KR101951343B1 - Implant comprising Bioactive color glass and preparing method thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to an implant using zirconia as a base material, and it is possible to prevent the adverse effect of deterioration in biocompatibility of the implant due to the multiple coating treatment and the surface etching treatment of bioactive glass, bioceramic ceramic, Thus, there is an excellent effect of promotion of bone formation, biocompatibility, and low bacterial deposition rate. Further, as the bonding force between zirconia and the coating layer is further improved, the mechanical properties such as durability, corrosion resistance and fracture resistance are remarkably improved, and the same color as natural teeth can be realized.

Description

TECHNICAL FIELD The present invention relates to a zirconia implant including a bioactive glass and a method of manufacturing the same.

The present invention relates to a zirconia implant including a bioactive glass and a method for producing the same.

An implant implies transplantation. It is used for transplanting an artificial material or a natural material into a defective part in order to complement the deficiency of a living tissue, , Artificial joints, artificial teeth, and guide lenses.

The second artificial tooth is also referred to as a third tooth. An implant used here is a body suitable for implanting a biocompatible implant body through bone grafting, osteogenesis, or the like, at a site where a tooth is missing or a jawbone It is used for dental treatment which restores the function of natural teeth.

Therefore, the implant should have excellent characteristics such as osseointegration, which is a morphological, physiological, and direct combination with the jaw bone in which the normal function is maintained. Several types of implants have been developed, and many methods have been proposed to lower the failure rate of dental implants applied to the living body and to increase the fixation strength with the bones. For example, a method of mechanically fixing the bone to the bone by designing the implant in a spiral shape is generally used. However, since the fixation force to the bone by mechanical fixation is not comparable to that of a natural tooth, much research is being conducted to further improve the bonding between the implant and the bone.

Accordingly, various methods have been proposed to further improve the fixation force and the bonding force between the implant and the bone, which can be classified into a physical method including the mechanical fixation described above, and a chemical method.

Physical methods include forming roughness on the surface of the implant, grinding, spraying (sand blasting, etc.), acid etching, and the like. Specifically, sandblasting is a method of inducing strengthening by phase change using alumina having a small particle size. Acid Etching is a method of etching the surface with an acid solution. It is a method mainly used with sandblasting because acid etching alone does not show the effect of surface treatment.

Implants with increased surface roughness with this physical method can achieve better mechanical constraint and strength by giving larger contact and fixation areas between the implant and bone tissue.

The chemical method is to change the chemical characteristics of the implant surface. For example, there is a method of coating calcium phosphate, which is an inorganic component similar to bone, on the surface of an implant to stimulate regeneration of bone tissue. Such a treatment method can induce biosynthesis to improve not only physical fixing force and binding force with bone but also chemical biocompatibility.

In addition to physical / chemical inherent properties such as physical properties, chemical properties, and biocompatibility properties, implants are also required to have esthetic properties in recent years. For example, in the case of the anterior teeth (front teeth), the characteristic of the tooth is also important, but it plays a very important role in the social aspect because it is a tooth that is directly exposed. In the case of anterior teeth, it is a reality that the aesthetic characteristic is required to be indistinguishable from that of a natural tooth, which is more apparent than the inherent performance of a tooth. In addition, the probability that the anterior teeth are damaged by physical impact is higher than that of the tooth teeth, and the probability of being replaced with implants is also very high. Therefore, physical and chemical properties such as physical properties, chemical properties, and biocompatibility characteristics are also important, but esthetics characteristics that are not different from actual teeth are required.

As the demand for the esthetics characteristic of the implant increases, Korean Patent Laid-Open Publication No. 2011-0041682 discloses a method of manufacturing a zirconia tooth in which an entire artificial tooth is molded into zirconia colored with a coloring liquid similar to natural color.

Zirconia is excellent in strength and biocompatibility and does not cause any inflammation or allergy when used in the human body because there is no corrosion. It is also widely used as an implant material to replace metals based on its excellent mechanical properties. Recently, it has been applied not only to the core of the crown bridge but also to the implant area. High biocompatibility, excellent mechanical properties and low bacterial deposition rate are highly evaluated as dental materials.

However, zirconia formed on the surface of the coating layer is difficult to form the surface roughness by the spraying method or the acid etching method unlike the general metal. Accordingly, there is a disadvantage in that the bonding strength is lowered even when the surface treatment of zirconia on the surface of which the coating layer is formed is performed using an acid etching method or a spraying method. This is caused by the delamination of the surface coating layer from zirconia, and is basically caused by the fact that the coefficient of thermal expansion of zirconia and the coating layer are not similar to each other, or the cooling rate is too fast.

Korean Patent No. 10-1430748 discloses a biologically active hue glass comprising silicon oxide, aluminum oxide, sodium oxide, magnesium oxide, barium oxide, calcium oxide, titanium oxide and niobium oxide, BACKGROUND ART [0002] It is known for a prosthesis for a tooth including a glass. It has been known that when a bioactive hue glass is coated on zirconia, the surface roughness is somewhat formed to improve fixation force and binding force with bone tissue, but it still has a disadvantage of poor biocompatibility.

Despite the many advantages of zirconia, there are many limitations in the processing process for improving bonding strength and fixing strength. In the process of forming the surface roughness required for the zirconia formed on the surface of the coating layer, a strong physical and chemical shock to zirconia may be caused. These impacts can lead to problems between zirconia and the coating layer, such as low cohesion of zirconia and coating layer, defects at zirconia and coating layer interface, and inaccurate thermal expansion coefficient of zirconia-coated layer, and mechanical properties of zirconia itself such as warpage of zirconia Can be greatly reduced. In some cases, biocompatibility may be lowered.

Therefore, although a lot of cost and time have been invested in order to make the implants replacing a part of the human body have the same or more characteristics and roles as those of the replacement object, It is true.

Korean Patent No. 10-1430748 (Aug. 2014)

[1] Valverde, Guilherme B., et al. "Surface characterization and bonding of Y-TZP following non-thermal plasma treatment." Journal of dentistry 41.1 (2013): 51-59. [2] dos Santos, Daniela Micheline, et al. "Aging effect of atmospheric air on lithium disilicate ceramic after nonthermal plasma treatment." The Journal of prosthetic dentistry 115.6 (2016): 780-787.

It is an object of the present invention to provide an implant using zirconia which can improve excellent characteristics such as biocompatibility, corrosion resistance, excellent mechanical properties and low bacterial deposition rate of zirconia itself and a method for producing the same.

The implant of the present invention is made of a material including zirconia; And a bioactive glass layer coated on the material, wherein the bioactive glass layer includes a bioactive glass, and the surface of the bioactive glass layer has a roughness.

The implant according to an exemplary embodiment of the present invention may further include a bio-inorganic coating layer coated on the bio-active glass layer, and the bio-inorganic coating layer may include any one or two selected from a bioactive glass and a bio- have. That is, the bio-inorganic coating layer may include a bio-active glass, may include a bio-ceramic, or may include a bio-active glass and a bio-ceramic together.

In one example of the present invention, the surface of the bioactive glass layer may have a roughness of 0.5 to 5.0 μm.

The method of manufacturing an implant of the present invention comprises the steps of: a) coating a bioactive glass on a material containing zirconia to form a bioactive glass layer, and b) forming a surface roughness on the bioactive glass layer .

The method of manufacturing an implant according to an exemplary embodiment of the present invention includes the steps of: (c) forming a bio-inorganic coating layer on a bio-active glass layer having surface roughness formed, the bio-inorganic coating layer including one or more selected from bioactive glass and bioceramic .

The method of manufacturing an implant according to an exemplary embodiment of the present invention may include a first sintering step of the bioactive glass layer between the step a) and a step b), and a second sintering step of the bio-inorganic coating layer after the step c) .

In one embodiment of the present invention, the first sintering may be performed at 1,200 to 1,700 ° C.

In one embodiment of the present invention, the second sintering may be performed at 800 to 1,200 ° C.

In one embodiment of the present invention, the bio-inorganic coating layer may include a bio-active glass, may include a bio-ceramic, or may include a bio-active glass and a bio-ceramic together.

In one embodiment of the present invention, the surface roughness in the step b) may be such that irregularities having an average size of 0.5 to 5.0 μm are formed.

In the present invention, the bioactive glass may include any one or two or more selected from silicon oxide, aluminum oxide, sodium oxide, magnesium oxide, barium oxide, calcium oxide, titanium oxide and niobium oxide. The bioactive glass may further include one or more selected from iron oxide, phosphorus pentoxide, boron oxide, potassium oxide, strontium oxide, and the like.

Bio ceramic in the present invention, hydroxide apatite _{(Ca 10 (PO 4) 6} (OH) 2, HA), phosphorus pentoxide (P ₂ O _5), a third calcium phosphate _{(Ca 3 (PO 4) 2} , TCP), octa (Ca ₈ H ₂ (PO ₄ ) 6 .5H ₂ O, OCP) and calcium tetraphosphate (Ca ₄ O (PO ₄ ) ₂ , 4CP), and the like.

INDUSTRIAL APPLICABILITY The implant according to the present invention can prevent the adverse effect that biocompatibility is lowered by coating treatment or surface treatment of zirconia as a base material with a bioactive glass or a bioceramic ceramic and the like, thereby promoting osteogenesis, biocompatibility, Rate and so on.

Further, since the bonding force between zirconia and the coating layer is further improved, mechanical properties such as durability, corrosion resistance and fracture resistance are remarkably improved, and the same color as natural teeth can be realized.

Therefore, the implant of the present invention is applicable to various medical fields and has a wide range of application.

It is to be understood that the effect described in the following specification, which is expected by the technical characteristics of the present invention, and its provisional effect are handled as described in the specification of the present invention even if the effect is not explicitly mentioned here.

Figs. 1 to 4 show the results of observing the degree of cell attachment according to Production Example 1, Production Example 2, Example 1 and Example 2 using a scanning electron microscope (24 hours after cell attachment) Observations at 100 magnifications from the past)
Fig. 5 shows the results of measurement of thermal expansion coefficient of the bioactive glass layer in Production Example 2. Fig.

Hereinafter, a zirconia implant including a bioactive glass of the present invention and a method of manufacturing the same will be described in detail with reference to the accompanying drawings.

The drawings described in the present invention are provided by way of example so that a person skilled in the art can sufficiently convey the idea of the present invention. Therefore, the present invention is not limited to the illustrated drawings, but may be embodied in other forms, and the drawings may be exaggerated in order to clarify the spirit of the present invention.

In addition, unless otherwise defined, technical terms and scientific terms used in the present invention have the same meanings as those of ordinary skill in the art to which the present invention belongs. In the following description and the accompanying drawings, Description of known functions and configurations that may unnecessarily obscure the subject matter will be omitted.

Also, units of% used unclearly in the present invention means weight percent.

The term " implant " as used in the present invention means an artificial material implanted into a human body and refers to a wide range of implants as artificial materials including artificial valves, artificial joints, artificial teeth, guide lenses and the like .

The present invention relates to a material comprising zirconia; And a bioactive glass layer coated on the material, wherein the surface of the bioactive glass layer has roughness. According to a second aspect of the present invention, there is further provided a bio-inorganic coating layer comprising a bioactive glass and / or a bioceramics coated on the bioactive glass layer.

In particular, the implant according to the present invention has excellent mechanical properties and biocompatibility properties as a coating layer of a single layer or a multilayer structure is formed on a zirconia material and surface roughness is formed in at least one coating layer of each coating layer. In addition, when the implant is manufactured by the method of manufacturing the implant according to the present invention, various side effects such as deterioration of mechanical properties and deterioration of biocompatibility due to peeling of the coating layer in the course of surface roughness formation can be prevented.

Generally, although zirconia is known to be excellent in biocompatibility because it does not cause inflammation reaction or allergy, its application range is not wide due to the side effects and the like, and coating treatment and surface treatment such as other metals are easy due to the characteristics of zirconia itself There is a limit in the prior art.

However, the inventors of the present invention have studied the configuration, order, and the like of each step of the method for manufacturing an implant, and as a result, the present invention has found that the present invention provides an implant having excellent surface roughness even though a coating layer of one or more layers is formed on zirconia, And a method for producing the same.

The method of manufacturing an implant of the present invention comprises the steps of: a) coating a bioactive glass on a material containing zirconia to form a bioactive glass layer, and b) forming a surface roughness on the bioactive glass layer . In addition, the method may further include a step of forming a bio-inorganic coating layer containing any one or two selected from bioactive glass and bioceramic on the bioactive glass layer having surface roughness after step b) .

The step a) is an essential step for forming the surface roughness of the step b) and a step for adding the characteristics of the bioactive glass. When the surface roughness is directly formed on the zirconia material, strong stress and heat are applied to the zirconia in the process of forming the surface roughness, resulting in a decrease in durability such as strength. Therefore, the zirconia material should be preceded by a bioactive glass layer forming process in step a) before the surface roughness forming process in step b).

The material of step a) refers to a material for implants containing zirconia (zirconium oxide), means a substrate on which a coating layer is formed, and may be a zirconia-based metal containing zirconia or a different element. Specific characteristics such as thickness, weight, density, shape and the like of the material are not limited because they can be suitably processed and adjusted according to the purpose of use according to the use target position of the implant. As a specific example, the above material can be produced by the following method. The zirconia powder can be put into a molding press, and then subjected to pressure molding to produce a zirconia base material for an implant. The pressure applied at this time can be appropriately adjusted according to the required molding density, for example, 50 to 300 MPa. However, this is merely an example, and the present invention is not limited thereto, and can be manufactured through various known literatures.

The method of manufacturing an implant according to an example of the present invention may further include pre-sintering the material including zirconia prior to the step a). When the durability of the zirconia material is further improved, the multi-step process such as the bioactive glass coating process in step a), the surface roughness forming process in step b), and the bioorganic coating layer forming process in step c) The deterioration of the mechanical properties of the zirconia material can be further prevented. In addition, the adhesion between the zirconia material and the interface between the layers, the compactness and the bonding strength are improved, and the overall mechanical properties of the implant are improved. The sintering temperature in the pre-sintering step is not limited as long as the above-mentioned effect can be achieved. For example, the sintering temperature is 800 to 1,700 ° C, preferably 1,000 to 1,700 ° C in terms of maximizing the effect.

The bioactive glass is used to further improve the biocompatibility and to suppress the occurrence of various side effects such as deterioration of the mechanical properties of the implant due to peeling of the coating layer and deterioration of biocompatibility during the process of forming the surface roughness in the step b).

The bioactive glass may be a glass-based compound having excellent biocompatibility, and specifically, silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), sodium oxide (Na ₂ O). And may include any one or two or more components selected from magnesium oxide (MgO), barium oxide (BaO), calcium oxide (CaO), titanium oxide (TiO ₂ ), and niobium oxide (Nb ₂ O ₅ ). Such a bioactive glass is coated on a zirconia material or coated on a surface of a bioactive glass layer having a surface roughness to improve mechanical properties such as fracture resistance, strength and abrasion resistance as well as aesthetic and chemical resistance properties as well as improvement of biocompatibility The physical properties can be further improved.

As a preferred example, the bioactive glass may comprise silicon oxide, aluminum oxide and sodium oxide. Specifically, the biocompatible glass may include 50 to 80% by weight of silicon oxide, 5 to 40% by weight of aluminum oxide, and 2 to 30% by weight of sodium oxide. If this is satisfied, improvement in biocompatibility properties as well as mechanical properties such as transparency, aesthetic properties such as gloss, abrasion resistance, impact resistance, durability, and chemical stability can be further improved. Further, since the density of the glass is further reduced and the characteristics such as the glass transition temperature, the softening temperature and the viscosity are improved, the bioactive glass layer can be firmly adhered to the surface of the zirconia and the thermal expansion of the zirconia material and the bioactive glass layer The difference in the rate can be further reduced.

As a more preferred example, the bioactive glass may include silicon oxide, aluminum oxide, sodium oxide, magnesium oxide, barium oxide, calcium oxide, titanium oxide and niobium oxide. Concretely, it is preferable to use a composition containing 60 to 75 wt% of silicon oxide, 8 to 18 wt% of aluminum oxide, 4 to 10 wt% of sodium oxide, 0.1 to 5 wt% of magnesium oxide, 0.1 to 5 wt% 0.1 to 5% by weight of titanium oxide, and 0.1 to 5% by weight of niobium oxide. If this is the case, even though a large number of coating layers are formed on the material and roughness is formed therebetween, mechanical properties such as abrasion resistance, abrasion resistance and durability, chemical resistance and water resistance of the manufactured implants are maximized The chemical properties can be remarkably improved. It can also be adjusted to reflect a broader range of visible light wavelengths to have a color very similar to that of living tissue. This can be attributed to the excellent crystallization of the glass during the production of the bioactive glass, and it is possible to minimize the occurrence of side effects such as mechanical property deterioration due to excessive phase change of zirconia at each step.

The bioactive glass may further include one or more additional components selected from iron oxide, phosphorus pentoxide, boron oxide, potassium oxide, strontium oxide, and the like. If it is satisfied, the transparency can be further improved, the glass crystallization can be improved, the mechanical properties such as strength can be further improved, and the thermal expansion coefficient of the zirconia material can be closer. In addition, the solubility of the bioactive glass is increased in the manufacturing process, the softening temperature is decreased, and the melting property is improved, so that the biocompatibility can be further improved. In addition, since the bioactive glass can have an appropriate brightness in the manufacturing process, it is possible to prevent the fracture of the glass, thereby making it possible to produce an implant that is more resistant to physical impact. In addition, the color of the implant can be more freely controlled by controlling the content of iron oxide and the like and the content thereof. When the bioactive glass further comprises the additional component, the additional component is added in an amount of 0.01 to 5% by weight, specifically 0.1 to 3% by weight, more specifically 0.1 to 1% by weight, relative to the total weight of the bioactive glass can do. If these are satisfied, the above effects can be further improved.

The thermal expansion coefficient of the bioactive glass is not limited to a great extent, and the thermal expansion coefficient of the zirconia material is preferably as much as possible. As a specific and preferable example, when the thermal expansion coefficient of the bioactive glass is 6.5 to 12.5 × 10 ^-6 , it can provide strong adhesion to zirconia in the step a) and the first sintering step described later, Lt; RTI ID = 0.0 > resistance. ≪ / RTI >

The above-mentioned composition and composition ratio of the bioactive glass can be independently applied to the bioactive glass of the step a) and the bioactive glass of the step c), respectively.

The bioactive glass may contain the above components in the form of particles, and for example, each component may be pulverized by a ball milling process to produce a bioactive glass. Specifically, the average particle diameter of the bioactive glass may be as long as it can be coated, for example, the average particle diameter may be 0.1 to 50 占 퐉. Preferably an average particle diameter of 0.5 to 5 mu m and a particle size range of 0.1 to 10 mu m. At this time, each component may be wet-mixed and pulverized together with a solvent such as water or an alcohol to produce a bioactive glass. The wet mixed and pulverized powder slurry may be dried, for example, at 60-120 < 0 > C for 0.5-12 hours. Thereafter, the powder slurry is fired at 1,200 to 17,00 ° C to be phase-transformed into a melt state, and the melt can be quenched by fritting into a glass to form a bioactive glass .

The coating method of step a) is not limited to a specific one and may be carried out by various methods such as dip coating, aerosol deposition (AD), spin coating, doctor blade, dry dipping, A hydrothermal reaction, a sol-gel method, a spray method, or an ion beam deposition method. As a specific example of dip coating, a zirconia material may be immersed in a mixture of a solvent such as water and a bioactive glass to form a bioactive glass layer on the surface of zirconia. At this time, the mixing ratio of the bioactive glass and the solvent may be such that the bioactive glass can be coated on the zirconia material by immersion, for example, 1 to 500 parts by weight of solvent relative to 1 part by weight of the bioactive glass. However, since the bioactive glass layer can be formed on the zirconia material by various methods, the present invention is not limited thereto.

The average thickness of the bioactive glass layer coated on the zirconia material in the step a) is not particularly limited as long as the above-mentioned effect can be achieved, and may be, for example, 5 to 120 탆.

The first sintering step may be further performed after forming the bioactive glass layer on the zirconia material in step a). That is, the method of manufacturing an implant according to the present invention may further include a first sintering step of a bioactive glass layer between steps a) and b). By performing the step up to the step of a) after the step a), the mechanical properties and interfacial bonding force (adhesion, compactness, etc.) of the bioactive glass layer on the zirconia material are remarkably improved. Therefore, the biocompatibility is further improved by the bioactive glass layer, and after the surface roughness formation process in the step b), it is possible to suppress the occurrence of various side effects such as deterioration of mechanical properties and biocompatibility due to peeling of the coating layer There is an effect. The sintering temperature is not limited as long as the above effect can be realized. For example, the sintering temperature is 700 to 1,700 ° C, specifically 1,200 to 1,700 ° C in terms of maximizing the effect.

As described above, by coating the bioactive glass on the zirconia material, it is possible to form the surface roughness of the step b) without lowering the mechanical properties of the zirconia material. For example, when surface roughness is first formed on a zirconia material, a physical / chemical impact or a thermal shock is directly applied to the zirconia material, resulting in deterioration of the mechanical properties of the zirconia material.

The step b) is a step of forming a surface roughness on the bioactive glass layer coated on the material in step a). The method of forming the surface roughness includes a method of forming irregularities on the surface of the material, for example, a mechanical etching method, a chemical etching method, and the like. Various methods may be used in combination. However, in terms of manufacturing of implants having high bending strength, Method is preferable. However, this is a preferred example, and the present invention is not limited thereto.

As a preferable example, a method such as sandblasting may be exemplified by a mechanical etching method. Sand blasting is a method of forming roughness on the surface of a material by spraying metal particles such as alumina or sand particles to the surface of the material under a strong pressure. Such methods are well known in the art and can be used with reference to various prior art documents. As a specific example, when particles having a small average particle diameter are used, strengthening by phase change can be induced. However, when particles having a large average particle diameter are used, scratches may increase and the strength may be excessively lowered. Therefore, it is preferable that the average particle size of the particles used for the sandblasting is 75 to 250 탆. In addition, since various parameters may be caused depending on the intensity of the injection pressure, it is preferably 0.1 to 6 MPa. The spraying time can be appropriately adjusted according to the degree of roughness to be formed, and can be, for example, 15 to 45 seconds. However, since the range of the above-described values is described as a preferred example, it is needless to say that the present invention is not limited thereto.

Examples of the chemical etching method include a method of forming irregularities by contacting an acid solution on the surface of a material. Specifically, the material is brought into contact with an acid solution containing hydrofluoric acid (HF) or the like to etch the surface of the material to form irregularities due to acid corrosion on the surface of the material. When a hydrofluoric acid aqueous solution is used, an aqueous solution containing 10 to 20% of hydrofluoric acid may be used. The contact time is not limited as it can be adjusted to such an extent that the required average size irregularities can be formed, but can be, for example, 10 to 60 minutes. The contact temperature may be a level that is not high enough to cause thermal shock to the material, for example, it may be 30 to 90 占 폚. However, this is merely a preferred example, and the present invention is not limited thereto.

In addition, the surface roughness can be formed by the plasma method. As a specific example, the surface roughness forming method using the plasma method can form a surface roughness with high uniformity by controlling the plasma density by RF power and etching by controlling the ion energy with the lower power. At this time, the plasma etching rate, selectivity and uniform reactivity can be influenced by various variables such as the kind of the reactive gas, the reactor type, the process conditions, etc., and the known non-patent documents 1 and 2 can be referred to .

The surface roughness in the step b) may be such that irregularities having an average size of 0.5 to 5.0 mu m, preferably 1.0 to 2.0 mu m, are formed. It is possible to prevent the problem that the strength is excessively lowered when the surface roughness in the upper range is formed. Further, since the process of forming sintering, bio-inorganic coating layer and the like is further performed, the effective surface roughness can be maintained, and the adhesion of the implant to the bone can be improved.

As described above, the implant according to the present invention is excellent in biocompatibility since it is manufactured by including the step a) of forming the bioactive glass layer and the step b) of forming the surface roughness, but the bioactive glass layer The zirconia material formed may be relatively less biocompatible than a pure zirconia material without a coating layer formed. However, by further coating the bioorganic coating layer of step c), biocompatibility such as biocompatibility and bone formation promotion can be remarkably increased. In addition, the fracture resistance is significantly increased, so that the surface roughness can be formed again without deteriorating the mechanical properties such as durability even though the process of forming the surface roughness can be performed again afterwards.

In the step c), a bio-inorganic coating layer is formed on the bio-active glass layer having the surface roughness of step b), wherein the bio-inorganic coating layer includes one or two selected from bioactive glass and bioceramic. Here, the bioactive glass is as described above for the bioactive glass of step a).

In the present invention, the bioceramics refers to a biocompatible inorganic compound, and specifically includes apatite hydroxide (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , HA), phosphorus pentoxide (P ₂ O ₅ ) ₃ (PO ₄₎ which is selected from _2, TCP), octa-calcium phosphate _{(Ca 8 H 2 (PO 4} ) 6 · 5H 2 O, OCP) , and tetra-calcium phosphate _{(Ca 4 O (PO 4)} 2, 4CP) And may include one or more components.

Particularly, if the bio-inorganic coating layer includes the bio-ceramic in the step c), degradation of biocompatibility due to the step a) can be prevented. Further, although the properties such as biocompatibility and low bacterial deposition rate are improved, mechanical properties such as fracture resistance can be improved. Specifically, even if the mechanical and chemical forces applied to the zirconia material strongly act in the step b), the bio-inorganic coating layer is formed on the bio-ceramic in step c) even if the mechanical properties such as the structural stability and strength of the zirconia are deteriorated. It is possible to suppress the occurrence of the side effect. Therefore, by minimizing the characteristics lost in the steps a) and b), the overall characteristics can be improved.

In addition, even though the bio-inorganic coating layer including the bioceramics is formed after the unevenness is formed, it is possible to obtain a bio-inorganic coating layer having substantially the same shape as the coating layer without being covered or clogged by the fine structural irregularities (point, dislocation, grain boundary, crack, folding, There is a remarkable effect to be maintained. Therefore, not only the biocompatibility is improved, but also the surface roughness is maintained and the fixation force with the bone tissue and the binding force characteristic are also excellent.

In one preferred embodiment, the bio-inorganic coating layer may include a bioactive glass and a bioceramic material. Specifically, the bioceramic material may contain 5 to 300 parts by weight, specifically 5 to 100 parts by weight, more specifically, 5 to 30 parts by weight, more particularly 5 to 15 parts by weight, based on the weight of the composition. If these are satisfied, the above-mentioned effects by the bioactive glass can be improved. In the case of a bioorganic coating layer including a bio-ceramic and a bio-active glass, the interlayer bonding force and biocompatibility can be further improved as compared with a bio-inorganic coating layer not including a bioactive glass. Further, since the color expression by the bioactive glass is further improved, the aesthetic property can be further improved.

The average thickness of the bio-inorganic coating layer is not limited as long as the effects described above can be realized, and may be, for example, 0.05 to 120 탆. If it is satisfied, it is possible to prevent the problem that the surface roughness formed in the step b) is reduced by the coating of the bioorganic-inorganic coating layer, and the thickness of the layer is too thin to reduce the durability Can be minimized. However, this is described as a preferable example, but the present invention is not limited thereto.

The coating method of the step c) may be carried out by various methods such as dip coating, aerosol deposition (AD), spin coating, doctor blade, dry dipping, hydrothermal ), A sol-gel method, a spray method, or an ion beam deposition method. Preferably, dip coating is preferable in terms of excellent process efficiency. However, this is a preferred example, and the present invention is not limited thereto, and the layer may be formed by various known coating methods.

When the bio-active glass layer containing the bioactive glass and / or the bioceramic ceramic is formed on the bio-active glass layer having the surface roughness of step b) in step c), the bioactive glass particles and / A method of coating a mixture obtained by dispersing bio-ceramic particles in a solvent on the bioactive glass layer can be exemplified. The solvent may be any solvent that does not react with a zirconia material, a bioactive glass, a bioceramic material, etc., and a neutral pH solvent such as water or ethanol may be exemplified. The amount of the solvent to be used may be such that the bioactive glass or the bio-ceramic can be coated on the bio-ceramic layer. For example, the solvent may be used in an amount of 1 to 500 parts by weight based on 1 part by weight of the bioactive glass or bio-ceramic.

The average particle size and the particle size range of the bioactive glass or the bioceramics may be as long as they can be coated, for example, the average particle size may be 0.1 to 50 μm. Preferably an average particle diameter of 0.5 to 5 mu m and a particle size range of 0.1 to 10 mu m. When this is satisfied, the bio-inorganic coating layer including the bioactive glass and / or the bioceramics can improve the adhesion strength, bonding strength and durability to the zirconia material.

And a second sintering step of the bio-inorganic coating layer after the step c). By performing the step from step c) to the step of sintering, the bio-inorganic coating layer is brought into close contact with and bonded to the bioactive glass layer and the mechanical properties of the layer are improved. In addition, since the zirconia material and the bioactive glass layer are sintered again, the structure stability and mechanical strength of the implant are further improved. The sintering temperature may be as long as the above effect can be achieved. For example, the sintering temperature is preferably 500 to 1,200 ° C, specifically 800 to 1,200 ° C, from the viewpoint of maximizing the effect.

The method of manufacturing an implant according to an exemplary embodiment of the present invention may further include forming a surface roughness on the bio-inorganic coating layer after step c), as the case may be. The implant to the c) stage has excellent mechanical properties, which can further improve the surface roughness. As the bio-inorganic coating layer is formed, the surface roughness may be reduced. However, since the step of forming the surface roughness can be further roughened, the bonding strength with the human body (bone) can be improved without deteriorating the mechanical properties such as durability and strength of the implant Can be further improved.

As described above, the implant of the present invention comprises a material containing zirconia; And a bioactive glass layer coated on the material, wherein roughness is formed on the surface of the bioactive glass layer. In addition, the implant of the present invention may further include a bio-inorganic coating layer coated on the bio-active glass layer having the surface roughness. The surface of the bioactive glass layer may have a roughness of 0.5 to 5.0 mu m. The bio-inorganic coating layer may include any one or two selected from bio-ceramics and bio-active glasses. At this time, the bioceramics and the bioactive glass are the same as described in the method of manufacturing the implant.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Preparation Examples and Examples. However, the present invention is described in more detail with reference to the following Examples, but the scope of the present invention is not limited by the following Examples.

[Production Example 1]

A disk-shaped zirconia (ZrO ₂ ) substrate having a diameter of 19 mm and a height of 1.4 mm was preliminarily sintered at 1,040 ° C. using a sintering furnace. The average surface roughness of pre - sintered zirconia was 0.025 ㎛, the hardness was 12.34 GPa, and the flexural strength was 425 MPa. Cytotoxic tests were also performed on the pre-sintered zirconia, and the results are shown in Table 1 below.

[Production Example 2]

A biologically active glass layer was formed on the surface of the pre-sintered zirconia of Preparation Example 1 as follows to perform a first sintering.

Specifically, 70% by weight of SiO ₂ powder, 20% by weight of Al ₂ O ₃ powder and 10% by weight of Na ₂ O powder were ball milled at 500 rpm for 50 minutes, mixed and pulverized. Lt; / RTI > After the melting, quenching was performed using cooling water to perform glass crystallization process. The crystallized glass was thoroughly dried and ball milled to form particles having an average particle diameter of 1.5 탆 at 500 rpm for 50 minutes to prepare a SiO ₂ -Al ₂ O ₃ -Na ₂ O -based bioactive glass powder.

Then, preliminarily sintered zirconia of Preparation Example 1 was immersed in a mixed solution obtained by mixing 100 parts by weight of distilled water with 1 part by weight of the bioactive glass powder and the bioactive glass powder. Then zirconia coated with the bioactive glass powder was first sintered at 1,450 ° C using a sintering furnace to prepare zirconia having a bioactive glass layer formed thereon.

The thermal expansion coefficient of the bioactive glass layer was about 10.12 × 10 ^-6 / ° C. as shown in FIG. 5, which is close to 10.65 × 10 ^-6 / ° C., which is the thermal expansion coefficient of zirconia.

The average surface roughness of the zirconia on which the bioactive glass layer was formed was 0.55 mu m, the hardness was 6.23 GPa, and the flexural strength was 850 MPa. In addition, a cytotoxic test was performed on zirconia on which the bioactive glass layer was formed, and the results are shown in Table 1 below.

Surface roughness was formed on the surface of the bioactive glass layer of zirconia on which the bioactive glass layer of Production Example 2 was formed by sandblasting.

Specifically, alumina particles having an average particle size of 90 탆 were sprayed for 30 seconds at a pressure of 3.5 MPa on the surface of the bioactive glass layer of the zirconia on which the bioactive glass layer of Production Example 2 was formed to form roughness on the surface. In this case, the linear distance between the tip of the nozzle through which the alumina particles are injected and the surface of the bioactive glass layer is set to 10 mm,

The average surface roughness of the roughness-formed zirconia was 1.25 mu m, the hardness was 10.60 GPa, and the flexural strength was 650 MPa. In addition, a cytotoxic test was performed on zirconia on which the bioactive glass layer was formed, and the results are shown in Table 1 below.

Surface roughness was formed on the surface of the bioactive glass layer of zirconia on which the bioactive glass layer of Production Example 2 was formed by acid etching.

Specifically, zirconia having a biologically active glass layer of Preparation Example 2 was immersed in a 15% by weight hydrofluoric acid (HF) aqueous solution at 55 캜 for 30 minutes, and the surface of the zirconia was etched to form a roughness on the surface.

The average surface roughness of the roughness-formed zirconia was 1.35 탆, the hardness was 12.00 GPa, and the flexural strength was 600 MPa. In addition, a cytotoxic test was performed on zirconia on which the bioactive glass layer was formed, and the results are shown in Table 1 below.

A bio-inorganic coating layer containing apatite hydroxide and a bioactive glass was formed on the surface of the rough-surfaced zirconia of Example 1 (surface of the bioactive glass layer) using a dipping method, and the second sintering was performed.

Specifically, the average particle diameter of 2 ㎛ a particle size range of 0.1 ~ 10 ㎛ hydroxide of the apatite powder and the SiO ₂ -Al ₂ O ₃ -Na ₂ Preparation O type 2 bioactive glass powder is 15: 1 by weight mixed with a mixed Powder and 100 parts by weight of distilled water with respect to 1 part by weight of the mixed powder was immersed in the mixed solution of the roughness of Example 1 to form a bioorganic coating layer on the surface of the bioactive glass layer of zirconia, The second sintering was performed to prepare zirconia having a bioorganic coating layer.

The zirconia having the bio-inorganic coating layer formed had an average surface roughness of 2.89 mu m and a flexural strength of 627 MPa. Cytotoxic test was performed on the zirconia in which the bio-inorganic coating layer was formed. The results are shown in Table 1 below.

Zirconia in which a bioorganic coating layer was formed was prepared in the same manner as in Example 3, except that the roughened zirconia of Example 2 was used instead of the roughness-formed zirconia of Example 1.

The zirconia having the bio-inorganic coating layer formed had an average surface roughness of 2.46 mu m and a flexural strength of 405 MPa. Cytotoxic test was performed on the zirconia in which the bio-inorganic coating layer was formed. The results are shown in Table 1 below.

[Comparative Example 1]

Zirconia having a bioorganic coating layer was prepared in the same manner as in Example 3, except that the pre-sintered zirconia of Preparation Example 1 was used instead of the roughness-formed zirconia of Example 1.

Cytotoxic test was performed on the zirconia in which the bio-inorganic coating layer was formed. The results are shown in Table 1 below.

The flexural strength referred to in the present invention means the strength with which the material can be held when the pressure is applied, and the flexural strength in the production examples, comparative examples and examples is measured according to the international standard ISO 6872. [

The above-mentioned cytotoxicity test was carried out by using the samples prepared in the respective preparation examples, comparative examples or examples by the following methods. Three specimens per group were placed in a 24-well plate, and the osteoblast MC3T3-E1 (ATCC Catalog No. CRL-2593) was dispensed at a density of 5 × 10 ⁵ cells / cm ^{2 in} a well containing the sample. Mu] l, and cultured in a 5% carbon dioxide incubator at 37 [deg.] C for 24 hours. Cells were cultured for 24 hours and quantitated by 20 ㎕ per well using EZ-Cytox (Itsbio, Korea). The cells were incubated in a 5% CO 2 incubator for 1 hour at 37 ° C, and then 100 μl each was dispensed into a 96-well plate. After removing the bubbles, an absorbance analyzer (ELISA reader: ELx 800UVⓡ, Bio-Tek Instrument. , USA). The absorbance of each well was measured at 450 nm. The reference wavelength was 630 nm. After cell culture, specimens were fixed for scanning electron microscopy and washed twice with PBS for 10 min each. Then, dehydration was carried out at 15 minute intervals in 40%, 50%, 60%, 70%, 80% and 90% ethanol for three times at intervals of 10 minutes in 100% ethanol. The specimens were dried in a 5% CO 2 incubator at 37 ° C and platinum coated for 1 minute using an ion sputter (EX-200®, Hitachi horiba, Japan) Were used to observe the degree of cell attachment and morphological changes on the surface of the specimen.

When the surface roughness was formed on the bioactive glass layer formed on the surface of zirconia as in Production Example 2, Example 1 and Example 2, the bending strength remarkably increased.

In the case of Example 3 in which a bio-inorganic coating layer was further formed after the surface roughness was formed, the bending strength was increased as compared with Example 1, but the bending strength was decreased in Example 4 as compared with Example 2. Therefore, it is preferable to form the surface roughness by the sand blasting method rather than the acid etching method in terms of the manufacturing of the implant having better bending strength.

In order to evaluate the fracture toughness in Production Example 1, Production Example 2, and Examples 1 to 4, each surface was subjected to indentation, and then its surface shape was observed. As a result, cracks were observed on the surface in the cases of Production Example 1 and Production Example 2 in which no coating was applied, but in Examples 1 to 4, cracks did not occur on the surface. Particularly, in the case of Example 3 and Example 4, it was confirmed that the surface irregularities appear as they are in Examples 1 and 2. It is considered that this is due to the improvement of adhesion and bonding force between the zirconia material and each layer. Thus, it can be seen that the composite implant coated with a multilayer structure has excellent structural stability. That is, even if a bio-inorganic coating layer is further formed on the bio-active glass layer having the surface roughness, the surface roughness is maintained, but the high fracture resistance is maintained and the structural stability is ensured.

Specifically, although the bio-inorganic coating layer is formed after the surface roughness is formed, the surface roughness is maintained without the appearance of unevenness on the bio-inorganic coating layer because the bio-inorganic coating layer is formed on the bio- Is maintained. These results are believed to be due to the introduction of various structural fine irregularities such as points, dislocations, grain boundaries, cracks, folds, and wrinkles as the irregularities are introduced into the surface of the bioactive glass layer.

Also, it was confirmed that a high surface roughness was formed, thereby improving cell adhesion properties. FIGS. 1, 2, 3 and 4 show the results of cell adhesion test in which the degree of cell adhesion according to Production Example 1, Production Example 2, Example 1 and Example 2 was observed using a scanning electron microscope . Specifically, the above results were observed at a magnification of 100 at a time point after 24 hours from the attachment of the cells to the zirconia finally produced in each production example or example. As a result of the cell attachment test, in the case of Production Example 2 (FIG. 2) in which a bioactive glass layer was formed, lower cell adhesion results were obtained than in Production Example 1 (FIG. 1) in which no layer was formed. On the other hand, in Examples 1 and 2 in which the roughness was formed after the bioactive glass layer was formed, high cell adhesion was observed. Also, although not shown separately in the drawings, in the case of Examples 3 and 4 in which the surface roughness was formed and the bioorganic coating layer was further formed after the bioactive glass layer was formed, high cell attachment results were obtained as in Examples 1 and 2 Respectively.

1 day 3 days Production Example 1 0.42 0.72 Production Example 2 0.38 0.64 Example 1 0.44 0.79 Example 2 0.45 0.81 Example 3 0.52 0.92 Example 4 0.54 0.94

Table 1 shows the biocompatibility results of Cytotoxic test for Production Example 1, Production Example 2, and Examples 1 to 4.

In the cytotoxicity test, in the case of Production Example 2 in which the bioactive glass layer was formed, the cell proliferation was decreased and the biocompatibility was lowered compared with the case of Production Example 1 which was not. However, in Examples 1 and 2 in which the surface roughness formation process was performed, the biocompatibility was improved, and in Examples 3 and 4 in which a bioorganic coating layer was further formed, the biocompatibility was remarkably improved.

In the case of Examples 5 and 6, which were carried out in the same manner as in Examples 3 and 4, but not including bioactive glass as a bioorganic coating layer and containing only apatite hydroxide, Compared with Example 3 and Example 4, the properties such as flexural strength, cell adhesion and biocompatibility were generally lowered.

Claims (12)

A material comprising zirconia;
A bioactive glass layer comprising a bioactive glass, coated on said material and etched to have a surface roughness; And
A bio-inorganic coating layer including a bio-ceramic and a bio-active glass, the bio-inorganic coating layer being coated on the etched bioactive glass layer and having a surface roughness;
/ RTI >
Wherein the bioactive glass comprises any one or two or more selected from silicon oxide, aluminum oxide, sodium oxide, magnesium oxide, barium oxide, calcium oxide, titanium oxide and niobium oxide. The method according to claim 1,
The body of ceramic is hydroxide, apatite _{(Ca 10 (PO 4) 6} (OH) 2, HA), phosphorus pentoxide (P ₂ O _5), a third calcium phosphate _{(Ca 3 (PO 4) 2} , TCP), octa-calcium phosphate (Ca ₈ H ₂ (PO ₄ ) ₆ .5H ₂ O, OCP) and calcium tetra phosphate (Ca ₄ O (PO ₄ ) ₂ , 4CP). delete The method according to claim 1,
Wherein the surface of the bioactive glass layer has a roughness of 0.5 to 5.0 占 퐉. The method according to claim 1,
Wherein the bioactive glass further comprises one or more selected from iron oxide, phosphorus pentoxide, boron oxide, potassium oxide and strontium oxide. a) coating a bioactive glass on a material comprising zirconia to form a bioactive glass layer; and
b) forming a surface roughness on the bioactive glass layer; and
c) forming a bio-inorganic coating layer including a bio-ceramic and a bio-active glass on the bio-active glass layer having surface roughness
/ RTI >
Wherein the bioactive glass comprises any one or two or more selected from silicon oxide, aluminum oxide, sodium oxide, magnesium oxide, barium oxide, calcium oxide, titanium oxide and niobium oxide. The method according to claim 6,
The body of ceramic is hydroxide, apatite _{(Ca 10 (PO 4) 6} (OH) 2, HA), phosphorus pentoxide (P ₂ O _5), a third calcium phosphate _{(Ca 3 (PO 4) 2} , TCP), octa-calcium phosphate _{(Ca 8 H 2 (PO 4} ) 6 · 5H 2 O, OCP) , and tetra-calcium phosphate method for producing implants comprising at least one or two selected from _{(Ca 4 O (PO 4)} 2, 4CP). delete The method according to claim 6,
B) sintering the bioactive glass layer between step a) and b)
Further comprising a second sintering of the bio-inorganic coating layer after step c). 10. The method of claim 9,
Wherein the first sintering is performed at 1,200 to 1,700 ° C, and the second sintering is performed at 800 to 1,200 ° C. The method according to claim 6,
Wherein the surface roughness of the step (b) is formed with irregularities having an average size of 0.5 to 5.0 占 퐉. The method according to claim 6,
Wherein the bioactive glass further comprises one or more selected from iron oxide, phosphorus pentoxide, boron oxide, potassium oxide and strontium oxide.

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