JP3012265B2 - Method for producing apatite sintered body - Google Patents
Method for producing apatite sintered bodyInfo
- Publication number
- JP3012265B2 JP3012265B2 JP2018181A JP1818190A JP3012265B2 JP 3012265 B2 JP3012265 B2 JP 3012265B2 JP 2018181 A JP2018181 A JP 2018181A JP 1818190 A JP1818190 A JP 1818190A JP 3012265 B2 JP3012265 B2 JP 3012265B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- sintered body
- cao
- sintered
- powder
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 「利用分野」 本発明は、生体材料として有用なアパタイト焼結体の
製造方法に関する。The present invention relates to a method for producing an apatite sintered body useful as a biomaterial.
「従来技術及びその問題点」 ハイドロキシアパタイトCa10（PO4）６（OH）２は、
カルシウム化合物とリン酸化合物から湿式法により製造
され、その焼結体は優れた生体親和性を有するため、人
工骨、人工歯根、骨補填材、経皮素子などの生体材料と
して利用されている。ハイドロキシアパタイト焼結体
は、通常、原料ハイドロキシアパタイトの成形体を900
〜1400℃の温度で焼成することによって製造されるが、
原料として用いるハイドロキシアパタイトが上記の式で
表わされる純粋なものであることは希であり、化学量論
組成のハイドロキシアパタイトを製造しようとしても、
Ca過剰のハイドロキシアパタイトとなることがある。こ
のようなCa過剰のハイドロキシアパタイトから成る成形
体を焼成すると、成形体の内部ではCaが吸収されて、よ
り一層緻密なハイドロキシパタイト焼結体となるが、そ
の焼結体の表面にはCaOが残留する。また、CaOが検出限
界以下であっても、Caが僅かでも過剰であれば、そのハ
イドロキシアパタイトの成形体を焼結させると、焼結中
に表面部分で脱水が起こり、CaOが生成していると考え
られる。“Prior art and its problems” Hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2
It is produced by a wet method from a calcium compound and a phosphate compound, and its sintered body has excellent biocompatibility, and is therefore used as a biomaterial such as an artificial bone, an artificial root, a bone filling material, a percutaneous device, and the like. A hydroxyapatite sintered body is usually produced by molding a raw material hydroxyapatite 900
It is manufactured by firing at a temperature of ~ 1400 ° C,
It is rare that the hydroxyapatite used as a raw material is pure represented by the above formula, and even if an attempt is made to produce hydroxyapatite having a stoichiometric composition,
Ca may become excess hydroxyapatite. When such a compact made of Ca-rich hydroxyapatite is fired, Ca is absorbed inside the compact to form a more dense hydroxypatite sintered body, but the surface of the sintered body contains CaO. Remain. Also, even if CaO is below the detection limit, if the Ca is slight or excessive, when the hydroxyapatite molded body is sintered, dehydration occurs on the surface during sintering, and CaO is generated it is conceivable that.
しかしながら、ハイドロキシアパタイト焼結体を生体
材料として使用する場合に、その焼結体中にCaOが存在
すると、CaOが体液に溶解するため、焼結体の強度が低
下するおそれがあり、また、溶解によって生成するCa
（OH）２がアルカリ性であるため、周辺の組織を損傷す
るおそれがあるという問題点がある。However, when a hydroxyapatite sintered body is used as a biomaterial, if CaO is present in the sintered body, CaO dissolves in the body fluid, and the strength of the sintered body may be reduced. Ca generated by
Since (OH) 2 is alkaline, there is a problem that the surrounding tissue may be damaged.
「発明の目的」 本発明は、焼結体の表面にもCaOが存在しないか、従
来に比べてCaO量が著しく減少したハイドロキシアパタ
イト焼結体を製造しうる方法を提供することを目的とす
る。"Object of the Invention" An object of the present invention is to provide a method capable of producing a hydroxyapatite sintered body in which CaO is not present on the surface of the sintered body or the amount of CaO is significantly reduced as compared with the conventional art. .
「発明の構成」 本発明によるハイドロキシアパタイト焼結体の製造方
法は、ハイドロキシアパタイトの成形体を、その成形体
の焼結温度より50℃以上高温で熱処理して不活性化した
セラミックス粉末中に埋め込んで焼結させることを特徴
とする。"Constitution of the Invention" The method for producing a hydroxyapatite sintered body according to the present invention comprises embedding a hydroxyapatite molded body in a ceramic powder which has been heat-treated at a temperature higher than 50 ° C or higher than the sintering temperature of the molded body and inactivated. Characterized by being sintered.
原料として用いるハイドロキシアパタイトは、湿式法
でCa/P比＝10/6を目標に合成されたものであって、熱処
理後にＸ線回折図から測定すると、CaOが検出され、Ca
が過剰であったと考えられるものである。このようなハ
イドロキシアパタイト粉末から湿式法又は乾式法で任意
の形状の成形体を製造する。Hydroxyapatite used as a raw material is synthesized by a wet method with a target of Ca / P ratio = 10/6. When measured from an X-ray diffraction diagram after heat treatment, CaO is detected, and CaO is detected.
Is considered to have been excessive. From such a hydroxyapatite powder, a molded article of any shape is produced by a wet method or a dry method.
本発明の方法においては、上記のようなハイドロキシ
アパタイトの成形体をセラミックス粉末中に埋め込んで
焼結させる。成形体をセラミックス粉末に埋め込む前
に、必要に応じて常法で仮焼することができる。埋め込
みに使用しうるセラミックスとしては、ハイドロキシア
パタイト、アルミナ、チタニア、カオリナイトなどが挙
げられる。これらのセラミックス粉末は、成形体のハイ
ドロキシアパタイトに対して不活性でなければならな
い。したがって、セラミックス粉末を、必要に応じて加
熱などの方法で不活性化してから使用すべきである。殊
に、セラミックス粉末として、ハイドロキシアパタイト
を用いる場合には、包埋焼結によって焼結体に粉末が固
着してしまうおそれがあるので、成形体の焼結温度より
も高温で熱処理を行う必要があり、焼結温度よりも50℃
以上高温、例えば1150〜1200℃で熱処理することが望ま
しい。さらに、この熱処理によって粉末が固まるので、
これをほぐす程度に軽く粉砕して不活性化することが必
要である。粉砕しすぎると、ハイドロキシアパタイト粉
末が活性化し、焼結体に付着して取れなくなる。In the method of the present invention, the hydroxyapatite compact as described above is embedded in ceramic powder and sintered. Before embedding the molded body in the ceramic powder, it can be calcined by an ordinary method, if necessary. Ceramics that can be used for embedding include hydroxyapatite, alumina, titania, kaolinite, and the like. These ceramic powders must be inert to the hydroxyapatite of the compact. Therefore, the ceramic powder should be used after being inactivated by a method such as heating if necessary. In particular, when hydroxyapatite is used as the ceramic powder, it is necessary to perform a heat treatment at a temperature higher than the sintering temperature of the molded body because the powder may be fixed to the sintered body by embedding sintering. Yes, 50 ° C above sintering temperature
It is desirable to perform the heat treatment at a high temperature, for example, 1150 to 1200 ° C. In addition, this heat treatment hardens the powder,
It is necessary to inactivate this by crushing it lightly enough to loosen it. If the pulverization is excessive, the hydroxyapatite powder is activated and adheres to the sintered body and cannot be removed.
また、包埋粉末層は、成形体表面から0.3mm以上の厚
さとすることが必要であり、１〜10mmの厚さとするのが
好ましい。この厚さが0.3mm未満であると、効果が発現
しない。この粉末層を0.3mm付近に薄くする場合は、前
記の粉砕後にさらにふるい（＃80程度）を通して粗大粉
を除去した包埋粉末を用いるのが好ましい。Also, the embedding powder layer needs to have a thickness of 0.3 mm or more from the surface of the molded body, and preferably has a thickness of 1 to 10 mm. If the thickness is less than 0.3 mm, no effect is exhibited. When this powder layer is thinned to about 0.3 mm, it is preferable to use an embedding powder from which coarse powder has been removed through a sieve (about # 80) after the above-mentioned pulverization.
本発明の方法によりハイドロキシアパタイト成形体を
セラミックス粉末中に埋め込んで焼結させると、表面に
CaOが存在しない（検出限界以下）か又は従来に比べて
著しく減少した焼結体が得られる。このメカニズムは、
完全には解明されていないが、表面を覆うことによって
成形体内部と同様に表面においても焼結の際にCaOの吸
収が起こり、緻密化が進行すること及び成形体の表面か
ら熱処理による脱水量が減少することに基づくものと考
えられる。When the hydroxyapatite molded body is embedded in ceramic powder and sintered by the method of the present invention,
A sintered body in which CaO is not present (below the detection limit) or significantly reduced as compared with the conventional one is obtained. This mechanism is
Although not completely elucidated, by covering the surface, CaO absorption occurs during sintering on the surface as well as inside the molded body, densification progresses, and the amount of dehydration by heat treatment from the surface of the molded body Is thought to be based on the decrease in
「発明の実施例」 次に、実施例に基づいて本発明をさらに詳しく説明す
るが、本発明はこれに限定されるものではない。"Examples of the Invention" Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
実施例１ 湿式合成法により製造したCa/P比1.67のハイドロキシ
アパタイト粉末のスラリーから直径25mm、厚さ10mmの円
柱形の成形体を製作した。得られた成形体を下記の第１
表に示す包埋粉末中に、成形体の周囲を５〜6mmの厚さ
で覆うように埋め込み、1050℃に４時間保持して焼結さ
せた。得られた焼結体の表面のＸ線回折図を作製し、検
量線からCaO量を算出し、結果を第１表に示す。さら
に、成形体をセラミックス粉末に埋め込まずに焼結させ
る従来法の場合と比べたCaO量の減少率（％）を第１表
に示す。Example 1 A cylindrical compact having a diameter of 25 mm and a thickness of 10 mm was manufactured from a slurry of hydroxyapatite powder having a Ca / P ratio of 1.67 produced by a wet synthesis method. The obtained molded body was subjected to the following first step.
The molded body was embedded in the embedding powder shown in the table so as to cover the periphery of the molded body with a thickness of 5 to 6 mm, and sintered at 1050 ° C. for 4 hours. An X-ray diffraction diagram of the surface of the obtained sintered body was prepared, and the CaO amount was calculated from the calibration curve. The results are shown in Table 1. Further, Table 1 shows the reduction rate (%) of the amount of CaO as compared with the conventional method in which the compact was sintered without being embedded in the ceramic powder.
なお、包埋粉末のうち、ハイドロキシアパタイト粉末
は予め1150℃で熱処理し、アルミナ粉末は1200℃で熱処
理し、不活性化させ、塊をほぐす程度に軽く粉砕して用
いた。なお、表中、HApはハイドロキシアパタイトを示
す。Among the embedding powders, hydroxyapatite powder was heat-treated at 1150 ° C. in advance, and alumina powder was heat-treated at 1200 ° C. to deactivate and lightly pulverize the lump to use. In the table, HAp indicates hydroxyapatite.
実施例２ 実施例１と同じハイドロキシアパタイト成形体を実施
例１で包埋粉末として用いたのと同じハイドロキシアパ
タイト粉末中に実施例と同様に包埋して1100℃で４時間
焼結させた。得られた焼結体の表面のCaO量を測定した
ところ、0.18重量％であり、従来法の場合に比べてCaO
量が40.0％減少していた。 Example 2 The same hydroxyapatite molded body as in Example 1 was embedded in the same hydroxyapatite powder as used as the embedding powder in Example 1, and sintered at 1100 ° C. for 4 hours. When the amount of CaO on the surface of the obtained sintered body was measured, it was 0.18% by weight.
The amount had decreased by 40.0%.
実施例３ 湿式法で合成した直径25mm、厚さ10mmの円柱形のハイ
ドロキシアパタイト成形体を従来法により1050℃に４時
間保持して焼結させ、得られた表面のCaO量が0.6重量％
のHAp焼結体の表面のＸ線回折図を第１図に示した。Example 3 A cylindrical hydroxyapatite molded body having a diameter of 25 mm and a thickness of 10 mm synthesized by a wet method was sintered by holding it at 1050 ° C. for 4 hours by a conventional method, and the obtained surface had a CaO content of 0.6% by weight.
FIG. 1 shows an X-ray diffraction diagram of the surface of the HAp sintered body of FIG.
同じハイドロキシアパタイト成形体を1150℃で熱処理
したハイドロキシアパタイト粉末で５〜6mmの厚さで覆
って包埋した以外は、上記と同じ条件で焼結させたHAp
焼結体の表面のＸ線回折図を第２図に示す。第１図にお
いて、ａはCaOのピークを示す。このａのピークは、第
２図には見られず、このHAp焼結体の表面にはCaOが存在
しないことが判る。HAp sintered under the same conditions as above except that the same hydroxyapatite molded body was covered with hydroxyapatite powder heat-treated at 1150 ° C. with a thickness of 5 to 6 mm and embedded.
FIG. 2 shows an X-ray diffraction diagram of the surface of the sintered body. In FIG. 1, a indicates the peak of CaO. The peak of a is not seen in FIG. 2, and it is understood that CaO does not exist on the surface of the HAp sintered body.
「発明の効果」 本発明の方法によれば、表面にCaOが存在しない（検
出限界以下）か又はCaO量が従来の1/2程度に減少したハ
イドロキシアパタイト焼結体が得られる。この焼結体
は、CaO量が従来に比べて著しく少ないので、使用中に
強度低下が起こらず、生体材料として好適である。[Effect of the Invention] According to the method of the present invention, a hydroxyapatite sintered body in which CaO does not exist on the surface (below the detection limit) or the amount of CaO is reduced to about 1/2 of the conventional level can be obtained. Since the sintered body has an extremely small CaO content as compared with the conventional one, the strength does not decrease during use and is suitable as a biomaterial.
第１図は実施例３で従来法で製造したハイドロキシアパ
タイト焼結体の表面のＸ線回折図、第２図は実施例３で
本発明の方法により製造したハイドロキシアパタイト焼
結体の表面のＸ線回折図である。 符号の説明 ａ……CaOのピークFIG. 1 is an X-ray diffraction diagram of the surface of the hydroxyapatite sintered body manufactured by the conventional method in Example 3, and FIG. 2 is an X-ray diffraction diagram of the surface of the hydroxyapatite sintered body manufactured by the method of the present invention in Example 3. FIG. Explanation of code a …… CaO peak
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭55−130854（ＪＰ，Ａ) 特開 昭63−225581（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/64 C04B 35/00 - 35/22 C04B 35/447 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-55-130854 (JP, A) JP-A-63-225581 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 35/64 C04B 35/00-35/22 C04B 35/447
Claims (2)
成形体の焼結温度より50℃以上高温で熱処理して不活性
化したセラミックス粉末中に埋め込んで焼結させること
を特徴とするアパタイト焼結体の製造方法。An apatite sintered body characterized in that a hydroxyapatite compact is embedded in a ceramic powder inactivated by heat treatment at a temperature higher than 50 ° C. higher than the sintering temperature of the compact and sintered. Manufacturing method.
ト、アルミナ、チタニア、カオリナイトなどである請求
項１記載のアパタイト焼結体の製造方法。2. The method according to claim 1, wherein the ceramic powder is hydroxyapatite, alumina, titania, kaolinite or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018181A JP3012265B2 (en) | 1990-01-29 | 1990-01-29 | Method for producing apatite sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018181A JP3012265B2 (en) | 1990-01-29 | 1990-01-29 | Method for producing apatite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03223150A JPH03223150A (en) | 1991-10-02 |
| JP3012265B2 true JP3012265B2 (en) | 2000-02-21 |
Family
ID=11964446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018181A Expired - Fee Related JP3012265B2 (en) | 1990-01-29 | 1990-01-29 | Method for producing apatite sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012265B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4540905B2 (en) * | 2001-11-13 | 2010-09-08 | Ｈｏｙａ株式会社 | Method for manufacturing sintered body |
| JP5854650B2 (en) * | 2011-06-02 | 2016-02-09 | 学校法人近畿大学 | Biocompatible transparent sheet, method for producing the same, and cell sheet |
-
1990
- 1990-01-29 JP JP2018181A patent/JP3012265B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03223150A (en) | 1991-10-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |