TWI584788B - Surface-treated artificial bone and surface treatment method - Google Patents

Description

Surface treated artificial bone material and surface treatment method thereof

The invention relates to an artificial bone material and a processing method thereof, in particular to a surface treated artificial bone material and a surface treatment method thereof, and the method has the characteristics suitable for mass production.

In the treatment of dental defects in the field of dental treatment, in addition to the traditional "fixed sputum" or "active dentures", "Dental Implant" has become popular as the mainstream option for dental treatment. One.

Looking back on the past, in 1969, Branemark published the results of the research on titanium alloy "dental implants" and opened the new year of "dental implants". In 1972, Predecki et al. observed that an irregular "tooth implant" surface promoted bone growth and had good mechanical fitting force. In 1976, Schroeder et al. first observed the direct contact between the bone and the "dental implant" in the tissue section. In 1992, Bower et al. also conducted histological studies to confirm the results of direct contact between these bones and "dental implants". Therefore, some scholars call this phenomenon "Osseointegration".

The success of implant surgery is influenced by many factors, such as bone mass, bone mass, implant geometry and surface properties. However, regardless of the surgical conditions and technical factors, the osseointegration of the "tooth implant" in the bone groove and the stability under the masticatory load are very important during the healing process of the implant bone. Among them, the titanium alloy "dental implant" has the biocompatibility of osseointegration, and the texture, cleanness and electrochemistry of the implant surface are related to the early bone integration and stability of the dental bed. Have Many studies on the surface structure and treatment of "tooth implants" are expected to further improve the early bone healing and stability of implants. However, after implanting the human body into the human body, how to quickly and effectively form the optimal surface pore size and roughness of the osseointegration to achieve a better initial and post-long-term stability, has not yet reached a clear conclusion, the pursuit of "tooth implants" Various surface modification methods and process parameters are the subject of research in recent years.

Many literatures document the effects of surface characteristics of "teeth implants" on different cell behaviors. For example, the implant surface is not treated, so-called cutting surfaces, such as Nobel Biocare's Branemark System (the company also has TiUnite products for titanium oxide surface treatment technology). According to the data of the world's national brands, there are many "dental implant" systems that carry out different surface treatment methods, or because of patent restrictions, they must avoid the commonly known surface treatment, and instead give different names, such as ACE. The RBM (Resorbable blast material) method, the Anthogyr BCP (Biphasic calcium phosphate) method, the BioHorizons RBT (Resorbable blast texturing) method, the Spline SBM (Soluble blast medium) method, etc., all of which are hydroxyl apatite Hydroxylapatite (HA) or Tricalcium phosphate (TCP) is used as a processing medium for surface blasting. In general, the surface modification of "tooth implants" is currently based on Straumann's SLA technology and Nobel Biocare's TiUnite surface oxidation method.

In general, the traditional ways of increasing the surface area, providing a tortuous macroscopic shape, and roughening the surface of the implant can be divided into the following two categories:

One is to add a coating on the surface of the "dental implant". Includes: HA plasma spray treatment, such as Steri-oss System, Integral System, Paragon Ssystem...etc. It is also treated with Titanium Plasma Spray (TPS), such as the early Straumann TPS, Steri-oss System... In addition, there are ways to use the electrochemical coating of the anode, such as the TiUnite method of Nobel Biocare, and the POI System method of Kyocera of Japan.

The other is to etch the surface of the "tooth implant" to increase the surface area and change the micro-texture or roughening. These surface treatment methods include sandblasting, such as the Ankylos System method and Acid Etching. Such as Biomet 3i System method; Sandblasted Large-grit Acid-etching SLA, such as Stranmann SLA method; hydrophilic treatment after sand blasting, such as Stranmann SLActive method; Soluble) Blast Medium, RBM), such as the Biohorizon System method, and the Osstem RBM method.

Analysis from the literature shows that the modification of different surface treatments (including cutting, sand blasting, hydroxyapatite coating, plasma sprayed titanium, acid etching, surface oxidation, erosion treatment of absorbable particulate matter and In the case of acid etched SLA after blasting, although the etch treatment method of absorbing particulate matter, and the hydroxyapatite coating and blasting acid etching method, the osseointegration of the "tooth implant" interface is better. The rate, however, provides an extremely rough surface topography environment that allows the deep integration of human osteogenic tissue as the primary factor in the effectiveness of osseointegration.

Therefore, in order to produce better artificial medical equipment for medical needs, it is necessary to develop a new "tooth implant" surface treatment technology to improve the surface roughness and osseointegration rate of the implant.

The invention provides a surface treated artificial bone material and a surface treatment method thereof, which can treat the surface of the artificial bone material to increase the surface area of the artificial bone material, thereby improving the overall osseointegration bonding rate of the artificial bone material.

The invention provides a surface treatment method for artificial bone material, which comprises the following steps: firstly providing an artificial bone material, sandblasting the artificial bone material, and then using the first acid liquid to perform the first acid on the artificial bone material. The etching treatment is followed by a second acid etching treatment on the artificial aggregate using the second acid solution. Wherein, the first acid liquid and the second acid liquid are respectively two acidic liquids, so that the surface of the artificial bone material forms a plurality of micropores. The surface of the artificial aggregate is measured by an optical three-dimensional surface roughness measuring instrument having a porous composite structure of 3 to 7 micrometers and a nanometer, that is, the surface of the artificial aggregate has a plurality of micropores. And the maximum height roughness (Rt) value is greater than 30um, and the contour average roughness (Rs) value is about 3-10um, so the surface area of the artificial aggregate can be effectively increased.

The invention also provides a surface treated artificial bone material comprising a fixed section and an implanted section. The surface of the fixed section is provided with a fine thread, and the implant section extends from one end of the fixed section, and the outer ring surface of the implant section is provided with a spirally distributed screw thread having a plurality of micro-holes on the surface thereof.

In summary, due to the use of two separate acidic liquids, the violent reaction generated when using acid solution or acid solution can be avoided to reduce the risk, and the chemicality can be maintained for a long time when unreacted, so it is suitable for mass production. use. The micro-holes of micron-scale and nano-scale are produced on the surface of the artificial aggregate, which can increase the surface area of the artificial bone. After being implanted into the human body, a large number of human osteoblasts can be attached and grown into the micro-holes for the human body. Osteogenesis The speed and stability of osseointegration between cells and implants is increased, thereby reducing the risk of postoperative artificial bone loosening and shortening the course of treatment, thereby improving the effect of osseointegration.

For a better understanding of the features and technical aspects of the present invention, reference should be made to the accompanying drawings.

The invention provides a surface treatment method for artificial bone material. Please refer to FIG. 1 . FIG. 1 is a flow chart of a surface treatment method for an artificial bone material according to the present invention, which comprises the following steps:

First, as described in step S102, artificial bone material is provided, wherein the artificial bone material may be pure titanium, titanium alloy or any metal containing titanium element, and after the metal implant is in contact with air, the surface thereof is usually There is an oxide layer which is mainly a titanium dioxide layer (TiO ₂ ).

Next, as described in step S104, the artificial bone material is sandblasted. Usually, sandblasting is also called shot peening. The hard sand is used to spray the sand particles at a high speed by external power to be processed. On the object, the surface produces a specific biting surface, and removes stain oxides, eliminates scratches and cleans the surface. The mechanism of sand blasting can be divided into dry type and wet type. Generally, the wet type is suitable for the blasting particle size of about 15 micrometers (μm) or less. The materials used for sand blasting generally include steel beads, stainless steel, alumina, lead, copper, iron sand, aluminum alloy, carbonized strontium, iron beads, glass beads, resin, strontium sand, and others such as ceramics and calcium carbonate. , sodium bicarbonate, hard plant fruit fragments, and the like. Due to the difference in size and size, sandblasts of different sizes have different effects from the treated ones. Generally, the blasting treatment method can be classified into a centrifugal type, a siphon type, and a pressurized type, but the type of the blasting treatment method is not limited to the above.

Thereafter, as described in step S106, the artificial acid material is subjected to a first acid etching treatment using the first acid liquid. Acid treatment removes oxides and contaminants from the surface of titanium metal to achieve a clean and uniform surface, while simultaneously increasing the roughness and forming tiny micropores for the growth of osteoblasts. In addition, Acid-Etching can also be used as a surface for the formation of finer roughness regions in the roughness region of a large area after sand blasting, or as a surface for attachment of osteoblasts. Therefore, the first acid liquid is selected as a strong acid having an etching ability for titanium or a titanium alloy, and may be, for example, hydrofluoric acid (HF), hydrochloric acid (HCL), sulfuric acid (H ₂ SO ₄ ), ammonia water (NH ₄ OH). ), phosphoric acid (H ₃ PO ₄ ), nitric acid (HNO ₃ ), or the like, or an acidic solution obtained by mixing the above two or more strong acids in different ratios, as the first acid solution of the present invention.

In this embodiment, the first acid etching treatment is to immerse the artificial bone material in the sulfuric acid solution by using a sulfuric acid solution, wherein the artificial bone material may be completely soaked or partially immersed in the sulfuric acid solution to make the artificial bone surface Micro- and nano-scale micropores are formed. With regard to the process parameters of the first acid etching process, the temperature range of the process may be between 100 and 130 ° C, and the time range may be between 5 minutes and 24 hours, however, the preferred embodiment, the artificial bone The time in the sulfuric acid solution is between 5 and 15 minutes. Next, the artificial bone material is subjected to a washing process, wherein the washing process can be carried out using an ultrasonic oscillating machine, and the pure water and the alcohol are used as a medium for washing and wetting.

Next, as described in step S108, the artificial bone material is subjected to a second acid etching treatment using the second acid liquid. The second acid is selected as a strong acid having an etching ability for titanium or a titanium alloy, and may be, for example, hydrofluoric acid (HF), hydrochloric acid (HCL), sulfuric acid (H ₂ SO ₄ ), ammonia (NH ₄ OH), phosphoric acid. (H ₃ PO ₄ ), nitric acid (HNO ₃ ), or the like, or an acidic solution obtained by mixing the above two or more strong acids in different ratios, and is the second acid solution of the present invention. Among them, two different acidic solutions are used in the use of the first acid solution and the second acid solution.

In this embodiment, the second acid etching treatment is to use a hydrochloric acid solution, which is an artificial bone material which has been etched and washed by sulfuric acid, and is immersed in a hydrochloric acid solution, wherein the artificial bone material may be completely soaked or partially immersed in the hydrochloric acid. The solution forms micro- and nano-scale micropores on the surface of the artificial aggregate. With regard to the process parameters of the second acid etching process, the temperature range of the process may be between 70 and 100 ° C, and the time range may be between 5 minutes and 48 hours, however, the preferred embodiment, the artificial bone The time in the hydrochloric acid solution is between 5 and 15 minutes. Next, the artificial bone material is subjected to a washing process, wherein the washing process can be carried out using an ultrasonic oscillating machine, and the pure water and the alcohol are used as a medium for washing and wetting. Specifically, the first and second acid etching treatments are performed, and the micro-holes and nano-scale micropores generated by the first and second acid etching processes are respectively larger than 1 μm and 15 nm, and are acid-etched with the artificial bone material. There is a significant difference in the front surface topography.

In another embodiment of the present invention, the artificial bone material has a natural oxide layer on the surface thereof, and the process steps include: firstly, sandblasting the artificial bone material, and then immersing the artificial bone material in the mixed acid liquid, wherein, mixing The acid solution may be a mixed acid solution of hydrochloric acid/sulfuric acid. It should be specially noted that the mixed acid solution of hydrochloric acid/sulfuric acid is mixed in an equal volume ratio or mixed in different volume ratios, wherein a volume ratio of hydrochloric acid to sulfuric acid is preferably 1:1 to 6:1, and the mixed acid solution is used. The process parameters of the acid etching treatment may be that the artificial bone material is used for 5 minutes in a mixed acid solution having a temperature of 100 to 130 ° C. From 24 hours to 24 hours, in the present embodiment, the artificial bone material is allowed to act in the mixed acid solution for 10 to 30 minutes. Next, the artificial bone material is subjected to a washing process, wherein the washing process can be carried out using an ultrasonic oscillating machine, and the pure water and the alcohol are used as a medium for washing and wetting.

Therefore, the present invention can have the following embodiments:

In the first embodiment, the volume ratio of hydrofluoric acid, nitric acid and water may be 4:2:76, and after mixing, soaking at room temperature for 5 seconds to 90 seconds.

In the second embodiment, the volume ratio of hydrochloric acid, sulfuric acid and water may be 10:80:10, and the soaking time after mixing is 5 seconds to 60 seconds.

In the third embodiment, the mixing ratio of hydrochloric acid, sulfuric acid and pure water may be 1:5:7, the post-mixing treatment temperature is 100 to 120 ° C, and the soaking time is 5 minutes to 15 minutes.

In the fourth embodiment, the volume ratio of hydrochloric acid to sulfuric acid may be 1:1 to 5:1, the post-mixing treatment temperature is 60 to 80 ° C, and the soaking time is 5 minutes to 25 minutes.

In the fifth embodiment, the hydrochloric acid may be first immersed in a temperature of 80 to 100 ° C for 5 minutes to 60 minutes, and then immersed in sulfuric acid at a temperature of 100 to 120 ° C for 5 minutes to 60 minutes.

In the sixth embodiment, the sulfuric acid at a temperature of 100 to 120 ° C may be first immersed for 5 minutes to 60 minutes, and then immersed in hydrochloric acid at a temperature of 80 to 100 ° C for 5 minutes to 60 minutes.

Referring to FIG. 2, the present invention also provides a surface treated artificial bone material 1 comprising a fixed section 14 and an implant section 12. The surface of the fixing section 14 is provided with a fine thread. The implant section 12 extends from one end of the fixing section 14. The outer ring surface of the implant section 12 is provided with a spirally distributed screw 121. The cross-section of the thread 121 is Ladder stepped . The outer diameter of the implant section 12 is tapered from the rear end toward the anterior segment to reduce the resistance generated when the surgical drill is drilled into the bone, while the end edge of the front end is machined into a circular arc shape. As shown in FIG. 3, the surface of the implanted section and the surface of the fixed section have a plurality of micro-holes 100, that is, the surface of the artificial aggregate 1 has a plurality of micro-holes 100. Wherein, the value of the surface roughness of the artificial aggregate 1 is detected, the center line average roughness (Ra) value is about 3 to 7 microns, the maximum height roughness (Rt) value is greater than 30 microns, and the contour average roughness (Rs) value It is about 3 to 10 microns.

Table 1 shows the surface roughness measured by an optical three-dimensional surface roughness measuring instrument, with an Ra value of about 4.28 μm, an Rs value of about 3.52 μm, and an Rt value of about 83.2 μm. Table 2 shows the results of the contact profilometer. The Ra and Rt values are smaller than the optical measurements.

Please refer to the attached table, which are the surface SEM images of the artificial aggregates treated by the above process, Annex 1 is the 5K times SEM image of the composite acid etched surface, and Annex 2 is the composite acid etching. 10K times SEM image of the surface of the surface, Annex 3 is a 10K times SEM image of the surface after the mixed acid etching, and Annex 4 is a 30K times SEM image of the surface which is subjected to the composite acid etching. As shown in the attached table, it is found that the surface of the artificial aggregate is an irregular and uniform rough surface formed by a plurality of micropores exhibiting a circular hole shape, and each of the micropores having a circular hole shape is approximately 1 to 2 μm and 100 apart, respectively. ~200nm.

In summary, the first acid etching treatment of the present invention mainly uses a high-temperature first acid liquid such as sulfuric acid to perform surface roughening treatment of the first artificial bone material, and micropores are formed on the surface of the artificial bone material. Thereafter, a second acid etching treatment is performed, and the second artificial acid material surface roughening treatment is mainly performed with a second acid solution such as hydrochloric acid at a high temperature to form micropores on the surface of the artificial bone material. In this way, not only the violent reaction generated when using the acid solution or the acid solution can be avoided to reduce the risk, and the micropores of the micron-scale and nano-scale are generated on the surface of the artificial bone material, which can increase the surface area of the artificial bone material, and plant After entering the human body, a large number of human osteoblasts can be attached and grown into micropores, so as to increase the speed and stability of bone integration between human osteoblasts and implants, thereby reducing postoperative risk and shortening the course of treatment.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalents of the present invention and the equivalents of the drawings are all included in the present invention. Within the scope of protection, it is given to Chen Ming.

1‧‧‧Artificial aggregate

100‧‧‧ micro holes

12‧‧‧ implant section

121‧‧‧ thread

14‧‧‧Fixed section

1 is a flow chart of a method of surface treatment of an artificial aggregate of the present invention.

2 is a schematic perspective view of a surface treated artificial bone material of the present invention.

Figure 3 is a schematic enlarged view of a surface treated artificial bone material of the present invention.

Claims (4)

A surface treatment method for artificial bone material, comprising the steps of: providing an artificial bone material selected from the group consisting of titanium and titanium alloy; sandblasting the artificial bone material; using the first acid The first acid etching treatment is performed on the artificial aggregate, the first acid liquid is sulfuric acid, the temperature range of the process is between 100 and 130 ° C, and the time range is between 5 and 15 minutes; The second acid solution is subjected to a second acid etching treatment on the artificial bone material to form a plurality of micropores on the surface of the artificial aggregate, and the second acid solution is hydrochloric acid, and the temperature range of the process is between 70 and 100 ° C. The time range is between 5 and 15 minutes. The surface treatment method of the artificial aggregate according to claim 1, wherein the blasting treatment is one of a centrifugal method, a siphon method, and a pressurized method. An artificial aggregate material treated by the surface treatment method of the artificial aggregate according to claim 1, comprising: a fixed section having a fine thread distributed on the surface; and an implant section from one end of the fixed section Extending out, the outer ring surface of the implant segment is provided with a spirally distributed thread; wherein the surface of the artificial bone has a plurality of micropores. The surface-treated artificial aggregate according to claim 3, wherein the artificial bone has a surface roughness value, and the center line average roughness (Ra) value is about 3 to 7 micrometers, and the maximum height is rough. The degree of (Rt) value is greater than 30 microns and the contour average roughness (Rs) value is about 3 to 10 microns.