TWI696473B - Slowly degraded alloy and method for producing the same - Google Patents

Abstract

The present invention relates to a slowly degraded alloy and a method for producing the same. The slowly degraded alloy comprises a degradable metal and a cladding layer. The degradable metal is completely covered with the cladding layer, such that a degraded velocity of the degradable metal is decreased. Further, because the cladding layer is made from polymer materials, the cladding layer does not be broken when a stress is applied to the slowly degraded alloy, thereby efficiently covering the degradable metal therein, further lowering the degraded velocity of the degradable metal

Description

Slow degradation alloy and its manufacturing method

The invention relates to a biomedical implant material, in particular to provide a slow-degradation alloy and a manufacturing method thereof.

When performing surgical operations, doctors often have to use biomedical implants for fixation or support. Although these biomedical implants have good biocompatibility, they must be left in the human body after surgery, which leads to the trouble of follow-up inspection. Accordingly, biomedical implants made of degradable metals have gradually replaced implants made of stainless steel or titanium.

Because degradable metals are degradable, their corrosion resistance is poor. Therefore, when degradable metals come into contact with body fluids in the human body, they will gradually be corroded and dissociated into metal ions, and these metal ions can be excreted with the metabolism of the human body, so they will not remain in the human body. However, if the dissociation rate of degradable metals is too fast, a large amount of metal ions can easily harm human tissues and harm the human body. Secondly, when the dissociation rate of degradable metals is too fast, the hydrogen evolution rate also increases, which increases the pH of the surrounding environment, thereby reducing the amount of heme oxygen carried and inducing abnormal reactions in the human body.

Therefore, in order to effectively delay the degradation rate of the degradable metal, an oxidation protection layer is generally formed on the surface of the degradable metal to isolate the degradable metal from body fluid contact. However, the mechanical properties of the oxidation protection layer are relatively hard and brittle, so when stress is required during surgery, or when the implant has to change its appearance, the oxidation protection layer may be damaged, resulting in the direct exposure of degradable metals, therefore oxidation The protective layer loses its effectiveness.

In view of this, there is an urgent need to provide a slow-degradation alloy and its manufacturing method to improve the defects of the conventional slow-degradation alloy.

Therefore, one aspect of the present invention is to provide a slow-degradation alloy that covers the degradable metal by the coating layer, and delays the degradation rate of the degradable metal.

Another aspect of the present invention is to provide a method for manufacturing a slow-degradation alloy, which can form a polymer layer on the surface of the degradable metal by immersing the degradable metal in the polymer solution, thereby reducing the degradable metal The degradation rate.

According to one aspect of the present invention, a slow degradation alloy is proposed. The slow-degradation alloy includes a degradable metal and a coating layer, wherein the coating layer completely covers the degradable metal, and the coating layer includes a plurality of polymer layers, and the material of each of these polymer layers includes Polysaccharide polymer.

According to an embodiment of the present invention, the aforementioned coating layer may optionally include at least one bonding layer, wherein each bonding layer is disposed between two adjacent layers in the polymer layer.

According to another embodiment of the present invention, the aforementioned bonding layer is formed of a compound having at least one carboxyl group.

According to yet another embodiment of the present invention, the compound having at least one carboxyl group includes sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, glutamic acid, oxalic acid, L-amino acid, and/or D -Amino acids.

According to yet another embodiment of the present invention, the aforementioned degradable metals include magnesium alloys and/or iron-based alloys.

According to yet another embodiment of the present invention, the aforementioned polysaccharide polymer includes chitin, sulfated chondroitin, hyaluronic acid, glucosamine, and/or starch.

According to another aspect of the present invention, a method for manufacturing a slow-degradation alloy is proposed. This manufacturing method first provides a degradable metal material, and performs a first coating process on the degradable metal material. The first coating process is to immerse the degradable metal material in the polymer solution to form the first degradable metal. Wherein, the polymer solution includes polysaccharide polymer, acetic acid solution and sodium hydroxide solution, and the pH value of the polymer solution is less than 7. Then, a first drying step is performed on the first degradable metal after soaking the polymer solution, so as to form a polymer layer on the surface of the degradable metal material, and a slow-degradation alloy is prepared.

According to an embodiment of the present invention, before the aforementioned first cladding process is performed, the manufacturing method can selectively soak the degradable metal material in an alkaline solution.

According to another embodiment of the present invention, the aforementioned first coating process is performed at least once.

According to yet another embodiment of the present invention, a second cladding process can be selectively performed between at least one set of the aforementioned first cladding process, followed by two. Wherein, the second coating process is to soak the first degradable metal in the bonding solution to form the second degradable metal. The binding solution contains a compound having at least one carboxyl group and water, and the concentration of the binding solution is 0.1% to 40% by weight. Then, a second drying step is performed on the second degradable metal to form a bonding layer on the polymer layer.

According to yet another embodiment of the present invention, the pH value of the aforementioned polymer solution is greater than or equal to 4 and less than 7.

By applying the slow-degradation alloy of the present invention and the manufacturing method thereof, the degradable metal in the slow-degradation alloy is coated with a specific polymer material to reduce the degradation rate of the degradable metal and avoid the excessive hydrogen evolution rate during degradation Damage to the implanted area. Secondly, when stress is applied to the slow-degradation alloy, the more flexible polymer layer is not easy to break, which can effectively prevent the degradable metal from being exposed.

100/300‧‧‧Method

110/121/123/130/140/310/321/323/331/333/341/343/350/360

120/320/330/340‧‧‧Coating process

200a/200b/400a/400b ‧‧‧ slow degradation alloy

210/410‧‧‧degradable metal materials

220/420‧‧‧ coating

221a/221b/421a/421b/421c‧‧‧‧polymer layer

423a/423b‧‧‧Combination layer

In order to have a more complete understanding of the embodiments of the present invention and its advantages, please refer to the following description and cooperate with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of the related drawings are explained as follows: [FIG. 1A] is a flowchart showing a method for manufacturing a slow-degradation alloy according to an embodiment of the present invention.

[FIG. 1B] is a schematic cross-sectional view of a slow-degradation alloy according to an embodiment of the invention.

[FIG. 1C] is a schematic cross-sectional view of a slow-degradation alloy according to another embodiment of the present invention.

[FIG. 2A] is a flowchart showing a method for manufacturing a slow-degradation alloy according to another embodiment of the present invention.

[FIG. 2B] is a schematic cross-sectional view of a slow-degradation alloy according to yet another embodiment of the present invention.

[FIG. 2C] is a schematic cross-sectional view of a slow-degradation alloy according to yet another embodiment of the present invention.

[FIG. 3] is a line chart showing degradation tests of the slow-down alloys according to Examples 1 to 3 and Comparative Example 1 of the present invention.

The manufacture and use of embodiments of the present invention are discussed in detail below. However, it can be understood that the embodiments provide many applicable inventive concepts that can be implemented in a variety of specific contents. The specific embodiments discussed are for illustration only and are not intended to limit the scope of the invention.

Please refer to FIG. 1A and FIG. 1B at the same time, wherein FIG. 1A is a flowchart of a method for manufacturing a slow-degradation alloy according to an embodiment of the present invention, and FIG. 1B is a slow-degradation alloy according to an embodiment of the present invention. Schematic cross-section. In the manufacturing method 100, the degradable metal material 210 is first provided, as shown in operation 110. The degradable metal material 210 of the present invention is biodegradable, and the metal ions generated by the degradation can be metabolized through the metabolism of the human body Completely eliminated from the body. In some embodiments, the degradable metal material 210 may include, but is not limited to, magnesium alloys, iron-based alloys, other suitable degradable metal materials, or any mixture of the foregoing materials. In some embodiments, the degradable metal material 210 may include magnesium, zinc, and calcium, or iron, zinc, and calcium. For example, based on the degradable metal material 210 being 100 weight percent, the degradable metal material 210 includes 84 weight percent to 99.8 weight percent magnesium, 0.01 weight percent to 8 weight percent zinc, and 0.01 weight percent to 8 weight percent. calcium.

Then, a coating process 120 is performed on the degradable metal material 210. The coating process 120 first immerses the degradable metal material 210 in the polymer solution, as shown in operation 121. The polymer solution includes polysaccharide polymer, acetic acid aqueous solution and sodium hydroxide aqueous solution, and the pH value of the polymer solution is less than 7. In some embodiments, the polysaccharide polymer may include but is not limited to chitin, chondroitin sulfate, hyaluronic acid, glucosamine, starch, other suitable polysaccharide polymers, Or any combination of the above polymer materials.

The preparation of the polymer solution is to first dissolve the aforementioned polysaccharide polymer in an aqueous solution of acetic acid, and after stirring to completely dissolve, then add an aqueous solution of sodium hydroxide to adjust the pH of the solution to prepare the polymer solution. The pH value of the polymer solution is less than 7. For example, the preparation of the polymer solution is to first add 0.1 to 10 weight percent of the polysaccharide polymer to 100 ml of acetic acid aqueous solution (the concentration is 0.1 to 30 volume percent), and wait for the polysaccharide polymer After dissolution, a sodium hydroxide aqueous solution with a concentration of 1M to 10M is added to adjust the pH of the polymer solution. In some In the embodiment, the pH value of the polymer solution is adjusted to be greater than or equal to 4 and less than 7.

In some embodiments, the immersion time of the degradable metal material 210 in the polymer solution may be 1 minute to 60 minutes. It should be particularly noted that the immersion time of the degradable metal material 210 in the polymer solution is not particularly limited, as long as the surface of the degradable metal material 210 can be completely covered with the polymer solution. In some embodiments, the immersion time of the degradable metal material 210 can be adjusted according to the difference in the viscosity of the polymer solution. In some specific examples, the immersion time of the degradable metal material 210 in the polymer solution may be 1 second to 1200 seconds. In some embodiments, the viscosity of the polymer solution may be 5 cp to 500 cp.

After operation 121, the degradable metal material soaked in the polymer solution is dried, as shown in operation 123. After performing the drying step, the dried polymer solution can form a coating layer 221a covering the surface of the degradable metal material 210. In some embodiments, the drying temperature of the drying step may be 60°C to 110°C. In some embodiments, the drying time of the drying step may be 1 hour to 2 hours.

In some embodiments, before performing the aforementioned cladding process 120, the degradable metal material 210 may be selectively immersed in an alkaline solution to alkalize the surface of the degradable metal material 210. Wherein, the alkaline solution may include but is not limited to aqueous sodium hydroxide solution, other suitable alkaline aqueous solution, or any mixture of the above solutions. In some specific examples, the alkaline solution may be a sodium hydroxide aqueous solution with a concentration of 1M to 10M. In these specific examples, the immersion time of the degradable metal material 210 in the sodium hydroxide aqueous solution may be 1 minute to 60 minutes. After soaking the alkaline solution, the surface-modified degradable metal material 210 is placed in an oven to dry the degradable metal material 210.

When performing the aforementioned coating process 120, the alkalized surface of the degradable metal material 210 helps to coat the polysaccharide polymer in the polymer solution on the surface. Among them, in addition to the physical surface immersion coating, the polysaccharide polymer can also be completely intact by the intermolecular force (that is, the force between the alkaline surface modifying group on the surface and the polysaccharide polymer) Cover the surface of the degradable metal material 210.

In some embodiments, before the alkaline solution is soaked, the degradable metal material 210 may also selectively undergo a polishing process to reduce the surface roughness of the degradable metal material 210. When the surface roughness of the degradable metal material 210 is reduced, the surface area of the degradable metal material 210 can be reduced, and the area where the degradable metal material 210 generates degradation reduction reaction is reduced. Therefore, when the degradable metal material 210 in the slowly degradable metal 200a is exposed, since the area where the reduction reaction can occur is reduced, the degradable metal material 210 can still have a lower degradation rate. In these embodiments, the degradable metal material 210 after polishing may be cleaned with an alcoholic solvent (eg, ethanol, etc.) and dried at a temperature of 60°C to 100°C to remove chips and chips generated during the polishing process /Or solvents or bacteria remaining on the surface of the degradable metal material 210 to avoid the adverse effects of the prepared slow-degradation alloy after implantation in the human body.

After the coating process 120 is performed, it is determined whether the coating layer 221a of the slow-degradation alloy 200a satisfies the set conditions, as shown in operation 130. In some embodiments, the set conditions may be the coating thickness, the number of coating layers, and/or other conditions. If the coating layer 221a satisfies the set conditions, it is prepared as shown in FIG. 1B The slow degradation alloy 200a of the present invention is shown as operation 140. If the coating layer 221a does not meet the set conditions, the prepared alloy material is subjected to the coating process 120 again, and the alloy material is soaked in the polymer solution (such as operation 121), and further drying steps (such as operation 123), and then the slow-degradation alloy 200b as shown in FIG. 1C is prepared.

In the slow-degradation alloy 200b, after the alloy material is immersed in the polymer solution again, the polymer layer 221b formed by drying covers the polymer layer 221a formed by the previous coating process 120. In this way, the cladding layer 220 of the slow degradation alloy 200b may include a plurality of polymer layers 221a and polymer layers 221b. Similarly, after the polymer layer 221b is formed on the polymer layer 221a, it is still necessary to determine whether the cladding layer 220 satisfies the set condition (ie, operation 130). If the set conditions are still not met, the alloy material is subjected to the aforementioned cladding process 120 again (that is, repeated for the third time). Since the process has been described as before, it will not be repeated here.

Please refer to FIGS. 2A and 2B, wherein FIG. 2A is a flowchart of a method for manufacturing a slow degradation alloy according to another embodiment of the present invention, and FIG. 2B is a slow degradation according to another embodiment of the present invention. A schematic cross-sectional view of the alloy. The flow of the manufacturing method 300 of FIG. 2A is substantially the same as the flow of the manufacturing method 100 of FIG. 1A. The difference between the two is that in the manufacturing method 300, after the first coating process 320 is performed, the first degradable metal system formed The second cladding process 330 and the third cladding process 340 are further performed.

In the second cladding process 330, the first degradable metal formed in the first cladding process 320 is immersed in the bonding solution to form the second degradable metal, as shown in operation 331. The binding solution contains one having at least one carboxyl group The compound and water, and the concentration of the combined solution is 0.1% by weight to 40% by weight. In some embodiments, the compound having at least one carboxyl group may include but is not limited to sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, glutamic acid, oxalic acid, L-amino acid, D-amino group Acid, other suitable compounds with long carbon chain and at least one carboxyl group, or any combination of the above materials.

In some embodiments, the first degradable metal may be immersed in the bonding solution for 1 minute to 60 minutes. It should be noted that the soaking time of the first degradable metal in the binding solution is not particularly limited, as long as the surface of the first degradable metal can be completely covered with the binding solution. In other words, the bonding solution is coated on the first degradable metal polymer layer 421a (that is, the polymer layer formed by drying the first coating process 320).

After operation 331, the first degradable metal soaked in the binding solution is subjected to a drying step, as shown in operation 333. After the bonding solution is dried, a bonding layer 423a covering the polymer layer 421a can be formed. In some embodiments, the drying temperature of the drying step may be 60°C to 110°C. In some embodiments, the drying time of the drying step may be 1 hour to 2 hours.

Then, a third coating process 340 is performed on the dried second degradable metal. The third cladding process 340 is to immerse the second degradable metal formed in the second cladding process 330 in the polymer solution, and perform a drying step after the immersion, as shown in operations 341 and 343. The polymer solution used in the third coating process 340 is the same as the polymer solution used in the first coating process 320. In some embodiments, the polysaccharide polymers in the polymer solution of the third coating process 340 and the first coating process 320 may be the same or different from each other. Secondly, the process parameters of the third cladding process 340 (for example: The soaking time, polymer solution concentration and drying parameters, etc.) may be the same or different from the process parameters of the second cladding process 330 to meet different application requirements.

During the operation 343 of the third coating process 340, the polymer solution coated on the surface of the second degradable metal may be dried to form another polymer layer 421b, and the polymer layer 421b is coated on the bonding layer 423a. Accordingly, the bonding layer 423a is located between the polymer layer 421a and the polymer layer 421b. In other words, the third degradable metal coating layer 420 includes a polymer layer 421a, a bonding layer 423a, and a polymer layer 421b.

Then, it is judged whether the coating layer of the third degradable metal after drying meets the set condition, as shown in operation 350. Similarly, the "setting conditions" described herein may be the thickness of the cladding layer, the number of sub-layers contained in the cladding layer, and/or other conditions. If the coating layer of the third degradable metal satisfies the set conditions, the slow-degradation alloy 400a of the present invention (as shown in FIG. 2B) is prepared, as shown in operation 360. In other words, when the coating layer of the third degradable metal satisfies the set condition, the third degradable metal is the slow-degradation alloy 400a. If the coating layer of the third degradable metal does not satisfy the set conditions, the third degradable metal system performs the second coating process 330 again, and then the third coating process 340 is continued. Accordingly, as shown in FIG. 2C, the third degradable metal is coated with another bonding layer 423b on the polymer layer 421b through the second cladding process 330, and the In the coating process 340, the polymer layer 421c is coated on the bonding layer 423b.

Please continue to refer to FIGS. 2A and 2C. After forming the polymer layer 421c, determine whether the coating layer (containing the polymer layer 421a, the bonding layer 423a, the polymer layer 421b, the bonding layer 423b, and the polymer layer 421c) is again determined The set condition is satisfied, as shown in operation 350. If the coating layer satisfies the set conditions, the slow-degradation alloy 400b of the present invention is prepared. If the cladding layer still does not satisfy the set conditions, the alloy material having the structure shown in FIG. 2C repeats the foregoing second cladding process 330 and third cladding process 340 again.

In the slow-degradation alloy 400b, the surface of the degradable alloy 410 is sequentially covered with a polymer layer 421a, a bonding layer 423a, a polymer layer 421b, a bonding layer 423b, and a polymer layer 421c. Wherein, the bonding layer 423a and the bonding layer 423b help to improve the bonding properties of the polymer layer 421a, the polymer layer 421b and the polymer layer 421c, and the stability of the cladding layer 420 and the slow degradation alloy 400b Nature.

It should be noted that the foregoing flow of FIG. 2A is only an illustration, and the present invention is not limited to this. Those skilled in the art can adjust the order of operations or omit some operations according to needs. In some embodiments, when the aforementioned operation 350 of FIG. 2A is performed, if the cladding layer does not satisfy the set conditions, in addition to performing the second cladding process 330 again on the third degradable metal as shown in FIG. 2A, Perform the first cladding process 320, the second cladding process 330, and the third cladding process again in sequence on the third degradable metal, or repeat the third cladding process 340. In other words, along the direction from the innermost layer (that is, the layer closest to the degradable metal material) of the prepared cladding layer to the outermost layer, the layers in the cladding layer are not interleaved by the polymer layer and the bonding layer as limit. In other embodiments, there is no bonding layer between the polymer layers partially stacked on each other in the coating layer. It should be noted that the outermost layer of the coating layer of the slow-degradation alloy must be a polymer layer. If the outermost layer of the cladding layer is not a polymer layer, the outermost layer of the slow-degradation alloy does not have the effect of slow degradation.

In an application example, the slow-degradation alloy of the present invention has a degradable metal material and a coating layer. Among them, since the coating layer completely covers the degradable metal material, the degradation rate of the degradable metal material can be effectively delayed. Secondly, since the coating layer is made of a polymer material, the coating layer has relatively flexible mechanical properties. Therefore, when stress is applied to the slow-degradation alloy, the coating layer will not be damaged due to the generated strain, so the coating layer can still effectively protect the degradable metal material therein. In addition, when a bonding layer is provided between two adjacent polymer layers, the bonding layer can further enhance the bonding properties of the polymer layer and enhance the stability of the degradation rate of the slow-degradation alloy.

The following uses embodiments to illustrate the application of the present invention, but it is not intended to limit the present invention. Anyone who is familiar with this art can make various modifications and retouching without departing from the spirit and scope of the present invention.

Making slow degradation alloy Example 1

First, configure 100 mL of an aqueous solution of acetic acid with a concentration of 0.1 to 30 volume percent, and add 0.1 to 10 weight percent of chitin to form a chitin solution, and the viscosity of the chitin solution will be between 5 cp and 500 cp. After stirring and dissolving, a sodium hydroxide aqueous solution with a concentration of 1M to 10M is added to the chitin solution to adjust the pH value of the chitin solution to 4 to 7 to form a polymer solution.

Secondly, the surface of the magnesium-based alloy is polished and cleaned with alcohol. After being dried in an oven, the magnesium-based alloy was soaked in a 5M sodium hydroxide aqueous solution for surface modification. After 10 minutes, remove The magnesium-based alloy is placed in an oven at 110°C. After drying for 1 hour, the magnesium-based alloy was immersed in the aforementioned polymer solution. After soaking for 10 minutes, the magnesium-based alloy was taken out and placed in an oven at 110°C. After drying for 1 hour, a magnesium-based alloy coated with a polymer layer on the surface can be prepared.

Next, this magnesium-based alloy is immersed in the polymer solution again. Similarly, after soaking for 10 minutes, the magnesium-based alloy was placed in an oven at 110°C. After drying for 1 hour, the slow-degradation alloy of Example 1 can be prepared. The coating layer of the slow-degradation alloy of Example 1 is composed of two polymer layers. The prepared slow-degradation alloy was evaluated by the evaluation method of the degradation test described below. The results obtained are shown in Table 1, and are not repeated here.

Example 2 and Example 3

The slow-degradation alloys of Example 2 and Example 3 use a manufacturing method similar to that of the slow-degradation alloy of Example 1, except that the magnesium-based alloy of Example 2 is immersed in the polymer solution four times and the combined solution three times. The magnesium-based alloy of Example 3 was soaked with the polymer solution six times and the combined solution five times. Wherein, the combination solution is to prepare L-glutamic acid as an aqueous solution with a concentration of 0.1% by weight to 40% by weight.

In Example 2 and Example 3, the operation of immersing the polymer solution and the operation of immersing the binding solution are interleaved. Therefore, the coating layer of the slow-degradation alloy of Example 2 is composed of four polymer layers and three interleaved The combination layer is composed of six layers of polymer layers and five layers of combination layers. The evaluation results of the prepared slow-degradation alloy are shown in Table 1, and are not repeated here.

Comparative example 1

Comparative Example 1 first polished the magnesium-based alloy and cleaned it with alcohol. Then, the cleaned magnesium-based alloy is placed in an oven. After drying, the magnesium-based alloy was directly evaluated by the following degradation test. The results obtained are shown in Table 1 and will not be repeated here.

Degradation test

First, the surface area of the slow-degradation alloys of Examples 1 to 3 and Comparative Example 1 was measured. Then, the slow-degradation alloys of Examples 1 to 3 and Comparative Example 1 are immersed in the same test liquid (for example: water or body fluid, etc.), and the retardation is measured by the method of hydrogen evolution test commonly used in the art. Hydrogen evolution amount (ml/cm ² ) of degraded alloy at different times.

Please refer to Table 1 and FIG. 3 at the same time. FIG. 3 is a line chart illustrating degradation tests according to Examples 1 to 3 and Comparative Example 1 of the present invention. Among them, the X axis represents the immersion days of the slowly degradable alloy, and the Y axis represents the amount of hydrogen evolution of the slowly degradable alloy.

According to the results of the degradation tests of Examples 1 to 3 and Comparative Example 1, it is known that the coating layer of the present invention can effectively coat the degradable metal material, and can effectively prevent the degradable metal material from contacting the test liquid. Secondly, when the degradable metal material is covered with at least one polymer layer, the amount of hydrogen evolution of the degradable metal material can be greatly reduced. Obviously, the coating layer composed of the polymer layer can effectively isolate the degradable metal material and the test liquid, and reduce the degradation rate of the slow-degradation alloy. As the number of cladding layers increases, the slope of the broken line of Examples 1 to 3 and Comparative Example 1 also gradually becomes flat, so the degradation rate of the slowly degraded alloy decreases accordingly.

In addition, compared with the coating layer consisting only of the polymer layer (ie, Example 1), when the coating layer of the slow-degradation alloy further includes a bonding layer (ie, Example 2 and Example 3), the amount of hydrogen gas evolved The standard deviation can be greatly reduced. Obviously, the bonding layer helps to improve the bonding properties between the polymer layers and improve the stability of the slow-degradation alloy.

According to this, the method for manufacturing the slow-degradation alloy of the present invention can produce materials with a low degradation rate, and can be applied to the field of biomedical implants. Among them, the coating layer made of the polymer material can effectively and completely cover the degradable metal material, thereby separating the degradable metal material and the body fluid, and can inhibit the degradation reaction of the degradable metal material, thereby reducing the degradation rate. Furthermore, by soaking the bonding solution, the bonding layer can be formed between adjacent polymer layers in the cladding layer to improve the bonding properties between the polymer layers, thereby improving the stability of the prepared slow-degradation alloy. In addition, since the coating layer is made of a polymer material, it is more flexible, and can avoid damage when stress is applied, so it can effectively protect the coated degradable metal material.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention belongs can make various changes without departing from the spirit and scope of the present invention. Retouching, therefore, the protection scope of the present invention shall be subject to the scope defined in the appended patent application.

100‧‧‧Method

110/121/123/130/140‧‧‧Operation

120‧‧‧ coating process

Claims (10)

A slow-degradation alloy, comprising: a degradable metal with an alkalized surface, wherein the alkalized surface is formed by soaking the degradable metal in an alkaline aqueous solution; and a coating layer, which is completely coated In the degradable metal, the coating layer includes a plurality of polymer layers, and a material of each of the polymer layers includes a polysaccharide polymer. The slow-degradation alloy as recited in item 1 of the patent application scope, wherein the coating layer further comprises: at least one bonding layer, wherein each of the at least one bonding layer is disposed between two adjacent layers of the polymer layers . The slow-degradation alloy as described in item 2 of the patent application range, wherein the at least one bonding layer is formed of a compound having at least one carboxyl group. The slow-degradation alloy as described in item 3 of the patent application scope, wherein the at least one carboxyl compound comprises sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, glutamic acid, oxalic acid, L-amino acid And/or D-amino acids. The slow-degradation alloy as described in item 1 of the patent application scope, wherein the degradable metal includes a magnesium alloy and/or an iron-based alloy. The slow-degradation alloy as described in item 1 of the patent application range, wherein the polysaccharide polymer comprises chitin, sulfated chondroitin, hyaluronic acid, glucosamine, and/or starch. A method for manufacturing a slow-degradation alloy includes: providing a degradable metal material; and performing a first cladding process at least once, wherein the first cladding process includes: immersing the degradable metal material in a polymer solution, To form a first degradable metal, wherein the polymer solution includes polysaccharide polymer, acetic acid solution and sodium hydroxide solution, and the pH value of the polymer solution is less than 7; The first drying step is to form a polymer layer on a surface of the degradable metal material to prepare the slow-degradation alloy. According to the method for manufacturing a slow-degradation alloy described in item 7 of the patent application scope, before the first coating process is performed, the manufacturing method further includes: immersing the degradable metal material in an alkaline solution. The method for manufacturing a slow-degradation alloy as described in item 8 of the patent application scope, wherein the first cladding process is performed a plurality of times. Between the first coating process, a second coating process is further included, wherein the second coating process includes: immersing the first degradable metal in a bonding solution to form a second degradable metal, wherein The binding solution includes a compound having at least one carboxyl group and water, and a concentration of the binding solution is 0.1% to 40% by weight; and a second drying step is performed on the second degradable metal to form a binding layer On the polymer layer. The method for manufacturing a slow-degradation alloy as described in item 7 of the patent application scope, wherein the pH value of the polymer solution is greater than or equal to 4 and less than 7.

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