Classifications

• • 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
  • A61L27/34—Macromolecular materials
• • 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
• • 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
  • A61L2400/00—Materials characterised by their function or physical properties
  • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
• • 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

Definitions

• the invention belongs to the field of dental implants, and particularly relates to a pure titanium dental implant with a surface covered with a low modulus periodontal membrane and a preparation method thereof. Background technique
• the natural tooth is suspended in the jaw bone through the periodontal ligament.
• the tooth When the tooth is stressed, the external force is evenly transmitted and dispersed through the periodontal membrane to the jaw bone, thereby causing a physiological response to the external force of the periodontal tissue; and the osseointegrated dental implant It is rigidly connected with the jaw bone, and the two are in direct contact with the lack of periodontal membrane.
• the elastic modulus of the dental implant When the elastic modulus of the dental implant is inconsistent with the elastic modulus of the jaw, the impact energy generated by the impact denture of the implant denture is through the dental implant. Directly transmitted to the surrounding bone tissue, which tends to cause stress concentration of the bone tissue around the dental implant, causing the surrounding bone to absorb or shrink, thereby causing manual implant failure.
• the elastic modulus of commercial pure titanium used in clinical dental implants is 110GPa, which is much higher than the elastic modulus of human mandibular cortical bone 10 ⁇ 18GPa and the elastic modulus of cancellous bone 1.5 ⁇ 2.5GPa.
• the smaller the elastic modulus of the implant material is the closer it is to the elastic modulus of the bone.
• the smaller the relative displacement caused by the strain difference when the stress is applied the less the tendency of the interface to loosen and avoid. Bone resorption and degradation caused by stress shielding.
• the elastic modulus of the metal material decreases, the strength and rigidity of the metal material decrease accordingly, so it is difficult to carry the complex stress environment of the oral cavity.
• the biomechanical compatibility of the dental implant can be solved simply by reducing the elastic modulus of the dental implant.
• sexual problems there is a suspicion of reluctance.
• Long-term clinical follow-up studies have shown that the excellent mechanical properties of pure titanium implants can well meet the complex bearing environment requirements of the oral cavity. If the mechanical compatibility problem can be effectively solved, the service life in the body can be far beyond the natural tooth. , significantly improve the long-term success rate of implant dentures.
• the object of the present invention is to overcome the deficiencies of the prior art, and to provide a bionic dental implant and a preparation method thereof for solving the problem of biomechanical compatibility of dental implants.
• the invention starts from the principle of bionics, introduces the concept of bionic periodontal film, prepares a low modulus polyurethane coating on the surface of pure titanium, mimics the biomechanical function of the natural periodontal ligament, imparts reasonable physiological mobility to the implant, and occludes the occlusion
• the force acts as a conduction and buffering force to make the stress distribution on the alveolar bone interface uniform, thus solving the biomechanical compatibility problem of pure titanium implants.
• the bionic dental implant of the present invention comprises a titanium matrix, a porous titanium dioxide layer impregnated with polyurethane, and a polyurethane layer as a biomimetic periodontal film, wherein the porous titanium dioxide layer impregnated with polyurethane is located between the titanium matrix and the polyurethane layer, respectively It is tightly integrated with the titanium matrix and polyurethane layer.
• the thickness of the bionic dental implant of the present invention is controlled to be 0.15 mm to 0.25 mm to meet the planting needs of patients of different ages.
• the preparation method of the bionic dental implant of the invention has the following steps:
• micron-sized titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting (EBM) to form micron and nanometer pores coexisting and interpenetrating and rich in Ti-OH.
• EBM electron beam melting
• a porous titanium dioxide layer of a reactive group the amount of the titanium dioxide powder being limited to a porous titanium dioxide layer capable of forming a thickness of 0.15 mm to 0.3 mm;
• isophorone diisocyanate from isophorone diisocyanate (IPDI), polyethylene glycol (PEG) or polytetrahydrofuran ether glycol (PTMG) or polycaprolactone (PCL)
• IPDI isophorone diisocyanate
• PEG polyethylene glycol
• PTMG polytetrahydrofuran ether glycol
• PCL polycaprolactone
• the polyurethane prepolymer prepared in step 2 is applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a closed container, vacuumed, and maintained at a negative pressure of 0.5 to 1 hour of O.OlMpa ⁇ 0.06 MPa.
• a polyurethane prepolymer is infiltrated into the pores of the porous titania layer, and a layer of unrolled liquid polyurethane is formed on the surface of the porous titania layer, the polyurethane prepolymer being formed to have a thickness of 0.15 mm to 0.25 mm.
• the polyurethane layer is limited;
• the composite having the polyurethane layer obtained in the step 3 is immersed in a chain extender solution having a chain extender concentration of 0.3 g/ml to 0.8 g/ml, and the catalyst stannous octoate is added, and then heated under normal pressure to After incubating at 50 °C ⁇ 55 °C for 2 h ⁇ 3 h, after the end of the heat preservation, the composite body is taken out from the chain extender solution, and air-dried in the air at room temperature to obtain a bionic dental implant. 2% ⁇ 0. 5% ⁇ The amount of the chain agent solution is 0. 2% ⁇ 0. 5%.
• the chain extender is triethanolamine or trimethylolpropane
• the chain extender solvent is acetone or N, N-dimethylformamide
• the particle diameter of the titanium dioxide powder is preferably 50 ⁇ m to 100 ⁇ m.
• the electron beam melting technology utilizes the heat generated by the high-energy electron beam to form a local high temperature, partially melts the titanium dioxide powder, and fuses the local melting portions to each other by continuous scanning, and joins the linear or planar metal layer to melt layer by layer.
• the mutually accumulating forms a porous titania layer which forms a coexistence of micro- and nano-scale pores and penetrates between pores and is rich in Ti-OH reactive groups.
• the process of electron beam melting technology can be referred to the paper "Mechanical properties of rapid fabrication of Ti-6A1-4V by electron beam melting (Lock Red Wave, et al., Aerospace Manufacturing Technology, 2009. 12(06): 18-22)".
• the polyurethane elastomer Since the outer surface of the bionic dental implant of the present invention is covered with a polyurethane layer, the polyurethane elastomer exhibits a low elastic modulus and a nonlinear viscous property very similar to that of the natural periodontal ligament, and has excellent wear resistance. Corrosion, flexibility and other characteristics, so biomechanical compatibility is better than existing dental implants, and the success rate of planting is improved.
• the pure titanium matrix of the bionic dental implant of the present invention is bonded to the polyurethane layer by a porous titanium dioxide layer infiltrated with polyurethane, the bonding is tight.
• the liquid polyurethane prepolymer is prepared by using isophorone diisocyanate, polyethylene glycol, polytetrahydrofuran ether glycol or polycaprolactone as raw materials, thereby forming
• the polyurethane layer is non-toxic and has no damage to the human body.
• the method for preparing a bionic dental implant according to the present invention uses an electron beam melting technique to form a porous titanium dioxide layer, thereby not only effectively eliminating the pollution and damage of materials caused by external chemical element impurities, but also enabling the chain extension reaction to proceed more. Sufficient, the monomer utilization is improved, and the polyurethane layer is firmly bonded to the substrate.
• the preparation method of the bionic dental implant of the present invention uses a vacuum suction method to fully infiltrate the liquid polyurethane prepolymer into the pores of the porous titanium dioxide layer, and forms a plurality of micro-nano-scale anti-reflections on the pure titanium substrate.
• the kettle is increased, and the reaction efficiency and speed are increased.
• the chain extension in this manner can control the thickness of the formed polyurethane coating by changing the speed and time of the chain extension reaction to meet the requirements of the dental implant.
• the preparation method of the bionic dental implant of the present invention uses conventional equipment to facilitate industrial production.
• Fig. 1 is a cross-sectional structural view showing a bionic dental implant of the present invention, wherein a titanium substrate, a porous titanium dioxide layer impregnated with polyurethane, and a 3-polyurethane layer are used. detailed description
• the process steps for preparing the bionic dental implant are as follows:
• the titanium matrix is treated with mixed acid composed of hydrochloric acid and sulfuric acid.
• the concentration of hydrochloric acid is 36%, the concentration of sulfuric acid is 98%, and 20ml is prepared.
• Mixed acid, mixed acid, the volume ratio of hydrochloric acid to sulfuric acid is 1: 1
• Treatment method The polished titanium substrate is placed in a beaker containing the mixed acid, and the beaker is sealed with plastic wrap and placed The titanium substrate was taken out in a water bath at 60 ° C for 30 minutes, and the titanium substrate was placed in an oven and dried at 50 ° C;
• Titanium dioxide powder is deposited layer by layer on the surface of the acid-treated pure titanium substrate by electron beam melting technology to form a porous titania layer in which micron and nanometer pores coexist and interpenetrating and rich in Ti-OH reactive groups, the titanium dioxide powder
• the particle diameter is 50 ⁇ m ⁇ 100 ⁇
• the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, a beam current of 2.0 mA, and a thickness of the porous titanium dioxide layer of 0.15 mm. ;
• step 2 1.2 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, evacuated, and maintained at a negative pressure of 0.06 MPa for 0.5 h to make the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
• step 4 7.0 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
• TMP chain extender trimethylolpropane
• DMF N, N-dimethylformamide
• the surface obtained in step 3 was polyurethane.
• the layer composite is immersed in the above chain extender solution, and 0.05 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 2 h. After the end of the heat preservation, the composite is removed from the mixture.
• the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of a pure titanium substrate 1, a porous titanium dioxide layer 2 infiltrated with polyurethane, and a polyurethane layer 3 as shown in FIG.
• the thickness of the polyurethane layer is about 0.20 mm.
• the bionic dental implant prepared in the present example was subjected to a scratch test.
• the test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
• the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the biomimetic dental implant biophase prepared in this example. Good compatibility.
• Example 2
• the process steps for preparing the bionic dental implant are as follows:
• the titanium substrate is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
• the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the acid-treated pure titanium surface by electron beam melting technology to form a porous body.
• the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
• the thickness of the porous titanium dioxide layer is 0.20 mm;
• step 3 The polyurethane prepolymer prepared in step 2 is coated on the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.06 MPa for 1 hour to make the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
• step 4 6.0 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
• TMP chain extender trimethylolpropane
• DMF N, N-dimethylformamide
• the surface obtained in step 3 was polyurethane.
• the layer composite is immersed in the above chain extender solution, and 0.03 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 3 h. After the end of the heat preservation, the composite is removed from the mixture.
• the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of a pure titanium substrate 1, a porous titanium dioxide layer 2 infiltrated with polyurethane, and a polyurethane layer 3 as shown in FIG.
• the polyurethane layer has a thickness of about 0.15 mm.
• the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
• the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the biomimetic dental implant biophase prepared in this example. Good compatibility.
• the process steps for preparing the bionic dental implant are as follows:
• the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
• the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
• the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
• the thickness of the porous titanium dioxide layer is 0.25 mm;
• step 3 1.5 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.5 MPa for the polyurethane prepolymer. Infiltrating into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
• step 4 7.5 g of the chain extender trimethylolpropane (TMP) and 10 ml of N, N-dimethylformamide (DMF) were formulated into a solution and placed in a 50 ml beaker.
• the surface obtained in step 3 was polyurethane.
• the layer composite is immersed in the above chain extender solution, and 0.05 ml of catalyst stannous octoate is added dropwise, and then the beaker is placed in an oven at 55 ° C for 2.5 h. After the heat preservation, the composite is removed from the mixture.
• the chain extender solution is taken out and naturally dried in the air at room temperature to obtain a bionic dental implant composed of the titanium substrate 1, the porous titanium dioxide layer 2 infiltrated with the polyurethane, and the polyurethane layer 3 as shown in FIG.
• the thickness of the layer is approximately 0.25 mm.
• the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
• the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.
• the process steps for preparing the bionic dental implant are as follows:
• the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
• the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
• the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
• the porous titanium dioxide layer has a thickness of 0.15 mm;
• step 3 1.5 g of the polyurethane prepolymer prepared in step 2 was applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, evacuated, and maintained at a negative pressure of 0.03 MPa for 1 hour to allow the polyurethane prepolymer to penetrate. Advancing into the pores of the porous titania layer and forming a layer of unrolled polyurethane on the surface of the porous titania layer;
• the bionic dental implant prepared in the present example was subjected to a scratch test. The test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
• the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.
• the process steps for preparing the bionic dental implant are as follows:
• the titanium matrix is a bone screw with a diameter of 4.5 mm and a length of 12 mm.
• the acid treatment of the titanium substrate is the same as in the first embodiment; the titanium dioxide powder is deposited layer by layer on the surface of the acid-treated titanium substrate by electron beam melting technology to form a porous body.
• the titanium dioxide layer has a particle diameter of 50 ⁇ m to 100 ⁇ m, the electron gun has a vacuum of 0.6 MPa, a power of 5.0 kW, an acceleration voltage of 30 to 60 kV, a scanning speed of 800 mm/min, and an electron beam current of 2.0 mA.
• the thickness of the porous titania layer is 0.30 mm;
• step 3 The polyurethane prepolymer prepared in step 2 is applied to the porous titanium dioxide layer deposited on the surface of the titanium substrate in step 1, and then placed in a vacuum pump, vacuumed, and maintained at a negative pressure of 0.03 MPa for 0.5 h to prepolymerize the polyurethane.
• the body penetrates into the pores of the porous titania layer, and forms a layer of unrolled polyurethane on the surface of the porous titania layer;
• the bionic dental implant prepared in the present example was subjected to a scratch test.
• the test results showed that when microcracks were generated in the polyurethane layer, the porous titanium dioxide layer infiltrated with the polyurethane and the polyurethane layer and the porous titanium dioxide layer infiltrated with the polyurethane and No detachment occurred between the titanium substrates, indicating that they were tightly bonded.
• the bionic dental implant prepared in this example was immersed in a supersaturated calcium phosphate solution at 37 ° C for 24 h, and a certain amount of HA-like crystals grew on the surface of the polyurethane layer, indicating the bionic dental implant organism prepared in the present example. Good compatibility.

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Transplantation (AREA)
• Dermatology (AREA)
• Medicinal Chemistry (AREA)
• Oral & Maxillofacial Surgery (AREA)
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• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Inorganic Chemistry (AREA)
• Materials For Medical Uses (AREA)
• Dental Preparations (AREA)

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• 2012
  • 2012-10-11 CN CN201210384731.1A patent/CN102861357B/zh not_active Expired - Fee Related
• 2013
  • 2013-07-10 WO PCT/CN2013/079112 patent/WO2014056336A1/fr not_active Ceased

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