JPH10287411A - Formation of hydroxyapatite film - Google Patents
Formation of hydroxyapatite filmInfo
- Publication number
- JPH10287411A JPH10287411A JP10522697A JP10522697A JPH10287411A JP H10287411 A JPH10287411 A JP H10287411A JP 10522697 A JP10522697 A JP 10522697A JP 10522697 A JP10522697 A JP 10522697A JP H10287411 A JPH10287411 A JP H10287411A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- aqueous solution
- composition
- apatite
- hydroxyapatite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、水酸アパタイト
膜を形成する方法に属する。この方法は、有機高分子か
らなる基材に水酸アパタイト膜を形成するのに適してい
る。この方法により水酸アパタイト膜が形成された有機
高分子基材は、フィルターや口鼻用マスクに好適に利用
されうる。[0001] The present invention relates to a method for forming a hydroxyapatite film. This method is suitable for forming a hydroxyapatite film on a substrate made of an organic polymer. The organic polymer base material on which the hydroxyapatite film is formed by this method can be suitably used for a filter or a mask for a mouth and a nose.
【０００２】[0002]
【従来の技術】生体インプラント基材等のある対象物に
アパタイト膜を形成する方法として、基材上に予めアパ
タイトの核形成を誘導するサイトを導入し、これを疑似
体液中に浸漬してアパタイト核を成長させる方法が知ら
れている。この方法は、高温での処理を必要としないの
で、有機高分子のような耐熱性の低い基材にも適用でき
る上、生体内のアパタイトと同じ性質のアパタイトを形
成できる利点を有する。核誘導サイトの導入手段とし
て、（ａ）生体活性ガラスとともにカルシウムイオン及
びリン酸イオンを含む水溶液に基材を浸漬する（特開平
６−２９３５０６号他）、（ｂ）基材をリン酸エステル
化する（ジャーナル オブ マテリアルズサイエンス：
マテリアルズ イン メディスン ６（１９９５）４０
９−４１９頁）等が提案されている。2. Description of the Related Art As a method of forming an apatite film on a certain object such as a biological implant substrate, a site for inducing apatite nucleation is introduced into the substrate in advance, and the site is immersed in a simulated body fluid to obtain apatite. Methods for growing nuclei are known. Since this method does not require treatment at high temperature, it can be applied to a substrate having low heat resistance such as an organic polymer and has an advantage that apatite having the same properties as apatite in a living body can be formed. As a means for introducing a nucleus induction site, (a) immersing a substrate in an aqueous solution containing calcium ions and phosphate ions together with bioactive glass (Japanese Patent Application Laid-Open No. 6-293506, etc.); Suru (Journal of Materials Science:
Materials in Medicine 6 (1995) 40
9-419).
【０００３】[0003]
【発明が解決しようとする課題】しかし、導入手段ａ
は、ガラスを溶融し、これを粉砕し篩い分けすることに
より、ガラス粒子を得る準備が必要である。また、導入
手段ｂは、基材をリン酸エステル化し、その後部分的な
加水分解をする工程が必要である。従って、いずれにし
ても面倒な操作をしなければならない。However, the introduction means a
It is necessary to prepare glass particles by melting glass, crushing and sieving the glass. In addition, the introduction means b requires a step of subjecting the base material to phosphoric esterification and then performing a partial hydrolysis. Therefore, in any case, a troublesome operation must be performed.
【０００４】それ故、この発明の目的は、耐熱性の基材
に対してはもちろん、耐熱性の低い基材に対しても簡単
な工程の組み合わせにより、生体内のアパタイトと同じ
性質の水酸アパタイト膜を形成することにある。[0004] Therefore, an object of the present invention is to provide a hydroxyl compound having the same properties as apatite in a living body by combining a simple process with a substrate having low heat resistance as well as a substrate having low heat resistance. It is to form an apatite film.
【０００５】[0005]
【課題を解決するための手段】その目的を達成するため
に、この発明の水酸アパタイト膜の形成方法は、以下の
第一工程及び第二工程の２つの工程を経るだけで足り
る。第一工程では、基材をカルシウムＣａとリンＰの元
素を含む第一の水溶液と接触させた後、乾燥する。これ
により、水溶液中に含まれるイオンが塩として基材表面
にて結晶化する。含有イオンのうち、Ｃａ2+及びＨＰＯ
4 2-についてはＣａＨＰＯ4等のリン酸カルシウムとして
析出する。水溶液中にＮａ+、Ｋ+、Ｃｌ-等が含まれる
場合はおそらくＮａＣｌ、ＫＣｌ等の塩も析出する。In order to achieve the object, the method for forming a hydroxyapatite film of the present invention only requires the following two steps, a first step and a second step. In the first step, the substrate is brought into contact with a first aqueous solution containing the elements of calcium Ca and phosphorus P, and then dried. Thereby, the ions contained in the aqueous solution are crystallized as salts on the surface of the base material. Of the ions contained, Ca 2+ and HPO
4 for 2 precipitates as calcium phosphate, such as CaHPO 4. When Na + , K + , Cl − and the like are contained in the aqueous solution, salts such as NaCl and KCl are probably precipitated.
【０００６】続く第二工程では、第一工程を経た基材
を、飽和ないし過飽和濃度のアパタイト成分を含む第二
の水溶液と接触させる。このとき、ＮａＣｌ、ＫＣｌ等
は水に可溶であるので、早期に溶液中に溶け出すが、Ｃ
ａＨＰＯ4は難溶性であるので、基材上に残り、アパタ
イト核を誘導するサイトとなる。そして、第二の水溶液
がアパタイト成分について飽和ないし過飽和になってい
るので、そのアパタイト誘導サイトによってアパタイト
核が形成され、そのアパタイト核が溶液中のＣａ2+及び
ＨＰＯ4 2-を取り込んで成長し、水酸アパタイト膜が形
成される。[0006] In the subsequent second step, the substrate having passed through the first step is brought into contact with a second aqueous solution containing a saturated or supersaturated apatite component. At this time, since NaCl, KCl, etc. are soluble in water, they are dissolved in the solution at an early stage, but C
Since aHPO 4 is hardly soluble, it remains on the substrate and becomes a site for inducing apatite nuclei. Then, since the second aqueous solution is saturated or supersaturated with respect to the apatite component, an apatite nucleus is formed by the apatite induction site, and the apatite nucleus grows by taking in Ca 2+ and HPO 4 2- in the solution. Then, a hydroxyapatite film is formed.
【０００７】[0007]
【発明の実施の形態】基材の材質としては、金属、セラ
ミック、有機高分子など種々適用可能であるが、この発
明は、高温での処理を必要としないので、有機高分子に
広く適用できる点で特に有利である。第一の水溶液は、
カルシウムＣａとリンＰの元素を含む限り、特に限定さ
れず、例えば第二の水溶液と同じ組成のものでも良い。
第二の水溶液としては体液にできるだけ近い組成を有す
るものが好ましい。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Various materials such as metals, ceramics, and organic polymers can be used as the material of a base material. However, the present invention does not require a high-temperature treatment, and thus can be widely applied to organic polymers. It is particularly advantageous in that respect. The first aqueous solution is
It is not particularly limited as long as it contains the elements of calcium Ca and phosphorus P. For example, it may have the same composition as the second aqueous solution.
The second aqueous solution preferably has a composition as close as possible to the body fluid.
【０００８】第一工程で第一の水溶液と接触させながら
超音波を基材に照射した場合、基材の細部にも溶液が浸
入するので、これを乾燥すると基材細部にまでリン酸カ
ルシウムが付着する。よって、より均一に基材に水酸ア
パタイト膜を形成することができる。When the substrate is irradiated with ultrasonic waves while being brought into contact with the first aqueous solution in the first step, the solution penetrates into the details of the substrate, and when this is dried, calcium phosphate adheres to the details of the substrate. . Therefore, the hydroxyapatite film can be more uniformly formed on the substrate.
【０００９】基材の表面は親水性であることが好まし
い。基材の表面の濡れ性が悪いと、第一工程においてリ
ン酸カルシウムが均一に付着しにくいからである。疎水
性の基材の場合、第一工程の前にその表面を予め粗面化
することにより、水溶液に対する濡れ性を改善すると良
い。Preferably, the surface of the substrate is hydrophilic. If the wettability of the surface of the substrate is poor, it is difficult for calcium phosphate to adhere uniformly in the first step. In the case of a hydrophobic substrate, it is preferable to improve the wettability to an aqueous solution by roughening the surface in advance before the first step.
【００１０】第二の水溶液の温度は１０〜７０℃が好ま
しい。１０℃未満ではアパタイトの析出速度が極端に遅
くなる。他方、７０℃を超えると第三リン酸カルシウム
（ＴＣＰ）等の他の化合物が形成されるからである。最
も好ましいのは３０〜５０℃である。[0010] The temperature of the second aqueous solution is preferably from 10 to 70 ° C. Below 10 ° C., the deposition rate of apatite becomes extremely slow. On the other hand, when the temperature exceeds 70 ° C., other compounds such as tricalcium phosphate (TCP) are formed. Most preferred is 30-50 ° C.
【００１１】[0011]
【実施例】以下の各実施例の第一工程及び第二工程で使
用する水溶液として、表１に示す１６種類の組成の溶液
を準備した。なお、表中の数値の単位はｍｍｏｌ／リッ
トルである。EXAMPLES As an aqueous solution used in the first step and the second step of each of the following examples, solutions having 16 kinds of compositions shown in Table 1 were prepared. The units of the numerical values in the table are mmol / liter.
【００１２】[0012]
【表１】 [Table 1]
【００１３】−実施例１− この例では、第一工程と第二工程で同じ水溶液を用い
る。組成Ｎｏ．１の溶液のｐＨをトリスヒドロキシメチ
ルアミノメタンと塩酸で７．２に調製し、これを第一の
水溶液及び第二の水溶液とした。なお、この組成Ｎｏ．
１の溶液は疑似体液の組成に相当するものである。この
水溶液２０ｍｌに、基材となる１００％セルロースの織
物０．０３０ｇを浸漬した。水溶液を含んだ基材を取り
出し、そのまま６０℃で乾燥した（第一工程）。次に、
乾燥した基材を上記と同組成の水溶液２５０ｍｌに浸漬
し、３６．５℃の恒温槽中に２日間放置した（第二工
程）。Example 1 In this example, the same aqueous solution is used in the first step and the second step. Composition No. The pH of solution 1 was adjusted to 7.2 with trishydroxymethylaminomethane and hydrochloric acid, which were used as a first aqueous solution and a second aqueous solution. In addition, this composition No.
Solution 1 corresponds to the composition of the simulated body fluid. In 20 ml of this aqueous solution, 0.030 g of a 100% cellulose fabric serving as a base material was immersed. The substrate containing the aqueous solution was taken out and dried as it was at 60 ° C. (first step). next,
The dried substrate was immersed in 250 ml of an aqueous solution having the same composition as above and left in a thermostat at 36.5 ° C. for 2 days (second step).
【００１４】基材を取り出し６０℃で乾燥してＸ線回折
法により分析したところ、基材の表面の大部分に水酸ア
パタイト膜が形成されていることが確認された。基材の
重量は０．０３９ｇに増えていた。When the substrate was taken out, dried at 60 ° C. and analyzed by X-ray diffraction, it was confirmed that a hydroxyapatite film was formed on most of the surface of the substrate. The weight of the substrate increased to 0.039 g.
【００１５】−実施例２− 第一工程で基材を水溶液に浸漬中に周波数４７Ｈｚの超
音波を１０分間照射した以外は、実施例１と同一条件で
実施した。基材の全領域にわたって水酸アパタイト膜が
形成されていた。基材の重量は０．０４８ｇに増えてい
た。-Example 2-The first step was carried out under the same conditions as in Example 1, except that ultrasonic waves having a frequency of 47 Hz were irradiated for 10 minutes while the substrate was immersed in the aqueous solution. A hydroxyapatite film was formed over the entire area of the substrate. The weight of the substrate increased to 0.048 g.
【００１６】−実施例３〜７− 第一工程で組成Ｎｏ．１に代えて組成Ｎｏ．２〜６の各
溶液のｐＨを塩酸で６．８に調製し、これを第一の水溶
液とした以外は、実施例２と同一条件で実施した。基材
の全領域にわたって水酸アパタイト膜が形成されてい
た。基材の重量は水溶液の組成Ｎｏ．の順に０．０４
８、０．０４８、０．０４７、０．０４９、０．０４８
ｇに増えていた。Examples 3 to 7 In the first step, the composition No. In place of composition No. 1, The same procedure as in Example 2 was carried out except that the pH of each of the solutions 2 to 6 was adjusted to 6.8 with hydrochloric acid and this was used as the first aqueous solution. A hydroxyapatite film was formed over the entire area of the substrate. The weight of the substrate was determined by the composition No. of the aqueous solution. 0.04 in the order
8, 0.048, 0.047, 0.049, 0.048
g.
【００１７】−実施例８− これは、基材として疎水性材料を用い、その表面を粗面
化した後に第一工程に入る例である。基材となる２０×
１０×２ｍｍのＰＭＭＡ板の１主面を＃３２０のサンド
ペーパーで擦って粗面化した。なお、この時の基材の重
量は０．７９ｇであった。この粗面上に実施例１で用い
たものと同じ水溶液を滴下し、粗面全体に溶液を濡らし
た。その後、６０℃で乾燥した（第一工程）。次に実施
例１の第二工程と同様の操作を行った。基材を溶液から
取り出し、６０℃で乾燥してＸ線回折法により分析した
ところ、基材の粗面の全領域にわたり水酸アパタイト膜
が形成されていることが確認された。基材の重量は０．
８０ｇに増えていた。Example 8 This is an example in which a hydrophobic material is used as a base material, and the first step is performed after the surface is roughened. 20 × to be the base material
One main surface of a 10 × 2 mm PMMA plate was rubbed with # 320 sandpaper to roughen the surface. The weight of the substrate at this time was 0.79 g. The same aqueous solution as that used in Example 1 was dropped on the rough surface to wet the entire rough surface. Then, it dried at 60 degreeC (1st process). Next, the same operation as in the second step of Example 1 was performed. The substrate was taken out of the solution, dried at 60 ° C., and analyzed by X-ray diffraction. As a result, it was confirmed that a hydroxyapatite film was formed over the entire rough surface of the substrate. The weight of the substrate is 0.
It had increased to 80g.
【００１８】−比較例１〜５− 第一工程で組成Ｎｏ．１に代えて組成Ｎｏ．７〜１１の
各溶液を調製し、これを第一の水溶液とした以外は、実
施例２と同一条件で実施した。その結果、組成Ｎｏ．
７、８、９の溶液を使用した場合には、どの基材にも水
酸アパタイト膜が認められなかった。基材の重量はいず
れも増加していなかった。これは、第一の水溶液がリン
Ｐ成分を含んでいなかったので、第一工程でアパタイト
核誘導サイトができなかったためであると思われる。Comparative Examples 1 to 5 In the first step, the composition No. In place of composition No. 1, Example 7 was carried out under the same conditions as in Example 2 except that solutions 7 to 11 were prepared and used as a first aqueous solution. As a result, the composition No.
When the solutions 7, 8, and 9 were used, no hydroxyapatite film was observed on any of the substrates. None of the substrates had increased in weight. This is presumably because the first aqueous solution did not contain the phosphorus P component, and thus the apatite nucleus induction site was not formed in the first step.
【００１９】また、組成Ｎｏ．１０、１１の溶液を使用
した場合には、各基材に不均一な水酸アパタイト膜が形
成された。ただし、第二の水溶液を入れた容器の内面に
も水酸アパタイトが析出した。従って、基材表面への水
酸アパタイトの析出効率が悪かった。これは、第一工程
で基材に付着した塩化カルシウムが第二工程で水溶液中
に溶解し、第二の水溶液中のカルシウムイオン濃度が高
まり、強制的に析出沈殿したためであると考えられる。The composition No. When the solutions 10 and 11 were used, a non-uniform hydroxyapatite film was formed on each substrate. However, hydroxyapatite also precipitated on the inner surface of the container containing the second aqueous solution. Therefore, the deposition efficiency of hydroxyapatite on the substrate surface was poor. This is considered to be because calcium chloride attached to the base material in the first step was dissolved in the aqueous solution in the second step, the calcium ion concentration in the second aqueous solution was increased, and the precipitate was forcibly precipitated.
【００２０】−比較例６〜１０− 第一工程で組成Ｎｏ．１に代えて組成Ｎｏ．１２〜１６
の各溶液を調製し、これを第一の水溶液とした以外は、
実施例２と同一条件で実施した。その結果、組成Ｎｏ．
１２、１３、１４の溶液を使用した場合には、どの基材
にも水酸アパタイト膜が認められなかった。基材の重量
はいずれも増加していなかった。これは、第一の水溶液
がカルシウムＣａ成分を含んでいなかったので、第一工
程でアパタイト核誘導サイトができなかったためである
と思われる。Comparative Examples 6 to 10 In the first step, the composition No. In place of composition No. 1, 12-16
Except that each solution was prepared and used as a first aqueous solution.
The operation was performed under the same conditions as in Example 2. As a result, the composition No.
When the solutions 12, 13, and 14 were used, no hydroxyapatite film was observed on any of the substrates. None of the substrates had increased in weight. This is presumably because the first aqueous solution did not contain the calcium Ca component, and thus the apatite nucleus induction site was not formed in the first step.
【００２１】また、組成Ｎｏ．１５、１６の溶液を使用
した場合には、各基材に不均一な水酸アパタイト膜が形
成された。ただし、第二の水溶液を入れた容器の内面に
も水酸アパタイトが析出した。従って、基材表面への水
酸アパタイトの析出効率が悪かった。これは、第一工程
で基材に付着したリン酸カリウムが第二工程で水溶液中
に溶解し、第二の水溶液中のリン酸イオン濃度が高ま
り、強制的に析出沈殿したためであると考えられる。The composition No. When the solutions 15 and 16 were used, a non-uniform hydroxyapatite film was formed on each substrate. However, hydroxyapatite also precipitated on the inner surface of the container containing the second aqueous solution. Therefore, the deposition efficiency of hydroxyapatite on the substrate surface was poor. This is considered to be because potassium phosphate attached to the base material in the first step was dissolved in the aqueous solution in the second step, and the phosphate ion concentration in the second aqueous solution was increased, forcibly precipitated and precipitated. .
【００２２】[0022]
【発明の効果】以上のように、この発明によれば、低温
で簡単に水酸アパタイト膜を形成できるので、得られる
水酸アパタイトは生体内のそれに近似している上、成形
の容易な有機高分子を基材として利用することができ
る。As described above, according to the present invention, a hydroxyapatite film can be easily formed at a low temperature, so that the obtained hydroxyapatite is similar to that in a living body and is easy to mold. Polymers can be used as substrates.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河本 ゆかり 埼玉県浦和市田島４丁目40番７号 ルエス ト浦和105号室 (72)発明者 西澤 かおり 愛知県尾張旭市吉岡町２丁目３番地の27 (72)発明者 永田 夫久江 愛知県名古屋市北区中丸町１丁目１番地 中丸団地１棟804号 (72)発明者 墨 秦志 愛知県名古屋市瑞穂区高辻町14番18号 日 本特殊陶業株式会社内 (72)発明者 岡田 光史 愛知県名古屋市瑞穂区高辻町14番18号 日 本特殊陶業株式会社内 (72)発明者 奥山 雅彦 愛知県名古屋市瑞穂区高辻町14番18号 日 本特殊陶業株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yukari Kawamoto 4-40-7 Tajima, Urawa City, Saitama Ruest Urawa Room 105 (72) Inventor Kaori Nishizawa 2-3-3 Yoshiokacho, Owariasahi City, Aichi Prefecture 27-27 72) Inventor Nagata Yukue 1-1-1, Nakamaru-cho, Kita-ku, Nagoya-shi, Aichi Prefecture Nakamaru housing complex, 804 (72) Inventor Sumi Hata 14-18, Takatsuji-cho, Mizuho-ku, Nagoya-shi, Aichi Japan Inside the company (72) Inventor Mitsumi Okada 14-18 Takatsuji-cho, Mizuho-ku, Nagoya-shi, Aichi Japan Inside (72) Inventor Masahiko Okuyama 14-18 Takatsuji-cho, Mizuho-ku, Nagoya-shi, Aichi Japan Ceramics Co., Ltd.
Claims (6)
む第一の水溶液と接触させた後、乾燥する第一工程と、 第一工程を経た基材を、飽和ないし過飽和濃度のアパタ
イト成分を含む第二の水溶液に接触させる第二工程とを
含むことを特徴とする水酸アパタイト膜の形成方法。1. A first step of contacting a base material with a first aqueous solution containing elements of calcium Ca and phosphorus P, followed by drying; and subjecting the base material after the first step to an apatite component having a saturated or supersaturated concentration. And a second step of contacting the aqueous solution with a second aqueous solution containing:
超音波を基材に照射する請求項１に記載の方法。2. The method according to claim 1, wherein the substrate is irradiated with ultrasonic waves while being brought into contact with the first aqueous solution in the first step.
２に記載の方法。3. The method according to claim 1, wherein the substrate has a hydrophilic surface.
いずれかに記載の方法。4. The method according to claim 1, wherein the substrate comprises an organic polymer.
予備工程を経る請求項１〜４のいずれかに記載の方法。5. The method according to claim 1, wherein a preliminary step of roughening the surface of the substrate is performed before the first step.
請求項１〜５のいずれかに記載の方法。6. The method according to claim 1, wherein the temperature of the second aqueous solution is 10 to 70 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10522697A JPH10287411A (en) | 1997-04-07 | 1997-04-07 | Formation of hydroxyapatite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10522697A JPH10287411A (en) | 1997-04-07 | 1997-04-07 | Formation of hydroxyapatite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10287411A true JPH10287411A (en) | 1998-10-27 |
Family
ID=14401761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10522697A Pending JPH10287411A (en) | 1997-04-07 | 1997-04-07 | Formation of hydroxyapatite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10287411A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100353141B1 (en) * | 1998-09-17 | 2002-09-18 | 주식회사 오스코텍 | Method for preparation of the supersaturated solution of calcium phosphate and the thin film of calcium phosphate crystal by using the solution |
| EP1547983A1 (en) * | 2003-12-09 | 2005-06-29 | Fujitsu Limited | Apatite-containing film and production process therefor |
| WO2007108373A1 (en) * | 2006-03-17 | 2007-09-27 | Kinki University | Biocompatible transparent sheet, method of producing the same and cell sheet |
| WO2007148682A1 (en) * | 2006-06-19 | 2007-12-27 | Kyoto University | Method of producing bioactive complex material |
| JP4515553B2 (en) * | 1999-05-11 | 2010-08-04 | 日油株式会社 | Method for producing hydroxyapatite composite, composite and biocompatible material |
| US7939187B2 (en) | 2003-12-09 | 2011-05-10 | Fujitsu Limited | Apatite-containing film having photocatalytic activity and a process for producing it |
| WO2014020446A3 (en) * | 2012-08-01 | 2014-03-20 | Sandvik Intellectual Property Ab | Hydroxyapatite coating process using microwave technology |
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1997
- 1997-04-07 JP JP10522697A patent/JPH10287411A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100353141B1 (en) * | 1998-09-17 | 2002-09-18 | 주식회사 오스코텍 | Method for preparation of the supersaturated solution of calcium phosphate and the thin film of calcium phosphate crystal by using the solution |
| JP4515553B2 (en) * | 1999-05-11 | 2010-08-04 | 日油株式会社 | Method for producing hydroxyapatite composite, composite and biocompatible material |
| EP1547983A1 (en) * | 2003-12-09 | 2005-06-29 | Fujitsu Limited | Apatite-containing film and production process therefor |
| US7939187B2 (en) | 2003-12-09 | 2011-05-10 | Fujitsu Limited | Apatite-containing film having photocatalytic activity and a process for producing it |
| US7989258B2 (en) | 2003-12-09 | 2011-08-02 | Fujitsu Limited | Apatite-containing film having photocatalytic activity and a process for producing it |
| WO2007108373A1 (en) * | 2006-03-17 | 2007-09-27 | Kinki University | Biocompatible transparent sheet, method of producing the same and cell sheet |
| KR101084429B1 (en) | 2006-03-17 | 2011-11-21 | 도꾸리쯔교세이호징 가가꾸 기쥬쯔 신꼬 기꼬 | Biocompatible transparent sheet, method of producing the same and cell sheet |
| US8454987B2 (en) | 2006-03-17 | 2013-06-04 | Kinki University | Biocompatible transparent sheet, method for producing the same, and cultured cell sheet used the same sheet |
| WO2007148682A1 (en) * | 2006-06-19 | 2007-12-27 | Kyoto University | Method of producing bioactive complex material |
| JP5252399B2 (en) * | 2006-06-19 | 2013-07-31 | 国立大学法人京都大学 | Method for producing bioactive composite material |
| US8512732B2 (en) | 2006-06-19 | 2013-08-20 | Kyoto University | Method for producing bioactive composites |
| WO2014020446A3 (en) * | 2012-08-01 | 2014-03-20 | Sandvik Intellectual Property Ab | Hydroxyapatite coating process using microwave technology |
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