CN111728726B

CN111728726B - Dental implant, dental implant and preparation method of dental implant

Info

Publication number: CN111728726B
Application number: CN202010809532.5A
Authority: CN
Inventors: 陈艳文; 曾达; 武羽岩; 杨问成; 王老乌; 陈淳淳; 林超越; 陈耀东
Original assignee: Shanghai Dabo Medical Technology Co ltd
Current assignee: Baishitai (Xiamen) Medical Technology Co.,Ltd.
Priority date: 2020-08-13
Filing date: 2020-08-13
Publication date: 2020-11-20
Anticipated expiration: 2040-08-13
Also published as: CN111728726A

Abstract

The invention belongs to the field of dental implants and surface treatment, and relates to a dental implant, a dental implant and a preparation method thereof. The dental implant is divided into a neck region and a body region along the axial direction, and the neck region has antibacterial property and the body region has osteogenesis property by controlling the surface microstructure. The dental implant provided by the invention has amphiphilicity super-hydrophilicity/hydrophobicity. Aiming at the neck of the implant, the implant has super-hydrophobicity and an antibacterial function based on a specific structure of the structure, so that the great clinical requirement of the falling-off of the implant caused by peri-implantitis due to the attachment and proliferation of oral bacteria in a dental soft and hard tissue junction area is solved, and effective biological sealing is formed; aiming at the implant body, the implant body has super-hydrophilicity and is more beneficial to the adhesion and proliferation of osteoblasts based on the surface structure of the multi-level micron morphology.

Description

Dental implant, dental implant and preparation method of dental implant

Technical Field

The invention belongs to the field of dental implants and surface treatment, and particularly relates to a dental implant and a dental implant for replacement under the conditions of falling off and defect and corresponding preparation methods thereof.

Background

The dental implant is divided into two sections along the axial direction, wherein one section is a body area of the dental implant and is contacted with the hard tissues of the alveolar bone of the dental; the other section is the neck area of the dental implant, which is in contact with the peripheral alveolar bone and soft tissue of the dental implant. The dental implant realizes and recovers the occlusion function of teeth, needs to realize quick osseointegration and prevent bacteria from adhering to the upper neck area of the implant, and prevents the problem that the implant falls off due to bone absorption caused by peri-implantitis of the bacterial adhesion growth forming mycoderm.

Based on the functional requirements of the implant in use, how to realize the overall stability of the implant as soon as possible and shorten the healing period from initial stability to secondary stability needs to perform special surface treatment on the surface of the implant in order to obtain faster bone formation efficiency and bone formation quality. The titanium and hydroxyapatite are sprayed by plasma in a conventional manner. Wherein, the rough and porous surface can be obtained by spraying the porous titanium rough layer on the surface of the implant to increase the bone contact area and promote the bone ingrowth of osteoblasts; the hydroxyapatite with bioactivity is sprayed on the surface of the implant, calcium phosphate in the hydroxyapatite is dissolved and slowly released in a body fluid environment, and ions such as calcium ions and phosphate radicals can be released, so that the hydroxyapatite is promoted to be dissolved and absorbed in the body fluid environment, and the in-vivo biological mineralization is promoted to form a stable mineralized hard bone tissue, thereby improving the osteogenic activity of the surface. However, the problem that the sprayed thickness is too thick, absorption and osteogenesis are not matched exists, and gaps between the implant and bone tissues are easily caused, so that the implant is loosened. Therefore, how to improve the osteogenic activity on the surface of the implant in the area contacted with the alveolar hard tissue, shorten the healing period and obtain higher osteogenic quality has great clinical use significance.

Meanwhile, with the wide application of the implant repair in clinical treatment, a large number of clinical cases increase, and the incidence of peri-implantitis is in a significantly rising trend. Peri-implant inflammation is the leading cause of post-implant failure, accounting for more than 30% of total failure cases, and has to be paid attention by oral physicians and materials scientists. The neck area of the implant is contacted with the marginal alveolar bone and soft tissues of the dentistry, so that the peri-implantitis early occurs in the neck area of the implant, the neck of the implant is generally positioned in a junction area of soft and hard tissues, the neck tissue structure of the implant is still different from that of natural teeth, and the surfaces of the implant are more easily attacked by microorganisms and toxic products thereof due to the weak links, so that various pathogenic bacteria in the oral cavity of the implant after implantation, such as porphyromonas gingivalis, actinomycete synbiotics and the like, are very easily adhered to the surface of the neck of the implant. To realize the antibacterial effect of the implant material, the traditional research mode is to adopt antibiotic load or Ag and Cu metal ions to obtain the antibacterial or bactericidal effect through the release of the antibiotic or the metal ions. However, the application of the method in a large amount can generate drug resistance and cross resistance, and an antibacterial technical method and an implant product for reducing bacterial adhesion and biofilm formation are obtained by regulating and controlling the surface, so that the method has important research and clinical use values.

Disclosure of Invention

The invention aims to overcome the defects of surface treatment of a dental implant by the conventional method, and provides a dental implant and an implant with high osteogenic activity and antibacterial property and preparation methods thereof.

Specifically, the present invention provides a dental implant which is divided into a neck region and a body region in an axial direction, the neck region having antibacterial properties and the body region having osteogenic properties by controlling a surface microstructure; the surface of the neck region is provided with a micro stripe structure, the stripe interval is 10-65 mu m, the stripe concave width is 4-40 mu m, the stripe concave depth is 1-30 mu m, and the included angle between the stripe and the dental implant in the axial direction is 45-90 degrees. The stripes may be distributed at equal intervals or at unequal intervals. The width of the concave surface between different stripes can be the same or different.

In a preferred embodiment of the invention, the surface antibacterial rate of the neck region is 70% or more.

In a preferred embodiment of the invention, the neck region has superhydrophobic properties with a contact angle of > 150 °; the body region has super-hydrophilic characteristic, and the contact angle of the body region is less than or equal to 10 degrees.

In a preferred embodiment of the present invention, the surface of the body region has a multi-level micro-scale hole structure, and the multi-level micro-scale hole structure includes a plurality of micro-scale pits, and a plurality of sub-micron-scale depressions are distributed in the pits.

In a preferred embodiment of the present invention, the diameter of the pits is 1 to 20 μm, and the diameter of the depressions is 1 to 8 μm.

In a preferred embodiment of the present invention, the surface of the body region has a multi-level micron-sized hole structure, the multi-level micron-sized hole structure includes a plurality of micron-sized protrusions and grooves, the protrusions are recessed inward to form concave holes, the grooves are distributed around the protrusions, the protrusions protrude from the grooves, the grooves are irregular, adjacent grooves are communicated with each other, and a plurality of sub-micron holes are distributed at the bottom of the grooves.

In a preferred embodiment of the present invention, the aperture of the concave hole is 1 to 5 μm, the aperture of the sub-micron hole is 0.5 to 1 μm, the height of the protrusion is 2 to 6 μm, and the width of the trench is 10 to 20 μm.

In a preferred embodiment of the present invention, the surface of the multi-level micron-sized pore structure is attached with nano-hydroxyapatite.

In a preferred embodiment of the present invention, the neck region is 0.1 to 10mm from the end of the dental implant extending toward the body region.

The invention also provides a preparation method of the dental implant, which comprises the following steps:

(1) carrying out acid washing treatment on the implant matrix to obtain a clean implant matrix;

(2) carrying out multi-level micron treatment or multi-level micro-nano treatment on the clean implant matrix to form a film layer with a multi-level micron-scale hole structure on the surface of the clean implant matrix so as to obtain a porous structure implant;

(3) carrying out ultraviolet light treatment or plasma treatment on the surface of the porous structure implant to remove organic matters on the surface of the porous structure implant and improve hydrophilicity so as to obtain a hydrophilic implant;

(4) and etching the surface of one end area of the hydrophilic implant to form a micro-stripe structure on the surface of the hydrophilic implant, so as to form the dental implant which is divided into a neck area and a body area along the axial direction.

In the present invention, the implant substrate may be a titanium or titanium alloy substrate.

In a preferred embodiment of the present invention, in the step (2), the multistage micron treatment is performed by sand blasting, acid etching or micro-arc oxidation.

In a preferred embodiment of the present invention, the blasting and acid etching includes blasting and acid etching in this order. Wherein the sand blasting treatment can adopt ceramic sand, and the component of the ceramic sand is ZrO₂、SiO₂、Al₂O₃And the sand blasting particle size can be 80-180 mu m, the sand blasting pressure can be 5-8 bar, and the sand blasting distance can be 0.5-2 cm. The components of the acid etching solution used for the acid etching treatment can contain sulfuric acid, hydrochloric acid, nitric acid, glycol, an acid mist inhibitor and water. Wherein, the content of sulfuric acid can be 15-40 wt%, the content of hydrochloric acid can be 1-8 wt%, the content of nitric acid can be 1-5 wt%, the content of glycol can be 0.2-5 wt%, the content of atomization inhibitor can be 0.02-0.08 g/L, and the balance is deionized water. The acid mist inhibitor may be potassium perfluorooctyl sulfonate. The temperature of the acid etching treatment can be 50-80 ℃, and the time can be 20-60 min.

In a preferred embodiment of the invention, the micro-arc oxidation is performed by placing a clean implant substrate in a micro-arc oxidation electrolyte, using the implant substrate as an anode and stainless steel as a cathode, and performing micro-arc oxidation treatment by using a direct current pulse micro-arc oxidation bioceramic device. According to a specific embodiment, the micro-arc oxidation electrolyte contains a main salt, a compound agent, an auxiliary additive and the balance of water. Wherein the main salt may be at least one selected from calcium formate, acetic anhydride, and calcium propionate. The compound agent can be at least one selected from sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid. The auxiliary additive can be at least one selected from polyethyleneimine, polyacrylamide, diethylenetriamine pentaacetate and N, N-dicarboxylic acid amino-2-hydroxy propyl sulfonate. Wherein the number average molecular weight of the polyethyleneimine can be 1000-5000. The number average molecular weight of the polyacrylamide can be 200-800 ten thousand. The addition concentration of the main salt can be 1-10 g/L, the addition concentration of the compound agent can be 2-10 mL/L, and the addition concentration of the auxiliary additive can be 5-22 g/L. According to a specific embodiment, the process parameters of the micro-arc oxidation include: the working voltage is 150-350V, the negative voltage is 0V, the duty ratio is 5-20%, the pulse frequency is 100-1200 Hz, the time is 3-10 min, and the operating temperature is 10-40 ℃.

In a preferred embodiment of the present invention, in the step (2), the multistage micro-nano treatment is performed by depositing nano-hydroxyapatite on the basis of multistage micro-nano treatment. Wherein, the nano-hydroxyapatite can be deposited by physical deposition, chemical deposition or electrochemical deposition, for example. According to a specific embodiment, the nano-hydroxyapatite is deposited by spraying nano-hydroxyapatite suspension on a substrate subjected to multistage micron treatment, and drying and sintering are sequentially performed after the spraying deposition is completed. The nano hydroxyapatite suspension contains ethanol, nano hydroxyapatite and a dispersing agent, wherein the dispersing agent is selected from at least one of polyethylene glycol, polyvinylpyrrolidone, sodium carboxymethylcellulose, sodium phosphate, sodium dodecyl sulfate, polyvinyl alcohol, polyacrylamide, ammonium polyacrylate, polyethyleneimine and tween 80. In addition, the content of ethanol in the nano-hydroxyapatite suspension is preferably 10-30 wt%, the content of nano-hydroxyapatite is preferably 10-50 g/L, the content of a dispersing agent is preferably 1-10 g/L, and the balance is a solvent. Wherein the ethanol functions as a dissolving dispersant. The dispersant plays a role in preventing the nano hydroxyapatite from agglomerating. The solvent contained in the nano-hydroxyapatite suspension is particularly preferably ethanol. In addition, the spray deposition conditions preferably include a spray distance of 1-5 cm and a spray deposition time of 10-30 s. The purpose of the sintering is to completely remove the dispersant and to some extent to increase the surface hydrophilicity. According to a preferred embodiment of the present invention, the sintering conditions include a sintering temperature of 500-700 ℃, a heating rate of 3-10 ℃/min, and a sintering time of 0.5-2 h.

In the present invention, the purpose of the ultraviolet light treatment or the plasma treatment in the step (3) is to remove organic substances on the surface of the porous structure implant and to improve the hydrophilicity. The ultraviolet light treatment mode is to irradiate the porous structure implant with ultraviolet light, and the specific conditions preferably include that the wavelength of the ultraviolet light is 180-260 nm, the irradiation distance is 0.5-5 cm, and the irradiation time is 5-30 min. The plasma treatment mode is vacuum plasma treatment, and the specific conditions preferably include the adoption of a mixed gas of argon and oxygen, the flow of the argon is 0-450 sccm, the flow of the oxygen is 0-200 sccm, the vacuum degree is-99.5 KPa, the treatment time is 60-600 s, and the cleaning power is 0-700W.

In a preferred embodiment of the invention, in the step (4), the etching treatment is laser etching or chemical etching, the etched region is a neck region, the surface of the neck region has a micro stripe structure, namely, the stripe interval is 10-65 μm, the stripe concave width is 4-40 μm, and the included angle between the stripe and the axial direction of the dental implant is 45-90 degrees; the unetched region is a body region, and the surface of the unetched region is provided with a multi-level micron-scale hole structure. In the etching treatment process, the etched part forms a concave surface, and the unetched part keeps the original appearance, so that a specific micro-stripe structure is obtained.

The laser etching realizes the selection of a laser path through the program control of laser processing, the stripe spacing, the concave surface width and the like in the formed micro stripe structure have a relation with the set parameters of the laser, and the concave surface width is etched according to different parameters, so that the technical personnel in the field can know that the concave surface width is different. In a preferred embodiment of the present invention, the laser etching is pulsed laser etching, and the pulse width of the laser is nanosecond, picosecond or femtosecond. Specifically, the preferable conditions of the laser etching include that the pulse width is 10 fs-100 ns, and the laser pulse flux is 10-20J/cm²And the processing frequency is 1-100 KHz.

In a preferred embodiment of the present invention, the chemical etching is alkali thermal etching or reactive ion etching. The specific mode of the alkali thermal etching is to place one end region of the hydrophilic implant in hot alkaline etching liquid for etching. The alkaline etching liquid is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The concentration of the etching liquid can be 1-6 mol/L. The conditions of the alkali thermal etching comprise that the etching temperature is preferably 200-300 ℃, and the etching time is preferably 2-8 h. The reactive ion etching mode is to contact one end region of the hydrophilic implant with etching gas, and the etching is realized through the corrosion of the etching gas. Wherein the etching gas is preferably chlorine gas. The reactive ion etching conditions comprise that the gas inflow is preferably 10-80 sccm, and the etching time is preferably 5-15 min. In the process of forming the micro-stripe structure by chemical etching, the stripe spacing and the stripe concave width need to be controlled by a template, which can be known by those skilled in the art and will not be described herein.

In addition, the invention also provides a dental implant, which comprises the dental implant and an artificial denture, wherein the neck region of the dental implant is connected with the artificial denture.

The invention has the beneficial effects that:

through surface treatment, on the same implant, an amphiphilic super-hydrophilic/hydrophobic implant with super-hydrophobic neck and super-hydrophilic body is obtained. Aiming at the neck of the implant, the implant has super-hydrophobicity and an antibacterial function based on a specific structure of the structure, solves the great clinical requirement of the falling-off of the implant caused by peri-implantitis due to the attachment and proliferation of oral bacteria in a dental soft and hard tissue junction area, and forms effective biological sealing. Aiming at the implant body, the implant body has super-hydrophilicity and is more beneficial to the adhesion and proliferation of osteoblasts based on the surface structure of the multi-level micron morphology.

Drawings

Fig. 1a is a schematic view of the overall structure of the dental implant provided by the present invention.

FIG. 1b is a schematic view of the microstructure of the neck region in the dental implant according to the present invention.

FIG. 2 is a Scanning Electron Microscope (SEM) image of the bulk region of the dental implant obtained in example 1.

FIG. 3 is an SEM photograph of osteoblast culture of the bulk region of the dental implant obtained in example 1.

FIG. 4 is a scanning electron micrograph of a neck region of the dental implant obtained in example 1.

FIG. 5 is a scanning electron micrograph of a bulk region of the dental implant obtained in example 2.

FIG. 6 is a scanning electron micrograph of a neck region of the dental implant obtained in example 2.

FIG. 7 is a scanning electron micrograph of a bulk region of the dental implant obtained in example 3.

Detailed Description

The present invention will be described in detail below by way of examples.

Example 1

(1) Placing a pure titanium implant matrix in a cleaning tank containing a surfactant (specifically PWC-401 cleaning agent, the same below), ultrasonically degreasing and cleaning for 10min at 60-70 ℃, rinsing with purified water, drying, pickling in an acidic mixed solution containing 12% by volume of nitric acid and 5% by volume of hydrofluoric acid at normal temperature for 15s, rinsing with purified water, and drying for later use;

(2) placing a clean implant matrix in a sand blasting machine, mixing 80 mu m and 180 mu m ceramic sand according to a mass ratio of 1:1 under the conditions of 5bar pressure and 0.5cm distance, then carrying out sand blasting treatment, then carrying out ultrasonic cleaning on the implant subjected to sand blasting in acetone, ethanol and deionized water for 10min in sequence, then placing the implant in a solution containing 15wt% of sulfuric acid, 8wt% of hydrochloric acid, 1wt% of nitric acid, 0.2wt% of ethylene glycol, 0.02g/L of potassium perfluorooctyl sulfonate and the balance of deionized water for 30min, carrying out high-temperature acid etching treatment at an acid etching temperature of 75 +/-5 ℃, rinsing with purified water after corrosion, and drying for later use, thereby obtaining a multi-level micron hole structure on the surface of the implant matrix and obtaining a porous structure implant;

(3) placing the porous structure implant under an ultraviolet lamp with the wavelength of 200nm for irradiation treatment, wherein the irradiation distance is 0.5cm, the irradiation time is 30min, and the heating setting temperature is 25 ℃, so as to obtain a hydrophilic implant;

(4) after irradiation treatment, the hydrophilic implant is clamped through a specific jig, laser etching treatment is carried out on the neck region under the protection of gas, the pulse width is 10ns, and the laser pulse flux is 20J/cm²The processing frequency is 100KHz, the space between etching stripes is 60 micrometers, the width of concave surfaces of the stripes is 32-40 micrometers, the depth of the concave surfaces of the stripes is 30.0 micrometers, the included angle between the stripes and the axial direction of the dental implant is 45 degrees, and the thread area is that the end surface of the implant extends 10mm towards the body part. Cleaning, drying, and packaging in a sealed bottle under the protection of gas to obtain the final dental implant product.

As shown in fig. 1a and 1b, the dental implant is divided into a neck region and a body region along an axial direction, and the surface of the neck region has a micro-stripe structure. Wherein the liquid-solid contact angle of the body region is 5 degrees. The scanning electron microscope and osteoblast culture SEM results of the bulk region are shown in fig. 2 and 3, respectively. As can be seen from FIG. 2, the surface of the body region is provided with a multi-level micron-sized hole structure, the multi-level micron-sized hole structure comprises a plurality of micron-sized pits, a plurality of submicron-sized recesses are distributed in the pits, the diameter of each pit is 1-20 μm, and the diameter of each recess is 1-8 μm. From the results of fig. 3, it can be seen that the cells pseudopodically adhered to the surface of the bulk region in a large amount, indicating good biocompatibility and high osteogenic activity. The liquid-solid contact angle of the neck region was 153 °. The scanning electron microscope results of the neck region are shown in fig. 4. As can be seen from FIG. 4, the surface of the neck region has a micro-stripe structure, the stripe interval is 60 μm, the stripe concave width is 32-40 μm, the stripe concave depth is 30.0 μm, and the included angle between the stripe and the dental implant in the axial direction is 45 °.

Testing antibacterial performance of Escherichia coli in neck region of dental implant by JIS Z2801 standard method, pre-culturing bacteria according to the standard method, selecting test piece with micro stripe structure on surface prepared by the same processing method as in example 1 as experimental group (selecting three groups of parallel tests), selecting standard PE piece as control group(three groups of parallel tests are selected), test bacteria liquid preparation, test bacteria liquid inoculation, test piece culture after inoculation, bacteria liquid elution and viable cell number calculation are sequentially carried out, and the average value of the viable cell number on three groups of experimental group samples after 24 hours of culture is 2.1 multiplied by 10⁵CFU/cm²The number of viable cells in the three control samples after 24 hours of culture averaged 8.4X 10⁵CFU/cm²And calculating the antibacterial rate according to a standard formula, wherein the antibacterial rate is (the average value of the number of living cells on samples of three groups of control groups after 24-hour culture-the average value of the number of living cells on samples of three groups of experimental groups after 24-hour culture)/the average value of the number of living cells on samples of three groups of control groups after 24-hour culture is multiplied by 100%. The result shows that the antibacterial rate can reach 75%.

Example 2

(1) Placing a pure titanium implant matrix into a cleaning tank containing a surfactant, ultrasonically removing oil and cleaning for 10min at 60-70 ℃, rinsing with purified water, drying, pickling in an acidic mixed solution containing 10% nitric acid and 5% hydrofluoric acid by volume fraction at normal temperature for 15s, rinsing with purified water, and drying for later use;

(2) placing a clean implant matrix in a prepared micro-arc oxidation treatment solution (1L of the micro-arc oxidation treatment solution contains 6g of calcium formate, 6mL of sulfuric acid, 4mL of hydrochloric acid and 6g of polypropyleneimine with the number average molecular weight of 4000), using the implant matrix as an anode and stainless steel as a cathode, and performing micro-arc oxidation treatment by using direct current pulse micro-arc oxidation biological ceramic equipment, wherein the process parameters of the micro-arc oxidation are set as follows: and in a constant voltage mode, the positive voltage is 150-300V, the negative voltage is 0V, the pulse frequency is 100Hz, the duty ratio is 5%, the reaction time is 4min, and the operating temperature is 40 ℃. Rinsing the purified water after micro-arc oxidation treatment, and drying for later use, thereby obtaining a multi-level micron hole structure on the surface of the implant matrix and obtaining the porous structure implant;

(3) placing the porous structure implant under an ultraviolet lamp with the wavelength of 200nm for irradiation treatment, wherein the irradiation distance is 3cm, the irradiation time is 10min, and the heating setting temperature is 40 ℃ to obtain a hydrophilic implant;

(4) after the irradiation treatment, by specifyingThe fixture clamps the hydrophilic implant, and under the protection of gas, the neck region is subjected to laser etching treatment by adopting the pulse width of 50fs and the laser pulse flux of 14J/cm²The processing frequency is 1KHz, the space between etching stripes is 30 μm, the width of the concave surface of the stripe is 10 μm, the depth of the concave surface of the stripe is 9.8 μm, the included angle between the stripe and the axial direction of the dental implant is 90 degrees, and the thread area is that the end surface of the implant extends 5mm towards the body part. Cleaning, drying, and packaging in a sealed bottle under the protection of gas to obtain the final dental implant product.

The dental implant is divided into a neck region and a body region along an axial direction, the neck region has an antibacterial property and the body region has an osteogenesis property. Wherein the liquid-solid contact angle of the body region is 3 degrees. The scanning electron microscope results of the bulk region are shown in fig. 5. As can be seen from fig. 5, the surface of the body region has a multi-level micron-sized hole structure, the multi-level micron-sized hole structure includes a plurality of micron-sized protrusions and grooves, the protrusions are recessed inward to form concave holes, the grooves are distributed around the protrusions, the protrusions protrude out of the grooves, the grooves are irregular, adjacent grooves are communicated with each other, and a plurality of submicron holes are distributed at the bottom of the grooves; the aperture of the submicron hole is 0.5-1 μm, the aperture of the concave hole is 1-5 μm, the height of the protruding part is 2-6 μm, and the groove width of the groove is 10-20 μm. The liquid-solid contact angle of the neck region was 152 °. The scanning electron microscope results of the neck region are shown in fig. 6. As can be seen from FIG. 6, the surface of the neck region has a micro-stripe structure with a stripe pitch of 30 μm, a stripe concavity depth of 9.8 μm and a stripe concavity width of 10 μm.

Example 3

(1) Placing a pure titanium implant matrix into a cleaning tank containing a surfactant, ultrasonically removing oil and cleaning for 10min at 60-70 ℃, rinsing with purified water, drying, pickling in an acidic mixed solution containing 8% nitric acid and 5% hydrofluoric acid by volume fraction at normal temperature for 20s, rinsing with purified water, and drying for later use;

(2) placing a clean implant matrix in a prepared micro-arc oxidation treatment solution (1L of the micro-arc oxidation treatment solution contains 8g of calcium acetate, 3mL of sulfuric acid, 4mL of nitric acid and 9g of sodium ethylene triamine pentaacetate), using the implant matrix as an anode and stainless steel as a cathode, and performing micro-arc oxidation treatment by using direct current pulse micro-arc oxidation biological ceramic equipment, wherein the process parameters of the micro-arc oxidation are set as follows: and in a constant voltage mode, the positive voltage is 150-300V, the negative voltage is 0V, the pulse frequency is 100Hz, the duty ratio is 5%, the reaction time is 4min, and the operating temperature is 40 ℃. Rinsing the purified water after micro-arc oxidation treatment, and drying for later use, thereby obtaining a multi-level micron hole structure on the surface of the implant matrix;

dispersing nano calcium phosphate in a suspension solution to obtain a nano hydroxyapatite suspension containing 10wt% of ethanol, 50g/L of nano hydroxyapatite and 10g/L of polyethylene glycol, performing spray deposition on a multistage microstructure of a body region through a spraying device (the spraying distance is 3cm, the spray deposition time is 20 s), drying the obtained deposited titanium implant at 60 ℃ for 60min, heating to 700 ℃ at the speed of 10 ℃/min after drying, performing heat preservation sintering for 0.5h to form a multistage micro-nano structure, and obtaining a porous structure implant deposited with the nano hydroxyapatite;

(3) placing the porous structure implant under an ultraviolet lamp with the wavelength of 200nm for irradiation treatment, wherein the irradiation distance is 0.5cm, the irradiation time is 20min, and the heating setting temperature is 30 ℃, so as to obtain a hydrophilic implant;

(4) after irradiation treatment, the hydrophilic implant is clamped through a specific jig, under the protection of gas, the neck area is subjected to laser etching treatment, and the pulse width of 50fs and the laser pulse flux of 14J/cm are adopted²The processing frequency is 1KHz, the space between etching stripes is 30 μm, the width of the concave surface of the stripe is 10 μm, the depth of the concave surface of the stripe is 20.3 μm, the included angle between the stripe and the axial direction of the dental implant is 80 degrees, and the thread area is that the end surface of the implant extends 5mm towards the body part. Cleaning, drying, and packaging in a sealed bottle under the protection of gas to obtain the final dental implant product.

The dental implant is divided into a neck region and a body region along an axial direction, the neck region has an antibacterial property and the body region has an osteogenesis property. Wherein the liquid-solid contact angle of the body region is 5 degrees. The scanning electron microscope results of the bulk region are shown in fig. 7. As can be seen from fig. 7, the surface of the body region has a multi-level micron-sized hole structure, the multi-level micron-sized hole structure includes a plurality of micron-sized protrusions and grooves, the protrusions are recessed inward to form concave holes, the grooves are distributed around the protrusions, the protrusions protrude out of the grooves, the grooves are irregular, adjacent grooves are communicated with each other, and a plurality of submicron holes are distributed at the bottom of the grooves; the aperture of the submicron hole is 0.5-1 μm, the aperture of the concave hole is 1-5 μm, the height of the protruding part is 2-6 μm, and the groove width of the groove is 10-20 μm. The liquid-solid contact angle of the neck region is 160 °. The surface of the neck region is provided with a micro stripe structure, the stripe interval is 30 mu m, the stripe concave width is 10 mu m, and the stripe concave depth is 20.3 mu m.

Comparative example 1

(1) - (3) same as in example 1.

(4) After irradiation treatment, the hydrophilic implant is clamped by a specific jig, a microporous structure is obtained at the neck part through micro-arc oxidation treatment, the neck part area has the microporous structure with the roughness arithmetic average value of 2.0 mu m Ra, and the microporous structure is cleaned, dried, filled into a sealing bottle under the protection of gas and packaged to obtain the final dental implant product. The osteoblast culture SEM results of the dental implant body region show that a great amount of cell pseudopodia is attached to the multi-level titanium surface. The neck area of the dental implant is subjected to an escherichia coli antibacterial performance test by adopting an operation method of JIS Z2801, a test piece with a surface having a micropore structure, which is prepared by adopting the same processing technology as that of comparative example 1, is selected as an experimental group, a standard PE piece is selected as a control group, and the specific test process is the same as that of example 1. The results showed that the average number of viable cells in the three groups of samples after 24 hours of culture was 1.6X 10⁵CFU/cm²The number of viable cells in the samples of the three control groups after 24 hours of culture averaged 1.7X 10⁵CFU/cm²The antibacterial rate is only 5.9% by calculation.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.

Claims

1. A dental implant, characterized in that the dental implant is divided into a neck region and a body region in an axial direction, the neck region having antibacterial properties and the body region having osteogenic properties by controlling a surface microstructure; the surface of the neck region is provided with a micro stripe structure, the stripe interval is 10-65 mu m, the stripe concave width is 4-40 mu m, the stripe concave depth is 1-30 mu m, and the included angle between the stripe and the axial direction of the dental implant is 45-90 degrees; the surface antibacterial rate of the neck region is more than or equal to 70 percent; the contact angle of the neck region is not less than 150 degrees, and the contact angle of the body region is not more than 10 degrees.

2. The dental implant of claim 1, wherein the surface of the body region has a multi-level micro-scale hole structure; the multi-level micron-sized hole structure comprises a plurality of micron-sized pits, and a plurality of submicron-sized recesses are distributed in the pits; or, multistage micron order hole structure includes the bellying and the slot of a plurality of microns, the bellying is inside sunken to form the shrinkage pool, the slot distributes around the bellying, the bellying salient in slot, the slot is irregular form, and adjacent slot communicates each other, the bottom of slot distributes and has a plurality of submicron holes.

3. Dental implant according to claim 2,

the diameter of the concave pit is 1-20 mu m, and the diameter of the concave pit is 1-8 mu m;

the aperture of the concave hole is 1-5 microns, the aperture of the submicron hole is 0.5-1 micron, the height of the protruding part is 2-6 microns, and the groove width of the groove is 10-20 microns;

the surface of the multilevel micron-sized hole structure is adhered with nano hydroxyapatite.

4. The dental implant of claim 1, wherein the neck region is 0.1-10 mm of the dental implant end-to-body region extension.

5. A method of preparing a dental implant according to any one of claims 1 to 4, comprising the steps of:

6. The method for preparing a dental implant according to claim 5, wherein in the step (2), the multistage micron treatment is sand blasting, acid etching or micro-arc oxidation; the multistage micro-nano treatment mode is to deposit nano hydroxyapatite on the basis of multistage micro treatment.

7. The method for preparing a dental implant according to claim 6,

the sand blasting and acid etching comprises sand blasting treatment and acid etching treatment in sequence; the conditions of the sand blasting treatment comprise that the sand blasting particle size is 80-180 mu m, the sand blasting pressure is 5-8 bar, and the sand blasting distance is 0.5-2 cm; the temperature of the acid etching treatment is 50-80 ℃, the time is 20-60 min, and the adopted acid etching solution contains 15-40 wt% of sulfuric acid, 1-8 wt% of hydrochloric acid, 1-5 wt% of nitric acid, 0.2-5 wt% of glycol, 0.02-0.08 g/L of potassium perfluorooctyl sulfonate and the balance of water;

the micro-arc oxidation electrolyte comprises main salt, a compound agent and an auxiliary additive, wherein the working voltage of the micro-arc oxidation is 150-350V, the negative voltage is 0V, the duty ratio is 5-20%, the pulse frequency is 100-1200 Hz, the time is 3-10 min, the operation temperature is 10-40 ℃, and the rest is water; the main salt is selected from at least one of calcium formate, acetic anhydride and calcium propionate; the compound agent is at least one selected from sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid; the auxiliary additive is selected from at least one of polyethyleneimine, polyacrylamide, diethylenetriamine pentaacetate and N, N-dicarboxylic acid amino-2-hydroxy propyl sulfonate;

the nano hydroxyapatite is deposited by adopting nano hydroxyapatite suspension to carry out spray deposition on the substrate subjected to multistage micron treatment, and drying and sintering are sequentially carried out after the spray deposition is finished; the nano hydroxyapatite suspension contains ethanol, nano hydroxyapatite and a dispersant, wherein the dispersant is selected from at least one of polyethylene glycol, polyvinylpyrrolidone, sodium carboxymethylcellulose, sodium phosphate, sodium dodecyl sulfate, polyvinyl alcohol, polyacrylamide, ammonium polyacrylate, polyethyleneimine and tween 80; the spray deposition conditions comprise that the spray distance is 1-5 cm, and the spray deposition time is 10-30 s; the sintering conditions comprise that the sintering temperature is 500-700 ℃, the heating rate is 3-10 ℃/min, and the sintering time is 0.5-2 h.

8. The method for preparing a dental implant according to claim 5, wherein in the step (3), the ultraviolet light treatment conditions include an ultraviolet light wavelength of 180 to 260nm, an irradiation distance of 0.5 to 5cm, and an irradiation time of 5 to 30 min; the plasma processing conditions comprise that a mixed gas of argon and oxygen is adopted, the flow of the argon is 0-450 sccm, the flow of the oxygen is 0-200 sccm, the vacuum degree is-99.5 KPa, the processing time is 60-600 s, and the cleaning power is 0-700W.

9. The method for preparing a dental implant according to claim 5, wherein in the step (4), the etching treatment is laser etching or chemical etching;

the laser etching adopts pulse laser etching, and the pulse width of the laser is nanosecond, picosecond or femtosecond; the conditions of the laser etching include that the pulse width is 10 fs-100 ns, and the laser pulse flux is 10-20J/cm²The processing frequency is 1-100 KHz;

the chemical etching adopts alkali thermal etching or reactive ion etching; the conditions of the alkali thermal etching comprise that etching liquid is 1-6 mol/L of sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate, the etching temperature is 200-300 ℃, and the etching time is 2-8 h; the conditions of the reactive ion etching comprise that etching gas is chlorine, the gas inlet flow is 10-80 sccm, and the etching time is 5-15 min.

10. A dental implant comprising an implant body and an artificial tooth, wherein the implant body is a dental implant according to any one of claims 1 to 4, and a neck region of the dental implant body is connected to the artificial tooth.