Implant with nano-pattern shallow concave surface and manufacturing method thereof

Abstract

The present invention relates to an implant having a nanopatterned shallow concave surface and a method for manufacturing the same, the method comprising: a step for forming titanium oxide nanotubes by anodizing an implant body made of titanium metal or a titanium alloy; and a step in which the titanium oxide nanotube is removed, thereby forming a shallow recess on the surface of the implant main body. Thus, the surface of the implant main body is anodized and then the anodized surface is removed to form a shallow recess on the surface of the implant main body, the anodized titanium oxide film is peeled off to prevent the titanium oxide film from falling into a living body, and impurities remaining on the surface can be effectively removed. Further, it is possible to maximize the surface area when transplanted into the inside of a living body by means of the use of titanium or a titanium alloy as a raw material for the implant main body and the dimples formed by surface anodic oxidation, thereby providing excellent biocompatibility, chemical stability, and mechanical stability.

Description

[0001] This application is a divisional application of the invention patent application with application number 201780026242X (international application number: PCT / KR2017 / 004776), application date May 8, 2017, entitled "Implant with shallow concave surface of nanopattern and manufacturing method thereof". Technical Field

[0002] This invention relates to an implant with a shallow concave surface featuring a nanopattern and a method for manufacturing the same. More particularly, it relates to an implant with a shallow concave surface featuring a nanopattern, which can form shallow concavities on the surface of the implant body by anodizing and then removing the anodized surface, and can prevent the anodized titanium oxide film from falling into the body by peeling it off. Background Technology

[0003] An implant is a shaped component, such as a membrane, fixation plate, or three-dimensional or spatial component, that can be transplanted into organs or viscera. It serves as a fixation method, similar to screws, pins, rivets, or anchors, to support or adhere tissue during treatment, or to separate tissue from other tissues. The biomaterials used to manufacture implants have superior strength, fatigue resistance, and machinability compared to other materials such as ceramics and polymers. They are currently the most widely used biomaterials in dentistry, orthopedic surgery, and plastic surgery for the regeneration and treatment of defects and damage in living organisms. The metals used for biological transplantation as described above include iron (Fe), chromium (Cr), nickel (Ni), stainless steel, cobalt alloy (Co alloy), titanium (Ti), titanium alloy (Ti alloy), zirconium (Zr), niobium (Nb), tantalum (Ta), gold (Au), and silver (Ag). Among these, stainless steel, titanium, titanium alloys, and gold are the most widely used in the human body due to their superior corrosion resistance and stability within human tissues compared to other metal materials.

[0004] Metals used for bioimplantation, as described above, for manufacturing implants inserted into living organisms, must meet the following two conditions. First, they must have excellent biocompatibility. That is, when using the metal as a substitute for biosupport, there should be no foreign body reaction and no toxicity to surrounding tissues. Second, they must have a surface capable of allowing osteoblasts and newly formed bone to fuse well with the transplanted metal surface. To manufacture the bioimplantation metals described above, researchers have been trying to improve bone-bonding strength by increasing the surface area of ​​the metal, changing its surface shape, or through physical and chemical surface treatments. Among these, the most representative are surface treatments such as threading, sandblasting, and electrochemical oxidation to strengthen the holding forces between bone tissues, and anodizing, plasma spraying, alkaline treatment, and ion implantation to form a corrosion-resistant coating and improve the bonding properties with bone.

[0005] Furthermore, existing technologies such as "Korean Patent No. 10-2009-0060833, Implant Material and Manufacturing Method Using Anodizing," "Korean Patent No. 10-2011-0082658, Surface Treatment Method for Titanium Implants and Implants Manufactured Using the Above Method," and "Korean Patent No. 10-2012-0101748, Implant Surface Treatment Solution and Surface Treatment Method Using the Above Solution and Implants Manufactured Using the Above Method" disclose techniques for forming nanotubes on the surface of metals through anodizing, thereby promoting metal-bone fusion. However, in existing technologies, the metal oxides on the metal substrate obtained by anodizing may peel off from the metal surface and fall into the body during insertion due to their relatively weak mechanical strength. Figure 1 These are SEM images illustrating the state of a metal surface during anodizing using existing methods. They reveal the separation of the metal oxides formed during anodizing. Furthermore, Figure 2 This is a SEM image illustrating the state where the internal metal is exposed due to the easy peeling off of the metal oxide. As mentioned above, anodized metal oxides are easily peeled off from the metal surface when subjected to physical forces such as bending. In this case, the peeled-off anodized metal oxides can fall into the organism and cause serious adverse effects. Furthermore, another problem with anodizing is surface contamination caused by the residue of electrolytes or chemicals used in the anodizing process. As mentioned above, the pores in the anodized surface are at the nanometer scale; the smaller the pore size, the more difficult it is to remove residual impurities. Summary of the Invention

[0006] The purpose of this invention is to provide an implant with a nano-patterned shallow concave surface that can form shallow depressions on the surface of the implant body by anodizing the surface and then removing the anodized surface, while preventing the anodized titanium oxide film from falling into the body by peeling it off, and removing the impurities remaining on the surface during peeling off, and the same method thereof.

[0007] Furthermore, another object of the present invention is to provide an implant with a nanopatterned shallow concave surface that provides excellent biocompatibility, chemical stability and mechanical stability when transplanted into a living organism by means of titanium or titanium alloy as the raw material of the implant body and by the shallow concavity formed by surface anodizing.

[0008] Furthermore, another object of the present invention is to provide an implant having a shallowly concave surface with nanopatterns of different sizes, which can be formed by performing anodizing while performing sandblasting or SLA (Sandblasted, Large-grit, Acid etched) processes, and a method thereof.

[0009] To achieve the objectives described above, the method for manufacturing an implant with a shallowly concave surface having a nanopattern, to which the present invention is applicable, is characterized by comprising: a step of forming titanium oxide nanotubes by anodizing an implant body made of titanium metal or titanium alloy; and a step of forming shallow grooves on the surface of the implant body by removing the titanium oxide nanotubes.

[0010] In the step of forming titanium dioxide nanotubes by performing anodizing, the implant body is impregnated with a solution containing fluoride ions (F... - It is advisable to perform anodic oxidation in an electrolyte solution.

[0011] In addition, after forming the shallow depression on the surface of the implant body, the procedure further includes: forming an oxide film with a thickness of 10 nm to 1,000 nm on the surface of the implant body by heat treatment.

[0012] The aforementioned shallow depression is hemispherical in shape with a diameter of 10 nm to 1,000 nm, and preferably includes micropores of a few nanometers in size on the surface of the hemispherical shallow depression.

[0013] The removal of the aforementioned titanium dioxide nanotubes is performed by immersing the implant body in hydrogen peroxide water (H2O2) and ultrasonically washing it, or by immersing it in an aqueous solution of organic acid or alkaline solution. It is preferable to further include a sandblasting process on the surface of the implant body before the step of forming titanium dioxide nanotubes. In the sandblasting process, it is preferable to form micron-sized shallow depressions of 50 μm to 500 μm on the surface of the implant body by impacting the surface of the implant body with a sandblasting medium.

[0014] Prior to the above-mentioned step of forming titanium oxide nanotubes, it is advisable to further include a step of surface treatment of the implant body using SLA (Sand blasted, Large-grit, Acid etched) process.

[0015] To achieve the objectives described above, the implant with a shallowly concave surface having a nanopattern is applicable to the present invention, characterized in that: titanium oxide nanotubes are formed by anodizing the implant body made of titanium metal or titanium alloy, and shallow concavities are formed on the surface of the implant body by removing the titanium oxide nanotubes.

[0016] The aforementioned shallow depression is hemispherical in shape, and the ratio of the diameter to the height of the shallow depression is diameter:height = 1:0.01 to 0.5. The diameter of the hemispherical shallow depression is preferably 10 nm to 1,000 nm, and the shallow depression also preferably includes micropores of a few nanometers in size.

[0017] It is preferable to form medium-sized shallow depressions of 1 μm to 50 μm larger than the aforementioned shallow depressions, and micron-sized shallow depressions of 50 μm to 500 μm larger than the aforementioned medium-sized shallow depressions, in the implant body.

[0018] To achieve the objectives described above, the implant with a shallow concave surface featuring a nanopattern is characterized by comprising: an implant body having a hemispherical shallow concave surface formed thereon.

[0019] The hemispherical shallow depression is formed by anodizing the implant body. The ratio of the diameter to the height of the hemispherical shallow depression is preferably 1:0.01 to 0.5, and the diameter of the hemispherical shallow depression is preferably 10 nm to 1,000 nm.

[0020] In addition, the hemispherical shallow depressions also include micropores of a few nanometers in size. It is preferable to form medium-sized shallow depressions of 1 μm to 50 μm larger than the shallow depressions and micron-sized shallow depressions of 50 μm to 500 μm larger than the medium-sized shallow depressions in the implant body.

[0021] With the configuration of the present invention as described above, shallow depressions can be formed on the surface of the implant body by anodizing the surface and then removing the anodized surface. At the same time, the anodized titanium oxide film can be peeled off to prevent it from falling into the body and to effectively remove impurities remaining on the surface.

[0022] Furthermore, by using titanium or titanium alloy as the raw material for the implant body and forming shallow depressions through surface anodizing, the surface area when transplanted into the organism can be maximized, thereby providing excellent biocompatibility, chemical stability and mechanical stability. Moreover, shallow depressions of different sizes, including nanopatterns, can be formed by performing anodizing while performing sandblasting or SLA (Sandblasted, Large-grit, Acid-etched) processes. Attached Figure Description

[0023] Figure 1 as well as Figure 2 These are SEM images of anodized metal oxides according to embodiments of the prior art.

[0024] Figure 3 This is a sequence diagram of the manufacturing method of an implant with a shallow concave surface having a nanopattern, according to Embodiment 1 of the present invention.

[0025] Figure 4 It is a schematic diagram illustrating the manufacturing process of implants.

[0026] Figure 5 This is a sequence diagram of the method for manufacturing an implant according to Embodiment 2 of the present invention.

[0027] Figure 6 This is a SEM image illustrating the surface of the implant before anodizing.

[0028] Figure 7 This is a schematic diagram illustrating the anodized state of the implant body.

[0029] Figure 8 This is a SEM image illustrating the state of the titanium oxide film formed in the implant body in the applicable embodiment 1.

[0030] Figure 9 This is an SEM image illustrating the state of shallow depressions formed on the surface of the implant body after the titanium oxide film has been removed, as described in Application Example 1.

[0031] Figure 10 as well as Figure 11 This is a SEM image illustrating the state of shallow depressions and micropores formed on the surface of the implant body after the titanium oxide film has been removed, as described in Application Example 1.

[0032] Figure 12 This is a graph illustrating the XPS surface composition analysis results of the titanium substrate before and after the nanopatterning process in Example 1.

[0033] Figure 13 This is an AFM photograph of the implant body surface after the titanium oxide film has been removed, applicable to Example 1.

[0034] Figure 14 This is an SEM image of the surface of the implant body that has undergone sandblasting treatment according to Example 2.

[0035] Figure 15 This is an SEM photograph illustrating the state of shallow depressions formed on the surface of the implant body after the titanium oxide film has been removed, as shown in Application Example 2.

[0036] Figure 16 This is an AFM photograph of the implant body surface after the titanium oxide film has been removed, applicable to Example 2.

[0037] Figure 17 These are SEM images of the implant body surface after SLA surface treatment in each step of Example 3, and after a titanium oxide film is formed on it and then removed. Detailed Implementation

[0038] Next, with reference to the accompanying drawings, a detailed description will be given of an implant with a nano-patterned shallow grooved surface and its manufacturing method applicable to embodiments of the present invention.

[0039] The implant manufacturing method applicable to Example 1 is as follows: Figure 3 As shown, firstly, in step S1a, titanium oxide nanotubes are formed on the surface of the implant by anodizing.

[0040] like Figure 4 As shown, after preparing the implant body 100 made of titanium (Ti) or titanium alloy (Ti alloy), titanium oxide nanotubes 200 with a surface in the shape of titanium nanotube structures are formed by anodizing the implant body 100. Because titanium or titanium alloy is a metal suitable for use as a biomaterial, the implant body 100 to which this invention is applied uses only titanium or titanium alloy as raw material.

[0041] At this point, a shallow groove is formed on the surface of the artificial tooth root by anodizing the fixation area in the implant body 100. The implant body 100 consists of a crown, an abutment, and an artificial tooth root. By forming a shallow groove in the artificial tooth root, which is positioned at the root of the tooth to induce bone fusion, the implant body 100 can be prevented from detaching from the root of the tooth and a longer service life can be guaranteed.

[0042] By immersing the implant body 100 as an anode in an electrolyte and then applying a voltage, titanium oxide nanotubes 200 composed of titanium oxide (TiO2) can be formed in the region in contact with the electrolyte. The titanium oxide nanotubes 200 are formed in a tubular shape on the surface of the implant body 100, while the boundary surface in contact with the implant body 100 forms a hemisphere-like shape similar to the lower part of the tubular structure. The diameter of the recessed region formed by the tubular shape is approximately tens to hundreds of nanometers, and this diameter can be adjusted by controlling the anodizing conditions.

[0043] The electrolyte contains fluoride ions (F). - The electrolyte is used to anodize the implant body 100 by immersing it in the electrolyte. The electrolyte containing fluoride ions is preferably prepared by mixing a salt containing fluoride ions, at least one solvent selected from the group consisting of inorganic acids, organic acids, polymers, polymeric alcohols, and mixtures thereof, and water. Preferably, the salt containing fluoride ions is a salt composed of hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH4F), and mixtures thereof, and a solvent selected from the group consisting of phosphoric acid (H3PO4), sulfuric acid (H2SO4), nitric acid (HNO3), glycerol, ethylene glycol, and mixtures thereof.

[0044] Halogen ions can effectively elute metals, causing pitting corrosion. However, when using halogen ions such as chloride ions (Cl... - ), bromide ions (Br) - When other halogens are used, it is difficult to form straight and uniformly sized nanotube structures. However, when anodizing is performed in an electrolyte containing fluoride ions, titanium oxide nanotubes 200 with uniform size and spacing can be formed. Therefore, an electrolyte containing fluoride ions is used in this invention.

[0045] Next, in step S2a, a hemispherical shallow depression 110 is formed on the surface of the implant body 100 by removing the titanium oxide nanotubes 200.

[0046] like Figure 1 as well as Figure 2 As shown, the titanium oxide nanotubes 200 formed by anodizing are prone to peeling off if subjected to physical forces inside the organism during or after the implant body 100, which is made of titanium or titanium alloy, is inserted into the organism. Figure 1 as well as Figure 2 The present invention utilizes the same conventional anodizing method as existing technologies to anodize metal surfaces. However, it has been found that even a small amount of external force can cause the metal oxide film to peel off. Therefore, when a metal implant manufactured using the aforementioned conventional technology is inserted into a living organism, the metal oxide film peels off, leading to problems such as cell necrosis and decreased bone fusion of the implant. Furthermore, when nanoscale micropores are formed through anodizing, it becomes difficult to effectively remove impurities remaining within the oxide film. To address these existing problems, the present invention removes the titanium dioxide nanotubes 200 formed on the implant body 100.

[0047] By removing the titanium oxide nanotubes 200 formed on the surface of the implant body 100 using physical or chemical methods, hemispherical shallow depressions 110 can be formed on the surface of the implant body 100. Even after removing the titanium oxide nanotubes 200, the hemispherical shallow depressions 110 formed by the titanium oxide nanotubes 200 will still remain on the surface of the implant body 100. Among these methods, it is preferable to use a physical method of ultrasonically washing the titanium oxide nanotubes 200 by immersing them in hydrogen peroxide water (H2O2), while it is preferable to use a chemical method of immersing the implant body 100 in an aqueous solution of organic acid or alkaline solution to peel off the titanium oxide nanotubes 200, but this method is not limited to these methods.

[0048] As described above, by removing the titanium oxide nanotubes 200 formed on the surface of the implant body 100, an implant body 100 can be obtained in which shallow depressions 110 of approximately hemispherical size are formed on the surface of the implant body 100, and micropores 111 of a size several nanometers smaller than the hemispherical shallow depressions 110 are formed inside the hemispherical shallow depressions 110. The diameter d of the hemispherical shallow depressions 110 can be from 10 to 1,000 nm. This can be achieved by adjusting the electrochemical conditions such as the loading voltage, electrolyte, and temperature during anodizing.

[0049] Regarding the ratio of diameter d to height h of the shallow concave 110, to ensure the shallow concave 110 forms a hemispherical shape, a ratio of diameter d:height h of 1:0.01 to 0.5 is preferable. When the height h of the shallow concave 110 is less than 0.01 times the diameter d, the surface roughness will be too low due to the excessively small height, which may further hinder bone fusion. Furthermore, because the shallow concave 110 needs to form a hemispherical shape, the ratio cannot exceed 0.5 times. Therefore, a ratio of diameter d:height h of 1:0.01 to 0.5 is preferable.

[0050] The surface of the implant body 100 obtained through steps S1a and S2a is passivated from metal to metal oxide, and therefore cannot be used directly. When manufacturing implants using existing technology, a separate process is required to passivate titanium into a titanium oxide form that can be used as a biological raw material and is resistant to oxidation. This passivation process is carried out by exposing the implant to high temperatures or by boiling it in hot water. However, the present invention can passivate the implant body 100 into a titanium oxide form and form shallow depressions on its surface through an anodizing process.

[0051] If necessary, additional steps as described below can be performed.

[0052] In step S3a, an oxide film 300 is formed on the surface of the implant body 100 by heat treatment.

[0053] An oxide film 300 is formed on the surface of the implant body 100 by heat treatment of the implant body 100, on which shallow depressions 110 have been formed. The oxide film 300 refers to an oxide film 300 comprising oxidized shallow depressions 310 and oxidized micropores 311 formed along the shallow depressions 110 and micropores 111 of the implant body 100, or an oxide film 300 having micropores formed internally. As described above, the oxide film 300 is preferably a thin film with a thickness of 10 to 1,000 nm. When the film thickness is less than 10 nm, performing heat treatment alone becomes meaningless, while when it is greater than 1,000 nm, the oxide film 300 may detach from the body 100 under external force.

[0054] Without heat treatment of the surface of the implant body 100 with the shallow depressions 110, the oxide film 300 is in an amorphous state; however, during heat treatment, it transforms into a crystalline surface. By transforming it into a crystalline surface as described above, its physicochemical properties, such as hydrophilicity, hardness, strength, and thickness, can be controlled. In the oxide film 300 described above, hemispherical shallow oxide depressions 310, including oxide micropores 311, are formed. The heat treatment temperature for forming the shallow oxide depressions 310 is preferably between 200 and 1200°C, at which temperature, a crystalline oxide film 300 is formed. When the heat treatment temperature is below 200°C, an amorphous oxide film is formed, while temperatures above 1200°C may cause deformation of the implant body 100.

[0055] The hemispherical shallow oxide depressions 310 formed on the oxide film 300 preferably have a diameter of 10 to 1,000 nm. When the diameter of the shallow oxide depressions 310 is less than 10 nm, it leads to lower biocompatibility, while shallow oxide depressions 310 larger than 1,000 nm can be effectively formed simply through chemical or physical methods. The diameter of the shallow oxide depressions 310, as described above, can be adjusted by controlling the anodic oxidation conditions. Furthermore, a rough surface with fine oxide micropores 311 several nanometers in size will also be formed on the surface of the shallow oxide depressions 310. By performing the heat treatment described above, a crystalline titanium oxide film 300 with high hardness and a thickness greater than 10 nm (more than that of the amorphous titanium oxide film) can be formed, thereby improving its biocompatibility and hydrophilicity.

[0056] When titanium (Ti) is used, an amorphous titanium oxide (TiO2) layer of 2 to 5 nm will form on the surface as a natural oxide layer after the removal of the titanium oxide nanotubes 200 formed by anodizing. When heat-treated at 200 to 1200 °C, anatase-type crystalline oxide film will form above 200 °C, and rutile-type crystalline oxide film 300 will form above 700 °C. The hardness order is rutile > anatase > amorphous, and the thickness of the oxide film 300 can be increased to more than 10 nm by performing heat treatment. That is, by performing heat treatment, not only can the hardness of the metal surface with hemispherical oxide pits 310 be increased, but the thickness of the oxide film 300 suitable for biological use can also be increased simultaneously.

[0057] In Example 1, a hemispherical shallow depression 110 was formed on the surface of the implant body 100 by anodizing only, while in Example 2, anodizing was performed simultaneously with sandblasting. The implant manufacturing method applicable to Example 2 is as follows: Figure 5As shown, firstly, in step S1b, the surface of the implant body is sandblasted.

[0058] Sandblasting is a type of blasting process where the sandblasting media used are small-diameter glide glass spheres, silica sand, sea sand, metal particles, etc. Sandblasting is a process that uses air to propel the sandblasting media as described above, or uses gravity to drop it, thereby creating fine, shallow depressions on the surface through impact. Specifically, to create micron-sized depressions on the surface of the implant, sandblasting particles of 1 to 100 μm are prepared and sprayed at 0.45 to 0.65 kgf / cm². 2 Pressure sandblasting is applied to the surface of the implant body. Specifically, when the sandblasting pressure is less than 0.45 kgf / cm², the sandblasting is applied to the surface of the implant body. 2 Sometimes, the sandblasting medium cannot properly impact the implant, resulting in the inability to form the desired shallow depression. Furthermore, when the sandblasting medium exceeds 0.65 kgf / cm², this can lead to problems. 2 This process may sometimes lead to damage to parts of the implant. Next, the sandblasting medium is washed away to thoroughly remove any remaining sandblasting medium from the implant surface. Through this process, shallow depressions of 50 to 500 μm in size are formed on the implant surface. Regarding these micron-sized depressions, it is difficult to create depressions smaller than 50 μm using sandblasting, while depressions larger than 500 μm may adversely affect the implant.

[0059] Next, an anodizing process will be performed on the implant body, which includes micron-sized shallow depressions. Since step S2b, which involves anodizing the implant body, and step S3b, which involves forming hemispherical shallow depressions on the surface of the implant body by removing titanium oxide nanotubes, are the same as steps S1a and S2a in Example 1, detailed descriptions will be omitted. Through the process described above, nanoscale shallow depressions, formed by anodizing, will be formed inside the micron-sized depressions.

[0060] In some cases, it is also possible to simultaneously perform an SLA (Sandblasted, Large-grit, Acid-etched) process and an anodizing process, which differs from the sandblasting process in Example 2. In the SLA process, the implant body, with shallow depressions of several hundred micrometers in size formed on its surface through sandblasting, is immersed in acid to perform an etching process. Through the etching process, medium-sized shallow depressions of 1 to 50 μm in size, smaller than the micrometer-sized shallow depressions obtained by sandblasting, can be obtained. Regarding medium-sized shallow depressions, it is difficult to form shallow depressions smaller than 1 μm by acid etching, and when the size is larger than 50 μm, it is not meaningful to perform sandblasting and acid etching separately because there is no difference in size from the large shallow depressions.

[0061] After acid etching, an alkaline washing step for neutralizing the acid will be performed sequentially, followed by a washing step using water or distilled water to remove the acid and alkali used in the neutralization process. Additionally, a step for washing away particles used in the sandblasting process will be performed. Next, the same anodizing process as in Examples 1 and 2 will be performed. Through Example 2 as described above, a medium-sized shallow depression will be formed inside the micron-sized shallow depression, and within the medium-sized shallow depression, a hemispherical nano-sized shallow depression will be formed.

[0062] The embodiments to which this invention applies will now be described in further detail.

[0063] <Example 1> In Example 1, a method was used to form hemispherical shallow depressions on the surface of an implant body made of pure titanium metal or titanium alloy by anodizing the surface. The surface of the implant body before surface treatment is as follows: Figure 6 As shown.

[0064] like Figure 7 As shown, titanium oxide nanotubes can be formed on the metal surface by anodizing a titanium (Ti) metal implant body 100 as the anode and an insoluble platinum (Pt) 10 metal as the cathode, and applying a DC voltage to both ends. Before anodizing, the implant body 100 is sequentially immersed in ethanol and acetone in an ultrasonic cleaner for 2 minutes each. Next, according to... Figure 7 The method shown involves immersing the titanium (Ti) metal implant body 100, which requires anodizing, and the reverse electrode, i.e., insoluble platinum 10 metal, into an electrolyte 20. At this time, an electrolyte 20 containing 0.01 to 10 wt% ammonium fluoride (NH4F) is added to a mixture of ethylene glycol and water. While maintaining the temperature of the electrolyte 20 at 10 to 80°C, a constant voltage of 10 to 200 V is applied for 1 to 300 minutes to obtain titanium oxide nanotubes larger than 200 nm. The titanium oxide (TiO2) nanotubes obtained through anodizing are shown below. Figure 8 As shown, the formed titanium dioxide nanotubes are in good condition.

[0065] The samples obtained through anodizing were soaked in water for 1 hour and washed. After washing, to remove the titanium dioxide nanotubes obtained through anodizing from the implant body, they were soaked in hydrogen peroxide (H2O2) solution and ultrasonically washed for 5 minutes at 2-100°C, followed by soaking in water and ultrasonic washing for 5 minutes, and finally soaking in ethanol and ultrasonic washing for 5 minutes. The washed samples were then dried using a hot air dryer and stored. At this point, the titanium dioxide nanotubes formed on the metal surface of the implant body are removed, thus forming a surface similar to... Figure 9 The hemispherical shallow concave shape shown. Upon further magnification, as... Figure 10 as well as Figure 11 As shown, tiny protrusions can be observed inside the shallow concave hemispherical cavity. Figure 12 This is an XPS analysis comparing the surfaces of traditional implants with those of implants after anodizing to form titanium dioxide nanotubes and then removing them. The XPS results show that the surface after the nanopatterning process is further oxidized and converted into titanium dioxide. Simultaneously, as shown in Table 1, impurities such as lead (Pb) are also removed. Lead may remain on the implant surface during manufacturing, but the process described in this invention, which involves removing titanium dioxide nanotubes after anodizing, effectively removes these impurities from the implant surface. At the same time, other impurities besides lead are also removed.

[0066] Table 1

[0067] exist Figure 13 The image shows an AFM (atomic force microscope) image of the implant body after the removal of anodized titanium dioxide nanotubes, which reveals the formation of uniform nanoscale shallow depressions.

[0068] When needed, the thickness of the titanium dioxide oxide film can be increased to approximately 10 nm to 1,000 nm by heat-treating the implant body sample at 200 to 1200 °C.

[0069] <Example 2> In Example 2, a process was used to form shallow depressions in resorbable blast media (RBM) on the surface of the implant body by performing sandblasting on the implant body made of pure titanium metal or titanium alloy and then anodizing it.

[0070] First, to prevent the implant from shifting under pressure, it is secured. Next, surface treatment is achieved by sandblasting the implant with a medium comprising calcium phosphate particles of 180 to 425 μm in size at appropriate pressure using a nozzle. The sand particles are at a concentration of 0.45 to 0.65 kgf / cm². 2 The pressure is used to perform sandblasting. After approximately 10 to 25 seconds of surface treatment, the treated implant body is washed using an ultrasonic cleaner for approximately 5 minutes. The implant body after sandblasting surface treatment as described above is as follows: Figure 14 As shown.

[0071] Next, anodizing was performed on the implant body that had already undergone sandblasting. The anodizing method was the same as in Example 1, in which the implant body was used as the anode and platinum as the cathode, and after immersion in an electrolyte, a voltage was applied to form titanium oxide nanotubes larger than 200 nm on the surface of the implant body.

[0072] After immersing the titanium oxide nanotubes obtained through anodizing sequentially in hydrogen peroxide, water, and ethanol, they are washed using an ultrasonic cleaner to remove the titanium oxide nanotubes. A shallowly concave implant body is then formed on the surface using the method described above. The surface includes micron-sized shallow depressions of 100 μm and nanon-sized shallow depressions ranging from a few nanometers to several hundred nanometers. Figure 15 as well as Figure 16 This is a photograph taken after the removal of titanium dioxide nanotubes following sandblasting and anodizing. It can be seen that hemispherical shallow depressions are uniformly formed on the micron-level roughness. Figure 17 The surface is formed by removing titanium dioxide nanotubes after SLA surface treatment and anodizing, resulting in a hemispherical shape. It can be observed that shallow depressions with nanopatterns are formed on top of these depressions while maintaining micron-level and medium-sized shallow depressions.

[0073] <Example 3> In Example 3, a shallow depression was formed on the surface of the implant body by performing an SLA (Sand blasted, Large-grit, Acid etche) process on the implant body made of pure titanium metal or titanium alloy and then anodizing it.

[0074] First, to prevent the implant from shifting under pressure, it is secured. Next, surface treatment is performed by sandblasting alumina (Al₂O₃) composed of 100μm-sized pebbles onto the implant using a nozzle at appropriate pressure. The alumina at this stage has a concentration of 0.45 to 0.65 kgf / cm². 2The pressure is used to perform sandblasting. Next, the surface of the sandblasted implant is etched by immersing it in acid, creating shallow depressions a few micrometers in size. Then, to neutralize the acid used in the etching process, a neutralization wash is performed using an alkali, followed by a wash with water or distilled water to remove the alkali used in the neutralization wash. Finally, an additional wash process is performed to completely remove the alumina used in the sandblasting process.

[0075] Next, anodizing was performed on the implant body that had already undergone sandblasting and etching. The anodizing method was the same as in Example 1, in which the implant body was used as the anode and platinum as the cathode, and after immersion in an electrolyte, a voltage was applied to form titanium oxide nanotubes larger than 200 nm on the surface of the implant body.

[0076] After immersing the titanium oxide nanotubes obtained through anodizing sequentially in water, hydrogen peroxide solution, and ethanol, the nanotubes are washed using an ultrasonic cleaner to remove them. A shallowly concave implant body is then formed on the surface using the method described above. The surface includes micron-sized shallow depressions of 100 μm, medium-sized shallow depressions of a few micrometers, and nanon-sized shallow depressions ranging from a few nanometers to several hundred nanometers.

[0077] <Example 4> In Example 4, the implant body made of pure titanium metal or titanium alloy was anodized in the same way as in Example 1 to form shallow depressions on the surface of the implant body, and then the film thickness was increased by heat treatment.

[0078] The anodizing method was the same as in Example 1. The implant body was used as the anode and platinum as the cathode, immersed in an electrolyte, and a voltage was applied to form nanotube structures larger than 200 nm on the surface of the implant body. Next, the titanium oxide nanotubes were removed by immersion in hydrogen peroxide and ethanol, followed by ultrasonic washing for 5 minutes each. After removing the titanium oxide nanotubes, the implant was dried in an oven at 100°C for 10 minutes, and then heat-treated in an electric furnace at 300°C for 1 hour. The thickness of the oxide film increased to approximately 50 nm after heat treatment.

[0079] Because the implants used for biotransplantation described above involve anodizing the surface of the implant body before removing the anodized surface, problems such as cell necrosis or decreased bone fusion caused by the peeling off of the anodized surface can be prevented. Furthermore, when implanting a hemispherical shallow concave metallic biomaterial formed by anodizing the implant surface into a living organism, surface roughness can be increased while maximizing its surface area, thereby providing excellent biocompatibility, chemical stability, and mechanical stability.

[0080] Industry availability This invention relates to an implant with a shallow concave surface featuring a nanopattern and a method for manufacturing the same. It is particularly applicable to the field of implants with a shallow concave surface featuring a nanopattern formed by anodizing the surface of the implant body and then removing the anodized surface, while preventing the anodized titanium oxide film from falling into the body.

Claims

1. A method for manufacturing an implant with a shallow concave surface featuring a nanopattern, characterized in that, Includes the following steps: 1) The surface of the implant body made of titanium metal or titanium alloy is sandblasted to form micron-sized shallow depressions of 50μm to 500μm. 2) The sandblasted surface of the implant body treated in step 1) is acid-etched to form a medium-sized shallow depression of 1μm to 50μm: 3) Titanium oxide nanotubes are formed by anodizing the implant substrate treated in step 2); and, 4) A shallow, hemispherical depression with a diameter of 10 nm to 1,000 nm is formed on the surface of the implant body by removing the titanium oxide nanotubes.

2. The method for manufacturing an implant with a shallow concave surface having a nanopattern according to claim 1, characterized in that: In step 3), By impregnating the implant body with a solution containing fluoride ions (F... - Anodizing is performed in the electrolyte.

3. The method for manufacturing an implant with a shallow concave surface having a nanopattern according to claim 2, characterized in that: The electrolyte is a mixture of ethylene glycol containing 0.01 to 10 wt% ammonium fluoride and water.

4. The method for manufacturing an implant with a shallow concave surface having a nanopattern according to claim 1, characterized in that: Following step 4), the following is also included: The step of forming an oxide film with a thickness of 10 nm to 1,000 nm on the surface of the implant body by heat treatment.

5. The method for manufacturing an implant with a shallow concave surface having a nanopattern according to claim 1, characterized in that: The shallow concave surface of the hemispherical shape also includes micropores a few nanometers in size.

6. The method for manufacturing an implant with a shallow concave surface having a nanopattern according to claim 1, characterized in that: The titanium dioxide nanotubes are removed by immersing the implant body in hydrogen peroxide water (H2O2) and ultrasonically washing it, or by immersing it in an aqueous solution of organic acid or alkaline solution.

7. An implant with a shallow concave surface having a nanopattern, prepared by the method according to any one of claims 1-6.

8. The implant with a shallow concave surface having a nanopattern as described in claim 7, characterized in that: The ratio of the diameter to the height of the shallow concave hemispherical shape is diameter:height = 1:0.01 to 0.

5.

9. The implant with a shallow concave surface having a nanopattern as described in claim 7, characterized in that: The hemispherical shallow depression also includes micropores a few nanometers in size.

10. The implant with a shallow concave surface having a nanopattern as described in claim 9, characterized in that: Medium-sized shallow depressions are formed inside the micrometer-sized shallow depressions, and hemispherical nanometer-sized shallow depressions are formed in the medium-sized shallow depressions.

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