KR102078331B1 - Method for coating bioceramic on a titanium implant surface and titanium implant prepared by the method - Google Patents

Abstract

The present invention relates to a method for manufacturing an implant material and an implant prepared accordingly, and more particularly, to a method for coating a bio ceramic on the surface of a titanium implant and a titanium implant prepared accordingly.
In particular, according to the manufacturing method of the implant material of the present invention, a thin film of titanium dioxide is formed between the implant base material and the bio ceramic particles, and titanium dioxide particles are dispersed and applied to increase the interface adhesion between the implant base material and the bio ceramic particles. It works.

Description

Method for coating bioceramic on a titanium implant surface and titanium implant prepared by the method

The present invention relates to a method for manufacturing an implant material and an implant prepared accordingly, and more particularly, to a method for coating a bio ceramic on the surface of a titanium implant and a titanium implant prepared accordingly.

Recently, with the progress of the aging society, there is an increasing number of cases in which bone defects need to be repaired due to diseases such as osteoporosis or car accidents. Conventionally, in such a case, autografts for collecting bones of other normal parts from the patient's own body and transplanting them to the defects, and homograft methods for transplanting allogeneic bones of others have been performed.

However, there was a drawback that autologous bone graft damages normal areas other than the area to be treated, and allogeneic bone graft methods have problems such as an immune response or infection.

As a method for overcoming the problem of autologous bone graft or allograft graft, there is an allograft using various artificial materials, and the material used for this purpose is referred to as a biomaterial.

In the field of grafting bones in recent years, the biggest concern is the shortening of the treatment period, and the most important factor in shortening the treatment period is obtaining and maintaining bone adhesion early. According to Albrektsson et al., Six factors of biocompatibility of the implant, design, surface condition, implantation condition, surgical operation method, and load control during the healing period after biotransplantation were suggested as factors for obtaining a successful bone adhesion.

Most commercially available biomaterials are considered to have high biocompatibility and have a surface suitable for healing, production, and maintenance of bone, but no biomaterial capable of completely overcoming adverse bone conditions has not emerged. Therefore, further studies on the surface of biomaterials are needed in the future.

On the other hand, the purpose of surface treatment in biomaterials is to 1) increase the surface area to obtain a better mechanical fixation between bone and biomaterial immediately after implantation, and 2) to provide a surface shape that can maintain blood clots well 3) to provide a surface shape that promotes the bone healing process.

The surface treatment method of commercialized titanium is being applied in the form of cutting (processing) treatment, plasma application, spray treatment, and acid corrosion.

First, in the machining (turned surface) method, titanium has a low specific gravity, and because of its high melting point, it is difficult to cast, so milling is used to process the desired shape. Regular grooves are generated by the mechanism. The surface of the Branemark implant, a screw-type and root-type implant that has been in use until recently, was developed in 1965 and began to be applied to clinical trials.

Titanium plasma spraying (TPS) sprays hot melted titanium particles inside a machine filled with argon gas with a nozzle and sprays it onto the surface of titanium at a high speed. Titanium plasma coating method can increase the surface area, so the initial fixation is excellent and the results of improving bone adhesion are reported. However, it has been reported that the implant implantation and subsequent surface particles fall off or Ti ion leakage occurs on the rough surface, resulting in a smaller amount of bone adhesion than other rough surfaces developed later. In addition, when exposed to the oral cavity, plaque deposition is remarkable, which may cause peri-implantitis.

In the case of the HA plasma sprayed surface (HA plasma sprayed surface) method, HA (hydroxyapatite) has a superior initial bone reaction compared to titanium, but has a disadvantage of breaking the functional load, so a method of coating with titanium as a plasma coating method has been used. . It has been reported that HA-coated implants have a high success rate of bone adhesion even in areas with large defects, maxillary molars, and poor bone quality, such as graft bones. However, as the functional load was applied over time, problems occurred, such as absorption of hydroxyapatite or dropping off the surface of the implant, resulting in a decrease in bone contact rate or absorption of surrounding bone.

The blasted surface method is a substractive process in which coarse particles of various diameters (25-250 µm) are sprayed onto a titanium surface to detach the surface.

In this regard, a method of using alumina (Al ₂ O ₃ ) has also been attempted because the method of spraying titania onto a titanium surface does not satisfy the required surface roughness.

However, the method using alumina has the advantage of increasing the surface roughness, but the effect of alumina on the surface of the implant has not yet been fully investigated, so it is not widely used in clinical practice.

On the other hand, a thin titania film naturally generated on the surface of titanium increases the adhesion strength (interface adhesion) between titanium and apatite in the process of coating the surface of titanium with titanium hydroxide, but because the thickness is very thin, the adhesion strength is increased. It has the disadvantage of not being able to maintain enough.

Korean Registered Patent No. 10-0953126

An object of the present invention is to provide a method of coating bioceramic on an implant material capable of increasing the adhesion strength between metal titanium (implant base material) and bioceramic (apatite hydroxide).

In addition, it is intended to provide an implant material manufactured accordingly.

In order to achieve the above object,

In one embodiment of the invention,

Forming a titanium dioxide (TiO ₂ ) thin film by applying and heat-treating a mixed solution containing a titanium precursor on the surface of the implant substrate;

Dispersing and coating titanium dioxide (TiO ₂ ) particles on the surface of the implant substrate on which the titanium dioxide thin film is formed; And

Dispersing and coating bio-ceramic particles on a part or all of the surface of titanium dioxide (TiO ₂ ) particles; It provides a method of manufacturing an implant material comprising a.

In addition, in one embodiment of the present invention,

Titanium or titanium alloy substrates;

A titanium dioxide (TiO ₂ ) thin film formed on the surface of a titanium or titanium alloy substrate; And

A particle layer formed on a surface of the titanium dioxide thin film and containing titanium dioxide particles and bio ceramic particles; It includes,

The particle layer

It provides an implant material characterized in that the bio-ceramic particles are attached to part or all of the titanium dioxide particle surface.

According to the method of manufacturing the implant material of one embodiment of the present invention, by coating the titanium dioxide thin film and the titanium dioxide particles on the surface of the titanium implant, respectively, and then coating the bio ceramic particles to increase the interfacial adhesion between the titanium implant and the bio ceramic particles It has the effect.

1 is a flow chart for explaining a method of manufacturing an implant material according to an embodiment of the present invention.
2 is a view showing a schematic view of an implant material manufactured according to the method for manufacturing an implant material of the present invention.
3 is a photograph showing an SEM image (× 10,000) of metallic titanium, (a) is the surface when titanium is heat-treated at 550 ° C. for 1 hour, and (b) is TTIP primary coating 3 times and then at 550 ° C. for 1 hour. It shows the surface when heat treated.
4 shows the EDS data of the surface when the titanium was heat treated at 550 ° C. for 1 hour.
FIG. 5 shows EDS data of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating.
FIG. 6 is a photograph ((a) × 10,000, (b) × 50,000) showing the SEM image of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating and 1 time of secondary coating.
FIG. 7 is a photograph showing EDS data on the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating and 1 time of secondary coating.
8 is a photograph showing a SEM image of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP 1st coating, 1 time of 2nd coating, and 1 time of 3rd coating ((a) × 10,000, (b) × 50,000 ) to be.
9 shows EDS data of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating, 1 time of secondary coating, and 1 time of tertiary coating.
Figure 10 is a photograph showing the SEM image of the surface when heat treated at 550 ° C for 1 hour after 3 times of TTIP, 3 times of 2nd coating, and 1 time of 3rd coating ((a) × 10,000, (b) × 50,000 ) to be.
11 is a photograph for comparing the interfacial adhesion between titanium metal and TiO ₂ particles according to the presence or absence of TTIP coating.

The present invention can be applied to various changes and may have various embodiments, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In the description of the present invention, when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted.

The terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present invention, terms such as “comprises” or “have” are intended to designate the existence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, actions, components, parts or combinations thereof are not excluded in advance.

The present invention relates to a method of manufacturing an implant material capable of increasing the adhesive strength between the implant base material and the bio ceramic, and an implant manufactured accordingly.

In particular, according to the method of manufacturing the implant material of the present invention, including the step of forming a titanium dioxide thin film and titanium dioxide particles between the implant base material and the bioceramic particles, the effect of increasing the interfacial adhesion between the titanium implant and the bioceramic particles There is.

In the present invention, the method of manufacturing an implant material means a method of forming bioceramics on the surface of an implant base material, and specifically, a method of forming or coating bioceramic particles on the surface of an implant base material of titanium or titanium alloy. do. Hereinafter, an implant material of titanium or a titanium alloy may be mixed with a titanium implant.

Meanwhile, hereinafter, 'coating' may mean covering a thin film or particles on the surface of a substrate, and may mean dispersing and coating the thin film material or a solution in which the mixed solution or particles are dispersed.

1 is a flow chart for explaining a method of manufacturing an implant material according to an embodiment of the present invention.

The present invention will be described in detail below with reference to FIG. 1.

The present invention in one embodiment,

(A) forming a titanium dioxide (TiO ₂ ) thin film by applying and heat-treating a mixed solution containing a titanium precursor on the surface of the implant substrate (S100);

(b) dispersing and coating titanium dioxide (TiO ₂ ) particles on the surface of the implant substrate on which the titanium dioxide thin film is formed (S200); And

(c) dispersing and applying bio-ceramic particles to a part or all of the titanium dioxide (TiO ₂ ) particle surface (S300); It provides a method of manufacturing an implant material comprising a.

First, the step (S100) of forming a titanium dioxide (TiO ₂ ) thin film will be described in detail.

In the step of forming a titanium dioxide (TiO ₂ ) thin film on the surface of the titanium implant, a coating film according to this step may be formed using a sol-gel method. Specifically, after immersing the implant substrate in a sol solution containing a material corresponding to the precursor of the material to be formed on the implant substrate, it means that a thin film is formed by performing the steps of aging, drying and heat treatment.

In addition, aerosol deposition (AD), spin coating, dip coating, doctor blade, dry dipping, hydro thermal reaction, which will be described later, A thin film may be formed by performing a plasma spraying method or an ion beam deposition method.

In one embodiment of the present invention, mixing a titanium precursor in a solvent to prepare a mixed solution; Dispersing the mixed solution by ultrasonic waves; And dispersing and coating the mixed solution dispersed by ultrasonic waves on the surface of the implant base material and drying. It may include.

Titanium precursors include metal salts such as halides containing titanium metal elements, titanium metal nitrates, titanium metal sulfates, titanium metal acetates, titanium metal carbonyls, and titanium metal alkoxides, Or hydrates thereof. Specifically, Ti (OCH (CH ₃ ) ₂ ) ₄ , Ti (OBu) ₄ , TiCl ₄ (Titanium tetrachloride), (C ₄ H ₉ O) ₄ Ti, Ti (OCH ₂ CH ₃ ) ₄ , ((CH ₃ ) ₂ CHO) ₂ Ti (C ₅ H ₇ O ₂ ) ₂ , Ti (OC ₂ H ₅ ) ₄ , Ti (OCH ₃ ) ₄ , Ti (C ₅ H ₇ O ₂ ) ₂ and TiOSO ₄ It may be one or more, preferably, TTIP (Titanium (IV) isopropoxide, Ti (OCH (CH ₃ ) ₂ ) ₄ ) may be used, but is not limited thereto.

In addition, as the solvent used in the present invention, anhydrous alcohol, for example, anhydrous ethanol, may be used to remove H ₂ O and the like in the titanium precursor as an alcohol-based solvent. Particularly, when the titanium precursor comes into contact with H ₂ O, it is preferable to use anhydrous alcohol because the solution becomes a suspension by generating nano-sized TiO ₂ particles.

At this time, with respect to 100 parts by volume of the solvent, the titanium precursor may be mixed with 5 to 30 parts by volume, preferably with respect to 100 parts by volume of the solvent, 7 to 27 parts by volume, 10 to 20 parts by volume, For example, 10 parts by volume may be mixed.

For reference, when the titanium precursor is less than 5 parts by volume, the amount of the titanium precursor relative to the solvent is too small to form a dense thin film on the surface of the titanium implant, and when it exceeds 30 parts by volume, the mixing amount of the titanium precursor relative to the solvent is too large. The titanium dioxide thin film layer becomes too thick, which may cause problems such as cracking and peeling on the coating surface.

In addition, it is possible to improve the dispersibility by dispersing the mixed solution by ultrasonic waves, which may be performed by ultrasonic treatment to maintain dispersibility even when the titanium implant is immersed in the mixed solution.

Particularly, when the implant substrate is immersed in the mixed solution, the descending and rising speeds can be maintained at a rate of 1 mm / sec, and the immersion time can be maintained at 10 sec.

The immersed implant substrate can be left to stand for 10 minutes at room temperature to proceed with natural drying, and heat-treated in an oven at 100 to 200 ° C for about 20 to 30 minutes to proceed with drying.

This coating process may be repeated 1 to 5 times, but it is preferable to proceed 2 to 5 times or 3 to 5 times repeatedly to form a thicker titanium dioxide (TiO ₂ ) thin film.

Meanwhile, the titanium implant or the implant substrate means a titanium substrate for a bio-implant, and may be a titanium or titanium alloy substrate.

Next, the step (S200) of dispersing and applying titanium dioxide (TiO ₂ ) particles on the surface of the titanium implant on which the titanium dioxide thin film is formed will be described in detail.

On the other hand, titanium dioxide (TiO ₂ ) particle coating (dispersion and application) on the surface of a titanium implant with a titanium dioxide thin film formed is aerosol deposition (AD), spin coating, dip coating, doctor It can be performed through a blade (doctor blade), dry dipping, hydro thermal reaction, sol-gel method, spray method (plasma spraying) or ion beam deposition.

Specifically, between the aerosol to the position (aerosol deposition, AD) the use of titanium dioxide (TiO ₂₎ in the case of coating the particle, with a vacuum chamber of titanium dioxide (TiO ₂₎ by spraying the particles onto the implant base material particles and the substrate The particle layer is formed by a strong collision. The particle layer thus formed exhibits a fine structure in which crystalline particles having nano-particle sizes and an amorphous phase are mixed, and in order to further improve the biocompatibility and stability in the body of the particle layer, after formation of the particle layer, heat treatment is performed in a furnace or as necessary. It is possible to improve the crystallinity of the titanium dioxide (TiO ₂ ) particles by additionally performing a step of hydrothermal treatment at a lower temperature.

In addition, when using the slurry to coat the titanium dioxide (TiO ₂ ) particles using the above, a known solution coating method, such as spin coating, spin coating, dip coating, doctor blade, etc. This step can be carried out through a process of drying after being applied onto an implant substrate, and at this time, the above-described coating process may be performed multiple times if more uniform particle layer thickness formation and particle layer thickness control are required. Depending on, it may further perform the step of heat treatment at a temperature below the corresponding particle decomposition temperature.

As another method for performing this step, a ceramic biomaterial is placed on the surface of the implant substrate while the metal substrate of the implant is melted by heating in a dry dipping state to titanium dioxide (TiO ₂ ) particles using the implant substrate. There is a way to ensure that the coating.

In addition, it is also possible to perform this step by using a hydrothermal reaction, which is performed by dissolving titanium dioxide (TiO ₂ ) particles in an aqueous solution of acid such as hydrochloric acid to insert an implant substrate into a solution obtained and then causing a hydrothermal reaction to generate ceramics. It is a method of coating a biomaterial on the surface of an implant substrate.

On the other hand, spin coating, dip coating, or doctor blade (which can control the thickness of the particle layer and the formation of a uniform thickness with high interfacial adhesion between the implant substrate and the titanium dioxide particles among the above-mentioned coating methods) It can be coated using a doctor blade), preferably can be coated using a dip coating.

Specifically, the step of dispersing and coating the titanium dioxide (TiO ₂ ) particles on the surface of the implant substrate on which the titanium dioxide thin film is formed is

Preparing a solution in which titanium dioxide particles are dispersed by adding titanium dioxide particles and a dispersant to a solvent and applying ultrasonic waves; And drying the solution by dispersing and coating the titanium dioxide thin film formed on the surface of the titanium implant; It may include.

In addition, as the solvent used in the present invention, anhydrous alcohol may be used as described above, and with respect to 100 parts by volume of the solvent, titanium dioxide particles may be dispersed in 5 to 30 parts by weight. As an example, a solution was prepared by dispersing 20 g of titanium dioxide particles in 200 ml of anhydrous ethanol, and 0.1 ml of dispersant was added.

In addition, the dispersibility can be improved by dispersing the solution with ultrasonic waves. However, when ultrasonic waves are applied when the titanium implant is immersed in the solution, ultrasonic waves are immersed due to fear of damage to the first formed titanium dioxide (TiO ₂ ) thin film. It is preferred not to process.

In particular, when the titanium implant is immersed in the solution, the descent and ascent rates can be maintained at a rate of 1 mm / sec, and the immersion time can be maintained at 10 sec.

The immersed titanium implant can be left to stand at room temperature for 10 minutes to naturally dry, and dried in an oven at 100 to 200 ° C for about 20 to 30 minutes.

This coating process can be repeated 1 to 5 times, but it is preferable to proceed 2 to 5 or 3 to 5 times repeatedly to perform thicker titanium dioxide (TiO ₂ ) particle coating.

In addition, a dispersant may be added to more stably disperse the titanium oxide particles in the solution, and any dispersant for stably dispersing the particles in the solution may be used.

Next, the step (S300) of coating the bio-ceramic particles on part or all of the surface of the titanium dioxide (TiO ₂ ) particles will be described.

Specifically, the step of coating the bio-ceramic particles may include introducing bio-ceramic particles and a dispersant into a solvent, and applying ultrasonic waves to prepare a solution in which the bio-ceramic particles are dispersed; And drying the solution by applying the titanium dioxide particles on the surface of the titanium implant. It may include.

In one specific example, the bio-ceramic is not particularly limited as long as it is a material having excellent biocompatibility and chemical resistance, but in detail, it is used as hydroxyapatite (HAP) and tricalcium phosphate (Beta TCP, Beta Tricalcium Phosphate). It may be one or more selected from the group consisting of, may be more specifically hydroxyapatite (HAP).

In addition, the average particle diameter of the bioceramic particles may range from 0.01 to 1 μm. When the diameter of the bio-ceramic particles exceeds the above range, it is difficult to obtain a film having a uniform bio-ceramic composition on the surface of the titanium implant, specifically, the titanium dioxide particle surface, and the roughness of the surface of the particle layer is too large, thereby deteriorating bone adhesion. There is a risk of this. On the other hand, the bio-ceramic particles may have a smaller average particle diameter than the titanium dioxide particles, which is for easier attachment to the space between the titanium dioxide particles.

The specific solution preparation method and drying method are the same as the above-described coating method of carbon dioxide particles, and thus will be omitted in this step.

On the other hand, instead of directly coating the bio-ceramic particles on the surface of the titanium implant, by forming a titanium dioxide thin film, dispersing and applying the titanium dioxide particles, and then dispersing and applying the bio-ceramic particles, the interfacial adhesion of the bio-ceramic particles is increased. There is an effect that can be made.

In addition, according to the method of manufacturing an implant material of an embodiment of the present invention, it is characterized in that it further comprises a heat treatment step after the coating step of the bio-ceramic particles.

Specifically, the heat treatment is to improve the interfacial adhesion, which is the bonding strength of the titanium dioxide thin film, titanium dioxide particles, bio-ceramic particles and titanium implants, and the heat treatment conditions start at room temperature (25 ° C) and raise the temperature from 2 to 15 ° C / min. Heat may be applied at a rate, and may be performed at 350 to 650 ° C. for 0.5 to 2 hours. For example, heat treatment may be performed at 550 ° C. for 1 hour by applying the temperature at a temperature increase rate of 10 ° C./min.

On the other hand, when the heating conditions are less than the above-mentioned temperature range, titanium dioxide (TiO ₂ ) particles and bio ceramic particles are not sufficiently sintered, so titanium dioxide (TiO ₂ ) particles and bio ceramic particles are incomplete on the surface of the titanium implant. There is a fear of forming a particle layer, and when the heating conditions exceed the range of the conditions defined above, the thickness of the particle layer containing titanium dioxide (TiO ₂ ) particles and bio-ceramic particles on the surface of the implant becomes too thick to coalesce the bone. There is a risk of causing problems. For example, the heat treatment temperature may be 550 ° C, which may be a temperature for maximally suppressing the oxidation of titanium.

In addition, through the heat treatment step, the titanium precursor forms a titanium dioxide thin film, and the titanium dioxide thin film may be coated with a thickness of 5 to 500 nm on the surface of the titanium implant.

FIG. 2 is a diagram schematically showing a titanium implant prepared according to a method of coating a bio-ceramic on the surface of a titanium implant of the present invention.

Referring to Figure 2, the present invention in another embodiment,

Titanium or titanium alloy substrates;

A titanium dioxide (TiO ₂ ) thin film formed on the surface of a titanium or titanium alloy substrate; And

A particle layer formed on a surface of the titanium dioxide thin film and containing titanium dioxide particles and bio ceramic particles; It includes,

The particle layer

It provides an implant material characterized in that the bio-ceramic particles are attached to part or all of the titanium dioxide particle surface.

On the other hand, since the titanium dioxide particles are first dispersed and applied, and then the bio ceramic particles are dispersed and applied, the concentration of the bio ceramic particles may increase as the titanium dioxide thin film surface goes to the outer surface of the particle layer.

That is, the part that is implanted in the living body and directly contacts the bone of the living body may be bio ceramic particles.

Specifically, a titanium dioxide (TiO ₂ ) thin film having a thickness of 5 to 500 nm and a particle layer having a thickness of 100 to 10000 nm may be sequentially stacked on a surface of a titanium or titanium alloy substrate formed of a titanium dioxide thin film.

The titanium dioxide (TiO ₂ ) thin film layer may be determined according to the conditions of the heat treatment temperature and the number of coatings.

Meanwhile, the titanium dioxide (TiO ₂ ) thin film layer may be 5 to 500 nm thick, and may be 5 to 300 nm, or 5 to 100 nm.

When the titanium dioxide (TiO ₂ ) thin film layer is less than 5 nm, the adhesion strength (interface adhesion) between the titanium dioxide particles and the bio ceramic particles stacked with the titanium implant is increased, but the adhesion strength is not sufficiently maintained because the thickness is too thin. , If it exceeds 500nm, the titanium dioxide (TiO ₂ ) thin film layer is too thick, there may be a problem that the adhesion strength (interface adhesion) between the titanium dioxide particles and the bio ceramic particles laminated with the titanium implant is lowered.

In addition, the particle layer including the titanium dioxide particles and the bio-ceramic particles may have a thickness of 100 to 10000 nm, may be 200 to 7000, or 300 to 5000 nm, and preferably have a thickness of 500 to 1500 nm.

At this time, the titanium dioxide particles and the bio-ceramic particles may be in a form attached to a part or all of the surface. On the other hand, it may be difficult to measure the thickness of each titanium dioxide particle layer and the bioceramic particle layer, but the titanium dioxide particle layer and the bioceramic particle layer may set the thickness of each particle layer according to the number of dispersion / application or particle size of each particle. For example. When the titanium dioxide particles having an average particle diameter of 200 nm and bio ceramic particles having an average particle diameter of 50 nm are dispersed / applied once, the thickness ratio of each particle layer may be 4: 1, and the titanium dioxide particles having an average particle diameter of 300 nm When the dispersion / application of bio-ceramic particles of and 50 nm is performed once, the thickness ratio of each particle layer may be 6: 1. If the number of dispersion / application of bio ceramics is increased, the titanium dioxide particle particle layer and the bio ceramic particle particle layer may form a 3: 2 thickness ratio.

Here, the particle layer refers to a shape formed by dispersing and coating each particle, rather than a layer substantially stacked on the titanium dioxide thin film, and may mean a group of the titanium dioxide particles and bio-ceramic particles. .

In conclusion, the implant material manufactured according to the method of forming bioceramics on the implant substrate of an embodiment of the present invention forms a titanium dioxide thin film on the surface of the implant material, disperses and applies the titanium dioxide particles, and then disperses the bioceramic particles and By applying, there is an effect that can increase the interface adhesion between the surface of the implant base material and the bio ceramic particles.

Hereinafter, the present invention will be described in more detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

<Example>

Example 1. Metal titanium surface pretreatment

1-1. Solution preparation

A solution was prepared by mixing 20 ml of titanium isopropoxide (TTIP, Titanium (IV) isopropoxide: Junsei, japan, 98%) and 180 ml of alcohol (Ethyl alcohol anhydrous, 99.9%), and in order to improve dispersibility, The solution was sonicated for 10 minutes to prepare a primary solution.

At this time, when TTIP and H ₂ O meet, the nano-sized TiO ₂ is immediately generated, resulting in a suspension, and anhydrous alcohol was used.

1-2. 1st coating

The first solution was coated by dipping metal titanium (5 cm horizontal 5 cm vertical).

Specifically, when the metal titanium was immersed in the primary solution, the descending and rising speed was 1 mm / sec, the immersion time was maintained for 10 seconds, and the dispersibility was maintained by ultrasonic treatment during immersion. Then, it was dried in an oven at 150 ° C for 30 minutes.

This coating process was repeated three times.

1-3. Heat treatment

Heat treatment was performed to improve the bonding strength of the coating material and metallic titanium.

Specifically, starting from the air (air) atmosphere, room temperature (25 ℃) was maintained at a heating rate of 10 ℃ / min, 550 ℃ 1 hour, the cooling rate was performed under the conditions of 10 ℃ / min.

Comparative Example 1

The metal titanium that was not coated was subjected to heat treatment in the same manner as in Example 1.

Example 2. Titanium oxide (TiO) on metallic titanium surface ₂ ) coating

2-1. Secondary solution preparation

20 g of TiO ₂ (Degussa P25) having an average size of 50 nm was dispersed in 200 ml of anhydrous ethanol to prepare a suspension.

At this time, 0.1 ml of a dispersing agent was added to enhance the dispersibility of TiO ₂ , and the secondary solution was prepared by improving the dispersibility by ultrasonic treatment for 30 minutes.

2-2. Second coating

The metallic titanium coated in Example 1-2 was coated by dipping in a secondary solution.

Specifically, when the primary coated metallic titanium was immersed in the secondary solution, the descending and rising speed was 1 mm / sec, and the immersion time was maintained for 10 seconds. At this time, the ultrasonic coating was not performed when immersed due to the fear of damage to the primary coated coating film, and the magnetic bar was stirred slowly.

Then, the immersed metal titanium was allowed to stand at room temperature for 10 minutes, and then dried naturally, and then dried in a 150 ° C. oven for 30 minutes.

This coating process was performed once.

2-3. Heat treatment

Heat treatment was performed to improve the bonding strength of the coating material (titanium oxide) and metallic titanium.

Specifically, starting from the air (air) atmosphere, room temperature (25 ℃) was maintained at a heating rate of 10 ℃ / min, 550 ℃ 1 hour, the cooling rate was performed under the conditions of 10 ℃ / min.

Example 3. Bio-ceramic coating on metallic titanium surface

3-1. Tertiary solution preparation

A suspension was prepared by dispersing 20 g of hydroxyapatite (HAP) having an average size of 50 nm in 200 ml of anhydrous ethanol.

In addition, 0.1 ml of a dispersant was added to enhance the dispersibility of the HAP, and a secondary solution was prepared by improving the dispersibility by ultrasonic treatment for 30 minutes.

3-2. Tertiary coating

The metallic titanium coated in Example 2-2 was coated by dipping in a tertiary solution.

Specifically, when the primary coated metallic titanium was immersed in the secondary solution, the descending and rising speed was 1 mm / sec, and the immersion time was maintained for 10 seconds. At this time, the ultrasonic coating was not performed when immersed due to the fear of damage to the primary coated coating film, and the magnetic bar was stirred slowly.

Then, the immersed metal titanium was allowed to stand at room temperature for 10 minutes, and then dried naturally, and then dried in a 150 ° C. oven for 30 minutes.

3-3. Heat treatment

Heat treatment was performed to improve the bonding strength of the coating material (titanium oxide and HAP) and metallic titanium.

Specifically, starting from the air (air) atmosphere, room temperature (25 ℃) was maintained at a heating rate of 10 ℃ / min, 550 ℃ 1 hour, the cooling rate was performed under the conditions of 10 ℃ / min.

Example 4. Bio-ceramic coating on metallic titanium surface

A bio-ceramic coating was performed on the metal titanium surface in the same manner as in Example 3, except that the secondary coating was performed twice.

In order to increase the amount of nano TiO ₂ on the titanium surface, secondary coating was performed three times.

<Experimental Example>

Experimental Example 1-1. SEM analysis

In order to observe the surface of the titanium material heat-treated by the present invention, the surface was analyzed using SEM (Hitachi S4700, Hitachi, Japan). As the substrate, titanium heat-treated for 1 hour at 550 ° C in Example 1 and Comparative Example 1 was used.

And, the results are shown in FIG. 3.

Specifically, Figure 3 (a) is to analyze the titanium surface of Comparative Example 1, Figure 3 (b) is to analyze the surface of Example 1.

3, it was confirmed that the surface of Example 1 was smoother than Comparative Example 1.

This confirmed that Example 1 had a film formed on the surface of the substrate through the coating.

Experimental Example 1-2. EDS analysis

The sample of Example 1 was photographed with a scanning electron microscope (SEM), and this was analyzed using energy dispersive X-RAY (EDS).

Figure 4 shows the EDS data of Comparative Example 1 (the surface when the titanium was heat-treated at 550 ° C. for 1 hour), and FIG. 5 is Example 1 (when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating 3 times) Surface) EDS data.

Referring to FIG. 4, in the case of the comparative example, it can be determined that oxidation did not proceed due to no oxygen being detected as a result of the EDS after the titanium heat treatment, and referring to FIG. 5, the sample coated with the primary coating (TTIP coating) If oxygen is detected, it can be seen that a uniform titanium oxide film was formed on the titanium metal surface.

Experimental Example 2. SEM and EDS analysis-secondary coating

In order to observe the surface of the titanium material heat-treated by the present invention (Example 2), the surface was analyzed using SEM (Hitachi S-4700, Hitachi, Japan), and energy dispersive X-RAY (EDS) was used. Surface analysis.

Figure 6 is a photograph showing the SEM image of the surface when heat treated at 550 ° C for 1 hour after 3 times of TTIP 1st coating and 1 time of 2nd coating ((a) × 10,000, (b) × 50,000). It shows EDS data of the surface when heat treated at 550 ℃ for 1 hour after 3 times of TTIP 1st coating and 1 time of 2nd coating.

Referring to FIG. 6, it can be seen that particles were formed on the surface of the titanium on which the secondary coating was completed.

In addition, referring to FIG. 7, more oxygen atoms were detected than when compared to FIG. 5. It can be seen that the titanium oxide film produced during the primary coating was formed thicker.

Experimental Example 3. SEM and EDS analysis-tertiary coating

In order to observe the surface of the titanium material heat-treated by the present invention (Example 3), the surface was analyzed using SEM (Hitachi S-4700, Hitachi, Japan), and energy dispersive X-RAY (EDS) was used. Surface analysis.

8 is a photograph showing a SEM image of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP 1st coating, 1 time of 2nd coating, and 3rd coating ((a) × 10,000, (b) × 50,000 8, it can be seen that nano-sized particles were attached on the secondary coated TiO ₂ particles.

9 shows EDS data of the surface when heat treated at 550 ° C. for 1 hour after 3 times of TTIP primary coating, 1 time of secondary coating, and 1 time of tertiary coating.

Referring to FIG. 9, it can be confirmed that phosphorus (P) and calcium (Ca) were detected, and it can be seen that nano-sized HAP was attached to TiO ₂ particles.

Experimental Example 4. SEM and EDS analysis-tertiary coating

In order to observe the surface of the titanium material heat-treated by the present invention (Example 4), the surface was analyzed using SEM (Hitachi S-4700, Hitachi, Japan), and energy dispersive X-RAY (EDS) was used. Surface analysis.

Figure 10 is a photograph showing the SEM image of the surface when heat treated at 550 ° C for 1 hour after 3 times of TTIP, 3 times of 2nd coating, and 1 time of 3rd coating ((a) × 10,000, (b) × 50,000 ) to be.

Referring to FIG. 10, it was observed that TiO ₂ particles were formed on most of the titanium surface, and HAP particles were formed on the formed TiO ₂ .

It was judged that TiO ₂ could be coated on metallic titanium to increase the surface roughness of metallic titanium and to compensate for the insufficient bone adhesion of titanium by applying HAP.

Experimental Example 4. Interfacial adhesion test with and without TTIP coating

The interfacial adhesion with or without TTIP coating on the titanium metal surface was tested. Specifically, TiO ₂ particles were coated on titanium metal without TTIP coating and titanium metal with TTIP coating, and the interfacial adhesion property of TiO ₂ was tested by comparing the cleaning power.

11 is a picture for comparing the interfacial adhesion with or without TTIP coating.

FIG. 11 (a) shows titanium film (left) and TTIP coated titanium film (right) not treated with TTIP coating, and 11 (b) titanium coated with TiO ₂ three times on each film of FIG. 11 (a). This is a photograph representing a film.

And, Figure 11 (c) is a photo of each of the 11 (b) after drying the oven and ultrasonic cleaning (no heat treatment).

Referring to FIG. 11 (c), it can be confirmed that a thin white mark remains on the right side (TTIP-treated titanium film) film. It was determined that TiO ₂ particles were not washed in the titanium film, but were attached.

It is judged that the interfacial adhesion between the titanium metal and TiO ₂ particles was increased by TTIP coating on the titanium metal.

Accordingly, even if HAP particles are coated on part or all of the TiO ₂ particles,

The interfacial adhesion between the titanium metal and TiO ₂ particles was increased by TTIP coating on titanium metal (implant), and even if HAP was coated on some or all of the TiO ₂ particles, the interfacial adhesion between the titanium metal and HAP was sufficiently maintained. I think it can be done.

Claims (13)

Forming a titanium dioxide (TiO ₂ ) thin film by applying and heat-treating a mixed solution containing a titanium precursor on the surface of the implant substrate;
Dispersing and coating titanium dioxide (TiO ₂ ) particles on the surface of the implant substrate on which the titanium dioxide thin film is formed; And
By dispersing and coating bio-ceramic particles on a part or all of the surface of titanium dioxide (TiO ₂ ) particles, it is formed by dispersing on a titanium dioxide thin film surface, containing titanium dioxide particles and bio-ceramic particles, or a part of the surface of the titanium dioxide particles or And forming a particle layer to which bio ceramic particles are attached,
The step of dispersing and applying titanium dioxide (TiO ₂ ) particles comprises: adding titanium dioxide particles and a dispersing agent to a solvent, and applying ultrasonic waves to prepare a solution in which titanium dioxide particles are dispersed; And dispersing and coating the solution on the surface of the implant substrate on which the titanium dioxide thin film is formed, followed by drying.
The average particle diameter of the titanium dioxide (TiO ₂ ) particles is in the range of 0.01 to 1 μm,
The average particle diameter of the bio ceramic particles is in the range of 0.01 to 1 μm,
The concentration of bio-ceramic particles increases from the surface of the titanium dioxide thin film to the outer surface of the particle layer,
A method of manufacturing an implant material in which a titanium dioxide (TiO ₂ ) thin film having a thickness of 5 to 500 nm and a particle layer having a thickness of 100 to 10000 nm are sequentially stacked on a surface of a titanium or titanium alloy substrate. According to claim 1,
Method of manufacturing an implant material, characterized in that it further comprises a heat treatment step after the step of dispersing and applying the bio-ceramic particles.
According to claim 2,
Heat treatment step
A method of manufacturing an implant material, characterized in that heat is applied at a heating rate of 2 to 15 ° C / min, and performed at 350 to 650 ° C for 0.5 to 2 hours.
According to claim 1,
The step of forming a titanium dioxide (TiO ₂ ) thin film is
Preparing a mixed solution by mixing a titanium precursor in a solvent;
Dispersing the mixed solution by ultrasonic waves; And
Applying the ultrasonically dispersed mixture to the surface of the implant substrate and drying the mixture; Method of manufacturing an implant material comprising a.
According to claim 4,
Titanium precursor
Ti (OCH (CH ₃ ) ₂ ) ₄ , Ti (OBu) ₄ , TiCl ₄ (Titanium tetrachloride), Ti (OCH ₂ CH ₃ ) ₄ , ((CH ₃ ) ₂ CHO) ₂ Ti (C ₅ H ₇ O ₂ ) ₂ , Ti (OC ₂ H ₅ ) ₄ , Ti (OCH ₃ ) ₄ , Ti (C ₅ H ₇ O ₂ ) ₂ and TiOSO ₄ One or more selected from the group consisting of implant material manufacturing method characterized in that .
delete delete According to claim 1,
The step of dispersing and applying the bio ceramic particles
Adding a bio ceramic particle and a dispersing agent to a solvent, and applying ultrasonic waves to prepare a solution in which the bio ceramic particle is dispersed; And
Dispersing and coating the solution on the surface of the implant substrate on which titanium dioxide particles are formed, followed by drying; Method of manufacturing an implant material comprising a.
The method of claim 8,
The bio ceramic particles
Method for producing an implant material, characterized in that at least one member selected from the group consisting of hydroxyapatite (HAP) and tricalcium phosphate (Beta TCP).
delete As an implant material manufactured by the method of manufacturing the implant material according to claim 1,
Titanium or titanium alloy substrates;
A titanium dioxide (TiO ₂ ) thin film formed on the surface of a titanium or titanium alloy substrate; And
It is formed by dispersing on a titanium dioxide thin film surface, and includes a particle layer containing titanium dioxide particles and bio ceramic particles,
Bio ceramic particles are attached to a part or all of the surface of the titanium dioxide particles in the particle layer,
The average particle diameter of the titanium dioxide (TiO ₂ ) particles is in the range of 0.01 to 1 μm,
The average particle diameter of the bio ceramic particles is in the range of 0.01 to 1 μm,
The concentration of bio-ceramic particles increases from the surface of the titanium dioxide thin film to the outer surface of the particle layer.
An implant material in which a titanium dioxide (TiO ₂ ) thin film having a thickness of 5 to 500 nm and a particle layer having a thickness of 100 to 10000 nm are sequentially stacked on a surface of a titanium or titanium alloy substrate. delete delete

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