JPH0723994A - Porous bone filler - Google Patents
Porous bone fillerInfo
- Publication number
- JPH0723994A JPH0723994A JP5165579A JP16557993A JPH0723994A JP H0723994 A JPH0723994 A JP H0723994A JP 5165579 A JP5165579 A JP 5165579A JP 16557993 A JP16557993 A JP 16557993A JP H0723994 A JPH0723994 A JP H0723994A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- slurry
- porous
- pores
- bone filler
- 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.)
- Withdrawn
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Prostheses (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医療分野、特に整形外
科、形成外科、脳神経外科等の分野に使用する多孔体骨
補填材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous bone filling material used in the medical field, particularly in the fields of orthopedics, plastic surgery, neurosurgery and the like.
【０００２】[0002]
【従来の技術】従来、ヒドロキシアパタイトは、生体適
合性が良く、且つ骨欠損部などの充填材として用いた場
合に、該充填材の周囲に直接新生骨を形成することが広
く知られている。例えば特開昭５６−１６６８４３号公
報及び特開平３−１９１９６３号公報において、三次元
網目構造の骨欠損部及び骨空隙部リン酸カルシウム多孔
質充填材が提案されている。2. Description of the Related Art Heretofore, hydroxyapatite has been widely known to have good biocompatibility and to form new bone directly around the filling material when used as a filling material for bone defects and the like. . For example, Japanese Patent Application Laid-Open No. 56-166843 and Japanese Patent Application Laid-Open No. 3-191963 propose a calcium phosphate porous filler having a three-dimensional network structure of bone defects and bone voids.
【０００３】しかしながら、前記多孔質充填材では、気
孔が三次元網目構造的に連通しているため、強度を向上
させるには多孔質充填材全体として、即ち多孔質充填材
の全方向においても均等に高強度化する必要がある。従
ってこのような高強度化を行なうには、多孔質充填材の
気孔率を大幅に低下させなければならず、気孔率を低下
させることにより、加工性が悪化し、骨芽細胞が多孔体
中心部まで侵入し得る連通気孔が減少する等の問題があ
る。一方、骨補填材においては、必ずしも全方向に対し
て強度を持たせる必要はなく、一方向に対して強度を有
する骨補填材も十分実用に供することができる場合があ
る。However, in the above-mentioned porous filler, since the pores communicate with each other in a three-dimensional network structure, in order to improve the strength, the porous filler as a whole, that is, it is even in all directions of the porous filler. It is necessary to increase the strength. Therefore, in order to achieve such high strength, the porosity of the porous filler must be significantly reduced, and by lowering the porosity, processability is deteriorated and the osteoblasts are mainly formed in the porous body. There is a problem such that the number of communicating vents that can penetrate into the area is reduced. On the other hand, the bone prosthetic material does not necessarily need to have strength in all directions, and a bone prosthetic material having strength in one direction may be sufficiently put into practical use.
【０００４】[0004]
【発明が解決しようとする課題】従って本発明の目的
は、気孔率を低下させることなく、一定方向に対して高
強度を有し、且つ気孔連通性及び加工性に優れた多孔体
骨補填材を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a porous bone bone filling material having a high strength in a certain direction without lowering the porosity, and having excellent pore communication and workability. To provide.
【０００５】本発明の別の目的は、骨補填材周囲及び内
部における早期新生骨形成機能に優れた多孔体骨補填材
を提供することにある。Another object of the present invention is to provide a porous bone filling material having an excellent early bone formation function around and inside the bone filling material.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、リン酸
カルシウム化合物からなる多孔体であって、該多孔体の
気孔が、一定の方向性を有し、且つその方向に沿って連
通してなることを特徴とする多孔体骨補填材が提供され
る。According to the present invention, there is provided a porous body made of a calcium phosphate compound, wherein the pores of the porous body have a certain directionality and are communicated along the direction. A porous bone substitute material is provided.
【０００７】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００８】本発明の多孔体骨補填材は、補填する骨と
の物性を近似させ、生体適合性を良好にするために、リ
ン酸カルシウム化合物により構成する。該リン酸カルシ
ウム化合物としては、特に生体適合性に優れるヒドロキ
シアパタイト、リン酸三カルシウム、リン酸四カルシウ
ム又はこれらの混合物等を最も好ましく挙げることがで
きる。また前記リン酸カルシウム化合物は、５００℃以
上、特に７００〜１２５０℃で熱処理して得た物が好ま
しい。上限温度については特に限定されるものではない
が、ヒドロキシアパタイトの分解温度以下とすべきであ
る。The porous bone filling material of the present invention is composed of a calcium phosphate compound in order to approximate the physical properties of the bone to be filled and to improve biocompatibility. The calcium phosphate compound is most preferably hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, or a mixture thereof, which are particularly excellent in biocompatibility. Further, the calcium phosphate compound is preferably obtained by heat treatment at 500 ° C. or higher, particularly 700 to 1250 ° C. The maximum temperature is not particularly limited, but it should be below the decomposition temperature of hydroxyapatite.
【０００９】本発明の多孔体骨補填材の形態は、多孔体
の気孔が一定の方向性を有しており、且つ気孔の方向に
沿って連通しておれば良い。即ち、多孔体におけるほと
んどの気孔が一定方向に連通しているものであり、従っ
てこの多孔体骨補填材は、連通気孔の方向と同一方向に
対して高強度を有し、該強度は、気孔が三次元網目構造
的に連通したものに比して気孔率の影響を受けにくい。
また気孔が一定方向に連通するため加工性にも優れる。
前記多孔体骨補填材における連通気孔の方向と同一方向
に対する圧縮強度は３０〜２０００ｋｇｆ／ｃｍ2の範
囲であるのが好ましい。また気孔率は３０〜８０％、平
均気孔径は５０〜５００μｍであることが好ましい。こ
の際、気孔率が３０％未満の場合には、加工性に劣り、
平均気孔径が５０μｍ未満の場合には、新生骨の侵入が
困難となるので好ましくなく、また気孔率が８０％を越
える場合には、圧縮強度が低下し、平均気孔径が５００
μｍを越える場合には、気孔内への骨の形成が遅れるの
で好ましくない。In the form of the porous bone filling material of the present invention, it is sufficient that the pores of the porous body have a certain directionality and that they communicate with each other along the direction of the pores. That is, most of the pores in the porous body communicate with each other in a fixed direction, and therefore this porous bone filling material has high strength in the same direction as the direction of the communicating pores, and the strength is Are less affected by porosity than those connected in a three-dimensional mesh structure.
Moreover, since the pores communicate with each other in a certain direction, workability is also excellent.
The compressive strength in the same direction as the direction of the communicating holes in the porous bone filling material is preferably in the range of 30 to 2000 kgf / cm 2 . The porosity is preferably 30 to 80% and the average pore diameter is preferably 50 to 500 μm. At this time, if the porosity is less than 30%, the workability is poor,
When the average pore diameter is less than 50 μm, it is not preferable because the invasion of new bone becomes difficult, and when the porosity exceeds 80%, the compressive strength decreases and the average pore diameter is 500.
When it exceeds μm, the formation of bone in the pores is delayed, which is not preferable.
【００１０】本発明のリン酸カルシウム質多孔体骨補填
材を調製するには、例えば、前記のリン酸カルシウム化
合物をスラリーとし、該スラリーにリン酸カルシウム系
微粉末を添加混合し、過酸化水素、尿素、硝酸アンモニ
ウム等の発泡剤を加えてリン酸カルシウム質スラリーを
調製する。更に必要に応じて該スラリーにポリビニール
アルコール、デンプン、メチルセルロース等の可燃性樹
脂を加えることもできる。次いで該リン酸カルシウム質
スラリーを所望形状の容器に充填し、定温乾燥機等によ
りまず優先的に上下面を乾燥させた後、全体を乾燥させ
る等の段階的方法によって乾燥させ、更に加熱する方法
等により得ることができる。この際リン酸カルシウム質
スラリーが可燃性樹脂を含有する場合には、前記加熱に
より除去することができる。前記方法において、リン酸
カルシウム質スラリーの平均粒径は好ましくは、０．１
〜２０μｍであり、リン酸カルシウム系微粉末の粒径
は、０．１〜３０μｍであるのが好ましい。また該スラ
リーに添加するリン酸カルシウム系微粉末の配合割合
は、リン酸カルシウム質スラリー全体に対して０．１〜
５０重量％であることが好ましく、また発泡剤の添加配
合割合は、０．１〜２０重量％であるのが好ましい。更
に必要に応じて添加することができる可燃性樹脂を使用
する場合の配合割合は、リン酸カルシウム質スラリー全
体に対して０．１〜５０重量％であることが好ましい。
この際リン酸カルシウム質スラリーは、全体で１００重
量％となるように調製する。更に前記乾燥及び加熱は、
各成分の種類により異なるが、乾燥する場合、３０〜１
１０℃にて１２〜１６０時間行なうのが好ましく、また
加熱は、５００〜１２５０℃にて行なうのが望ましい。
この際乾燥及び加熱は数回に分割して行なうこともでき
る。In order to prepare the calcium phosphate-based porous bone filling material of the present invention, for example, the above-mentioned calcium phosphate compound is made into a slurry, and the calcium phosphate-based fine powder is added to and mixed with the slurry, and hydrogen peroxide, urea, ammonium nitrate or the like is added. A foaming agent is added to prepare a calcium phosphate slurry. If necessary, flammable resins such as polyvinyl alcohol, starch and methyl cellulose may be added to the slurry. Then, the calcium phosphate slurry is filled in a container having a desired shape, and the upper and lower surfaces are first preferentially dried by a constant temperature dryer or the like, and then the whole is dried by a stepwise method such as drying and further heating. Obtainable. At this time, when the calcium phosphate slurry contains a flammable resin, it can be removed by the heating. In the above method, the average particle size of the calcium phosphate slurry is preferably 0.1
The particle size of the calcium phosphate-based fine powder is preferably 0.1 to 30 μm. Further, the blending ratio of the calcium phosphate-based fine powder added to the slurry is 0.1 to the entire calcium phosphate slurry.
It is preferably 50% by weight, and the proportion of the foaming agent added is preferably 0.1 to 20% by weight. Furthermore, when using a flammable resin that can be added as necessary, the blending ratio is preferably 0.1 to 50% by weight based on the entire calcium phosphate slurry.
At this time, the calcium phosphate slurry is prepared to be 100% by weight as a whole. Further, the drying and heating are
Depending on the type of each component, when dried, 30 to 1
The heating is preferably carried out at 10 ° C. for 12 to 160 hours, and the heating is preferably carried out at 500 to 1250 ° C.
At this time, the drying and heating may be divided into several times.
【００１１】前記方法において、乾燥する箇所を変え
て、段階的に乾燥すること等により、一定の方向性を有
する連通気孔を形成することができる。In the above-mentioned method, by changing the drying place and drying stepwise, it is possible to form the continuous ventilation hole having a certain directionality.
【００１２】[0012]
【発明の効果】本発明の多孔体骨補填材は、リン酸カル
シウム化合物からなるので生体適合性に優れ、また気孔
が一定の方向性を有するため、その気孔の方向に対する
強度及び加工性にも優れている。更には気孔が一定方向
に連通しているので、早期新生骨形成機能に優れる。一
方気孔の連通性が少ない方向においては、感染及び上皮
のダウングロースの防止に有効である。The porous bone filling material of the present invention is excellent in biocompatibility because it is made of a calcium phosphate compound, and has excellent strength and workability in the direction of pores because the pores have a certain directionality. There is. Furthermore, since the pores communicate with each other in a certain direction, it has an excellent early bone formation function. On the other hand, it is effective in preventing infection and downgrowth of the epithelium in the direction in which the connectivity of the stomata is low.
【００１３】[0013]
【実施例】以下実施例及び比較例により本発明を更に詳
細に説明するが、本発明はこれらに限定されるものでは
ない。The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００１４】[0014]
【実施例１】平均粒径２μｍのヒドロキシアパタイトス
ラリー３００ｇに、粒径１〜２０μｍのヒドロキシアパ
タイト微粉末９０ｇ及びポリビニールアルコール粉末１
０ｇを添加混合した後、３０％過酸化水素を１５ｍｌ加
えてリン酸カルシウム質スラリーを調製した。更に得ら
れたスラリーを容器に充填し、定温乾燥機（ヤマト社
製）により容器の上下面を１００℃で乾燥し、更に全体
を５０℃、２４時間の条件で乾燥した。次に得られた乾
燥物を容器から取り出し、ボックス炉（光洋リンドバー
グ社製）で室温〜９００℃まで１℃／分で昇温し、その
後９００℃で３時間保持した後、５℃／分で室温まで降
温し、平均気孔率６１．７％、平均気孔径３００μｍで
あり、水平方向に気孔が連通した多孔体骨補填材を得
た。得られた多孔体骨補填材を１×１×１ｃｍに切断し
強度試験試料を作製した。この試料の連通気孔の方向と
同じ方向に対する圧縮強度を商品名「ＩＮＳＴＲＯＮＭ
ＯＤＥＬ １１２５」（インストロン社製）によって測
定したところ、２６３ｋｇｆ／ｃｍ2であった。Example 1 300 g of hydroxyapatite slurry having an average particle size of 2 μm, 90 g of hydroxyapatite fine powder having a particle size of 1 to 20 μm, and polyvinyl alcohol powder 1
After adding and mixing 0 g, 15 ml of 30% hydrogen peroxide was added to prepare a calcium phosphate slurry. Further, the obtained slurry was filled in a container, the upper and lower surfaces of the container were dried at 100 ° C. by a constant temperature dryer (manufactured by Yamato), and further the whole was dried at 50 ° C. for 24 hours. Next, the obtained dried product was taken out of the container, heated in a box furnace (manufactured by Koyo Lindbergh) from room temperature to 900 ° C. at 1 ° C./min, and then held at 900 ° C. for 3 hours, and then at 5 ° C./min. The temperature was lowered to room temperature to obtain a porous bone filling material having an average porosity of 61.7%, an average pore diameter of 300 μm, and pores communicating in the horizontal direction. The obtained porous bone filling material was cut into 1 × 1 × 1 cm to prepare a strength test sample. The compressive strength of this sample in the same direction as the direction of the continuous ventilation hole is indicated by the trade name "INSTRONM
It was 263 kgf / cm 2 as measured by ODEL 1125 ”(manufactured by Instron).
【００１５】[0015]
【比較例１】実施例１と同様のリン酸カルシウム質スラ
リーをウレタンホームに注入し、乾燥機により、１１０
℃、２４時間の条件で発泡乾燥を行った。次に得られた
乾燥物をボックス炉（光洋リンドバーグ社製）で室温〜
９００℃まで１℃／分で昇温し、その後９００℃で３時
間保持した後、５℃／分で室温まで降温し、平均気孔率
６１．８％、平均気孔径３００μｍの三次元網目構造の
多孔体骨補填材を得た。得られた三次元網目構造の多孔
体骨補填材から実施例１と同様に試料を作製し、圧縮強
度を実施例１と同様に測定したところ、１５５ｋｇｆ／
ｃｍ2であった。[Comparative Example 1] The same calcium phosphate slurry as in Example 1 was poured into a urethane home and dried at 110 by a dryer.
Foam-drying was performed under the conditions of ° C and 24 hours. Next, the obtained dried product is stored in a box furnace (manufactured by Koyo Lindbergh) at room temperature to
The temperature was raised to 900 ° C. at 1 ° C./min, then held at 900 ° C. for 3 hours, and then lowered to room temperature at 5 ° C./min to obtain a three-dimensional network structure having an average porosity of 61.8% and an average pore diameter of 300 μm. A porous bone filling material was obtained. A sample was prepared from the obtained porous bone filling material having a three-dimensional network structure in the same manner as in Example 1, and the compressive strength was measured in the same manner as in Example 1. As a result, 155 kgf /
It was cm 2 .
【００１６】[0016]
【実施例２】平均粒径２μｍのヒドロキシアパタイトス
ラリー４５０ｇに、粒径１〜２０μｍのヒドロキシアパ
タイト微粉末１５０ｇ及びポリビニールアルコール粉末
１０ｇを添加混合した後、３０％過酸化水素を２４ｍｌ
加えてリン酸カルシウム質スラリーを調製した。更に得
られたスラリーを容器に充填し、定温乾燥機（ヤマト社
製）により容器の上下面を１００℃、更に全体を５０
℃、２４時間の条件で乾燥した。次に得られた乾燥物を
容器から取り出し、ボックス炉（光洋リンドバーグ社
製）で室温〜９００℃まで１℃／分で昇温し、その後９
００℃で３時間保持した後、５℃／分で室温まで降温
し、平均気孔率６２％、平均気孔径３００μｍであり、
水平方向に気孔が連通した多孔体骨補填材を得た。得ら
れた多孔体骨補填材を１×１×１ｃｍに切断して透水試
験試料を作製し、ダルシーの法則に基づき連通気孔方向
の透水試験を行なった。即ち連通気孔方向の側面を油粘
土で固定し、水頭圧１００ｃｍＨ2Ｏと一定にしたタン
クより水を落下させて、多孔体を通過する水の量と時間
を測定した。その結果連通方向の透水率は０．０１３５
ｃｍ／秒であった。Example 2 To 450 g of hydroxyapatite slurry having an average particle size of 2 μm, 150 g of hydroxyapatite fine powder having a particle size of 1 to 20 μm and 10 g of polyvinyl alcohol powder were added and mixed, and then 24 ml of 30% hydrogen peroxide was added.
In addition, a calcium phosphate slurry was prepared. Further, the obtained slurry is filled in a container, and the upper and lower surfaces of the container are heated to 100 ° C. by a constant temperature dryer (Yamato Co., Ltd.).
It was dried under the conditions of ℃ and 24 hours. Next, the obtained dried product was taken out of the container, heated in a box furnace (manufactured by Koyo Lindbergh) from room temperature to 900 ° C. at 1 ° C./min, and then 9
After holding at 00 ° C. for 3 hours, the temperature was lowered to room temperature at 5 ° C./min, the average porosity was 62%, the average pore size was 300 μm,
A porous bone filling material having pores communicating in the horizontal direction was obtained. The obtained porous bone filling material was cut into 1 × 1 × 1 cm to prepare a water permeation test sample, and a water permeation test in the direction of the continuous air holes was performed based on Darcy's law. That is, the side surface in the direction of the continuous ventilation hole was fixed with oil clay, and water was dropped from a tank whose head pressure was kept constant at 100 cmH 2 O, and the amount and time of water passing through the porous body were measured. As a result, the water permeability in the communication direction is 0.0135.
It was cm / sec.
【００１７】[0017]
【比較例２】特開昭５６−１６６８４３号公報に準じ、
以下のようにリン酸カルシウム質多孔体を作製した。リ
ン酸カルシウム質スラリーを有機質連続多孔体に含浸さ
せ、室温で乾燥させ、室温〜９００℃まで１℃／分で昇
温し、その後９００℃で３時間保持した後、５℃／分で
室温まで降温し、平均気孔率６０％、平均気孔径２００
μｍの三次元網目構造のリン酸カルシウム多孔体を得
た。得られた多孔体を１×１×１ｃｍに切断して透水試
験試料を作製し、実施例２と同様に透水率を測定したと
ころ、０．００５０ｃｍ／秒であった。以上の結果か
ら、本発明のリン酸カルシウム質多孔体が特に一方向に
おける連通性に優れていることが判った。Comparative Example 2 According to JP-A-56-166843,
A calcium phosphate porous body was prepared as follows. An organic continuous porous material is impregnated with a calcium phosphate slurry, dried at room temperature, heated from room temperature to 900 ° C. at 1 ° C./min, then held at 900 ° C. for 3 hours, and then cooled to room temperature at 5 ° C./min. , Average porosity 60%, average pore diameter 200
A calcium phosphate porous body having a three-dimensional network structure of μm was obtained. The obtained porous body was cut into 1 × 1 × 1 cm to prepare a water permeability test sample, and the water permeability was measured in the same manner as in Example 2. The water permeability was 0.0050 cm / sec. From the above results, it was found that the calcium phosphate-based porous body of the present invention is particularly excellent in communication in one direction.
【００１８】[0018]
【実施例３】実施例１で製造した多孔体骨補填材を５×
５×５ｍｍに切断し、ビーグル犬の脛骨に埋入した。こ
の時、多孔体骨補填材の連通気孔方向が骨の切断面に垂
直になるように埋入した。４週間後、多孔体骨補填材を
取り出し、切断して、切断面の新生骨量を観察したとこ
ろ、良好に新生骨が形成されていた。また、これと同時
に比較例１で作製した多孔体を骨の欠損部に埋入し、新
生骨の形成状態を観察したところ、本発明により作製し
た多孔体骨補填材の方が新生骨の生成が多いことが判明
した。Example 3 The porous bone filling material produced in Example 1 was used in 5 ×.
It was cut into 5 × 5 mm and embedded in the tibia of a beagle dog. At this time, the porous bone filling material was embedded so that the direction of the continuous ventilation holes was perpendicular to the cut surface of the bone. After 4 weeks, the porous bone filling material was taken out and cut, and the amount of new bone on the cut surface was observed. As a result, new bone was well formed. At the same time, the porous body prepared in Comparative Example 1 was embedded in the defect portion of the bone and the state of formation of new bone was observed. The porous bone bone filling material prepared according to the present invention produced new bone. It turned out that there are many.
Claims (1)
あって、該多孔体の気孔が、一定の方向性を有し、且つ
その方向に沿って連通してなることを特徴とする多孔体
骨補填材。1. A bone filling material for a porous body, which is a porous body made of a calcium phosphate compound, wherein pores of the porous body have a certain directionality and are communicated along the direction. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5165579A JPH0723994A (en) | 1993-07-05 | 1993-07-05 | Porous bone filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5165579A JPH0723994A (en) | 1993-07-05 | 1993-07-05 | Porous bone filler |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0723994A true JPH0723994A (en) | 1995-01-27 |
Family
ID=15815042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5165579A Withdrawn JPH0723994A (en) | 1993-07-05 | 1993-07-05 | Porous bone filler |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0723994A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2348872A (en) * | 1999-04-13 | 2000-10-18 | Toshiba Ceramics Co | Calcium phosphate porous sintered body and production thereof |
| JP2002274968A (en) * | 2001-03-22 | 2002-09-25 | Foundation For Nara Institute Of Science & Technology | Novel porous calcium phosphate body and method of preparation for the same |
| WO2003035576A1 (en) * | 2001-10-21 | 2003-05-01 | National Institute Of Advanced Industrial Science And Technology | Porous article of sintered calcium phosphate, process for producing the same and artificial bone and histomorphological scaffold using the same |
| EP1155705A3 (en) * | 2000-05-19 | 2003-10-15 | Ochi, Takahiro, Ph. D. | Biomaterial |
| RU2535580C1 (en) * | 2013-12-12 | 2014-12-20 | Юлия Алексеевна Щепочкина | Charge for filling of porous filler |
| US10286102B2 (en) | 2010-05-11 | 2019-05-14 | Howmedica Osteonics Corp | Organophosphorous, multivalent metal compounds, and polymer adhesive interpenetrating network compositions and methods |
-
1993
- 1993-07-05 JP JP5165579A patent/JPH0723994A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2348872A (en) * | 1999-04-13 | 2000-10-18 | Toshiba Ceramics Co | Calcium phosphate porous sintered body and production thereof |
| US6340648B1 (en) | 1999-04-13 | 2002-01-22 | Toshiba Ceramics Co., Ltd. | Calcium phosphate porous sintered body and production thereof |
| GB2348872B (en) * | 1999-04-13 | 2003-03-26 | Toshiba Ceramics Co | Calcium phosphate porous sintered body and production thereof |
| EP1155705A3 (en) * | 2000-05-19 | 2003-10-15 | Ochi, Takahiro, Ph. D. | Biomaterial |
| JP2002274968A (en) * | 2001-03-22 | 2002-09-25 | Foundation For Nara Institute Of Science & Technology | Novel porous calcium phosphate body and method of preparation for the same |
| JP4683590B2 (en) * | 2001-03-22 | 2011-05-18 | 国立大学法人 奈良先端科学技術大学院大学 | Novel porous calcium phosphate and method for producing the same |
| WO2003035576A1 (en) * | 2001-10-21 | 2003-05-01 | National Institute Of Advanced Industrial Science And Technology | Porous article of sintered calcium phosphate, process for producing the same and artificial bone and histomorphological scaffold using the same |
| US10286102B2 (en) | 2010-05-11 | 2019-05-14 | Howmedica Osteonics Corp | Organophosphorous, multivalent metal compounds, and polymer adhesive interpenetrating network compositions and methods |
| RU2535580C1 (en) * | 2013-12-12 | 2014-12-20 | Юлия Алексеевна Щепочкина | Charge for filling of porous filler |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000905 |