Dental implants with excellent antibacterial properties and antibacterial coating methods

Abstract

Disclosed is a dental implant comprising a titanium substrate and a silver-titanium oxide matrix coated on at least a portion of a surface of the substrate, the silver-titanium oxide matrix having a peak P1 at a binding energy of 570-580 eV and a peak P2 at a binding energy of 360-375 eV as measured by XPS, and an intensity I1 of P1 and an intensity I2 of P2 satisfying the following formula: JPEG2024545346000009.jpg5130

Description

Technical Field

[0001] Relates to a dental implant with excellent antibacterial properties and an antibacterial coating method.

Background Art

[0002] Dental implants are artificial teeth that can permanently replace missing teeth and are widely used to restore the chewing function of partial or completely edentulous areas. Therefore, implants must be manufactured so that they can not only functionally serve the role of actual teeth, but also appropriately disperse the load applied to the teeth and can be used for a long time.

[0003] To increase the success rate of implants, it depends on the stability of the implant, that is, the fixing force, depending on the patient's bone mass and bone quality. The stability of the implant is expressed as the sum of the primary stability generated by the implant contacting the surrounding bone and the secondary stability obtained by the formation of new bone tissue and bone adhesion after implant placement. In particular, improving the early stability after implant placement is an important factor in enhancing the medium- and long-term stability and ultimately the success rate of the implant.

[0004] The main factors for early implant failure can occur due to the disappearance of the bone around the implant or the reduction of the fixing force due to various causes such as product defects, surgical factors, and patient factors. Especially when the bone around the implant disappears, the reduction of the fixing force of the implant due to the disappearance is inevitable. Therefore, as a result of analyzing the early failure cases due to the disappearance of the bone around the implant, early failure due to periodontitis or bacterial detection accounts for about 90%, and as a result of analyzing the products recovered from customers, anaerobic bacteria were detected in about 60%.

[0005] To address these problems, a method has been proposed to construct a system that can actively protect against contaminated saliva and bacteria by imparting antibacterial properties to the surface of the implant. In particular, to reduce the rate of early implant failure, the antibacterial properties must be maintained even during the initial implantation period. Therefore, there is a need for research and development of antibacterial coating methods that impart antibacterial properties to the surface of the implant and maintain them during the initial implantation period, as well as dental implants using such coatings. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] This invention provides dental implants and antibacterial coating methods with excellent antibacterial properties. [Means for solving the problem]

[0007] According to one embodiment, a dental implant is provided comprising a titanium substrate and a silver-titanium oxide matrix coated on at least a portion of the surface of the substrate, wherein the silver-titanium oxide matrix has a peak P1 with a binding energy of 570-580 eV and a peak P2 with a binding energy of 360-375 eV as measured by XPS, and the strengths I1 of P1 and I2 of P2 satisfy the following formula.

[0008]

number

[0009] In one embodiment, the dental implant may release 1 ppm / day or less of silver for at least one week in an inorganic solvent at 37°C.

[0010] In another embodiment, a method for antimicrobial coating of dental implants is provided, comprising the steps of (a) dissolving a silver precursor to support a titanium substrate in a coating solution having an Ag concentration of 10 to 300 mM, and (b) heating the coating solution and subjecting it to hydrothermal treatment.

[0011] In one embodiment, the silver precursor may be one selected from the group consisting of silver nitrate (AgNO3), silver perchlorate (AgClO4), silver tetrafluoroborate (AgBF4), silver hexafluorophosphate (AgPF6), silver acetate (CH3COOAg), silver trifluoromethanesulfonic acid (AgCF3SO3), silver sulfate (Ag2SO4), silver 2,4-pentanedione (CH3COCH=COCH3Ag), silver oxides (AgO, Ag2O, Ag2O2, Ag2O3), and mixtures of two or more of these.

[0012] In one embodiment, the pretreatment step may be further included, in which the titanium substrate is treated by at least one of the following methods before performing step (a): sandblasting, etching, washing, and drying.

[0013] In one embodiment, step (b) may be carried out under conditions of 150 to 300°C and 1 to 5 hours. [Effects of the Invention]

[0014] According to one embodiment, a dental implant and antibacterial coating method with excellent antibacterial properties have a silver-titanium oxide matrix formed on the surface of the implant, which can improve the antibacterial properties of the implant. Silver ions are slowly released from the silver-titanium oxide matrix during the initial period after implantation, which can impart and maintain the antibacterial properties of the implant. As a result, the early failure rate of the dental implant can be reduced, and ultimately the success rate of the implant can be improved.

[0015] The effects of any aspect of this specification are not limited to those described herein and should be understood to include all effects that can be inferred from the detailed description or claims of this specification. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 is an antimicrobial performance evaluation graph for selecting antimicrobial ions in this specification. [Figure 2]Figure 2 is a removal torque graph for the selection of the antibacterial coating method in this specification. [Figure 3] Figure 3 is an antibacterial performance evaluation graph according to the hydrothermal treatment conditions. [Figure 4] Figure 4 is an FE-SEM analysis image of the examples and comparative examples in this specification. [Figure 5] Figure 5 is the result of analyzing the SEM image and element distribution map by position of the examples in this specification. [Figure 6] Figure 6 is an EDS analysis image of the examples and comparative examples in this specification. [Figure 7] Figure 7 is an XPS analysis graph of the examples and comparative examples in this specification. [Figure 8] Figure 8 is an Ag release amount graph of the examples in this specification. [Figure 9] Figure 9 is an antibacterial performance evaluation graph according to the loading period of the examples in this specification. [Figure 10] Figure 10 is an antibacterial performance evaluation graph according to the cleaning conditions of the examples and comparative examples in this specification.

Mode for Carrying Out the Invention

[0017] Hereinafter, an aspect of this specification will be described with reference to the accompanying drawings. However, the matters described in this specification can be embodied in various different forms, and therefore, it is not limited to the examples described here. Also, in the drawings, in order to clearly explain an aspect of this specification, parts not related to the explanation are omitted, and similar reference numerals are given to similar parts throughout the specification.

[0018] Throughout the specification, when a part is said to be "connected" to another part, this includes not only the case where it is "directly connected", but also the case where it is "indirectly connected" through other elements in between. Also, when a part is said to "include" a certain component, this means that, unless otherwise stated to the contrary, it can further include other components rather than excluding other components.

[0019] In this specification, when a numerical value range is described, unless a specific range is particularly described, the value has the precision of significant figures provided in accordance with the standard rules in chemistry for significant figures. For example, 10 includes the range of 5.0 to 14.9, and the number 10.0 includes the range of 9.50 to 10.49.

[0020] Hereinafter, referring to the accompanying drawings, one embodiment of this specification will be described in detail.

[0021] Dental implants with excellent antibacterial properties According to one aspect, there is provided a dental implant including a titanium substrate and a silver-titanium oxide matrix coated on at least a part of the surface of the substrate, wherein the silver-titanium oxide matrix has a peak P1 with a binding energy of 570 to 580 eV and a peak P2 with a binding energy of 360 to 375 eV measured by XPS, and the intensity I1 of P1 and the intensity I2 of P2 satisfy the following formula.

[0022]

Number

[0023] To increase the success rate of dental implants, a stable bond with the surrounding bone of the user must be formed during the initial implantation period. Among the various factors for implantation failure, the early implantation failure rate due to bacterial infection accounts for a large proportion.

[0024] The dental implant of this specification may include a titanium substrate and a silver-titanium oxide matrix coated on at least a part of the surface of the substrate and have antibacterial properties. The silver-titanium oxide matrix can block quorum sensing and suppress the formation of biofilms on the surface of the implant. Thereby, the implantation failure due to bacterial infection during the implantation can be minimized.

[0025] As used herein, "quorum sensing" refers to a bacterial density-dependent gene expression regulation mechanism that accumulates in proportion to cell density during bacterial growth, and where the collective metabolic activity of bacteria is regulated when a certain concentration is reached. In other words, it refers to the phenomenon in which, when bacterial cell concentration reaches a so-called quorum for decision-making, specific traits not observed in low-density cells are collectively induced and expressed. In particular, in pathogenic bacteria, quorum sensing can induce pathogenicity and cause infection.

[0026] The silver-titanium oxide matrix can kill bacteria by releasing silver ions, which are antimicrobial ions. As a result, it can suppress the phenomenon of bacteria adhering to the surface of the implant. The silver ions can bind to the cysteine ​​group of the bacterial film and inactivate proteins. This can induce the release of reactive oxygen species from the bound cells, thereby killing the bacteria. Through the mechanism described above, silver ions can kill bacteria and effectively suppress biofilm formation, maintaining sustained antimicrobial activity without antimicrobial resistance.

[0027] The aforementioned silver-titanium oxide matrix may contain antibacterial components in various forms. As a result, it possesses the necessary level of antibacterial activity in the initial stages of planting and can maintain its antibacterial effect for a long period of time.

[0028] Peaks P1 and I1 with binding energies of 570-580 eV represent the peak range and intensity value of Ag2p. Peaks P2 and I2 with binding energies of 360-375 eV represent the peak range and intensity value of Ag3d. Ag2p represents silver metal, and Ag3d represents oxidized silver ions. A silver-titanium oxide matrix whose intensities I1 and I2 satisfy specific conditions can simultaneously contain silver metal and silver ions and embody a slow-release effect. Furthermore, if I1 and I2 satisfy specific conditions, the success rate of early implantation of the dental implant can be effectively increased.

[0029] The conditions I1 and I2 expressed in the above formulas refer to the ratio of silver metal to silver ions measured by the XPS graph. I2 is at least twice I1 and may be five times or less. In one example, I2 may be at least twice, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, 3 times, 3.1 times, 3.2 times, 3.3 times, or 3.4 times I1. In another example, I2 may be five times or less I1, 4.9 times or less, 4.8 times or less, 4.7 times or less, 4.6 times or less, 4.5 times or less, 4.4 times or less, 4.3 times or less, 4.2 times or less, 4.1 times or less, 4 times or less, 3.9 times or less, 3.8 times or less, 3.7 times or less, or 3.6 times or less I1.

[0030] Dental implants that meet the above conditions have a high initial silver release rate and can have antibacterial effects such as bacterial death and adhesion inhibition during the initial implantation period. Furthermore, they can maintain their antibacterial effect over time by having a slow-release effect in which silver is released gradually.

[0031] For example, the dental implant may release at least 1 ppm / day of silver per week in an inorganic solvent at 37°C. The slow-release effect of the dental implant may last for at least one week, one month, two months, three months, or longer. The slow-release effect of the dental implant means that it exhibits a sustained antibacterial effect by releasing at least one of silver ions and silver metal over a long period of time. The inorganic solvent means water such as purified water or deionized water. The dental implant may release at least 1 ppb / day, 5 ppb / day, or 10 ppb / day of silver during the aforementioned period.

[0032] As a non-restrictive example, the titanium substrate means a material consisting of pure titanium or an alloy of titanium with another metal on the periodic table. The titanium alloy may be, but is not limited to, one selected from the group consisting of titanium (Ti) and aluminum (Al), silicon (Si), vanadium (V), niobium (Nb), zirconium (Zr), molybdenum (Mo), chromium (Cr), tin (Sn), tantalum (Ta), palladium (Pd), and at least one combination thereof.

[0033] Antibacterial coating method for dental implants In another embodiment, a method for antimicrobial coating of dental implants is provided, comprising the steps of (a) dissolving a silver precursor to support a titanium substrate in a coating solution having an Ag concentration of 10 to 300 mM, and (b) heating the coating solution and subjecting it to hydrothermal treatment.

[0034] The step in (a) above may involve supporting a titanium substrate in a coating solution in which a silver precursor is dissolved. The silver precursor may be, but is not limited to, one selected from the group consisting of silver nitrate (AgNO3), silver perchlorate (AgClO4), silver tetrafluoroborate (AgBF4), silver hexafluorophosphate (AgPF6), silver acetate (CH3COOAg), silver trifluoromethanesulfonic acid (AgCF3SO3), silver sulfate (Ag2SO4), silver 2,4-pentanedione (CH3COCH=COCH3Ag), silver oxides (AgO, Ag2O, Ag2O2, Ag2O3), and mixtures of two or more of these.

[0035] As an example, the Ag concentration of the coating solution may be 10 to 300 mM. For example, 10 mM, 11 mM, 12 mM, 13 mM, 14 mM, 15 mM, 16 mM, 17 mM, 18 mM, 19 mM, 20 mM, 21 mM, 22 mM, 23 mM, 24 mM, 25 mM, 26 mM, 27 mM, 28 mM, 29 mM, 30 mM, 31 mM, 32 mM, 33 mM, 34 mM, 35 mM, 36 mM, 37 mM, 38 mM, 39 mM, 4 0mM, 41mM, 42mM, 43mM, 44mM, 45mM, 46mM, 47mM, 48mM, 49mM, 50mM, 51mM, 52mM, 53mM, 54mM, 55m M, 56mM, 57mM, 58mM, 59mM, 60mM, 61mM, 62mM, 63mM, 64mM, 65mM, 66mM, 67mM, 68mM, 69mM, 70mM, 7 1mM, 72mM, 73mM, 74mM, 75mM, 76mM, 77mM, 78mM, 79mM, 80mM, 81mM, 82mM, 83mM, 84mM, 85mM, 86m M, 87mM, 88mM, 89mM, 90mM, 91mM, 92mM, 93mM, 94mM, 95mM, 96mM, 97mM, 98mM, 99mM, 100mM, 110mM The Ag concentration may be 120mM, 130mM, 140mM, 150mM, 160mM, 170mM, 180mM, 190mM, 200mM, 210mM, 220mM, 230mM, 240mM, 250mM, 260mM, 270mM, 280mM, 290mM, 300mM, or a range between two of these values, but is not limited thereto. If the Ag concentration is below the above range, the amount of silver may be insufficient and the antibacterial properties may decrease, and if it exceeds the above range, it may be difficult to form the coating solution or the formation of the coating layer may be poor due to viscosity or other problems.

[0036] As an example, the process may further include a pretreatment step in which the titanium substrate is treated by at least one of the following methods before performing step (a): sandblasting, etching, washing, and drying. This is not the only example.

[0037] When the titanium substrate is sandblasted or etched to impart surface roughness, the bone fusion properties can be improved, but the adhesion to bacteria may also increase. The titanium substrate can be washed or dried to remove foreign matter from the surface of the substrate, and a subsequent antibacterial coating layer can be effectively formed.

[0038] The (b) step may involve heating the coating solution and performing hydrothermal treatment to form a silver-titanium oxide matrix on the surface of the titanium substrate.

[0039] In one example, step (b) may be carried out under conditions of 150 to 300°C and 1 to 5 hours. Step (b) may be carried out at temperatures in the range of 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, 300°C, or between two of these values, but is not limited thereto. The temperature conditions of step (b) can affect the amount of silver coating on the silver-titanium oxide matrix and the resulting antibacterial performance. Furthermore, step b) may be performed, for example, over a period of time of 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or a range of time between two of these values.

[0040] After step (b) above, the surface of the titanium substrate may be cleaned to remove unbound silver ions. However, such cleaning may be carried out in a manner that does not impair the antibacterial properties of the silver-titanium oxide matrix formed on the surface of the titanium substrate. For example, it may be carried out by immersing the substrate in one of the following: purified water, alcohol, and mixtures thereof, followed by stirring.

[0041] The examples of this specification will be described in more detail below. However, the experimental results described below represent only representative results from the aforementioned examples, and the scope and content of this specification cannot be narrowed or limited by these examples. The effects of various examples of this specification not explicitly presented below will be described in detail in the relevant sections.

[0042] Experimental Example 1: Selection of Antimicrobial Ions To select antimicrobial ions, the salivary bacterial contamination rate was evaluated. Saliva (SA) was prepared as the control group, and 100 ml each of physiological saline (Saline), hydrated solution (EC), magnesium ion salt, and silver ion salt were prepared as the experimental group. 1 ml of salivary bacterial suspension isolated from the prepared saliva was added to each of the control and experimental group solutions, and the solutions were maintained at 37°C under anaerobic conditions for 16 hours. After 16 hours, the salivary bacterial contamination rate was measured, and the results are shown in Figure 1. The salivary bacterial contamination rate of the control group saliva was set to 100%, and the salivary bacterial contamination rate of the experimental group was measured.

[0043] Referring to Figure 1, physiological saline and hydrated solution (EC) showed salivary bacterial contamination rates of 52.45% and 23.6%, respectively, compared to saliva. Magnesium ion salt, an antimicrobial ion salt, showed the highest salivary bacterial contamination rate at 102.34%. In contrast, silver ion salt showed a salivary bacterial contamination rate of 0.28%, representing a 99.7% reduction in bacterial contamination compared to saliva. Therefore, silver ions were selected as the antimicrobial ion.

[0044] Experimental Example 2: Selection of an antibacterial coating method Animal experiments were conducted to select an antimicrobial coating method. Titanium implants were prepared as a control group. For the experimental group, titanium implants treated with a solution containing silver ion salt and hydrogen peroxide, and titanium implants hydrothermally treated with a solution containing silver ion salt were prepared. Eight implant samples of each type were prepared. The prepared implants were contaminated by being placed in saliva for 24 hours before implantation, then implanted in the tibia of rabbits and maintained for 21 days to allow bone formation, after which the removal torque was evaluated. The experimental results are shown in Figure 2.

[0045] Referring to Figure 2, Figure 2(a) shows the average removal torque for each of the eight samples. Figure 2(b) shows the removal torque for each of the eight samples. Untreated titanium implants showed an average removal torque of 26.95 N, indicating the worst performance, with 2 implantation failures out of 8. In contrast, implants coated with silver ions showed values ​​of 46.43 N and 52.11 N, respectively, confirming a reduction in saliva contamination by silver ions. Furthermore, implants coated with silver ions by hydrothermal treatment showed the best removal torque, with 0 implantation failures out of 8. Therefore, the excellent antibacterial properties of silver ions against salivary bacteria were confirmed, and hydrothermal treatment was selected as the coating method.

[0046] Experimental Example 3: Selection of Hydrothermal Treatment Conditions 1 To select the hydrothermal treatment conditions, antibacterial performance was evaluated based on temperature, time, and silver ion concentration.

[0047] For evaluation, a titanium substrate was measured in 3 x 3 cm. 2 Nine samples were prepared as size samples. The hydrothermal treatment conditions for each titanium substrate were as follows: temperatures of 180°C, 200°C, and 250°C, treatment times of 1 hour, 2 hours, and 3 hours, and silver ion concentrations of 30 mM, 60 mM, and 100 mM.

[0048] As salivary bacteria, Aggregatilacter actinomycetemcomitans ATCC 33384 and Porphyromonas gingivalis, which are causative agents of acute periodontitis and peri-implantitis, were used. The prepared salivary bacteria were inoculated into BHI (Brain Heart Infusion Broth, Merck) medium and cultured at 37°C under anaerobic conditions for 16-24 hours. The culture solutions were diluted in BHI medium until the absorbance at 600 nm was 0.1, and then further diluted in BHI medium to reduce the bacterial concentration to 1 / 10 to produce two types of salivary bacterial suspensions.

[0049] The nine titanium substrates were sterilized by exposing them to UV light in a clean bench for 30 minutes, and then placed one in each well of a 24-well plate. One mL of the prepared salivary bacterial suspension was added to each well, and the plates were incubated at 37°C under anaerobic conditions for 16 hours. One mL of 0.1 wt% crystal violet solution was added to each well of a new 24-well plate. After transferring the samples to each well of the plate containing crystal violet, the plates were incubated at room temperature for 10 minutes to stain the bacteria purple.

[0050] A new 24-well plate was prepared by adding 1 mL of phosphate-buffered saline (PBS) solution to each well. After transferring each stained sample to its respective well, the process was repeated. The samples washed with PBS were transferred to a dry tissue, and the bottom surface of the samples was wiped. 500 μL of 30 wt% acetic acid solution was added to each well of a new 24-well plate, and each sample was transferred to its respective well. The samples were then incubated at room temperature for 20 minutes to dissolve the stain. 200 μL of the dissolved solution was added to each 96-well plate, and the absorbance (595 nm) was measured using a microplate reader. The results are shown in Figure 3. For comparison with the samples, the absorbance (OD, 595 nm) was measured for media uninoculated with salivary bacteria and untreated titanium substrate samples, along with a control group treated with a salivary bacteria suspension as described above.

[0051] The hydrothermal treatment conditions for each of the nine samples are shown in Table 1 below.

[0052] [Table 1]

[0053] Referring to Table 1 and Figure 3, all samples except for samples 1 and 4 showed an OD (595nm) value of 0.08 or less, confirming the excellent inhibitory effect of silver ions on salivary bacteria.

[0054] To determine the optimal hydrothermal treatment conditions, the OD(595nm) values ​​were aggregated for different temperatures, time intervals, and silver ion concentrations, and are shown in Table 2.

[0055] [Table 2]

[0056] Referring to Table 2, the OD(595nm) values ​​under different temperature conditions during hydrothermal treatment were 0.246 and 0.212 at 200°C and 250°C, respectively, confirming improved antibacterial activity compared to hydrothermal treatment at 180°C. Furthermore, the salivary bacterial contamination rate under different time conditions was excellent at 2 hours and 3 hours, and the salivary bacterial contamination rate under different silver ion concentrations was excellent at 60 mM and 100 mM. Therefore, the optimal hydrothermal treatment conditions for improving antibacterial activity were determined to be a temperature of 200-250°C, a time of 2-3 hours, and a silver ion concentration of 60-100 mM.

[0057] Experimental Example 4: Selection of Hydrothermal Treatment Conditions 2 To select the hydrothermal treatment conditions, we evaluated the H2O2 concentration (chemical treatment), temperature, the rate of suppression of salivary bacterial contamination over time, the initial titanium (Ti) ion elution amount, and the silver (Ag) ion release amount during hydrothermal treatment.

[0058] For evaluation, a titanium substrate was measured in 3 x 3 cm. 2 Nine samples were prepared as size samples. For the hydrothermal treatment of each titanium substrate, the H2O2 concentrations were set to 0% by weight (no additive), 1% by weight, and 2% by weight. The temperatures were set to 180°C, 200°C, and 250°C, and the treatment times were set to 1 hour, 2 hours, and 3 hours. The silver ion concentration was fixed at 100 mM.

[0059] The inhibition rate of salivary bacterial contamination was determined in the same manner as the antimicrobial performance evaluation described in Experimental Example 3. The inhibition rate of salivary bacterial contamination was derived using the OD (595nm) value of an untreated titanium substrate sample contaminated with salivary bacteria as the baseline.

[0060]

number

[0061] Table 3 shows the combined values ​​of the salivary bacterial contamination inhibition rate, initial Ti elution amount, and Ag release amount for each H2O2 concentration, temperature, and time.

[0062] [Table 3]

[0063] Referring to Table 3, the reduction rate of salivary bacterial contamination under H2O2 concentration conditions during hydrothermal treatment showed only a slight difference of 0.08 between the maximum and minimum values. However, it was confirmed that the initial Ti elution amount increased significantly with increasing concentration. Therefore, H2O2 was not used during hydrothermal treatment. Furthermore, under temperature conditions, Ag ion release was excellent at temperatures above 200°C, and the initial Ti ion elution was low, showing a significant result. Under time conditions, the reduction rate of salivary bacterial contamination was highest at 3 hours, the amount of Ag ion release was highest at 2 hours, and the initial Ti ion elution was lowest at 3 hours.

[0064] Examples and comparative examples were established according to the antimicrobial ion selection and hydrothermal treatment conditions described in Experimental Examples 1-4 above.

[0065] Examples A disc-shaped (cylindrical) Cp-Ti (Titanium Grade 4) specimen with a diameter of 6 mm, a thickness of 2 mm, and a length of 10 mm was prepared. The specimen was supported in a 100 mM silver nitrate solution, and then heated and hydrothermally treated at 200°C for 3 hours. After the hydrothermal treatment, it was washed by being supported in purified water (Deionized Water) for 5 minutes to complete the antimicrobial coating of the specimen.

[0066] Comparative Example 1 The procedure was the same as in the examples, except that the silver precursor solution was replaced with purified water and hydrothermal treatment was performed.

[0067] Comparative Example 2 The procedure was the same as in the examples, except that after hydrothermal treatment, the material was supported in purified water and ultrasonically cleaned for 5 minutes.

[0068] Experimental Example 5: FE-SEM and EDS Analysis FE-SEM and EDS analysis were performed for the surface analysis of the examples and comparative examples, and the results are shown in Figures 4 to 6. Figure 4 shows FE-SEM analysis images of the examples and comparative examples described herein. Referring to Figure 4, it can be seen that silver particles are formed on the surface of the example. In contrast, it can be seen that no coating particles are formed on the surface of Comparative Example 1, and it can be seen that the silver particle coating is reduced in Comparative Example 2 compared to the example.

[0069] Figure 5 shows an analysis of the elemental distribution of titanium and silver at different locations in the SEM images of the example. Referring to Figure 5, location 1 shows 99.79 at% titanium and 0.21 at% silver, location 2 shows 99.69 at% titanium and 0.31 at% silver, and location 3 shows 94.16 at% titanium and 5.84 at% silver. At location 3, it can be confirmed that bulk silver particles were formed, causing an increase in the at% of silver.

[0070] Figure 6 shows EDS analysis images of the examples and comparative examples described herein. Referring to Figure 6, it can be seen that in the examples, silver is uniformly distributed on the surface of the titanium substrate. In Comparative Example 1, it can be seen that no antibacterial coating layer is formed, and only titanium elements are distributed. In Comparative Example 2, silver is uniformly distributed on the surface of the titanium substrate, but in a smaller amount compared to the examples.

[0071] Experiment Example 6: XPS Analysis XPS analysis was performed to analyze the atomic states of the examples and comparative examples, and the results are shown in Figure 7. Untreated Cp-Ti (Titanium Grade 4) specimens were also subjected to XPS analysis as a control group.

[0072] Referring to Figure 7, it can be seen that in the analysis graph of the example, peaks for Ag metal (Ag2p) and oxidized Ag ions (Ag3d) were detected simultaneously. This confirms that the silver particles were effectively coated onto the surface of the titanium substrate in the example. In contrast, no peak for Ag was detected in the comparative example, and only peaks for Ti (Ti2s, Ti2p) were detected. The control group showed a peak pattern almost similar to the comparative example, but it could be seen that surface treatment was not achieved and a weak peak of oxidized Ti ions appeared.

[0073] Comparing the heights of the Ag metal peak and the oxidized Ag ion peak, it can be seen that the Ag3d peak (360-375 eV) is approximately 3.5 times higher than the Ag2p peak (570-580 eV).

[0074] Experimental Example 7: Evaluation of Ag Release Amount To evaluate the amount of Ag released during the loading period of the examples, the specimens from the examples were loaded into purified water (DW), and the amount of Ag released over 90 days was measured. The amount of Ag released was measured using an ICP-MS analyzer, and the results are shown in Figure 8.

[0075] Referring to Figure 8, the amount of Ag ions released was over 250 ppb immediately after loading, and over 100 ppb three days after loading. After three days, the amount of Ag ions released gradually decreased, and after 30 days, it was confirmed that Ag ions were slowly released at a rate of over 50 ppb. After 60 days of loading, the amount of Ag ions released was over 30 ppb. Therefore, when the examples described herein are applied to dental implants, it can be predicted that silver ions, which are antimicrobial ions, will be slowly released during the initial implantation period (approximately 3 months), and the initial implantation failure rate will be significantly reduced.

[0076] Experimental Example 8: Evaluation of antibacterial performance based on Ag ion release period The antimicrobial performance of the examples was evaluated based on the Ag ion release period. For comparison with the examples, the inhibition rate of salivary bacterial contamination was measured for both a culture medium without salivary bacteria inoculation (Media) and a culture medium containing only a suspension of salivary bacteria (control group), and the results are shown in Figure 9.

[0077] Referring to Figure 9, the example showed a reduction in salivary bacterial contamination of over 80% on day 3, depending on the Ag ion release period. Over 90 days, the reduction in salivary bacterial contamination gradually decreased, but still showed a reduction of over 60%. This confirms that Ag ions are released gradually within 90 days.

[0078] Experimental Example 9: Evaluation of antibacterial performance under washing conditions The antibacterial performance of the examples and comparative examples was evaluated under the Ag washing conditions. For evaluation, the examples and Comparative Example 2, which was ultrasonically washed with purified water after hydrothermal treatment, were selected. In Comparative Example 2, the ultrasonic washing time was subdivided into 1 minute, 3 minutes, and 5 minutes, and these were set as Comparative Examples 2-1, 2-2, and 2-3, respectively. Comparative Example 3 was set by replacing the washing solution with ethanol, and the ultrasonic washing time was subdivided into 1 minute, 3 minutes, and 5 minutes, and these were set as Comparative Examples 3-1, 3-2, and 3-3, respectively. The antibacterial performance was evaluated as described above in Experimental Example 3, and the absorbance OD (595 nm) value was measured, and the results are shown in Figure 10.

[0079] Referring to Figure 10, the antibacterial properties of the example in which the sample was supported in purified water and washed were the best. In contrast, Comparative Examples 2 (2-1, 2-2, 2-3) and 3 (3-1, 3-2, 3-3), which underwent ultrasonic cleaning, showed a slight decrease in antibacterial performance. This can be predicted to be because ultrasonic cleaning removes some of the bulk ion particles, affecting the antibacterial performance. It can be confirmed that the antibacterial performance is hardly affected by the cleaning solution.

[0080] The descriptions herein provided herein are illustrative, and a person with ordinary skill in the art to which one aspect of this specification belongs will understand that it is possible to easily modify it into other specific forms without altering the technical ideas or essential features described herein. Therefore, the embodiments described herein should be understood in all respects as illustrative and not limiting. For example, each component described in a single form may be carried out in a dispersed manner, and similarly, components described as dispersed may be carried out in a combined manner.

[0081] The scope of this specification is defined by the claims set forth below, and all modifications or alterations derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included within the scope of this specification.

Claims

1. (a) A step of supporting a titanium substrate in a coating solution in which a silver precursor is dissolved and the Ag concentration is 60 to 100 mM, and (b) The coating solution is subjected to hydrothermal treatment by heating it at 200 to 250°C for 2 to 3 hours to form a silver-titanium oxide matrix on at least a portion of the surface of the titanium substrate, The aforementioned silver-titanium oxide matrix has a peak P of binding energy of 570-580 eV as measured by XPS. １ and peak P of 360-375 eV ２ It has, P １ Strength I １ and P ２ Strength I ２ This is an antibacterial coating method for dental implants that satisfies the following formula. [Math 1]

2. The silver precursor is silver nitrate (AgNO ３ ), silver perchlorate (AgClO ４ ), silver tetrafluoroborate (AgBF ４ ), silver hexafluorophosphate (AgPF ６ ), silver acetate (CH ３ COOAg), silver trifluoromethanesulfonate (AgCF ３ SO ３ ), silver sulfate (Ag ２ SO ４ ), silver 2,4-pentanedionate (CH ３ COCH=COCH ３ Ag), silver oxides (AgO, Ag ２ O, Ag ２ O ２ , Ag ２ O ３ ), and one selected from the group consisting of mixtures of two or more of them, the method for antibacterial coating of a dental implant according to claim 1.

3. The antimicrobial coating method for a dental implant according to claim 1, further comprising a pretreatment step of treating the titanium substrate by at least one of sandblasting, etching, cleaning, and drying before performing step (a) above.

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