 1b is a photograph using an anodic oxidation electrolyte solution for nitrogen doping including 0.1M diethanolamine, and Fig. 1c is a photograph showing an anode oxidation electrolyte solution for nitrogen doping containing 0.2 M diethanolamine. .
FIG. 2 is a TEM vertical cross-sectional view of a specimen having nitrogen-doped titania nanotubes formed thereon. In FIG. 2A, Ti represents a titanium layer and Nanotube represents a nanotube.
FIG. 3 shows the results of X-ray diffraction analysis (FIG. 3A) and X-ray photoelectron spectroscopy (FIG. 3B and FIG. 3C) of nitrogen-doped titania nanotubes treated with general titania nanobeads and 0.1 M diethanolamine Graph. 3A is a graph of a nitrogen doped titania nanotube, and the bottom is a graph of a general titania nanotube. 3A shows the X-ray diffraction intensity, and the horizontal axis shows the X-ray diffraction angle. 3B represents the photoelectron intensity, the horizontal axis represents the binding energy, the vertical axis of FIG. 3C represents the photoelectron intensity, and the horizontal axis represents the binding energy.
FIG. 4 is a graph showing the difference in the amount of elution of antibiotic-loaded nanotubes according to PLA mixing. The vertical axis of the graph represents the concentration of tetracycline, and the horizontal axis represents the elution time after the antibiotic is supported on the nanotubes. In the graph, the symbol represents the case where only tetracycline is carried, and the symbol represents the case where a mixture of tetracycline and polylactic acid is carried.
5 is a graph showing the difference in drug elution between a general nanotube and a nitrogen-doped nanotube. In the abscissa of the graph, TiO ₂ NT means that antibiotics are contained in the general titania nanotube coating layer, and N-doped TiO ₂ NT means that the antibiotic is supported on the nitrogen-doped titania nanotube coating layer. In FIG. 5A, the vertical axis represents the concentration of tetracycline, and the vertical axis of FIG. 5B represents the concentration of chlorhexidine.
6 is a photograph showing a process of performing an experiment using the dental radiograph and the light irradiator.
7 shows an FE-SEM photograph of a general titania nanotube.
Fig. 8 is a view showing a dental implant, and a part indicated by yellow indicates an abutment part.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Manufacturing example : Nanotube Specimen Production

Manufacturing example  One. Titania  Fabrication of Nanotube Specimen

The machined titanium plate (thickness 0.2mm, 99.5%; Hyundai Titanium, Korea) was washed with acetone, ethanol and distilled water in the order of 6% perchloric acid (Sigma, USA), 37% butoxyethanol glycol butadiene glycol, JunseiI, Japan), and 59% methanol (Methanol, Sigma, USA), and polishing was performed to produce a titanium plate having a flatness of 5 nm or less.

The electrolytically polished titanium plate was immersed in a solution of 0.5 wt% hydrofluoric acid (48 w / v%; Sigma, USA), water and acetic acid in an electrolyte solution (water / acetic acid mixture ratio of 7: 1) And anodized for 30 minutes.

After completion of the anodic oxidation, the specimen was washed with distilled water, dried in an oven at 60 ° C. for 24 hours, and then subjected to heat treatment at 500 ° C. for 2 hours (heat treatment in air, heating and cooling rate = 1 K / min) A titanium plate was produced.

Manufacturing example  2. Nitrogen doping Titania  Nanotube fabrication

The machined titanium plate (thickness 0.2mm, 99.5%; Hyundai Titanium, Korea) was washed with acetone, ethanol and distilled water in the order of 6% perchloric acid (Sigma, USA), 37% butoxyethanol glycol butadiene glycol, JunseiI, Japan), and 59% methanol (Methanol, Sigma, USA), and polishing was performed to produce a titanium plate having a flatness of 5 nm or less.

The electrolytically polished titanium plate was immersed in a solution containing 0.5 wt% hydrofluoric acid (48 w / v%; Sigma, USA), water and acetic acid mixture as an electrolyte solution (water / acetic acid mixture volume ratio = 7: 0.05 mol (5.25 g), 0.1 mol (10.5 g) and 0.2 mol (21 g) of diethanolamine (DEA, 105.14 g / mol) were added to the anodic oxidation electrolyte solution for nitrogen doping . The electrolyte solution for nitrogen doping was anodized for 30 minutes with an applied voltage of 20V.

After completion of the anodic oxidation, the specimen was washed with distilled water, dried in an oven at 60 ° C for 24 hours, and then heat-treated at 500 ° C for 2 hours (heat treatment in air, temperature elevation and cooling rate = 1K / min) to obtain a nitrogen-doped titania nanotube A coated titanium plate was produced.

Manufacturing example  3. Shape and surface analysis of specimen

The morphology and surface analysis of the nitrogen-doped titania nanotubes were carried out with a field emission scanning electron microscope (FE-SEM, S4800; Hitachi.Horiba, Japan) and a transmission electron microscope (TEM, Tecnai G2; FEI Co., USA, power: 300 kV) (XPS, K-Alpha ESKA system; Termo, USA) for nitrogen doping. The contact angle of the experimental specimen was measured with a contact angle meter (Theta Optical Tensiometer, KSV, Finland), and distilled water was used as the contact angle measuring solvent.

The FE-SEM image verification results are shown in Fig.

As shown in FIGS. 1A and 1B, nitrogen doped titania nanotubes were formed in the anodic oxidation electrolyte solution for nitrogen doping with 0.05 M and 0.1 M DEA added. However, in the electrolyte solution containing DEA of 0.2 M in FIG. 1C No nitrogen doped titania nanotubes were formed. Therefore, it was confirmed that the concentration of DEA capable of forming nitrogen-doped titania nanotubes is 0.1 M or less. 0.1M of DEA was added to analyze nitrogen doped titania nanotubes.

The results of TEM vertical cross-sectional image confirmation of the nitrogen-doped titania nanotubes are shown in FIG.

As shown in FIGS. 2A and 2B, a titanium layer, a titania nanotube and a new layer having a thickness of 100 nm were observed. As a result of a high-magnification TEM observation of a new layer having a thickness of 100 nm, anatase, a titania crystal phase with a lattice constant of 0.35 nm, Respectively.

The content of doped nitrogen in the lattice of the titania nanotube was analyzed by X-ray photoelectron spectroscopy and is shown in FIG.

As shown in FIG. 3, the nitrogen content of the pure titania nanotubes and the nitrogen-doped titania nanotubes were 0.57 and 3.39 atomic%, respectively. As shown in FIGS. 3B and 3C, N1s peak analysis showed that the binding energy of NO and NO ₂ ^- in nitrogen doped titanate nanotubes was 406.1 eV and 402.5 eV, respectively, indicating that interstitial nitrogen-doped titania nanotubes were formed Respectively.

Experimental Example : Nitrogen doping Titania  Identification of antimicrobial properties of nanotubes

Experimental Example  1. Mounting antibiotics

In order to contain the antibiotic in the nitrogen-doped titania nanotube, the antibiotic was carried in the nitrogen-doped titania nanotube.

For the supporting method, the antibiotics were dissolved in the methylsulfoxide (DMSO) solution, the PLA was dissolved in tetrahydrofuran, and the two solutions were mixed to the respective concentrations. Specifically, in an embodiment of the present invention, 2 g of PLA is dissolved in 100 g of tetrahydrofuran, 20 g of antibiotic, specifically tetracycline (Sigma, USA) is dissolved in 100 g of DMSO, (1.27 X 1.27 cm < 2 >) was immersed in a nitrogen-doped titania nanotube specimen and stirred for 30 minutes. Then, the specimen was taken out and dried at 23 ± 2 ° C. As a control, 20 g of tetracycline was dissolved in 200 g of DMSO, and a nitrogen-doped titania nanotube specimen (1.27 X 1.27 cm 2) was immersed in a solution of 10% (w / w) tetracycline .

The dried samples were immersed in distilled water, placed in an oven at 37 ° C, taken out at each elution time, and extracted with distilled water. The concentrations of antimicrobial drugs eluted in distilled water were measured using a microplate ELISA reader.

In order to confirm the dissolution characteristics of the antibiotics, 10% (w / w) tetracycline (Sigma, USA) solution containing 10% (w / w) tetracycline , USA) solution and a 1% (w / w) PLA solution, the dissolution characteristics of the antibiotic were confirmed and shown in FIG.

As shown in FIG. 4, the antimicrobial drug not mixed with PLA exhibited an initial mass release behavior. However, when antibiotics were mixed with PLA and mounted on nitrogen-doped titania nanotubes, it was confirmed that the antibiotics dissolve more slowly than antibiotics alone can do. Therefore, when the nitrogen-doped titania nanotube coating layer having the antimicrobial material mixed with PLA is formed on the abutment of the dental implant, the dissolution of the antimicrobial substance gradually occurs, so that the antibacterial implant having the characteristic of the sustained release agent can be provided .

Experimental Example  2. On light irradiation  Identification of antimicrobial activity by

To confirm the antimicrobial activity of the nitrogen-doped titania nanotube coating layer and the titania nanotube coating layer by the photocatalyst, the titania nanotube specimens prepared above were dissolved in 10% (w / w) tetracycline (Sigma, USA) and 1% (Sigma, USA) and 1% (w / w) PLA mixed solution (Comparative Example 1), and then loaded on a 10% (w / w) The nitrogen-doped titania nanotube specimens prepared above were each loaded on a 10% (w / w) tetracycline (Sigma, USA) and 1% (w / w) PLA mixed solution (Example 1) w / w) chlorhexidine (Sigma, USA) and 1% (w / w) PLA mixed solution (Example 2).

A remote controlled drug elution test using a photopolymerizer was carried out on the specimens of Comparative Examples 1 and 2 and Examples 1 and 2 using a dental light curing machine and the results are shown in FIG.

As shown in FIG. 7, it was confirmed that the elution of the drug after irradiation with the photopolymerization initiator of Examples and Comparative Examples significantly increased in both tetracycline and chlorhexidine. Therefore, since the photocatalytic effect of the nitrogen-doped titania nanotubes is better in the visible light region, in the case of the implant including the abutment having the nitrogen-doped titania nanotube coating layer, the photocatalyst can be generated by the visible light region, .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (8)

1. A dental implant comprising an abutment having a nitrogen-doped titania nanotube coating layer, wherein the nitrogen-doped titania nanotube coating layer comprises an antibiotic and a mixture of polylactic acid. The method according to claim 1,
Wherein the mixing ratio of the antibiotic and the polylactic acid mixture is 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid) based on the weight ratio. The method according to claim 1,
Wherein the nitrogen-doped titania nanotube coating layer is formed of an anodic oxidation electrolyte solution for nitrogen doping containing 0.01 M to 0.15 M of diethanolamine. The method of claim 3,
The anodizing electrolyte solution for nitrogen doping is prepared by adding hydrofluoric acid to a mixture of water and acetic acid in an amount of 0.4 to 0.6 wt% (w / w) based on the weight of hydrofluoric acid based on the total weight of the electrolytic solution, Is 6: 1 (water: acetic acid) to 8: 1 (water: acetic acid) based on the volume ratio. The method according to claim 1,
Wherein the antibiotic is any one selected from the group consisting of tetracycline, chlorhexidine, and combinations thereof. Preparing an anodic oxidation electrolyte solution for nitrogen doping by mixing 0.01 M to 0.15 M of diethanolamine (DEA) in an anodic oxidation electrolyte solution,
Anodizing the anodic oxidation electrolyte solution for nitrogen doping at an applied voltage of 5 to 25 V for 20 to 50 minutes to form a nitrogen doped titania nanotube gating layer on the surface of the dental implant;
Immersing the dental implant in which the nitrogen-doped titania nanotube coating layer is formed in a mixture of an antibiotic and a polylactic acid to thereby include the mixture in the nanotube coating layer
Of the implant surface. The method according to claim 6,
Wherein the mixing ratio of the antibiotic and the polylactic acid mixture is 8: 1 (antibiotic: polylactic acid) to 12: 1 (antibiotic: polylactic acid) based on the weight ratio. The method according to claim 6,
The anodic oxidation electrolyte solution is prepared by adding hydrofluoric acid to a mixed solution of water and acetic acid in an amount of 0.4 to 0.6 wt% (w / w) based on the weight of hydrofluoric acid based on the total weight of the electrolytic solution, Wherein the base is 6: 1 (water: acetic acid) to 8: 1 (water: acetic acid).

Images