JP2011019786A - Titanium oxide film material and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a titanium oxide film material having high bone conduction performance. <P>SOLUTION: This titanium oxide film material includes a titanium part containing titanium, and a covering part covering the titanium part. The covering part contains low crystalline anatase type titanium oxide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a titanium oxide coating material coated with titanium oxide. The present invention particularly relates to a titanium oxide coating material having high osteoconductivity.

  Titanium is excellent in mechanical properties such as strength, corrosion resistance, and heat resistance, and is used in various fields. In these fields, a technique for coating the surface of titanium with titanium oxide has been developed in order to improve or impart characteristics according to applications.

  For example, titanium is known to have excellent biocompatibility and is used as a biomaterial, particularly a bone substitute material. Patent Document 1 discloses a technique for coating the surface of titanium with titanium oxide using an anodic oxidation method in order to further improve the biocompatibility.

  In the anodizing method of Patent Document 1, an electrolytic solution of 1 M or less sulfuric acid, phosphoric acid, or sodium hydroxide is used. The titanium oxide film produced with the electrolytic solution in this concentration range is a highly crystalline anatase type excellent in crystallinity. As disclosed in Patent Document 1, when spark discharge or heat treatment is performed, highly crystalline anatase-type titanium oxide can be transformed into rutile-type titanium oxide. Patent Document 1 discloses a highly crystalline anatase-type titanium oxide film and a highly crystalline anatase-type titanium oxide film and a rutile-type titanium oxide film.

JP 2003-190272 A

  All of the titanium oxide films disclosed in Patent Document 1 are composed of a highly crystalline anatase type or rutile type having excellent crystallinity. Patent Document 1 makes no mention of the crystallinity of titanium oxide and does not disclose a titanium oxide film having low crystallinity.

  An object of the technology disclosed in the present specification is to provide a titanium oxide film material having a novel titanium oxide film and a method for producing the same.

  The titanium oxide disclosed in the present specification is characterized by being a low crystalline anatase type having low crystallinity. All of the conventional titanium oxides are highly crystalline anatase type or rutile type. This is because, as disclosed in Patent Document 1, a highly crystalline titanium oxide film is formed by an anodic oxidation method using an electrolytic solution of 1 M or less. Usually, the electrolytic solution used in the anodizing method is considered to be sufficient if it has a concentration necessary for the anodic oxidation reaction to proceed, and an electrolytic solution that is more concentrated than necessary is not used. However, the present inventors have produced a novel low-crystalline anatase-type titanium oxide film by carrying out an anodic oxidation method using a high-concentration electrolytic solution exceeding the scope of common technical knowledge. Successful.

  The titanium oxide coating material disclosed in this specification includes a titanium portion containing titanium and a covering portion that covers the titanium portion. The covering portion has a low crystalline anatase type titanium oxide. A titanium oxide coating material coated with a low crystalline anatase type titanium oxide can be used in various applications and can provide a useful effect in various applications. Especially, the titanium oxide film material which has a low crystalline anatase type titanium oxide is useful as a biomaterial.

  The titanium oxide of the titanium oxide film material disclosed in the present specification preferably has an anatase type peak having a half width of 7.0 degrees or more in X-ray diffraction (XRD). The low-crystalline anatase-type titanium oxide having such physical properties is first realized by the anodizing method disclosed in this specification. X-ray diffraction is preferably based on thin film X-ray diffraction.

  The titanium oxide coating material disclosed in the present specification is preferably used by being implanted in bone in a living body. The titanium oxide coating material disclosed herein has been demonstrated to have excellent osteoconductivity.

  The method for producing a titanium oxide film material disclosed in the present specification includes an anodizing step of anodizing a material having a titanium portion containing titanium at least on the surface layer. The anodizing step is performed under the condition that an electrolytic solution having a phosphoric acid concentration of 4M or more is used and no spark discharge occurs. According to this anodic oxidation method, at least the surface of a material having a titanium portion containing titanium in the surface layer is coated with low crystalline anatase type titanium oxide.

  In the anodic oxidation step, it is preferable to increase the applied voltage over time. By increasing the applied voltage over time, it is easy to perform anodic oxidation under conditions where no spark discharge occurs.

  According to the technology disclosed in the present specification, a novel titanium oxide coating material having a low crystalline anatase type titanium oxide is provided. Furthermore, this titanium oxide coating material has the property of high osteoconductivity, and is particularly useful in applications that are used by being implanted in bones in vivo. Further, according to the technique disclosed in the present specification, a novel anodizing method is provided in which the surface of a titanium portion is coated with a low crystalline anatase type titanium oxide.

An outline of a configuration of an electrolysis apparatus used in an anodic oxidation method is shown. The top view of the electrolytic cell of the electrolytic device of FIG. 1 is shown. The X-ray-diffraction result of the titanium oxide produced by the anodic oxidation method using the electrolyte solution of different phosphoric acid concentration is shown. The relationship between the phosphoric acid concentration of an electrolytic solution and the half width in the X-ray diffraction of titanium oxide is shown. The X-ray-diffraction result of the titanium oxide produced by the anodic oxidation method using a different ultimate voltage is shown. The result of the bone conductivity evaluation (cortical bone) of the titanium oxide coating material produced by the anodic oxidation method using the electrolytic solution of different phosphoric acid concentration is shown. The result of the bone conductivity evaluation (cancellous bone) of the titanium oxide coating material produced by the anodic oxidation method using the electrolyte solution of different phosphoric acid concentration is shown.

  The technology disclosed in the present specification provides a titanium oxide coating material having a low crystalline anatase type titanium oxide and a method for producing the same. The titanium oxide coating material disclosed in the present specification can be used in various applications in which titanium oxide is used, for example, biomaterials, photocatalytically active materials, and photoelectric conversion element materials. In particular, since the titanium oxide coating material disclosed in this specification has high osteoconductivity, it is desirable to be used for an application utilizing the characteristics. The titanium oxide coating material disclosed in the present specification is desirably used in, for example, an application to be implanted in bone, and specifically, desirably used as a bone screw, bone root, or hip joint stem. . Conventionally, these materials for implanting bone cannot be firmly adhered to bone unless used in combination with bone cement. The use of bone cement has a risk of inducing shock symptoms, and the operation using bone cement has a problem that it depends largely on the skill of the executor. The titanium oxide coating material disclosed in the present specification has extremely high osteoconductivity, and can be firmly bonded to bone without using bone cement. Therefore, the titanium oxide coating material disclosed in this specification is extremely useful as a material for implanting bone. In addition, since the osteoconductivity is high, it is suggested that the adhesiveness with a certain kind of cell is high, and it can be used as a scaffold for adhering that kind of cell. Specifically, it is desirable to be used in a culture apparatus for culturing certain cells two-dimensionally or three-dimensionally. Thus, the titanium oxide coating material disclosed herein is a novel material that provides useful effects in various applications.

  Hereinafter, preferred embodiments of the titanium oxide film material and the manufacturing method thereof disclosed in this specification will be described.

(Titanium oxide coating material)
The titanium oxide coating material disclosed in this specification includes a titanium portion containing titanium and a covering portion that covers the titanium portion. The titanium portion may be any material that contains at least titanium as a constituent atom, and typically, titanium or a titanium alloy is desirably used as the material. Moreover, the titanium part should just exist in the at least surface layer of a base. The entire base is preferably a titanium part. It is desirable that the covering portion covers the entire surface of the base portion.

  Furthermore, it is preferable that the coating portion contains a low crystalline anatase type titanium oxide. In the present specification, the “low crystalline anatase” refers to an anatase exhibiting specific crystallinity specified by X-ray diffraction analysis (XRD). The “low crystalline anatase” is different from an amorphous material having no specific peak in X-ray diffraction analysis, and is a crystalline material having a sharp (shallow) peak corresponding to the diffraction surface (101 surface) of anatase. Unlike anatase, it shows an amorphous-like peak. Here, the amorphous-like peak means that the half-value width of the peak of the specific diffraction surface of anatase is 1.0 degree or more. The half width of the amorphous-like peak is preferably 4.0 degrees or more, more preferably 5.0 degrees or more, still more preferably 6.0 degrees or more, and still more preferably 7.0 degrees or more. It is. In order to determine whether or not the anatase-type titanium oxide contained in the coating is low crystalline, the half-width at the peak indicating the 101 plane of anatase (typically appearing at 2θ = 25.28 °) is used as an index. It can be.

  The film thickness of the titanium oxide film is appropriately adjusted according to the application. For example, the thickness can be about 100 nm to 200 nm.

  The covering portion may contain a material other than the low crystalline anatase type titanium oxide. For example, the covering portion may include a kind of material containing atoms different from titanium oxide, titanium oxide having a different crystal structure, and / or titanium oxide having a different crystallinity. Specifically, the coating portion may contain highly crystalline anatase-type titanium oxide. That is, a low crystalline anatase type titanium oxide and a highly crystalline anatase type titanium oxide may be mixed in the covering portion. In this case, in X-ray diffraction analysis (XRD), a peak of low-crystal anatase-type titanium oxide and a peak of high-crystal anatase-type titanium oxide are observed. For example, in X-ray diffraction analysis (XRD), the peak of anatase type titanium oxide having a half width of 5.0 degrees or more and the anatase type having a half width of less than 5.0 degrees (preferably less than 1.0 degree). It is desirable to observe a titanium oxide peak. Further, the covering portion may contain a high crystal rutile type or brookite type titanium oxide and a low crystal type rutile type or brookite type titanium oxide.

  It is preferable that the entire coating portion is composed of a single phase of a low crystal anatase type titanium oxide coating. Here, the “single phase” means a state composed of only one type of crystal phase. In this case, in the X-ray diffraction analysis (XRD), only a peak of a low crystal anatase type titanium oxide is observed. For example, in X-ray diffraction (XRD), the full width at half maximum of the peak representing the 101 plane of anatase is not less than the predetermined value (4.0 degrees or more, preferably 5.0 degrees or more, more preferably 5.0 degrees or more). Furthermore, it is desirable that the peak of the 101 plane of anatase-type titanium oxide at 6.0 degrees or more, more preferably 7.0 degrees or more is observed. The titanium oxide film is preferably an anodized film produced by an anodic oxidation method.

(Anodic oxidation method)
The method for producing a titanium oxide film material disclosed in the present specification includes an anodizing step of anodizing a material having a titanium portion containing titanium at least on the surface layer. In the anodizing step, it is desirable to use an electrolytic solution containing phosphoric acid. Phosphoric acid is a major component of bone and is suitable for making biomaterials, especially materials for bone implants.

  In the anodic oxidation step, a film containing a low crystalline anatase-type titanium oxide can be formed on the surface of the titanium portion by adjusting the phosphoric acid concentration and voltage application conditions. According to the research results of the present inventors, the higher the phosphoric acid concentration, the easier it is to form a low-crystalline anatase-type titanium oxide film, and the formation of highly crystalline anatase-type titanium oxide is suppressed. A single-phase low-crystalline anatase-type titanium oxide film is easily formed. Furthermore, the higher the ultimate voltage to be applied, the easier it is to form a low crystalline anatase-type titanium oxide film. Thus, for example, when the phosphoric acid concentration is constant, the higher the ultimate voltage, the lower the anatase-type titanium oxide film that is produced. In addition, when the ultimate voltage is constant, the higher the phosphoric acid concentration, the lower the anatase-type titanium oxide film that is produced. The conventional anodic oxidation method uses a low phosphoric acid concentration range, and such a low concentration phosphoric acid solution can provide only a highly crystalline anatase-type titanium oxide film. It has not been known at all that a low crystalline anatase-type titanium oxide film can be obtained by carrying out the anodic oxidation method under a condition where the phosphoric acid concentration is high.

  In order to give an appropriate phosphoric acid concentration in the anodizing step, an appropriate phosphoric acid source that dissolves in water or the like and generates phosphate ions may be used. Phosphoric acid source selected from phosphoric acid and sodium phosphate, potassium phosphate, calcium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc. Phosphates that can be used. As phosphoric acid, only 1 type may be used among these and it may use it in combination of 2 or more types. The phosphate source is preferably phosphoric acid. The aqueous phosphoric acid solution itself can satisfy pH conditions suitable for the anodic oxidation step of the present method. That is, it can be used in the anodizing step while avoiding or suppressing pH adjustment. Conversely, when other phosphates are used, it may be necessary to adjust the pH with an acid or an alkali. In addition, by using phosphoric acid, it is possible to avoid or suppress the presence of metal ions such as alkali metal ions and alkaline earth metal ions in the electrolytic aqueous solution, so when these metal ions adversely affect osteoconductivity The adverse effect can be avoided or suppressed.

  For example, the phosphoric acid concentration is preferably 2M or more, more preferably 3M or more, and further preferably 4M or more. As the phosphoric acid concentration is higher, the applied voltage condition can be relaxed. When the phosphoric acid concentration is 4 M or more, the low crystallinity of the resulting anatase-type titanium oxide tends to be constant. For example, when the phosphoric acid concentration is 2 M or more and less than 4 M, an ultimate voltage of 170 V or more, more preferably 180 V or more, and still more preferably 200 V or more, produces a low crystalline anatase-type titanium oxide film. Cheap. When the phosphoric acid concentration is 4 M or more, a low crystalline anatase-type titanium oxide film tends to be formed when the ultimate voltage is 170 V or more, more preferably 180 V or more, and even more preferably 190 V or more. In addition, it is desirable that the anodizing step be performed under conditions that do not cause spark discharge in order to suppress the generation of rutile titanium oxide.

  In addition, in the anodizing step disclosed in this specification, it is possible to adjust the ultimate voltage to be applied and the boosting speed of the applied voltage. Such adjustment of the application condition is useful for obtaining a low crystalline anatase-type titanium oxide film while suppressing spark discharge. For example, the lower the pressure increase rate, the better. However, when it is 0.1 V / sec or less, spark discharge can be effectively suppressed.

  In addition, when the voltage application condition is constant, a highly crystalline anatase-type titanium oxide film is formed when the phosphoric acid concentration is low, and a low-crystalline anatase type is used when the phosphoric acid concentration is high. In addition to the formation of a titanium oxide film, it is known that a film containing a mixture of high crystalline and low crystalline anatase-type titanium oxide is formed when the phosphoric acid concentration is in a medium concentration range. Therefore, in the anodic oxidation process disclosed in this specification, a highly crystalline and low crystalline anatase-type titanium oxide are mixed by appropriately setting the phosphoric acid concentration and voltage application conditions, and a film containing these. Can also be formed. The medium phosphoric acid concentration for obtaining such a mixed crystal titanium oxide film is realized for the first time at a concentration higher than at least 1 M conventionally used. Typically, such a mixed crystal type titanium oxide film can be easily formed in a phosphoric acid concentration range of 2.0 M or more and 4.0 M or less. The voltage application conditions can be appropriately set by evaluating the crystallinity of the obtained titanium oxide coating film by X-ray diffraction analysis. For example, the boosting speed can be 0.1 V / sec, and the ultimate voltage can be 200 V.

(Titanium oxide coating material and manufacturing method thereof)
Hereinafter, an embodiment that embodies the technology disclosed in this specification will be described with reference to the drawings. In FIG. 1, the outline | summary of a structure of the electrolyzer 10 for an anodic oxidation method is shown. As shown in FIG. 1, the electrolyzer 10 includes a DC power supply device 12, an electrolyzer 14, and a thermostat 16.

  The DC power supply device 12 has an anode terminal 12a and a cathode terminal 12b, and generates a DC voltage between the anode terminal 12a and the cathode terminal 12b. The DC power supply device 12 has a control unit (not shown). The control unit is configured to be able to control the magnitude of the DC voltage to be generated and the boosting speed.

FIG. 2 shows a top view of the electrolytic cell 14 of the electrolysis apparatus 10 of FIG. As shown in FIG. 2, the electrolytic cell 14 has a cylindrical shape. On the inner wall of the electrolytic cell 14, four cathode electrode plates 24a, 24b, 24c, and 24d made of platinum are provided. The cathode electrode plates 24 a and 24 c are arranged symmetrically with respect to the center of the electrolytic cell 14, and the cathode electrode plates 24 b and 24 d are arranged symmetrically with respect to the center of the electrolytic cell 14. The central angles of adjacent cathode electrode plates 24 are all equiangular, and in this example, 90 °. As shown in FIG. 1, the four cathode electrode plates 24 a, 24 b, 24 c, 24 d are electrically connected to the cathode terminal 12 b of the DC power supply device 12. The electrolytic cell 14 is filled with an electrolytic aqueous solution of phosphoric acid (H ₃ PO ₄ ). The cathode electrode plate 24 is more desirably provided in a round along the inner wall of the electrolytic cell 14.

  As shown in FIG. 1, the thermostatic chamber 16 is filled with water, and the temperature of the water can be adjusted to be constant. In this embodiment, the temperature of the water in the thermostatic chamber 16 is adjusted to 20 ° C.

Next, the procedure of the anodic oxidation method performed using the above electrolysis apparatus 10 will be described.
First, a sample 22 (hereinafter referred to as a titanium sample) made of cylindrical titanium having a diameter of 5 mm was prepared. Next, as shown in FIGS. 1 and 2, the titanium sample 22 was electrically connected to the anode terminal 12 a of the DC power supply device 12, and the titanium sample 22 was disposed at the center of the electrolytic cell 14.

  Next, a DC voltage was applied between the titanium sample 22 and the cathode electrode plate 24 using the DC power supply device 12. The applied DC voltage was boosted from 0 V at a predetermined boosting speed and boosted to a desired ultimate voltage. While the applied voltage was boosted from 0 V to the ultimate voltage, the boosting rate of the applied voltage was adjusted to 0.1 V / sec so that no spark discharge occurred. Actually, no spark discharge occurred in all the titanium samples 22. When the voltage was boosted to the desired ultimate voltage, the application of the DC voltage was stopped. The titanium sample 22 was taken out of the electrolytic cell 14 and then washed with water and air-dried. The titanium sample 22 produced by such a procedure had a surface coated with a single-phase titanium oxide film, and had a thickness of about 100 to 200 nm.

  In this example, several titanium samples 22 were produced in which the phosphoric acid concentration and the ultimate voltage of the electrolytic solution were changed. Table 1 shows the prepared titanium sample 22 in an organized manner.

  Next, the crystal structure and surface roughness (Ra) of the titanium oxide film of the titanium sample 22 were evaluated. The crystal structure was evaluated by X-ray diffraction using CuKα rays. The surface roughness (Ra) was evaluated by surface analysis in a range of 150 μm × 112 μm with a non-contact surface roughness meter using a laser microscope.

  Table 2 shows the full width at half maximum of the titanium oxide film and the surface roughness (Ra) of the titanium oxide film of the titanium sample 22 obtained by X-ray diffraction analysis.

  FIG. 3 shows the X-ray diffraction analysis results of (a) to (f), (h), (i), (k), and (l) of the titanium sample 22 described above. The diffraction angle (2θ) of 101 surface of anatase type titanium oxide is 25.28 °, and the diffraction angle (2θ) of rutile type 110 surface titanium oxide is 27.45 °. As shown in FIG. 3, the titanium oxide coatings of all titanium samples 22 were anatase type titanium oxide, and no rutile type titanium oxide was observed. Further, in (a) to (c) of the titanium sample 22, a diffraction peak of one 101 plane having a small half-value width was observed, and the titanium oxide film was a highly crystalline anatase type titanium oxide. . In (d) and (e) of the titanium sample 22, both a 101-plane diffraction peak with a small half-value width and a 101-plane diffraction peak with a large half-value width are observed, and the titanium oxide film has a highly crystalline anatase type. Of titanium oxide and low-crystalline anatase-type titanium oxide. In (f), (h), (i), (k), and (l) of the titanium sample 22, a 101-plane diffraction peak having a large half-value width is observed, and the titanium oxide film has a low crystalline anatase. It was a type of titanium oxide.

  FIG. 4 shows the full width at half maximum obtained by the X-ray diffraction analysis of FIG. As shown in FIG. 4, the crystallinity of the titanium oxide film of the titanium sample 22 depends on the phosphoric acid concentration of the electrolytic solution. In the range where the phosphoric acid concentration is low (less than 2M), the titanium oxide film of the titanium sample 22 is a highly crystalline anatase type titanium oxide. When the phosphoric acid concentration is in the medium concentration range (2 M or more and less than 4 M), the titanium oxide film of the titanium sample 22 is a mixture of high crystalline anatase type titanium oxide and low crystalline anatase type titanium oxide. When the phosphoric acid concentration is in a high concentration range (4 M or more), the titanium oxide film of the titanium sample 22 is a low crystalline anatase type titanium oxide. Thus, it was found that the crystallinity of the titanium oxide film of the titanium sample 22 transitions to three states depending on the phosphoric acid concentration. As shown in FIG. 4, when the phosphoric acid concentration is 4M or more, the half-value width converges between 7.0 and 8.0. In order to obtain a low crystalline anatase type titanium oxide film, it was found that a phosphoric acid concentration of 4 M or more is preferable.

  Further, as shown in Table 2 above, it was found that the surface roughness (Ra) increases as the phosphoric acid concentration increases. In each of the titanium samples 22 coated with the low crystalline anatase type titanium oxide film, the surface roughness (Ra) exceeds 0.3 μm.

  Next, the effect of the ultimate voltage was examined. When the electrolytic solution was constant, the effect of the ultimate voltage on the crystallinity of the anodized film was examined. FIG. 5 shows the X-ray diffraction analysis results of (m), (n), and (i) of the titanium sample 22. For reference, a chart in the vicinity of the 101-plane peak (2θ = 25.28 °) obtained by X-ray diffraction analysis of (a) of the titanium sample 22 is also shown. As shown in FIG. 5, when the ultimate voltage was 100 V, no peak indicating crystallinity was observed. When the ultimate voltage was 160 V, it was similar to the peak on the 101 plane of FIGS. 3 (d) and 3 (e). When the ultimate voltage was 200 V, the titanium oxide film of the titanium sample 22 was a low crystalline anatase type titanium oxide. From this result, it was confirmed that the crystallinity of the titanium oxide film of the titanium sample 22 depends on the ultimate voltage, and the higher the ultimate voltage, the lower the crystalline titanium oxide.

(Evaluation of osteoconductivity of titanium oxide coating material)
Next, the osteoconductivity of the titanium sample 22 produced in the above example was evaluated. For evaluation of osteoconductivity, a titanium sample 22 was implanted in the tibia of a rat, and follow-up was performed 14 days after the implantation. Osteoconductivity was evaluated by how much bone tissue adhered to the surface of the titanium sample 22. Specifically, the rat tibia is removed 14 days after implantation, and a cross section of the rat tibia in which the titanium sample 22 is implanted is prepared. In this cross section, the titanium sample 22 and the rat tibia contact each other. Of the total length, the ratio of the length of the adhered bone tissue was calculated. 6 and 7 show the bone conductivity of the titanium sample 22 (a), (b), (c), (g), (j), and the polished titanium obtained by polishing the surface of metal titanium. Show. FIG. 6 shows osteoconductivity in the cortical bone of the rat tibia. FIG. 7 shows osteoconductivity in cancellous bone of rat tibia. Table 3 also shows the results of the skeleton conductivity and the surface roughness.

  As described above, the titanium oxide coatings (g) and (j) of the titanium sample 22 are low crystalline anatase type titanium oxide. As shown in Table 3 and FIGS. 6 and 7, it can be seen that (g) and (j) of the titanium sample 22 are clearly improved in osteoconductivity as compared with the other samples. From this result, it was confirmed that low crystalline anatase-type titanium oxide greatly contributes to osteoconductivity. In addition, as shown in FIG. 6, (g) and (j) of the titanium sample 22 have an osteoconductivity of more than 30% in the cortical bone and are firmly bonded to the cortical bone. I understand. Adhesion with cortical bone is an important indicator for the stable fixation of the implant material in vivo. From the result that (g) and (j) of the titanium sample 22 have an osteoconductivity exceeding 30%, the titanium oxide coating material coated with the low crystalline anatase type titanium oxide coating is embedded in the bone. It was suggested that it is useful as a planting material.

Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.
The technical elements described in this specification or the drawings exhibit technical usefulness alone or in various combinations, and are not limited to the combinations described in the claims at the time of filing. In addition, the technology exemplified in this specification or the drawings can achieve a plurality of objects at the same time, and has technical usefulness by achieving one of the objects.

10: Electrolyzer 12: DC power supply device 12a: Anode terminal 12b: Cathode terminal 14: Electrolyzer 16: Thermostatic chamber 22: Titanium sample 24: Cathode electrode plate

Claims (6)

A titanium part containing titanium;
And a covering portion that covers the titanium portion,
The said coating | coated part is a titanium oxide film material containing a low crystalline anatase type titanium oxide.   2. The titanium oxide film material according to claim 1, wherein the titanium oxide has an anatase type peak having a half width of 7.0 degrees or more in X-ray diffraction (XRD).   The titanium oxide coating material according to claim 1 or 2, which is used by being implanted in bone in a living body. A method for producing a titanium oxide coating material comprising:
Comprising an anodizing step for anodizing a material having at least a titanium portion containing titanium in the surface layer;
The anodic oxidation step is a manufacturing method in which an electrolytic solution having a phosphoric acid concentration of 4 M or more is used and a spark discharge does not occur.   The manufacturing method according to claim 4, wherein in the anodizing step, the applied voltage is increased with time.   The manufacturing method according to claim 4 or 5, wherein the titanium oxide coating material is used by being implanted in a bone in a living body.

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