WO2010147308A2 - 망상 또는 섬 형상의 저결정 수산화아파타이트로 코팅된 임플란트 및 이의 코팅 방법 - Google Patents
망상 또는 섬 형상의 저결정 수산화아파타이트로 코팅된 임플란트 및 이의 코팅 방법 Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
- A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00004—(bio)absorbable, (bio)resorbable, resorptive
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00526—Methods of manufacturing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00831—Material properties
- A61B2017/00933—Material properties bone or bone-like
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00982—General structural features
- A61B2017/00995—General structural features having a thin film
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to a method of coating a titanium implant surface widely used as a graft material with low crystalline apatite having bioabsorbability, and an implant coated by the present method.
- apatite hydroxide (Hydroxyapatite) is used a lot. Hydroxyapatite is chemically and crystallographically identical to the minerals that make up bones and teeth in the human body, and when implanted in the human body, it has good bioactivity that goes well with surrounding cells and forms fast chemical bonds directly with bones at the junctions. . Pure hydroxyapatite crystals composed of calcium ions, phosphate ions, and hydroxide ions are stoichiometic crystals arranged in a long rod-like structure with high crystallinity.
- biocrystals isolated from bone or calcified cartilage have low crystallinity as nonstoichiometirc hydroxide apatite. Studies in Inorganic Chemistry 18, Amsterdam: Elsevier, pp 111-190 (1994).
- Titanium is widely used as an implant material because its physical properties are similar to human bones and its mechanical strength is excellent. It is also widely used as a metal that does not cause inflammatory or other immune responses in the body. In order to impart bioactivity to titanium itself, various modifications (such as Korean Patent Application No. 98-23075 and others) have been applied to industries such as blasting surfaces or etching with acids. However, titanium is less biocompatible than ceramic materials such as apatite hydroxide, and when there is a long period in the human body, the dissolution of metal ions proceeds, resulting in the generation of inorganic substances.
- the plasma spray method which is most used among the above methods, has a disadvantage in that the coating layer is unevenly exposed due to instantaneous exposure to a high temperature of 10,000 ° C. or more, and it is difficult to coat a thickness of less than about 10 ⁇ m.
- the crystallinity of the apatite hydroxide coated on the surface is very high, there is a problem that the bioreactivity is very low, such as not degraded in vivo or removed by osteoclasts.
- the method is known to simultaneously produce calcium phosphates, calcium hydroxides and the like having different phases as by-products [H.-G. Pfaff et al., Properties of HA-Coatings in 'Bioceramics', vol.
- sputtering or ion implantation has caused many problems such as complex shapes and uniformity of the uneven portion coating layer without having to discuss expensive equipment, and dropping of the implant due to peeling from the human body.
- calcium phosphate solution or an analog solution as a wet coating method.
- the production or coating of various forms of calcium phosphate is initiated from calcium phosphate ion solutions.
- These calcium phosphate compounds can be prepared by mixing calcium ions and phosphate ions in an aqueous solution under various conditions, and the type and form of the compounds are greatly influenced by the concentration of ions, Ca / P ratio, and pH.
- concentration of ions Ca / P ratio
- pH Known for: Ayako Oyane, Kazuo Onuma, Tadashi Kokubo, and Atsuo Ito J. Phys. Chem. B 1999, 103, 8230-8235, Elliott J. C.
- Calcium phosphate compounds using the wet method have different equilibria depending on the temperature and the wastewater value.
- Calcium phosphate coating according to the wet method of the prior art is a method using calcium phosphate solubility, so that the solubility of calcium phosphate is lowered as the process temperature increases.
- the initial process must be carried out at a low temperature between 2 °C ⁇ 5 °C, it is very difficult to obtain a coating film as well as a colloid of calcium phosphate without raising the temperature.
- the wastewater of the solution is generally terminated between 6.0 and 6.5.
- the exact calcium phosphate equilibrium of the conventional wet calcium phosphate coating membrane compound has not been analyzed and known, but it can be inferred as OCP in the correlation between the temperature of the calcium phosphate solution and the wastewater.
- the conventional wet method uses a difference in the solubility according to the temperature change of calcium phosphate, and there is a limit in that the temperature and / or pH control, the temperature raising process, and the complex procedure are required to form the calcium phosphate coating film. Accordingly, the present invention is to solve the complexity of the procedure of the conventional wet method to provide a coating method of apatite hydroxide with excellent productivity in a relatively simple process and low cost without the process of temperature and pH adjustment or temperature increase.
- the present invention overcomes the limitations of the conventional hydroxyapatite coating layer with high crystallinity and is absorbed by osteoclasts in vivo and participates in the bone remodeling process so that low crystalline apatite-coated hydroxide can be applied for a long time without being isolated from new bone. It is an object of the invention to provide an implant.
- the present invention is a relatively simple procedure compared to the conventional wet method, economical, excellent bioactivity, low-crystalline apatite hydroxide coating method without the need to strictly control the reaction conditions such as temperature and / or pH adjustment, temperature rising process To provide a for the purpose of the invention.
- the titanium or titanium alloy implant in a state immersed in a calcium phosphate ion solution, wherein the low crystalline apatite produced by the above method is characterized in that it is in the form of a network, an island or a thin film, and is bioabsorbable.
- the implant coating method according to the present invention has an advantage that it can be applied for a long time without being isolated from new bone by being absorbed by osteoclasts in vivo and participating in the bone remodeling process.
- the bioactivity imparted to the titanium implant surface induces strong interface bonding with implant bone and dental tissue, promotes bone conduction or bone formation, and due to the bioabsorbability of low-crystalline apatite hydroxide as a coating layer.
- Implant success rate can be improved by preventing the implant dropout by peeling of a surface coating layer.
- the present invention it is possible to manufacture excellent dental implants at a very simple process and at a low cost, and the thickness and shape of the coating layer can be adjusted as necessary, such as a thin coating layer, a thick coating layer, and a surface on which the titanium and coating layers are simultaneously exposed.
- the coating layer can be adjusted as necessary, such as a thin coating layer, a thick coating layer, and a surface on which the titanium and coating layers are simultaneously exposed.
- orthopedics can be used for various purposes.
- 1 is a scanning electron micrograph of the uncoated titanium implant surface.
- FIG. 2 is a scanning electron micrograph of a thick network of low crystalline apatite hydroxide coated on a titanium implant surface.
- FIG. 3 is a scanning electron micrograph in which low crystalline apatite hydroxide is thinly coated on a titanium implant surface in a network and island shape.
- FIG. 5 is a transmission electron micrograph of a thin, network and island-like coated membrane of low crystalline apatite hydroxide on a titanium implant surface.
- FIG. 7 is a schematic process flow diagram of the present invention.
- FIG. 8 is a photograph of a lattice structure obtained from a high resolution transmission electron microscope of a sigma aldrich hydroxide apatite and a low crystalline apatite hydroxide coated surface coated with the present invention.
- FIG. 9 is a distance and angle measurement result from each center to each atom that can be obtained from the lattice structure comparison photograph of FIG. 6.
- FIG. 10 shows the results of low crystalline apatite hydroxide coated on a titanium implant using an elemental analyzer in a high resolution transmission electron microscope.
- FIG. 11 is a graph comparing the differentiation of mesenchymal stem cells into osteoblasts for 14 days in an RBM treated titanium substrate and an implant substrate coated with low crystalline apatite hydroxide.
- FIG. 12 is a graph comparing the degree of calcification of mesenchymal stem cells for 14 days / 28 days in an RBM-treated titanium substrate and an implant substrate coated with low crystalline apatite hydroxide.
- FIG. 13 is a scanning electron micrograph showing the degree of bioabsorption of the coating film 2 weeks / 6 weeks after the implantation of low crystalline apatite hydroxide.
- the present invention relates to an implant coated with a hydroxide of apatite excellent in bone growth and bone conduction on a titanium surface for biological implants having excellent mechanical properties, and to a method for a titanium implant in a low concentration aqueous solution of calcium phosphate at room temperature of 10 ° C to 35 ° C.
- a method for a titanium implant in a low concentration aqueous solution of calcium phosphate at room temperature of 10 ° C to 35 ° C Provided are techniques for inducing low crystalline apatite hydroxide growth in a network or island.
- the coating method according to the present invention can be used for implants using titanium alloy as a raw material, in addition to pure titanium, and the surface constituting the implant can also be used for surface treatment by various methods using titanium as a raw material.
- the process time may be slightly different from the embodiment of the present invention, but a person skilled in the art who is familiar with the technique of coating apatite hydroxide on the implant surface may easily adjust the reaction time.
- the coating method of the present invention is an implant coating method according to the present invention
- the pretreatment step may include, for example, RBM (Resorbable Blasting Media) method for surface treatment using absorbent spray particles, SLA (Sand-blasted Large grit, and Acid etched) surface treatment method for etching in acid after aluminum blasting, 300 ° C. or more.
- RBM Resorbable Blasting Media
- SLA Sand-blasted Large grit, and Acid etched
- a method commonly used in the market or research may be used, such as one or more selected from the group consisting of heat treatment, anodizing, acid treatment, and base treatment at temperature, and titanium or surface treated in the same manner as described above.
- the pretreatment step may be omitted.
- the pretreatment step includes a method of ultrasonicating the titanium or titanium alloy implant in distilled water, calcium ion solution, phosphate ion solution or calcium phosphate solution for at least 1 minute, and then performing the ultrasonic treatment after performing the above-described RBM, SLA or heat treatment. Can be carried out.
- the method may further include the step of cleaning the implant with an acid solution or a base solution before the ultrasonication of the titanium or titanium alloy implant.
- the acid solution may be, for example, a nitric acid, hydrochloric acid, sulfuric acid or hydrofluoric acid solution, preferably nitric acid.
- the base solution may be, for example, sodium hydroxide, potassium hydroxide, ammonia, etc., preferably sodium hydroxide or potassium hydroxide.
- Implants containing titanium or titanium alloys can optionally remove carbon hydroxide on the surface using the acid or base solution.
- the acid solution or base solution is preferably about 4 v / v% to 60 v / v%.
- the acid or base solution cleaning process may be omitted.
- the surface may be washed with distilled water to remove residual acid or base on the surface. This may also be omitted on surfaces where the acid or base solution cleaning process is omitted.
- the low concentration (about 1.0 mM to about 10 mM) calcium ion solution presented herein is a calcium nitrate series (Ca (NO 3 ) 2 or Ca (NO 3 ) 2 ⁇ 4H 2 O, etc.) or calcium chloride (Calcium chloride).
- a calcium nitrate series Ca (NO 3 ) 2 or Ca (NO 3 ) 2 ⁇ 4H 2 O, etc.
- calcium chloride Calcium chloride
- the low concentration (about 1.0mM to about 10mM) phosphate solution of the present application is ammonium phosphate series ((NH 4 ) 2 HPO 4, etc.) or sodium phosphate series (Na 2 HPO 4 or Na 2 Simple method of dissolving HPO 4 2H 2 O or Na 2 HPO 4 7H 2 O, etc. or Potassium phosphate series (K 2 HPO 4 or K 2 HPO 4 3H 2 O, etc.) in distilled water. It can be prepared by.
- Calcium phosphate ion solution may be prepared by mixing the prepared phosphate ion solution and calcium ion solution and applied to the implant substrate.
- the calcium phosphate ion solution is added to the implant substrate within 0 to 30 minutes after preparation. It is.
- 0 minutes after the preparation means adding the phosphate ion solution and the calcium ion solution, respectively, on the implant substrate immediately after preparing the calcium phosphate ion solution or on the implant substrate.
- the concentration of calcium phosphate solution is 1.0 mM to 10 mM.
- soaking time may be applied differently in order to control the state, shape, and thickness of the surface.
- the immersion temperature is about 10 ° C to about 35 ° C, preferably about 15 ° C to about 30 ° C, the temperature may be kept constant or raised. The immersion time and immersion temperature will be readily selected and applied to those skilled in the art according to the purpose and purpose.
- Low concentration calcium ion solution and phosphate ion solution are added to the titanium implant, respectively, and soaked for 30 minutes or more, preferably 1 hour or more, and then the titanium implant is removed and simply washed with distilled water to obtain a network or island shape ( Low crystalline apatite with islands may be coated on the titanium or titanium alloy implant surface.
- the coating method according to the present invention does not need to adjust the pH of the calcium phosphate solution, and there is an advantage that does not need to be stirred in mixing the phosphate ion solution and the calcium ion solution.
- the low crystalline apatite hydroxide coating method proposed in the present invention has a dissociation constant of hydrogen phosphate (HPO 4 2- ) present in the phosphate ion solution by mixing the calcium phosphate solution with the phenomenon that the solubility of the calcium phosphate solution is decreased at room temperature.
- HPO 4 2- hydrogen phosphate
- the phosphate ion solution has a very low dissociation constant for hydrogen phosphate ions. Therefore, the amount of hydrogen phosphate ions dissociated in the solution is very small.
- the present invention unlike the prior art that uses the solubility of calcium phosphate in accordance with the buffer solution or temperature, utilizes the dissociation constant change of hydrogen phosphate ions generated during the mixing process of the calcium ion solution and the phosphate ion solution, calcium in the phosphate ion solution The addition of an ionic solution promotes dissociation of hydrogen phosphate ions.
- Dissociation of hydrogen phosphate ions occurs continuously and varies slightly depending on the process concentration and temperature, but rapidly dissociates hydrogen phosphate ions at about one hour of processing time, and slowly dissociates slowly over time. Therefore, a network coating film can be obtained at a process time when abrupt dissociation of hydrogen phosphate ions occurs, and a thick low crystalline apatite coating film due to continuous dissociation of hydrogen phosphate ions when the process is performed for a longer time (more than 3 hours) Can be obtained.
- the low crystalline apatite hydroxide thin film thickness is about 10 nm or less, and a thicker thin film can be obtained as the immersion time becomes longer.
- the pretreatment is a process of imparting activity to the surface of the implant in order to ensure that the calcium phosphate crystals are uniformly and well coated on the titanium implant surface in the calcium phosphate solution.
- the calcium phosphate crystal formation rate is very fast in the calcium phosphate solution at room temperature, so that the proper implant is not coated on the surface of the titanium implant, or the adhesion thereof is significantly reduced.
- the pretreatment of the titanium implant surface can be said to be a method of increasing the crystal growth ability on the implant surface with respect to the formation and growth of calcium phosphate solution or calcium phosphate on the implant surface.
- the coating uniformity of low-crystalline apatite hydroxide on the implant surface is improved through the pretreatment, and the repeatability and reproducibility are also greatly improved.
- the pretreatment method herein is as described above, and preferably, the titanium or titanium alloy implant is subjected to ultrasonic waves in distilled water, calcium ion solution, phosphate ion solution or calcium phosphate solution for at least 1 minute.
- the low crystalline apatite hydroxide produced by the coating method according to the invention is characterized by being nonstoichiometric and also bioabsorbable.
- the low crystalline apatite hydroxide coated implant of the present invention has a double surface in which the mesh surface or island-like coating layer and the implant titanium surface are exposed together, whereby the effect of the titanium cell adhesion and the bone conduction ability of the apatite hydroxide is mutually increased. It acts to improve bone formation.
- the coating of low crystalline apatite having a network or island in calcium phosphate solution can determine the desired thickness depending on its concentration, temperature and process time. This can be confirmed by the scanning electron microscope, and because the process is very simple, it is possible to control the degree of low crystalline apataart coating to suit its purpose in various implant areas besides teeth.
- SLA Surface Treatment Method of Acid Etching after Aluminum Blasting
- HNO 3 12% nitric acid
- H 2 O distilled water
- 12% nitric acid solution was prepared by mixing 60% nitric acid solution 1: 1 with distilled water (H 2 O).
- Implants whose surface impurities are removed by washing in nitric acid solution are immersed in distilled water and sonicated for 15 minutes.
- Preparation of the calcium phosphate solution begins with the preparation of high concentration 200 mM calcium (Ca) ion solution and phosphoric acid (PO 4 ) ion solution.
- a high concentration of calcium ion solution was prepared by dissolving calcium chloride (CaCl 2 ) in distilled water (H 2 O), and a high concentration of phosphate ion solution was prepared by dissolving sodium diphosphate (Na 2 HPO 4 ) in distilled water (H 2 O).
- a high concentration of 200 mM calcium ion solution and phosphate ion solution were each diluted with distilled water to 5 mM.
- the low concentration of 5 mM calcium ion solution and phosphate ion solution were stored at the same temperature as the coating process. Preferably, it is stored in an incubator to proceed with the coating process.
- the final pre-treated implant in distilled water was put in a reaction vessel, and then mixed with 5 mM low phosphate ion solution and calcium ion solution in the same amount, respectively, to prepare a 2.5 mM calcium phosphate solution.
- the reaction vessel containing titanium implant and 2.5 mM calcium phosphate solution is stored at 20 ° C. for 60 minutes. After removing the titanium implant from the reaction vessel, simply washed with distilled water and dried to coat the surface of the network (network) shape.
- the pre-treated implant In order to control the thickness, it can be stored in a thermostat for more than 180 minutes to coat a thick low-crystalline apatite, and after preparing the calcium phosphate solution first, the pre-treated implant is put into the reaction container for 60 minutes after 1 to 3 minutes. When stored, it is possible to obtain an island-like coating surface in which titanium and low crystalline apatite hydroxide coexist externally.
- Example 1 the titanium implants of the experimental group subjected to the ultrasonic pretreatment in distilled water and the control group not subjected to the pretreatment were carried out as in Examples 2 and 3.
- ALP alkaline phosphatase
- alkaline phosphatase activity of mesenchymal stem cells in the titanium disk coated with a low-crystalline apatite hydroxide mixed with the network (island) prepared in the above embodiment This suggests that implants coated with low-crystalline apatite hydroxide promote differentiation into osteoblasts rather than RBM-treated implants used as the base material. .
- Bone marrow-derived mesenchymal stem cells were seeded on a titanium disc coated with low crystalline apatite based on a titanium disc treated with RBM (surface treatment method using absorbing jet particles) and a specimen thereof in the same manner as in Experimental Example 1.
- RBM surface treatment method using absorbing jet particles
- To induce differentiation into osteoblasts differentiation induction cultures were treated and cultured for 2 or 4 weeks. The cultured cells were washed with PBS and then fixed with 4% paraformaldehyde for 15 minutes and then washed with distilled water. Alizarin Red solution prepared at pH 4.2 was added for 20 minutes and then washed with distilled water to remove the remaining solution.
- absorbance was measured by eluting the dyed dye by adding 10% wt / vol of Cetylpyridinium Chloride to Sodiumphosphate solution (pH7).
- the implants coated with the low crystalline apatite hydroxide prepared in Example were implanted into the rabbit long bone to confirm whether the coating film remained before and after bone remodeling.
- a titanium implant coated with RBM surface treatment method using absorbing jet particles
- a specimen thereof were implanted into a long bone of New Zealand white rabbit coated with low crystalline apatite hydroxide.
- the diameter of the implant is 3.5 mm and the length is 8.5 mm.
- the iliac bone of the rabbit was drilled to a diameter of 3.6mm and the implant was pushed by hand.
- the rabbits were sacrificed and the implants were removed from the rabbits and observed with a scanning electron microscope.
- the implant coated with low crystalline apatite hydroxide mixed with network and island shape promotes cell differentiation and calcification nodule formation.
- the implant coated with the low crystalline apatite hydroxide of the present invention has excellent biocompatibility, and participates in the bone remodeling process, has bioabsorbability, and has an effect of improving the exfoliation of the coating film and the resulting dropout of the implant. It can be seen that it can be used as.
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Inorganic Chemistry (AREA)
- Transplantation (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Engineering & Computer Science (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dentistry (AREA)
- Surgery (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
Description
구분 | 얇은 망상 & 섬형상 | 두꺼운 망상 | 섬형상 |
임플란트 | 제품 | 제품 | 제품 |
전처리 | 실시 | 실시 | 실시 |
용액 혼합후 대기 시간 | 0 분 | 0 분 | 3 분 |
공정 농도 | 2.5mM | 2.5mM | 2.5mM |
공정 온도 | 20℃ | 20℃ | 20℃ |
공정 시간 | 60 분 | 180 분 | 60 분 |
결과 (도) | 도 3 참조 | 도 2 참조 | 도 4 참조 |
구분 | 실험군 | 대조군 |
임플란트 | 제품 | 제품 |
전처리 | 실시 | 미실시 |
공정 농도 | 2.5mM | 2.5mM |
공정 온도 | 20℃ | 20℃ |
공정 시간 | 60 분 | 60 분 |
결 과 | 망상형상 | 코팅 안됨 |
Claims (11)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012515963A JP5757943B2 (ja) | 2009-06-18 | 2010-05-18 | 網状又は島状の低結晶水酸化アパタイトでコーティングされたインプラント及びそのコーティング方法 |
PL10789635.9T PL2444027T5 (pl) | 2009-06-18 | 2010-05-18 | Sposób powlekania implantu niskokrystalicznym hydroksyapatytem o kształcie sieciowym lub wyspowym |
DK10789635.9T DK2444027T4 (da) | 2009-06-18 | 2010-05-18 | Implantat belagt med netformet eller ø-formet lav-krystalliseret hydroxyapatit og fremgangsmåde til belægning af dette implantat |
CN201080026540.7A CN102802557B (zh) | 2009-06-18 | 2010-05-18 | 涂有呈网状或岛状的低结晶羟磷灰石的植入体以及其涂覆方法 |
ES10789635T ES2721475T5 (es) | 2009-06-18 | 2010-05-18 | Método para recubrir un implante con hidroxiapatita de baja cristalización en forma de red o en forma de isla |
US13/378,029 US9517187B2 (en) | 2009-06-18 | 2010-05-18 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating same |
EP10789635.9A EP2444027B2 (en) | 2009-06-18 | 2010-05-18 | Method for coating an implant with net-shaped or island-shaped low-crystallized hydroxyapatite |
US14/702,545 US20150230842A1 (en) | 2009-06-18 | 2015-05-01 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020090054315A KR101091589B1 (ko) | 2009-06-18 | 2009-06-18 | 망상 또는 섬 형상의 저결정 수산화아파타이트로 코팅된 임플란트 및 이의 코팅 방법 |
KR10-2009-0054315 | 2009-06-18 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/378,029 A-371-Of-International US9517187B2 (en) | 2009-06-18 | 2010-05-18 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating same |
US14/702,545 Division US20150230842A1 (en) | 2009-06-18 | 2015-05-01 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating same |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2010147308A2 true WO2010147308A2 (ko) | 2010-12-23 |
WO2010147308A3 WO2010147308A3 (ko) | 2011-03-31 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/KR2010/003132 WO2010147308A2 (ko) | 2009-06-18 | 2010-05-18 | 망상 또는 섬 형상의 저결정 수산화아파타이트로 코팅된 임플란트 및 이의 코팅 방법 |
Country Status (11)
Country | Link |
---|---|
US (2) | US9517187B2 (ko) |
EP (1) | EP2444027B2 (ko) |
JP (1) | JP5757943B2 (ko) |
KR (1) | KR101091589B1 (ko) |
CN (1) | CN102802557B (ko) |
DK (1) | DK2444027T4 (ko) |
ES (1) | ES2721475T5 (ko) |
PL (1) | PL2444027T5 (ko) |
PT (1) | PT2444027T (ko) |
TR (1) | TR201906595T4 (ko) |
WO (1) | WO2010147308A2 (ko) |
Families Citing this family (11)
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KR101353338B1 (ko) * | 2012-02-07 | 2014-01-22 | 재단법인 포항산업과학연구원 | 생체 친화성 임플란트의 제조방법 |
RU2524764C1 (ru) * | 2013-02-28 | 2014-08-10 | Дмитрий Константинович Юдин | Способ получения дентального имплантата погружного типа из титана или титанового сплава и дентальный имплантат из титана или титанового сплава |
KR101311990B1 (ko) * | 2013-07-18 | 2013-09-27 | 오스템임플란트 주식회사 | 임플란트 표면의 생체활성과 골결합력 및 골융합을 증진시키는 물질이 코팅된 임플란트와 그 제조방법 및 임플란트의 보관 방법 |
KR20160061991A (ko) * | 2013-09-27 | 2016-06-01 | 비타 찬파브릭 하. 라우터 게엠베하 & 코.카게 | 분해가능한 코팅을 포함하는 임플란트 |
CN103598919B (zh) * | 2013-11-15 | 2016-05-18 | 温州医科大学附属口腔医院 | 一种牙种植体表面生物梯度涂层的制备方法 |
KR101589115B1 (ko) * | 2014-07-10 | 2016-01-28 | 이상훈 | 치과용 금속 구조물의 제조 방법 |
PL226891B1 (pl) | 2015-05-05 | 2017-09-29 | Inst Wysokich Ciśnień Polskiej Akademii Nauk | Sposób wytwarzania implantu kostnego iimplant kostny |
WO2017027593A1 (en) * | 2015-08-11 | 2017-02-16 | Biomet 3I, Llc | Surface treatment for an implant surface |
KR20180078620A (ko) * | 2016-12-30 | 2018-07-10 | 주식회사 네오바이오텍 | 친수성 표면을 갖는 임플란트의 제조방법 |
US10537661B2 (en) | 2017-03-28 | 2020-01-21 | DePuy Synthes Products, Inc. | Orthopedic implant having a crystalline calcium phosphate coating and methods for making the same |
US10537658B2 (en) | 2017-03-28 | 2020-01-21 | DePuy Synthes Products, Inc. | Orthopedic implant having a crystalline gallium-containing hydroxyapatite coating and methods for making the same |
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- 2010-05-18 DK DK10789635.9T patent/DK2444027T4/da active
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See also references of EP2444027A4 |
Also Published As
Publication number | Publication date |
---|---|
KR20100136122A (ko) | 2010-12-28 |
PL2444027T3 (pl) | 2019-09-30 |
DK2444027T4 (da) | 2022-04-19 |
EP2444027A2 (en) | 2012-04-25 |
EP2444027B1 (en) | 2019-02-20 |
JP2012530520A (ja) | 2012-12-06 |
US20150230842A1 (en) | 2015-08-20 |
JP5757943B2 (ja) | 2015-08-05 |
KR101091589B1 (ko) | 2011-12-13 |
US9517187B2 (en) | 2016-12-13 |
WO2010147308A3 (ko) | 2011-03-31 |
ES2721475T5 (es) | 2022-04-26 |
EP2444027B2 (en) | 2022-01-19 |
CN102802557A (zh) | 2012-11-28 |
DK2444027T3 (da) | 2019-05-13 |
PL2444027T5 (pl) | 2022-12-05 |
US20120088100A1 (en) | 2012-04-12 |
CN102802557B (zh) | 2015-12-16 |
PT2444027T (pt) | 2019-05-31 |
EP2444027A4 (en) | 2014-01-15 |
TR201906595T4 (tr) | 2019-05-21 |
ES2721475T3 (es) | 2019-07-31 |
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