JPH09290018A - Calcium phosphate organism prosthetic material - Google Patents
Calcium phosphate organism prosthetic materialInfo
- Publication number
- JPH09290018A JPH09290018A JP8108124A JP10812496A JPH09290018A JP H09290018 A JPH09290018 A JP H09290018A JP 8108124 A JP8108124 A JP 8108124A JP 10812496 A JP10812496 A JP 10812496A JP H09290018 A JPH09290018 A JP H09290018A
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- calcium
- grain size
- crystal grain
- calcium phosphate
- 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.)
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- Materials For Medical Uses (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は人工骨などを構成す
るリン酸カルシウム系生体補綴部材に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calcium phosphate bioprosthesis member that constitutes artificial bone or the like.
【０００２】[0002]
【従来の技術】従来より、生体組織や細胞との親和性に
優れた生体材料としてリン酸カルシウム系材料が研究さ
れている。2. Description of the Related Art Calcium phosphate-based materials have been studied as biomaterials having excellent affinity with living tissues and cells.
【０００３】このような技術として、特開昭５５−１４
０７５６号には原料のＣａ／Ｐ＝１．４〜１．７５（モ
ル比）で合成し、ハイドロキシアパタイト（ＨＡＰ）と
第三リン酸カルシウム（ＴＣＰ）を主成分とし、リン酸
カルシウム系ガラスを含有した焼結体を得る技術が記載
されている。As such a technique, Japanese Patent Laid-Open No. 55-14
No. 0756 was synthesized by using Ca / P = 1.4 to 1.75 (molar ratio) as a raw material, and contained hydroxyapatite (HAP) and tricalcium phosphate (TCP) as main components, and contained calcium phosphate-based glass. Techniques for gaining body are described.
【０００４】また特開昭６１−１０６１６６号にはＨＡ
Ｐ（５〜９５重量％）と他の第三リン酸カルシウムや第
四リン酸カルシウムなどのリン酸カルシウム（９５〜５
重量％）からなり、綿状体をした生体補綴材に関する技
術が記載されている。Also, Japanese Patent Laid-Open No. 61-106166 discloses HA.
P (5 to 95% by weight) and other calcium phosphates such as tricalcium phosphate and tetracalcium phosphate (95 to 5%)
% By weight) and describes a technique for a cotton-like bioprosthetic material.
【０００５】さらに、特公昭６０−５０７４３号には
（Ｃａ，Ｍｇ）3 （ＰＯ4 ）2 を０．０１〜３重量％含
んだＨＡＰを成形、焼成して得られる生体補綴材に関す
る技術が記載されている。Further, Japanese Patent Publication No. 60-50743 discloses a technique relating to a bioprosthetic material obtained by molding and firing HAP containing 0.01 to 3% by weight of (Ca, Mg) 3 (PO 4 ) 2. Has been done.
【０００６】しかしながら、このような技術は、いずれ
も大きな荷重を受ける部位へ適用するには焼結体の機械
的強度が不充分であり、このため機械的強度を改善が試
みられている。However, in all of these techniques, the mechanical strength of the sintered body is insufficient to be applied to a site subjected to a large load, and therefore, attempts have been made to improve the mechanical strength.
【０００７】そのような試みとして、まずＨＩＰ、ホッ
トプレスにて低温で焼結させることが行われている。そ
の他、焼結助剤としてガラスを使用すること、ジルコニ
アを含有させたＨＡＰを得ること、さらにＨＡＰとβ−
ＴＣＰの複合材料を得ることなどが行われてきた。As such an attempt, first of all, HIP and hot pressing are performed at low temperature. In addition, using glass as a sintering aid, obtaining HAP containing zirconia, and HAP and β-
For example, obtaining a composite material of TCP has been performed.
【０００８】[0008]
【従来技術の課題】しかしながら、上記のような強度改
善の試みも以下のような問題点を有してた。However, the attempts to improve the strength as described above also have the following problems.
【０００９】すなわち、ＨＩＰ、ホットプレスにて低温
で焼結させるには、工程が増え、装置が高価なものとな
り、したがって量産性と経済性に問題点があった。That is, in order to sinter at a low temperature by HIP or hot pressing, the number of steps is increased and the apparatus becomes expensive, so that there are problems in mass productivity and economical efficiency.
【００１０】また焼結助剤としてガラスを使用すると、
生体内で経時的にガラスが溶出し、生体に悪影響を与え
る恐れがあるとともに、強度も低下していくという問題
点があった。When glass is used as a sintering aid,
There is a problem in that the glass may be eluted in the living body over time, which may adversely affect the living body, and the strength may decrease.
【００１１】次に、ＨＡＰにジルコニアを含有させると
部材表面でのＨＡＰの含有率が低下するのでＨＡＰの特
性である骨伝導性が低下する問題があった。Next, when zirconia is contained in HAP, the content of HAP on the surface of the member is lowered, so that there is a problem that osteoconductivity, which is a characteristic of HAP, is lowered.
【００１２】さらに、ＨＡＰとβ−ＴＣＰの複合材料で
は、大気焼成で焼結させる際に、１２００℃以上の温度
が必要であり、この時、β−ＴＣＰがα−ＴＣＰに変位
してしまう恐れがあり、これを防ぐにはＭｇ等の添加物
が必要であるため、工程が複雑であるという問題点があ
った。Further, the composite material of HAP and β-TCP requires a temperature of 1200 ° C. or higher when it is sintered by firing in air, and at this time, β-TCP may be displaced to α-TCP. However, in order to prevent this, an additive such as Mg is necessary, which causes a problem that the process is complicated.
【００１３】[0013]
【課題を解決するための手段】このような従来技術の課
題を解決すべく、鋭意検討の結果、第三リン酸カルシウ
ムとハイドロキシアパタイトの焼結体において、焼成面
としての焼放し面から内部にかけての第三リン酸カルシ
ウムの含有率、平均結晶粒径を抑え、且つその値が急変
しないようにすることによって機械的強度が大幅に改善
されること、また、このような生体補綴部材において、
表面を研削しても、表面粗さをＲａ＝０．０５〜０．４
０とすることによって、焼結体の機械的強度はほとんど
低下しないことを見いだした。[Means for Solving the Problems] In order to solve the problems of the prior art, as a result of intensive studies, as a result, in a sintered body of tricalcium phosphate and hydroxyapatite, the first surface from the unburned surface to the interior The content of calcium triphosphate, the average crystal grain size is suppressed, and the mechanical strength is significantly improved by preventing the value from changing rapidly, and in such a bioprosthesis member,
Even if the surface is ground, the surface roughness Ra = 0.05 to 0.4
It was found that by setting the value to 0, the mechanical strength of the sintered body was hardly reduced.
【００１４】この結果、上記課題を解決する手段として
の本発明は、実質的に第三リン酸カルシウムとハイドロ
キシアパタイトのみから構成された、焼放し面を有する
焼結体からなる生体補綴部材であって、上記焼放し面で
の、第三リン酸カルシウムとハイドロキシアパタイトの
全含有量に対する第三リン酸カルシウムの含有率、およ
び平均結晶粒径が、それぞれ１〜１０重量％、０．０５
μｍ〜５．０μｍであるとともに、上記焼放し面から５
０μｍの深さにおける上記第三リン酸カルシウムの含有
率および平均結晶粒径がともに上記焼放し面に比して５
０％〜１００％であることを特徴とするリン酸カルシウ
ム系生体補綴部材、および実質的に第三リン酸カルシウ
ムとハイドロキシアパタイトのみから構成された、研削
面を有する焼結体からなる生体補綴部材であって、上記
研削面での上記第三リン酸カルシウムの含有率、平均結
晶粒径および表面粗さが、それぞれ１〜１０重量％、
０．０５μｍ〜５．０μｍ、Ｒａ＝０．０５〜０．４０
μｍであることを特徴とするリン酸カルシウム系補綴部
材を提供する。As a result, the present invention as a means for solving the above-mentioned problems is a bioprosthesis member consisting of a sintered body having an unburned surface, which is composed essentially of tricalcium phosphate and hydroxyapatite. The content of tricalcium phosphate with respect to the total content of tricalcium phosphate and hydroxyapatite and the average crystal grain size on the burned-out surface are 1 to 10% by weight and 0.05, respectively.
μm to 5.0 μm and 5 from the exposed surface
Both the content of the above-mentioned tricalcium phosphate and the average crystal grain size at a depth of 0 μm are 5 compared with the above-mentioned burnt surface.
A bioprosthesis member comprising a calcium phosphate-based bioprosthesis member characterized by being 0% to 100%, and a sintered body having a grinding surface, which is substantially composed of tricalcium phosphate and hydroxyapatite, The content of the tricalcium phosphate on the ground surface, the average crystal grain size and the surface roughness are each 1 to 10% by weight,
0.05 μm to 5.0 μm, Ra = 0.05 to 0.40
Provided is a calcium phosphate-based prosthesis member having a size of μm.
【００１５】[0015]
【００１６】[0016]
【実施例１】以下、本発明の実施例を説明する。 （ａ）非晶質リン酸カルシウムの合成 カルシウムイオン：Ｃａ（ＯＨ）2 の水溶液にリン酸イ
オン：Ｈ3 （ＰＯ3 ）の水溶液を滴下し、カルシウムと
リンの比を１．６３〜１．７１に調整した後、約１日熟
成し、非晶質リン酸カルシウム化合物を合成した。Example 1 An example of the present invention will be described below. (A) Synthesis of Amorphous Calcium Phosphate An aqueous solution of phosphate ion: H 3 (PO 3 ) is dropped into an aqueous solution of calcium ion: Ca (OH) 2 to adjust the ratio of calcium to phosphorus to 1.63 to 1.71. After adjustment, the mixture was aged for about 1 day to synthesize an amorphous calcium phosphate compound.
【００１７】（ｂ）原料の作製 上記非晶質リン酸カルシウム化合物を７００℃〜９００
℃にて仮焼後、原子吸光等の光析機器にて、カルシウム
とリンのモル比の測定を行った。約２日間湿式粉砕し、
バインダーを添加した後、スプレードライ等の造粒装置
を用いて、数十μｍ程度の大きさの球状顆粒に造粒を行
い、プレス用原料を作製した。(B) Preparation of raw material The above amorphous calcium phosphate compound was added at 700 ° C. to 900 ° C.
After calcination at ℃, the molar ratio of calcium and phosphorus was measured by a photodeposition instrument such as atomic absorption. Wet grind for about 2 days,
After the binder was added, a granulating device such as spray drying was used to granulate spherical granules having a size of about several tens of μm to prepare a raw material for pressing.
【００１８】（ｃ）成形 金型又はラバーに上記原料を充填後、成形圧約１０００
（ｋｇｆ／ｃｍ2 ）にて加圧成形した。(C) Molding After filling the above materials into a mold or rubber, a molding pressure of about 1000
It was pressure molded at (kgf / cm 2 ).
【００１９】（ｄ）焼成 大気中、１１００℃〜１３５０℃の温度で、２時間〜４
時間の焼成を行い、ほぼ全体が第三リン酸カルシウムと
ハイドロキシアパタイトのみから構成された、３×４×
１６ｃｍのリン酸カルシウム系生体補綴部材を得た。そ
して、その焼肌面としての焼放し面の結晶構造等を分析
し、第三リン酸カルシウムとハイドロキシアパタイトの
全含有量に対する第三リン酸カルシウムの含有率、平均
結晶粒径を通法に従って測定した。(D) Firing In air, at a temperature of 1100 ° C to 1350 ° C for 2 hours to 4
Calcination for 3 hours, 3x4x, consisting almost entirely of tricalcium phosphate and hydroxyapatite
A 16 cm calcium phosphate bioprosthesis member was obtained. Then, the crystal structure and the like of the as-baked surface as the burnt surface were analyzed, and the content ratio of tribasic calcium phosphate to the total content of tribasic calcium phosphate and hydroxyapatite, and the average crystal grain size were measured according to a conventional method.
【００２０】（ｅ）研削 さらに、上記焼成品の一部表面を、♯６００の砥石にて
深さ５０μｍまで研削し、その研削面の上記第三リン酸
カルシウムの含有量、平均結晶粒径を通法に従って測定
した。(E) Grinding Further, a part of the surface of the fired product is ground to a depth of 50 μm with a # 600 grindstone, and the content of the above-mentioned tricalcium phosphate on the ground surface and the average crystal grain size are passed. Was measured according to.
【００２１】このような上記（ａ）〜（ｅ）に従って作
製された各焼成品について、湿式合成時のカルシウムと
モル比、焼成温度および焼成時間、前記第三リン酸カル
シウムの含有率［Ｔ／（Ｔ＋Ｈ）（ｗｔ％）］、平均結
晶粒径の値、さらにＪＩＳＲ１６０１に準拠した３点曲
げ試験測定にて得られた抗折強度の値を表１に示す。For each of the calcined products prepared according to the above (a) to (e), the molar ratio of calcium to the wet synthesis, the calcining temperature and the calcining time, the content ratio of the tricalcium phosphate [T / (T + H ) (Wt%)], the value of the average crystal grain size, and the value of the bending strength obtained by the three-point bending test measurement based on JISR1601 are shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１中、二重線で囲んだものは、いずれも
抗折強度が１３０Ｍｐａ〜１６０Ｍｐａと従来品の１０
０Ｍｐａ〜１２０Ｍｐａに比して大きく改善されてお
り、かつ、これらの焼成品は、上記焼放し面での前記第
三リン酸カルシウムの含有率および平均結晶粒径が、そ
れぞれ１〜１０重量％、０．０５μｍ〜５．０μｍであ
るとともに、上記焼放し面から５０μｍの深さでは第三
リン酸カルシウムの含有率および平均結晶粒径がともに
上記焼放し面に比して５０％〜１００％である、という
範囲を充たすものであった。In Table 1, those enclosed by a double line have a bending strength of 130 MPa to 160 MPa, which is 10 of the conventional product.
0 Mpa to 120 Mpa, which are greatly improved, and in these fired products, the content of the tricalcium phosphate and the average crystal grain size on the burnt surface are 1 to 10% by weight and 0. In the range of 05 μm to 5.0 μm, both the content of tricalcium phosphate and the average crystal grain size at the depth of 50 μm from the burnt surface are 50% to 100% of the burnt surface. Was satisfied.
【００２４】これに対して、その他の焼成品について
は、いずれも上記範囲外のものであり、かつ抗折強度も
１００Ｍｐａ〜１２０Ｍｐａと従来品と同等程度であっ
た。On the other hand, the other fired products were out of the above range, and the bending strength was 100 Mpa to 120 Mpa, which was about the same as the conventional products.
【００２５】また、表１の結果から、上記範囲を充たす
リン酸カルシウム系生体補綴部材を得るためには、前記
（ａ）〜（ｅ）の製造方法において、カルシウムイオン
水溶液にリン酸イオン水溶液を滴下して得られた水溶液
のカルシウムとリンのモル比を１．６５〜１．７１、焼
成温度を１１５０℃〜１３００℃とすることが好ましい
ことが判った。From the results shown in Table 1, in order to obtain a calcium phosphate-based bioprosthesis member satisfying the above range, the phosphate ion aqueous solution was dropped into the calcium ion aqueous solution in the production methods (a) to (e). It was found that it is preferable to set the molar ratio of calcium to phosphorus in the obtained aqueous solution to 1.65 to 1.71 and the firing temperature to 1150 ° C to 1300 ° C.
【００２６】ただし、上記モル比を１．７０以上で調整
する場合には、以下のような点に留意する必要がある。
すなわち、上記モル比が大きくなれば過剰なＣａが、焼
成後にＣａＯとなる場合もあり、このＣａＯは塩基性で
あるため生体材料にはなるべく含有されていないことが
好ましい。However, when adjusting the above molar ratio to 1.70 or more, it is necessary to pay attention to the following points.
That is, if the above molar ratio becomes large, excess Ca may become CaO after firing, and since CaO is basic, it is preferable that it is not contained in the biomaterial as much as possible.
【００２７】なお、用いられるカルシウムイオン水溶液
は上記Ｃａ（ＯＨ）2 に限定されるものではなく、Ｃａ
（ＮＯ）3 等、適宜選択し得るものであり、同様に、リ
ン酸イオン水溶液も上記Ｈ3 （ＰＯ3 ）のみでなく、
（ＮＨ4 ）2 ＨＰＯ3 等、適宜選択し得るものである。The calcium ion aqueous solution used is not limited to the above-mentioned Ca (OH) 2 , but Ca
(NO) 3 or the like can be appropriately selected. Similarly, the phosphate ion aqueous solution is not limited to the above H 3 (PO 3 ),
(NH 4 ) 2 HPO 3 or the like can be appropriately selected.
【００２８】[0028]
【実施例２】前記（ａ）〜（ｅ）の製法において、カル
シウムとリンのモル比を１．６７、焼成を１２００℃×
２時間、♯４００〜♯１５００の砥石（研削ダイヤ）で
焼成体の全表面を５０μｍ研削した研削品を得、これら
の研削面における前記第三リン酸カルシウムの含有率、
平均結晶粒径、表面粗さ、３点曲げ抗折強度を通法に従
って測定した。用いた砥石の番手、及びこれらの結果を
表２に示す。Example 2 In the production methods (a) to (e) above, the molar ratio of calcium to phosphorus was 1.67, and firing was 1200 ° C.
A grinded product was obtained by grinding the entire surface of the fired body by 50 μm with a # 400 to # 1500 grindstone for 2 hours, and the content of the tricalcium phosphate in these ground surfaces was obtained.
The average crystal grain size, the surface roughness, and the three-point bending transverse strength were measured by a conventional method. Table 2 shows the grindstone counts used and the results thereof.
【００２９】[0029]
【表２】 [Table 2]
【００３０】表２中、二重線で囲んだものは、いずれも
抗折強度が１３０Ｍｐａ〜１６０Ｍｐａと従来品の１０
０Ｍｐａ〜１２０Ｍｐａに比して大きく改善されてお
り、かつ、これらの焼成品は、研削面での前記第三リン
酸カルシウムの含有率および平均結晶粒径が、それぞれ
１〜１０重量％、０．０５μｍ〜５．０μｍであるとと
もに、表面粗さをＲａ＝０．０５〜０．４０という範囲
を充たすものであった。In Table 2, those surrounded by double lines have a bending strength of 130 MPa to 160 MPa, which is 10 of the conventional product.
Compared with 0 Mpa to 120 Mpa, these burned products have a content rate of the tricalcium phosphate on the ground surface and an average crystal grain size of 1 to 10% by weight and 0.05 μm to, respectively. The surface roughness was 5.0 μm and the surface roughness Ra was in the range of 0.05 to 0.40.
【００３１】これに対して、その他の研削品について
は、いずれも上記範囲外のものであり、かつ抗折強度も
１００Ｍｐａ〜１２０Ｍｐａと従来品と同等程度であっ
た。On the other hand, the other ground products were out of the above range, and the bending strength was 100 Mpa to 120 Mpa, which was about the same as the conventional products.
【００３２】したがって、本発明のリン酸カルシウム系
生体補綴部材は、非研削部分のみでなく、研削して滑面
を形成して用いる場合も、表面粗さをＲａ＝０．０５〜
０．４０とすることによって、研削部分も抗折強度が１
３０Ｍｐａ〜１６０Ｍｐａと従来より大きな強度に保こ
とができ、したがって、研削品あるいは非研削部分と研
削部分の混合品として用いることが可能である。Therefore, the calcium phosphate bioprosthesis member of the present invention has a surface roughness of Ra = 0.05 to not only in the non-ground portion but also in the case where it is ground to form a smooth surface.
By setting 0.40, the bending strength of the ground part is 1 as well.
The strength can be maintained at 30 Mpa to 160 Mpa, which is higher than the conventional strength. Therefore, it can be used as a ground product or a mixed product of a non-ground portion and a ground portion.
【００３３】なお、研削に用いる砥石の番手としては♯
６００〜♯１０００が好ましいことが判った。The number of the grindstone used for grinding is #
It has been found that 600 to # 1000 is preferable.
【００３４】[0034]
【発明の効果】叙上のように、本発明のリン酸カルシウ
ム系生体補綴部材は、実質的に第三リン酸カルシウムと
ハイドロキシアパタイトのみから構成された、焼放し面
を有する焼結体からなる生体補綴部材であって、上記焼
放し面での、第三リン酸カルシウムとハイドロキシアパ
タイトの全含有量に対する第三リン酸カルシウムの含有
率、および平均結晶粒径が、それぞれ１〜１０重量％、
０．０５μｍ〜５．０μｍであるとともに、上記焼放し
面から５０μｍの深さにおける上記第三リン酸カルシウ
ムの含有率および平均結晶粒径がともに上記焼放し面に
比して５０％〜１００％としたことにより、機械的強度
が飛躍的に改善されて高荷重部位への適用が可能とな
り、さらに、このようなリン酸カルシウム系生体補綴部
材は、特に添加物を必要とせずに大気焼成で簡便且つ大
量に作製することが可能でき、経済的で安全であり、骨
伝導性も充分維持されたものである、という極めて優れ
た効果を奏するものである。INDUSTRIAL APPLICABILITY As described above, the calcium phosphate-based bioprosthesis member of the present invention is a bioprosthesis member composed of a sintered body having an unburned surface, which is substantially composed of tricalcium phosphate and hydroxyapatite. Then, the content of tricalcium phosphate with respect to the total content of tricalcium phosphate and hydroxyapatite, and the average crystal grain size on the burnt surface are 1 to 10% by weight, respectively.
The content of the tricalcium phosphate and the average crystal grain size at a depth of 50 μm from the burnt surface were both 50% to 100% compared with the burnt surface. As a result, mechanical strength is dramatically improved and application to high load sites becomes possible.Furthermore, such a calcium phosphate-based bioprosthesis member can be simply and large-scaled by atmospheric firing without the need for additives. It has an extremely excellent effect that it can be produced, is economical and safe, and has sufficient osteoconductivity.
【００３５】また、本発明のリン酸カルシウム系生体補
綴部材は、表面粗さがＲａ＝０．０５〜０．４０なるよ
うに研削することによって、研削部分の機械的強度も非
研削部分同様の大きさに維持することができるので、表
面を研削により滑面として高荷重部位に適用することも
でき、適用の幅が広い。The calcium phosphate bioprosthesis member of the present invention is ground so that the surface roughness is Ra = 0.05 to 0.40, so that the mechanical strength of the ground portion is the same as that of the non-ground portion. Since it can be maintained at a high level, it can be applied to a high load part as a smooth surface by grinding, and the application range is wide.
Claims (2)
ロキシアパタイトのみから構成された、焼放し面を有す
る焼結体からなる生体補綴部材であって、上記焼放し面
での、第三リン酸カルシウムとハイドロキシアパタイト
の全含有量に対する第三リン酸カルシウムの含有率、お
よび平均結晶粒径が、それぞれ１〜１０重量％、０．０
５μｍ〜５．０μｍであるとともに、上記焼放し面から
５０μｍの深さにおける上記第三リン酸カルシウムの含
有率および平均結晶粒径がともに上記焼放し面に比して
５０％〜１００％であることを特徴とするリン酸カルシ
ウム系生体補綴部材。1. A bioprosthesis member comprising a sintered body having an unburned surface, which is substantially composed of only tricalcium phosphate and hydroxyapatite, wherein the unburned surface has tricalcium phosphate and hydroxyapatite. Content of tribasic calcium phosphate and average crystal grain size are 1 to 10% by weight and 0.0
It is 5 μm to 5.0 μm, and the content of the tricalcium phosphate and the average crystal grain size at a depth of 50 μm from the burnt surface are both 50% to 100% of the burnt surface. A characteristic calcium phosphate bioprosthesis member.
ロキシアパタイトのみから構成された、研削面を有する
焼結体からなる生体補綴部材であって、上記研削面での
上記第三リン酸カルシウムの含有率、平均結晶粒径およ
び表面粗さが、それぞれ１〜１０重量％、０．０５μｍ
〜５．０μｍ、Ｒａ＝０．０５〜０．４０μｍであるこ
とを特徴とするリン酸カルシウム系補綴部材。2. A bioprosthesis member consisting of a sintered body having a ground surface, which is composed essentially of tricalcium phosphate and hydroxyapatite, wherein the content of the tricalcium phosphate in the ground surface is average, The crystal grain size and the surface roughness are 1 to 10% by weight and 0.05 μm, respectively.
˜5.0 μm, Ra = 0.05 to 0.40 μm, a calcium phosphate-based prosthetic member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10812496A JP3464096B2 (en) | 1996-04-26 | 1996-04-26 | Calcium phosphate bioprosthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10812496A JP3464096B2 (en) | 1996-04-26 | 1996-04-26 | Calcium phosphate bioprosthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09290018A true JPH09290018A (en) | 1997-11-11 |
| JP3464096B2 JP3464096B2 (en) | 2003-11-05 |
Family
ID=14476549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10812496A Expired - Fee Related JP3464096B2 (en) | 1996-04-26 | 1996-04-26 | Calcium phosphate bioprosthesis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3464096B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008066106A1 (en) * | 2006-11-30 | 2008-06-05 | Nihon University | Layered gradient material for biological use and method for producing the same |
-
1996
- 1996-04-26 JP JP10812496A patent/JP3464096B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008066106A1 (en) * | 2006-11-30 | 2008-06-05 | Nihon University | Layered gradient material for biological use and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3464096B2 (en) | 2003-11-05 |
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