JP2010172449A - Method of manufacturing alternative material for solid body tissue, and treatment solution used in the manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an alternative material for solid body tissues, for forming a film with affinity with solid body tissues on a surface of a base of a metal material by a simple way, securing a high bonding strength between the metal and apatite, and moreover achieving the film with a stabilized color tone. <P>SOLUTION: The base 11 of the metal-made alternative material 1 for solid body tissues is immersed in an aqueous alkaline solution to form the film 12, having affinity with the solid body tissue and containing the metal material and oxygen, on the surface of the base 11 (S104). Then, the base 11 is heated to disperse oxygen over the surface of the base 11, and to increase the film 12 in thickness to stabilize the film 12 (S106). The aqueous alkaline solution used in the alkali treatment of the material 1 is adjusted so that the metallic ion concentration in the aqueous alkaline solution is within a predetermined range (S102). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a manufacturing method of a hard tissue replacement material for manufacturing a hard tissue replacement material that is implanted so as to be replaced with a hard tissue in a living body, and a treatment solution used in the manufacturing method.

  As a hard tissue substitute material that is implanted so as to replace hard tissues such as bones and roots in vivo, a metal material such as titanium or titanium alloy is used as a base, and the surface of the base has an affinity for hard tissues The thing which formed the membrane | film | coat which has this is known (refer patent document 1). Fracture toughness of metal materials by forming a hard tissue compatible film that forms an apatite phase of the same kind as the inorganic substance of the hard tissue on the surface of the metal material substrate in the living body and directly binds to the hard tissue And hard tissue affinity are compatible in the hard tissue substitute material. And in patent document 1, the base | substrate formed with titanium or titanium alloy is immersed in alkaline aqueous solution, the film | membrane which has hard tissue affinity is formed, and also the base | substrate is heated and oxygen is diffused on the surface of a base | substrate. A method of manufacturing a hard tissue substitute material that increases the thickness of the coating is disclosed. In Patent Document 2, the titanium base (substrate) is treated with the same alkaline aqueous solution, then washed with warm water, and heated to a temperature at which at least the precipitation of anatase is observed. A bioimplant material joined to a material is disclosed. According to these manufacturing methods, unlike the plasma coating method using hydroxide apatite on the metal surface, an expensive plasma spraying device that increases the manufacturing cost is unnecessary, and the substrate is simply immersed in an aqueous alkali solution and heated. Hard tissue affinity can be imparted by the method, and further, an effect that a metal and apatite can be strongly bonded can be obtained.

Japanese Patent No. 2775523 Japanese Patent No. 3877505

  According to the manufacturing method of the hard tissue substitute material disclosed in Patent Document 1, a film having a hard tissue affinity can be formed on the surface of the base material of the metal material by a simple method, and the high bonding strength between the metal and the apatite Can be produced. However, when the inventor of the present application manufactured a hard tissue substitute material by the manufacturing method disclosed in Patent Document 1, there is no change in the structure or crystal structure of the film having a hard tissue affinity on the substrate surface, but the difference in the manufacturing lot It was confirmed that the color tone of the film was greatly different. In product manufacturing management, quality control including appearance is performed, and thus it is necessary to unify the appearance. Thus, it becomes a problem that the color tone becomes unstable depending on the product.

  In view of the above circumstances, the present invention can form a film having a hard tissue affinity on the surface of a metal material substrate by a simple method and ensure high bonding strength between the metal and the apatite. Furthermore, an object of the present invention is to provide a method for producing a hard tissue substitute material capable of realizing a stable film color tone, and to provide a treatment solution used in the production method.

  In order to achieve the above object, a method of manufacturing a hard tissue substitute material according to the first invention is a method of manufacturing a hard tissue substitute material for producing a hard tissue substitute material that is implanted so as to replace a hard tissue in a living body. A method for treating a substrate of a hard tissue substitute material formed of a metal material with an alkaline aqueous solution containing alkali metal ions and / or alkaline earth metal ions (that is, of alkali metal ions and alkaline earth metal ions). An alkaline treatment step of immersing in an alkaline aqueous solution containing at least one of them to form a film containing the metal material and oxygen and having an affinity for a hard tissue on the surface of the substrate, and the alkaline treatment step And a heat treatment step for increasing the thickness and stability of the film, which is a treatment layer on the surface of the substrate, by heating the substrate after the completion of the process. And the manufacturing method of the hard-tissue substitute material which concerns on 1st invention WHEREIN: The said alkaline aqueous solution used at the said alkali treatment process is metal ion concentration other than the said alkali metal ion and / or the said alkaline-earth metal ion in the said alkaline aqueous solution. Is adjusted to fall within a predetermined range.

  According to this invention, a substrate having a hard tissue affinity is formed on a substrate surface by immersing the substrate formed of a metal material in an alkaline aqueous solution, and oxygen is diffused by heating the substrate to serve as a treatment layer. The thickness of the film can be increased and the stability of the film structure can be increased. Accordingly, a hard tissue substitute material capable of forming a hard tissue-compatible film on the surface of a metal material substrate by a simple method and ensuring high bonding strength between the metal and the apatite is manufactured. Can do. Further, as a result of intensive studies by the inventor of the present application, it has been found that the color tone of the film varies greatly depending on the difference in the conditions of the alkaline aqueous solution used in the alkaline treatment step and in which the substrate is immersed. The inventors of the present application can adjust the color tone of the film to a predetermined color tone and stabilize even if the production lot is different by adjusting the metal ion concentration in the alkaline aqueous solution to be within a predetermined range. Confirmed by. For this reason, a stable color tone can be realized with respect to the film formed on the surface of the substrate by performing the alkali treatment step and the heat treatment step in the present invention on the substrate of the metal material.

  Therefore, according to the present invention, a film having a hard tissue affinity can be formed on the surface of the base material of the metal material by a simple method, and a high bonding strength between the metal and the apatite can be secured, and further stable. It is possible to provide a method for producing a hard tissue substitute material capable of realizing the color tone of the coated film.

  The method for producing a hard tissue substitute material according to the second invention is the method for producing a hard tissue substitute material according to the first invention, wherein the alkali aqueous solution used in the alkali treatment step has a saturation concentration of the metal ion concentration in the alkali aqueous solution. The metal ion concentration is adjusted so as to fall within a predetermined range.

  According to the present invention, the metal ion concentration in the alkaline aqueous solution can be easily adjusted to achieve a stable color tone for the film formed on the surface of the substrate simply by adjusting the metal ion concentration in the alkaline aqueous solution to be saturated. be able to. In addition, it was confirmed by the present inventor that the color tone of the film is unified and stabilized to a predetermined color tone even if the production lot is different by adjusting the metal ion concentration in the aqueous alkali solution to the saturated concentration. .

  The method for producing a hard tissue substitute material according to the third invention is the method for producing a hard tissue substitute material according to the first invention or the second invention, wherein the metal ion concentration adjusted in the alkaline aqueous solution used in the alkali treatment step is The metal ion concentration is the same as that of the metal element constituting the metal material.

  According to the present invention, since the metal ion concentration adjusted in the alkaline aqueous solution is the same metal ion concentration as the metal element constituting the metal material of the substrate, the metal ion eluted from the substrate into the alkaline aqueous solution can also be contained in the alkaline aqueous solution. The metal ion concentration in can be adjusted. For this reason, the metal ion concentration in the alkaline aqueous solution can be adjusted more easily. In addition, since the metal ion concentration adjusted in the alkaline aqueous solution is the same metal ion concentration as the metal element constituting the metal material of the substrate, the color tone of the film is further stabilized and the color tone is highly uniform. This has been confirmed by the present inventors.

  The method for producing a hard tissue substitute material according to a fourth invention is the method for producing a hard tissue substitute material according to any one of the first invention to the third invention, wherein the metal material is titanium or a titanium alloy, It contains an alkali titanate.

  According to the present invention, the substrate is composed of titanium and a titanium alloy having excellent mechanical properties, corrosion resistance to body fluids, extremely low toxicity to living bodies, and exhibiting the best hard tissue affinity among metal materials. Can do. And, by immersing the substrate in an alkaline aqueous solution and heating it, a film containing alkali titanate is formed on the surface of the substrate, and has high hard tissue affinity and high bonding strength between metal and apatite It is possible to configure a film that can realize the above.

  The method for producing a hard tissue substitute material according to a fifth aspect of the invention is the method for producing a hard tissue substitute material of the fourth invention, wherein the alkali aqueous solution used in the alkali treatment step has a metal ion concentration of 1. It is characterized by being adjusted to be within a range of 3 mg / L or more and 1.6 mg / L or less.

  According to this invention, the color tone of the film is adjusted by adjusting the titanium ion concentration, which is the metal ion concentration adjusted in the alkaline aqueous solution, to be within the range of 1.3 mg / L to 1.6 mg / L. It was further confirmed by the present inventor that the color tone is more stable and has a high uniformity.

  Further, as another aspect of the invention for achieving the above-described object, an invention of a treatment solution used in any of the above-described methods for producing a hard tissue substitute material can be configured. That is, the treatment solution according to the sixth invention is formed of a metal material and the substrate of the hard tissue substitute material is immersed in an alkaline aqueous solution containing alkali metal ions and / or alkaline earth metal ions, and is applied to the surface of the substrate. In the alkali treatment step of forming a film containing the metal material and oxygen and having an affinity for hard tissue, the metal ion concentration other than the alkali metal ions and / or the alkaline earth metal ions is within a predetermined range. It is used as said alkaline aqueous solution adjusted so that it may fit in.

  According to the present invention, a film having a hard tissue affinity can be formed on the surface of a base of a metal material by a simple method, and a high bonding strength between the metal and the apatite can be secured, and a stable film The processing solution used for the manufacturing method of the hard tissue substitute material which can implement | achieve this color tone can be provided.

  According to the present invention, a film having a hard tissue affinity can be formed on the surface of a substrate of a metal material by a simple method, a high bonding strength between the metal and apatite can be secured, and a stable film It is possible to provide a method for producing a hard tissue substitute material and a treatment solution used in the method for producing the hard tissue substitute material.

It is a front view which shows the hard tissue substitute material manufactured by the manufacturing method of the hard tissue substitute material which concerns on embodiment of this invention. It is sectional drawing which shows the state in which the hard tissue alternative material shown in FIG. 1 was used in the artificial hip joint. It is process drawing which shows the manufacturing process which concerns on the manufacturing method of the hard tissue substitute material which concerns on embodiment of this invention. It is a figure explaining the conditions of the experiment determined about the color tone of the film | membrane of the hard tissue substitute material manufactured with the manufacturing method of the hard tissue substitute material shown in FIG. It is a figure explaining the result of the experiment determined about the color tone of the film | membrane of the hard tissue substitute material manufactured with the manufacturing method of the hard tissue substitute material shown in FIG.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. In the present embodiment, a manufacturing method and a treatment solution used in the manufacturing method will be described by taking a femoral component implanted as a substitute for a part of a femur which is a hard tissue in a living body as an example. . However, the present invention is not limited to this example, and the present invention can be applied to a hard tissue substitute material that is substituted for various hard tissues of bones and teeth other than the femur. That is, the present invention is widely applied as a manufacturing method of a hard tissue replacement material for manufacturing a hard tissue replacement material to be implanted so as to be replaced with a hard tissue in vivo, and a treatment solution used in the manufacturing method. It is something that can be done.

(Hard tissue substitute material)
FIG. 1 is a front view showing a hard tissue substitute material 1 manufactured by a method for manufacturing a hard tissue substitute material according to an embodiment of the present invention. This hard tissue substitute material 1 is formed as a femoral component used in an artificial hip joint. FIG. 2 is a cross-sectional view showing a state in which the hard tissue replacement material 1 is used in an artificial hip joint, and shows a part of the cross section of the femur 100 and the pelvis 101 (in FIG. 2, the pelvis 101 is shown in cross section). The hatched lines indicating the state are omitted). As shown in FIGS. 1 and 2, the hard tissue substitute material 1 formed as a femoral component is configured as a stem member formed in a rod shape in which one end side is implanted in the medullary cavity portion 100 a of the femur 100. Yes. The hard tissue substitute material 1 is applied as an artificial hip joint in a state where it is combined with the bone head ball member 102. The femoral head ball member 102 is disposed on the acetabulum 101 a side of the pelvis 101 in the femur 100. The bone head ball member 102 is arranged on the acetabulum 101a and slidably slides on the outer spherical surface portion with respect to the acetabular cup 103 having the outer and inner two-layer hemispherical shell members. .

  Moreover, the hard tissue substitute material 1 shown in FIG.1 and FIG.2 is formed with the base | substrate 11 by the titanium or titanium alloy which is a metal material. The base 11 is provided with a stem portion 11 a on one end side that is implanted in the femur 100 and a neck portion 11 b on the other end side that is fitted to the head ball member 102. A film 12 having a hard tissue affinity is formed on a part of the surface of the substrate 11 and formed in the stem portion 11a through an alkali treatment step S104 and a heat treatment step S106 described later. When the hard tissue substitute material 1 is implanted in the femur 100, an apatite phase is formed on the surface of the coating 12, and the hard tissue substitute material 1 and the bone are directly bonded.

(Method of manufacturing hard tissue substitute material)
Next, the manufacturing method of the hard tissue substitute material which concerns on this embodiment for manufacturing the hard tissue substitute material 1 is demonstrated in detail. FIG. 3 is a process diagram showing a manufacturing process according to the manufacturing method of the hard tissue substitute material of the present embodiment. As shown in FIG. 3, the manufacturing process in the manufacturing method of the hard tissue substitute material includes a substrate forming process S101, an alkaline aqueous solution manufacturing process S102, a degreasing process S103, an alkali treatment process S104, a cleaning process S105, and a heat treatment process S106. Is provided. FIG. 3 illustrates the case where the alkaline aqueous solution preparation step S102 is performed only at the timing between the base body formation step S101 and the degreasing step S103. May be performed at an arbitrary timing before the alkali treatment step S104.

  In the base body forming step S101, in the present embodiment, the base body 11 provided with the stem portion 11a and the neck portion 11b described above is formed using titanium or a titanium alloy as a material. At this time, the film 12 is not yet formed on the surface of the substrate 11.

In the alkaline aqueous solution production step S102, an alkaline aqueous solution containing alkali metal ions and used in the alkali treatment step S104 described later is produced. The alkaline aqueous solution is preferably an aqueous solution containing at least one alkali metal ion and / or alkaline earth metal ion among sodium ions (Na ⁺ ), potassium ions (K ⁺ ), and calcium ions (Ca ²⁺ ). For example, 5M (molar concentration) NaOH or KOH aqueous solution. The concentration of alkali metal ions and / or alkaline earth metal ions in the aqueous alkali solution is preferably set to about 2M to 10M. In the alkaline aqueous solution preparation step S102, the alkaline aqueous solution has a saturated metal ion concentration (a metal ion concentration of a predetermined metal other than an alkali metal ion and / or an alkaline earth metal ion). By adjusting, the metal ion concentration is adjusted to be within a predetermined range (in the present embodiment, a range of 1.3 mg / L to 1.6 mg / L).

  In this embodiment, in this alkaline aqueous solution, the metal ion concentration (titanium ion concentration) of titanium constituting the substrate 11 is adjusted to the predetermined range. Specifically, a solution prepared as a 5M NaOH aqueous solution or a KOH aqueous solution is set at a temperature of, for example, 60 ° C., and a titanium alloy or pure titanium ingot, or a titanium alloy or pure titanium powder is added to this solution. And maintain at the above temperature (60 ° C.) for 24 hours. At this time, the titanium alloy or pure titanium to be charged is charged until a white precipitate is generated in the solution so as to obtain a saturated concentration. Thereby, the titanium ion concentration in the aqueous alkali solution is adjusted so as to fall within the range of 1.3 mg / L to 1.6 mg / L. Thus, alkaline aqueous solution is produced by performing said process in alkaline aqueous solution preparation process S102.

  In the present embodiment, the alkaline aqueous solution produced in the alkaline aqueous solution production step S102 falls within the range of the titanium ion concentration of 1.3 mg / L to 1.6 mg / L in the alkali treatment step S104 described later. Thus, a treatment solution used as an alkaline aqueous solution is prepared. That is, this aqueous alkaline solution constitutes the treatment solution of this embodiment used in the method for producing a hard tissue substitute material of this embodiment.

  In the degreasing step S103, oil or the like adhering to the surface of the substrate 11 formed in the substrate forming step S101 is degreased. In the degreasing step S103, for example, degreasing and cleaning are first performed with acetone, and then cleaning with distilled water is performed, and the degreasing process is completed.

  In the alkali treatment step S104, the substrate 11 that has been degreased in the degreasing step S103 is immersed in the alkaline aqueous solution produced in the alkaline aqueous solution production step S102. At this time, the alkaline aqueous solution in which the substrate 11 is immersed is maintained at a temperature of 60 ° C. for 24 hours. The base 11 is sealed (sealed) so that the portion of the stem portion 11a except the portion where the coating 12 is formed is not in contact with the alkaline aqueous solution (that is, the coating 12 is formed). In a state where only the portion exposed to be in contact with the alkaline aqueous solution) is immersed in the alkaline aqueous solution. When the immersion treatment (alkali treatment) in the alkaline aqueous solution for 24 hours is completed, the substrate 11 is taken out from the alkaline aqueous solution. In the alkali treatment step S104, it is desirable that the alkaline aqueous solution is set to a temperature of 40 ° C. to 70 ° C., and the immersion time of the substrate 11 in the alkaline aqueous solution is secured for about 1 hour to 48 hours.

By the alkali treatment described above, a film 12 having a hard tissue affinity is formed on the surface of the substrate 11 by containing titanium or a titanium alloy, an alkali metal such as sodium or potassium, and oxygen. Specifically, a film 12 containing an alkali titanate and having a hard tissue affinity is formed on the surface of the substrate 11 that has undergone the alkali treatment. In addition, a thin film made of an oxide having a composition close to TiO ₂ which is an amphoteric substance that reacts with both a strong acid and a strong base originally exists on the surfaces of titanium and a titanium alloy. For this reason, when the substrate 11 formed of titanium or a titanium alloy is immersed in an alkaline aqueous solution in an alkali treatment step, the surface of the substrate 11 has a concentration gradient that gradually increases from the inside with a small amount of reaction toward the outside with a large amount of reaction. Alkaline titanate is formed at the same time.

  In the above description, the case where the titanium ion concentration in the alkaline aqueous solution is adjusted to fall within a predetermined range in the alkaline aqueous solution production step S102 has been described, but this need not be the case. That is, the titanium ion concentration in the alkaline aqueous solution is appropriately adjusted so as to be within a predetermined range in the alkaline aqueous solution preparation step S102 and the alkaline treatment step S104. For example, in the alkaline treatment step S104, the alkali ions are alkalinized by the titanium ions eluted from the substrate 11. The titanium ion concentration in the aqueous solution may be further adjusted. Further, in the alkali treatment step S104, the titanium ion concentration in the alkaline aqueous solution may be further adjusted by further introducing a titanium alloy or pure titanium powder.

  In the cleaning step S105, the surface of the substrate 11 after the alkali treatment step S104 is cleaned. In this cleaning step S105, for example, a cleaning process with several tens of minutes of distilled water is performed using an ultrasonic cleaning device.

  In the heat treatment step S106, heat treatment is performed to heat the substrate 11 after the alkali treatment step S104 and the cleaning step S105. In this heat treatment step S106, heating is performed at a temperature not higher than 300 ° C. and not higher than 800 ° C., which is lower than the transition temperature of titanium or a titanium alloy, for a predetermined time within 1 hour to 24 hours. By performing the heat treatment in this manner, oxygen diffuses on the surface of the substrate 11, the thickness of the coating 12 that is the treatment layer increases, and the stability of the coating structure also increases. The heating temperature of the substrate 11 in the heat treatment may be 300 ° C. to 800 ° C. as described above, but it is desirable to heat in the range of 550 ° C. to 650 ° C. When the substrate 11 is formed of titanium or a titanium alloy, if the temperature of the heat treatment is less than 300 ° C., oxygen is not sufficiently diffused and supplied on the surface of the substrate 11, and the thickness of the coating 12 is sufficiently ensured. It becomes difficult. On the other hand, if the temperature of the heat treatment exceeds 800 ° C., the transition temperature of titanium is reached, which leads to a decrease in the mechanical strength of the substrate 11, which is not desirable.

  When the heat treatment step S106 is completed, the manufacture of the hard tissue substitute material 1 shown in FIG. 1 is completed. On the surface of the hard tissue substitute material 1, a coating 12 is formed in which titanium metal gradually decreases toward the outside, while titanium oxide and alkali titanate gradually increase toward the outside. Since the coating 12 contains titanium oxide and alkali titanate so that the concentration gradient changes gently in this way, the interface with the coating 12 on the surface of the substrate 11 is firmly bonded. . When the hard tissue substitute material 1 is implanted in the living body and is in contact with the body fluid, a titanium hydroxide group that easily reacts with calcium or phosphorus is generated on the surface of the coating 12. This titanium hydroxide group is rich in reactivity and reacts with the bone-forming component in the body fluid to produce apatite nuclei. In addition, before implanting the hard tissue substitute material 1 in the living body, the hard tissue substitute material 1 is immersed in an aqueous solution containing calcium and phosphorus having a solubility equal to or higher than that of apatite, preferably in a simulated body fluid. Apatite nuclei can also be formed on the surface of 12.

  Next, the experimental result determined about the color tone of the film | membrane 12 of the hard tissue substitute material 1 manufactured with the manufacturing method of the hard tissue substitute material which concerns on this embodiment is demonstrated. The color tone determination experiment was evaluated by changing the alkali treatment lot in the alkali treatment step S104 to produce a plurality (20) of hard tissue substitute materials and judging the color tone of each hard tissue substitute material. Specifically, an alkaline aqueous solution having a titanium ion concentration of 0 mg / L is used in the first alkaline treatment lot, and an alkaline aqueous solution having a titanium ion concentration of 1.2 mg / L is used in the second alkaline treatment lot. In the alkali treatment lot, an alkaline aqueous solution having a titanium ion concentration of 1.3 mg / L is used. In the fourth to twentieth alkaline treatment lot, an alkaline aqueous solution having a titanium ion concentration in the range of 1.3 mg / L to 1.6 mg / L is used. Used for alkali treatment. Moreover, about the manufacturing conditions other than the conditions of the alkali aqueous solution mentioned above, all the said 20 hard tissue alternative materials were manufactured as the same. In addition, since the titanium ion concentration of the alkaline aqueous solution becomes a saturated concentration at about 1.5 mg / L to 1.6 mg / L, it does not exceed 1.6 mg / L, and the upper limit at which 1.6 mg / L can be adjusted. Of titanium ion concentration.

  FIG. 4 is a graph showing the titanium ion concentration for each of the first to 20th alkali treatment lots in the above experiment. Moreover, in FIG. 4, about the titanium ion density | concentration in the 4th time, the 5th time, the 7th to 9th time, and the 11th to 19th alkali treatment lots, the titanium ion concentration data of those lots are shown from a viewpoint of making it easier to see. The symbols (circles) are not shown and are shown as regression lines. When the titanium ion concentration in the fourth, fifth, 7-9th, and 11-19th alkaline treatment lots is illustrated in FIG. 4, the deviation amount is 0.1 mg / L or less with respect to the regression line. It was in a state of being distributed within the range. Further, FIG. 5 shows the color tone of 20 hard tissue substitute materials manufactured by changing the alkali treatment lot as described above, and the determination results are arranged in relation to the titanium ion concentration. . The color tone determination was performed in a state where the heat treatment step S106 was completed and the manufacture of the hard tissue substitute material was completed.

  In a hard tissue substitute material that has been subjected to alkali treatment using an aqueous alkali solution with a titanium ion concentration of 0 mg / L, the film that has been subjected to alkali treatment consists of a light pinkish part and a light greenish part. The colors were mixed with unevenness. In a hard tissue substitute material that has been subjected to alkali treatment using an alkaline aqueous solution having a titanium ion concentration of 1.2 mg / L, the coating film that has been subjected to alkali treatment has a lot of light greenish overall, and is a light pink The color tone was in a state where the colored portion was partially uneven. On the other hand, in a hard tissue substitute material that has been subjected to alkali treatment using an alkaline aqueous solution having a titanium ion concentration of 1.3 mg / L or more and 1.6 mg / L or less, Even in the hard tissue substitute materials, the color tone of light green was unified as a whole, and in any case, uneven color tone was not seen, and a stable color tone was obtained. For this reason, in the color tone determination, as shown in FIG. 5, when the titanium ion concentration is less than 1.3 mg / L, it becomes defective as indicated by the cross mark in the drawing, and the titanium ion concentration is 1.3 mg / L or more and 1.6 mg / L. Below L, it became favorable as shown by a circle in the figure. That is, when the titanium ion concentration is less than 1.3 mg / L, the color tone of the hard tissue substitute material film is not stable, and when the titanium ion concentration is 1.3 mg / L or more and 1.6 mg / L or less, the film of the hard tissue substitute material is not stable. It was confirmed that the color tone was stable.

(Effect of this embodiment)
According to the manufacturing method of the hard tissue substitute material of the present embodiment described above, a coating 12 having a hard tissue affinity is formed on the surface of the base 11 by immersing the base 11 formed of a metal material in an alkaline aqueous solution. By heating the substrate 11, oxygen can be diffused to increase the thickness of the coating 12 as a treatment layer, and the stability of the coating structure can be increased. Thereby, the hard tissue substitute material 1 that can form the coating 12 having a hard tissue affinity on the surface of the base 11 of the metal material by a simple method and can secure a high bonding strength between the metal and the apatite. Can be manufactured. In addition, as described above, by adjusting the metal ion concentration in the alkaline aqueous solution to be within a predetermined range, the color tone of the film 12 is unified and stabilized even when the production lot is different. That was confirmed. For this reason, when the alkali treatment step S104 and the heat treatment step S106 are performed on the base material 11 of the metal material, a stable color tone can be realized with respect to the film 12 formed on the surface of the base material 11.

  Therefore, according to the present embodiment, the film 12 having a hard tissue affinity can be formed on the surface of the base 11 of the metal material by a simple method, and a high bonding strength between the metal and the apatite can be ensured. Furthermore, the manufacturing method of the hard tissue substitute material which can implement | achieve the stable color tone of the membrane | film | coat 12 can be provided.

  Moreover, according to the manufacturing method of the hard tissue substitute material of this embodiment, in order to implement | achieve the stable color tone about the membrane | film | coat 12 formed in the surface of the base | substrate 11 only by adjusting so that the metal ion concentration in alkaline aqueous solution may be saturated. The metal ion concentration in the alkaline aqueous solution can be easily adjusted. As described above, it is confirmed that the color tone of the film is unified and stabilized even when the production lot is different by adjusting the metal ion concentration in the alkaline aqueous solution to the saturated concentration. It was.

  Moreover, according to the manufacturing method of the hard tissue substitute material of this embodiment, the metal ion concentration adjusted in the alkaline aqueous solution is the same kind of metal as the metal element (titanium) constituting the metal material (titanium or titanium alloy) of the base 11. Because of the ion concentration (titanium ion concentration), the metal ion concentration in the alkaline aqueous solution can also be adjusted by the metal ions eluted from the substrate into the alkaline aqueous solution. For this reason, the metal ion concentration in the alkaline aqueous solution can be adjusted more easily. As described above, since the metal ion concentration adjusted in the alkaline aqueous solution is the same metal ion concentration as the metal element constituting the metal material of the substrate 11, the color tone of the film is further stabilized and unified. It was confirmed that the color tone was high.

  In addition, according to the manufacturing method of the hard tissue substitute material of the present embodiment, it has excellent mechanical properties, corrosion resistance to body fluids, extremely low toxicity to the living body, and exhibits the best hard tissue affinity among metal materials. The substrate 11 can be made of titanium and titanium alloy. And the base | substrate 11 is immersed in an alkaline aqueous solution and it heats, By forming the membrane | film | coat 12 containing an alkali titanate on the surface of the base | substrate 11, it has high hard tissue affinity, and a metal and apatite The film 12 that can realize high bonding strength can be configured.

  Moreover, according to the manufacturing method of the hard tissue substitute material of this embodiment, as described above, the titanium ion concentration, which is the metal ion concentration adjusted in the alkaline aqueous solution, is 1.3 mg / L or more and 1.6 mg / L or less. It was confirmed that the color tone of the film 12 is further stabilized and adjusted to a color tone with high uniformity by adjusting so as to fall within the range.

  Moreover, according to the processing solution (alkaline aqueous solution) used in the manufacturing method of the hard tissue substitute material of this embodiment, the film 12 having hard tissue affinity can be formed on the surface of the base 11 of the metal material by a simple method. In addition, it is possible to provide a treatment solution used in the method for producing a hard tissue substitute material that can secure a high bonding strength between the metal and the apatite and can realize a stable color tone of the coating film 12.

(Modification)
Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made as long as they are described in the claims. For example, the following modifications may be made.

(1) In this embodiment, the femur has been described as an example of the hard tissue to which the hard tissue substitute material is applied. However, this need not be the case, and the present invention can be applied to various hard tissues of bones and teeth other than the femur. The present invention can also be applied as a manufacturing method for a hard tissue substitute material.

(2) In the present embodiment, the case where the metal ion concentration in the alkaline aqueous solution is adjusted to be the saturation concentration has been described as an example. However, this need not necessarily be the case, and a predetermined value that includes a concentration lower than the saturation concentration may be used. In this range, the metal ion concentration may be adjusted. Further, in the present embodiment, the case where the metal ion concentration adjusted in the alkaline aqueous solution is the metal ion concentration of the metal material constituting the base of the hard tissue substitute material has been described as an example. The metal ion concentration of the metal material other than the metal material forming the base of the hard tissue substitute material may be adjusted.

(3) In the present embodiment, the case where the metal material forming the substrate is titanium or a titanium alloy has been described as an example. However, the present invention is not limited to this example, and tantalum (Ta), which is a metal material having biocompatibility, is also used. Even when the substrate is formed using zirconium (Zr) and an alloy thereof, the same effect can be obtained by the manufacturing method based on the technical idea of the present invention.

  INDUSTRIAL APPLICABILITY The present invention can be widely applied as a manufacturing method of a hard tissue replacement material for manufacturing a hard tissue replacement material that is implanted so as to be replaced with a hard tissue in vivo, and a treatment solution used in the manufacturing method. It can be done.

1 Hard tissue substitute material 11 Base 12 Coating

Claims (6)

A method for producing a hard tissue substitute material for producing a hard tissue substitute material to be implanted so as to be substituted for a hard tissue in vivo,
A substrate of the hard tissue substitute material formed of a metal material is immersed in an alkaline aqueous solution containing alkali metal ions and / or alkaline earth metal ions, and the surface of the substrate contains the metal material and oxygen. An alkali treatment step for forming a film having an affinity for hard tissue;
A heating treatment step of heating the substrate after the alkali treatment step to increase the thickness and stability of the coating that is a treatment layer on the surface of the substrate;
With
The alkaline aqueous solution used in the alkaline treatment step is adjusted so that the concentration of metal ions other than the alkali metal ions and / or the alkaline earth metal ions in the alkaline aqueous solution is within a predetermined range. , Manufacturing method of hard tissue substitute material. It is a manufacturing method of the hard tissue substitute material according to claim 1,
The alkali aqueous solution used in the alkali treatment step is adjusted so that the metal ion concentration in the alkali aqueous solution is a saturated concentration, so that the metal ion concentration is within a predetermined range. A method for producing a hard tissue substitute material, which is characterized. A method for producing a hard tissue substitute material according to claim 1 or 2,
The method for producing a hard tissue substitute material, wherein the metal ion concentration adjusted in the alkaline aqueous solution used in the alkali treatment step is a metal ion concentration of the same kind as a metal element constituting the metal material. A method for manufacturing a hard tissue substitute material according to any one of claims 1 to 3,
The metal material is titanium or a titanium alloy,
The method for producing a hard tissue substitute material, wherein the film contains an alkali titanate. It is a manufacturing method of the hard tissue substitute material according to claim 4,
The alkaline aqueous solution used in the alkaline treatment step is adjusted so that the metal ion concentration in the alkaline aqueous solution is within a range of 1.3 mg / L to 1.6 mg / L. Manufacturing method of tissue substitute material. A treatment solution used in the method for producing a hard tissue substitute material according to any one of claims 1 to 5,
The substrate of the hard tissue substitute material formed of a metal material is immersed in an alkaline aqueous solution containing alkali metal ions and / or alkaline earth metal ions, and the surface of the substrate contains the metal material and oxygen. In the alkaline treatment step of forming a film having affinity for hard tissue, the alkaline aqueous solution is adjusted so that the concentration of metal ions other than the alkali metal ions and / or the alkaline earth metal ions is within a predetermined range. A processing solution, characterized in that it is used.

Images