JP2009084147A - Porous body of calcium phosphate-based shaped body and its production method - Google Patents
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本発明は、セラミックスの製造分野における、溶解析出反応を利用したリン酸カルシウム系成形体の多孔体の製造技術に関するものであり、更に詳しくは、本発明は、溶解析出反応により、α−ＴＣＰ成形体の構成粒子の間隙近傍に分解しやすい部分（脆弱部位）を設け、該部分を熱分解除去することにより、成形体の構成粒子同士を焼結により高強度化すると共に、成形体構成粒子の間隙を拡張し、脆弱部位の分解残渣を伴ったサンゴ様のｎｏｄｅ−ｓｔｒｕｔ構造と拡張した気孔構造、即ち、焼結で強度を向上させ、かつ気孔径を拡張することを特徴とした、リン酸カルシウム系の多孔質成形体及びその製造方法に関するものである。 The present invention relates to a manufacturing technique of a porous body of a calcium phosphate-based molded body using a dissolution and precipitation reaction in the field of manufacturing ceramics. More specifically, the present invention relates to an α-TCP molded body by a dissolution and precipitation reaction. By providing a portion (fragile portion) that is easily decomposed in the vicinity of the gap between the constituent particles, and removing the portion by thermal decomposition, the constituent particles of the molded body are strengthened by sintering and the gap between the constituent particles of the molded body is increased. Expanded, coral-like node-strut structure with fragile residue decomposition residue and expanded pore structure, that is, a calcium phosphate-based porous material characterized in that the strength is increased by sintering and the pore diameter is expanded The present invention relates to a molded product and a method for producing the same.
本発明は、例えば、人工骨、薬剤担体、触媒担体、フィルターなどを製造するための手段として好適に利用しうるリン酸カルシウム系成形体の多孔体の製造技術及びその製品を提供するものである。 The present invention provides a technique for producing a porous body of a calcium phosphate-based molded article that can be suitably used as a means for producing, for example, artificial bones, drug carriers, catalyst carriers, filters, and the like, and products thereof.
あらゆる疾病に関して再生的な治療方法が模索されているが、硬組織治療手段に関しては、セラミック人工骨の成熟が目覚ましい。そのような中で、人工骨の開発思想は、「荷重支持機能優先」から「骨伝導優先」にシフトしてきた。よく知られる人工骨への骨伝導機能付与の手段は、人工骨の多孔化である。多孔化は、材料強度を確実に低下させるが、自家骨再生が速やかであれば、材料自身の機械的特性は、再生骨により補われるので問題とならない、との考え方が、世間に受け入れられ始めた。 Regenerative treatment methods are being sought for all diseases, but ceramic artificial bone maturation is remarkable as a hard tissue treatment means. Under such circumstances, the development philosophy of artificial bone has shifted from “load support function priority” to “bone conduction priority”. A well-known means for imparting a bone conduction function to an artificial bone is to make the artificial bone porous. Porosity will surely reduce the strength of the material, but the idea that if the autogenous bone regeneration is rapid, the mechanical properties of the material itself will be compensated by the regenerated bone will not be a problem. It was.
自家骨の再生が速やかである気孔候補としては、骨伝導を預かる数百ミクロンの“マクロポア”から、人工骨の液性成分との親和性と溶解性を高める数ミクロンの“ミクロポア”に至るワイドレンジの気孔がノミネートされている。然るに、人工骨の開発は、人工骨を徹底的に多孔質化することを課題に定めるに至った。セラミックスの多孔化の方法は、多様であり、確実に認知された名称をあげるのは難しいが、例えば、発砲法や骨材焼失法が、一般的、かつ成熟した方法と考えられる。 Pore candidates for rapid regeneration of autologous bones range from “macropores” of several hundred microns that maintain bone conduction to “micropores” of several microns that increase the affinity and solubility of artificial bones for liquid components. Range pores are nominated. However, the development of artificial bone has led to the task of thoroughly making the artificial bone porous. There are various methods for making ceramics porous, and it is difficult to give a well-recognized name. However, for example, the firing method and the aggregate burning method are considered to be general and mature methods.
それらのうち、発砲法は、成形対象スラリー中に気泡を導入し、その状態を適宜の方法で保ちつつ、乾燥、焼結し、セラミックス多孔体を得る方法である（例えば、特許文献８）。骨材焼失法は、成形対象スラリーに焼結時に焼き飛ぶ材質の骨材（例えば、プラスチックビーズやウレタンフォーム）を混ぜたものを、所望の形状に成型し、乾燥、焼結して、セラミックス多孔体を得る方法である（例えば、非特許文献１）。 Among them, the firing method is a method for introducing a bubble into a slurry to be molded and drying and sintering it while maintaining the state by an appropriate method to obtain a ceramic porous body (for example, Patent Document 8). In the aggregate burn-out method, a mixture of an aggregate material (for example, plastic beads or urethane foam) that burns away during molding is molded into a desired shape, dried, sintered, This is a method for obtaining a body (for example, Non-Patent Document 1).
上記方法で得られる気孔径は、比較的大きく、マクロポーラス人工骨を製造する方法として簡便であり、広く利用されている。しかしながら、上記方法は、ミクロポーラス人工骨の製造には向かない。発泡法においては、よく知られる範囲において、数ミクロンの気孔を作るための微小気泡の発生手段が未成熟である。 The pore diameter obtained by the above method is relatively large and is a simple and widely used method for producing macroporous artificial bone. However, the above method is not suitable for producing microporous artificial bone. In the foaming method, within a well-known range, the means for generating microbubbles for producing pores of several microns is immature.
骨材焼失法においては、微小気孔を残せるような焼失骨材の分散や、スラリーを含浸させた焼失フォームの乾燥、焼結がテクニカルである。また、しばしば、骨材の焼失に伴うガスの環境への影響が問題視される。ミクロポーラスセラミックスの製造方法に関して、原料粉体の大きさや、充填、成形に解を求めることもあるが、特に、本発明が扱う人工骨材料α−ＴＣＰに関して、実用的な強度の成形体を得ることは難しい。 In the aggregate burning method, it is technical to disperse burned aggregate that can leave micropores, and to dry and sinter burned foam impregnated with slurry. In addition, the environmental impact of gas accompanying the burning of aggregates is often regarded as a problem. Regarding the manufacturing method of microporous ceramics, there are cases where solutions are required for the size, filling, and molding of the raw material powder. In particular, regarding the artificial bone material α-TCP handled by the present invention, a molded body having practical strength is obtained. It ’s difficult.
リン酸カルシウム系多孔質焼結体及びその製造方法に関しては、先行技術として、例えば、生体活性且つ高強度を有するセラミックスであって、連続気孔を有する多孔質焼結体で、焼結体の表面にリン酸三カルシウムを主成分とする被膜が形成されているリン酸カルシウムセラミックスが提案されている（特許文献１）。 Regarding the calcium phosphate porous sintered body and the manufacturing method thereof, as a prior art, for example, a ceramic having bioactivity and high strength, which is a porous sintered body having continuous pores, phosphorous is formed on the surface of the sintered body. Calcium phosphate ceramics in which a coating composed mainly of tricalcium oxide has been proposed (Patent Document 1).
また、他の例として、リン酸カルシウム系多孔質焼結体の骨格部分が概略緻密化したリン酸カルシウム系焼結体からなり、その表面部分が微細な凹凸若しくは多孔質焼結体より成る層を有し、比表面積が０．１ｍ２／ｃｍ以上であるリン酸カルシウム系多孔質焼結体が提案されている（特許文献２）。 Further, as another example, the skeleton portion of the calcium phosphate porous sintered body is composed of a calcium phosphate sintered body in which the skeleton portion is substantially densified, and the surface portion has a layer made of fine irregularities or a porous sintered body, A calcium phosphate porous sintered body having a specific surface area of 0.1 m 2 / cm or more has been proposed (Patent Document 2).
また、他の例として、細胞や組織との初期接着をよくするリン酸カルシウム系生体用セラミック焼結体であって、金属イオンにより焼結体が表面修飾されていて、骨の再生成長を促す高分子が焼結体の表面に配置されているリン酸カルシウム系生体用セラミック焼結体が提案されている（特許文献３）。 As another example, a calcium phosphate biosintered ceramic sintered body that improves initial adhesion with cells and tissues, and the sintered body is surface-modified with metal ions to promote bone regeneration and growth. There has been proposed a calcium phosphate-based bioceramic sintered body for living body in which is disposed on the surface of the sintered body (Patent Document 3).
また、他の例として、機械的強度が高く、細胞・組織が侵入することができるような多孔体の特徴を兼ね備えたリン酸カルシウム系多孔質焼結体であって、気孔率が５％以下から８５％以上まで実質的に連続して傾斜的に分布しているリン酸カルシウム系多孔質焼結体が提案されている（特許文献４）。 Another example is a calcium phosphate-based porous sintered body that has the characteristics of a porous body that has high mechanical strength and allows cells and tissues to enter, and has a porosity of 5% or less to 85. A calcium phosphate-based porous sintered body that has been distributed substantially continuously and in a gradient up to% or more has been proposed (Patent Document 4).
また、他の例として、血管や細胞が侵入するのに適した連通孔と、高い強度を併せ持つインプラント用材料であって、直径が１０〜５００μｍで、一方向に配向して貫通している気孔を有する多孔質セラミックスインプラント材料が提案されている（特許文献５）。 As another example, a communicating hole suitable for invasion of blood vessels and cells and an implant material having both high strength and having a diameter of 10 to 500 μm and oriented and penetrating in one direction There has been proposed a porous ceramics implant material having (Patent Document 5).
また、他の例として、高気孔率を有する多孔質リン酸カルシウム系セラミックス焼結体の製造方法であって、リン酸カルシウム系セラミックス粉体を含有するスラリーを起泡させ、一対の微多孔質樹脂シートを型枠を介して対向させてなる成形型内に注入し、ゲル化させ、乾燥後に焼結することからなる多孔質リン酸カルシウム系セラミックス焼結体の製造方法が提案されている（特許文献６）。 As another example, a method for producing a porous calcium phosphate ceramic sintered body having a high porosity, in which a slurry containing calcium phosphate ceramic powder is foamed, and a pair of microporous resin sheets is molded There has been proposed a method for producing a porous calcium phosphate ceramic sintered body which is injected into a molding die facing through a frame, gelled, and sintered after drying (Patent Document 6).
更に、他の例として、多孔体としての優れた生体親和性及び細胞、薬剤等の侵入容易性と、緻密体として優れた強度特性とを兼ね備えたリン酸カルシウム系多孔質焼結体であって、平均気孔径０ｍｍから３ｍｍ以下までの気孔が連続的に傾斜して形成されているリン酸カルシウム系多孔質焼結体が提案されている（特許文献７）。 Furthermore, as another example, a calcium phosphate based porous sintered body having excellent biocompatibility as a porous body and ease of invasion of cells, drugs, etc., and excellent strength characteristics as a dense body, A calcium phosphate porous sintered body in which pores having a pore diameter of 0 mm to 3 mm or less are continuously inclined has been proposed (Patent Document 7).
しかしながら、従来、人工骨材料α−ＴＣＰに関して、α−ＴＣＰ成形体であって、多孔体構造と実用的な強度を両立させたα−ＴＣＰ成形体の多孔体を簡便な手法で実現させることは困難であった。 However, conventionally, regarding an artificial bone material α-TCP, it is an α-TCP molded body, and it is possible to realize a porous body of an α-TCP molded body having both a porous structure and practical strength by a simple method. It was difficult.
このような状況の中で、本発明者は、上記従来技術に鑑みて、上記従来技術における諸問題を確実に解消することができる新しいリン酸カルシウム系成形体の多孔化方法と、その新しい利用形態、その製品及び運用方法等を、多角的な視点から検討、開発することを目標として鋭意研究を積み重ねた結果、適宜の液体中でα−ＴＣＰ成形体の溶液暴露部の溶解析出反応を促進することにより、α−ＴＣＰ成形体構成粒子の間隙近傍に脆弱部位を設け、該脆弱部位を加熱除去して成形体構成粒子の間隙を拡張することにより所期の目的を達成し得ることを見出し、本発明を完成させるに至った。 In such a situation, in view of the prior art, the present inventor has made a new method for making a porous calcium phosphate-based molded body that can reliably solve the problems in the prior art, and a new form of use thereof, As a result of intensive research aimed at studying and developing the product and operation method from various viewpoints, the dissolution precipitation reaction of the solution exposed part of the α-TCP molded body should be promoted in an appropriate liquid. Thus, it has been found that the intended purpose can be achieved by providing a fragile site in the vicinity of the gap between the α-TCP molded body constituent particles and expanding the gap between the molded body constituent particles by removing the fragile site by heating. The invention has been completed.
本発明のリン酸カルシウム系成形体の多孔化方法により、α−ＴＣＰ成形体、及び該α−ＴＣＰから派生的に調製できる水酸アパタイト（ＨＡ）、β−ＴＣＰ成形体に、数ミクロンの流路幅を持つ気孔ネットワークを、発泡法や骨材焼失法を用いることなく付与することができる。すなわち、本発明は、数ミクロンの流路幅を持つサンゴ様構造の細孔を持つリン酸カルシウム系成形体の多孔体、その製造方法及びその部材を提供することを目的とするものである。 By the method for making a calcium phosphate-based molded body of the present invention porous, α-TCP molded body, and hydroxyapatite (HA) and β-TCP molded body, which can be prepared derivatively from α-TCP, have a flow path width of several microns. It is possible to provide a pore network having a without using a foaming method or an aggregate burning method. That is, an object of the present invention is to provide a porous body of a calcium phosphate-based molded body having coral-like pores having a flow path width of several microns, a manufacturing method thereof, and a member thereof.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）下記２ステップによりリン酸カルシウム系成形体の多孔体を製造する方法であって、
１）液体中で多孔化対象のα−ＴＣＰ成形体の液体暴露部の溶解析出反応を促し、熱で分解しやすい脆弱部位の部分を設け、
２）該成形体を熱処理することにより、上記脆弱部位を分解、除去し、構成粒子同士を焼結すると共に、成形体構成粒子の間隙を拡張する、
ことを特徴とする、リン酸カルシウム系成形体の多孔体の製造方法。
（２）上記溶解析出反応が、多孔化対象のα−ＴＣＰ成形体の液体中への浸漬による浸漬溶液中のリン、カルシウムの濃度上昇とｐＨ上昇により、成形体の表面及び微小気孔にリン酸カルシウムを析出させる反応である、前記（１）記載のリン酸カルシウム系成形体の多孔体の製造方法。
（３）上記溶解析出反応におけるα−ＴＣＰ成形体の液体中への浸漬環境が、静置である、前記（１）又は（２）記載のリン酸カルシウム系成形体の多孔体の製造方法。
（４）上記溶解析出反応に用いる液体として、α−ＴＣＰ成形体が溶解しうる液体を用いる、前記（１）〜（３）のいずれかに記載のリン酸カルシウム系成形体の多孔体の製造方法。
（５）α−ＴＣＰ成形体の液体暴露部の溶解析出反応により出現する脆弱部位が、Ｘ線的、或いは形態的に、ＭＣＰＭ、ＤＣＰ、ＤＣＰＤ、ＯＣＰのいずれか、若しくはそれらの混合物である、前記（１）〜（４）のいずれかに記載のリン酸カルシウム系成形体の多孔体の製造方法。
（６）α−ＴＣＰ成形体が、湿潤物、乾燥物、又は焼成物である、前記（１）〜（５）のいずれかに記載のリン酸カルシウム系成形体の多孔体の製造方法。
（７）熱処理温度及び／又は熱処理時間の制御により、成形体の一部若しくは全部をβ−ＴＣＰ化する、前記（１）〜（６）のいずれかに記載のリン酸カルシウム系成形体の多孔体の製造方法。
（８）上記溶解析出反応を促す方法が、温度、又はｐＨを制御若しくは変化させる方法であって、温度を０−２００℃の範囲、ｐＨをｐＨ１−９の範囲に制御若しくは変化させる、前記（１）〜（７）のいずれかに記載のリン酸カルシウム系成形体の多孔体の製造方法。
（９）溶解析出処理後のα−ＴＣＰ成形体を焼成して得られるリン酸カルシウム系成形体の多孔体であって、
α−ＴＣＰ成形体の焼結と、溶解析出反応で形成された脆弱部位の分解によりできた、脆弱部位の分解残渣を伴ったサンゴ様のｎｏｄｅ−ｓｔｒｕｔ構造と拡張した気孔構造を有し、焼結で強度が上がり、かつ気孔径が拡張した、無処理の焼成品と比べて比較的高い気孔率、吸水性、及び実用的な強度を実現していることを特徴とするリン酸カルシウム系成形体の多孔体。
（１０）上記リン酸カルシウムが、α−ＴＣＰ、β−ＴＣＰ、又は水酸アパタイトである、前記（８）記載のリン酸カルシウム系成形体の多孔体。
（１１）前記（９）記載のα−ＴＣＰ成形体を焼成して得られるリン酸カルシウム系成形体の多孔体を水熱処理することにより得られる、水酸アパタイト若しくは水酸アパタイトを含むリン酸カルシウム系成形体の多孔体。
（１２）前記（９）から（１１）のいずれかに記載のリン酸カルシウム系成形体の多孔体からなることを特徴とするリン酸カルシウム多孔体部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) A method for producing a calcium phosphate-based porous body by the following two steps,
1) Promote dissolution and precipitation reaction of the liquid exposed portion of the α-TCP molded body to be made porous in the liquid, and provide a portion of a fragile portion that is easily decomposed by heat.
2) By heat-treating the molded body, the fragile site is decomposed and removed, the constituent particles are sintered with each other, and the gap between the molded body constituent particles is expanded.
The manufacturing method of the porous body of the calcium-phosphate type molded object characterized by the above-mentioned.
(2) The dissolution and precipitation reaction causes calcium phosphate to be added to the surface and micropores of the molded body by increasing the concentration and pH of phosphorus and calcium in the immersion solution by dipping the α-TCP molded body to be porous into a liquid. The manufacturing method of the porous body of the calcium-phosphate type molded object as described in said (1) which is reaction to precipitate.
(3) The manufacturing method of the porous body of the calcium-phosphate type molded object of the said (1) or (2) description that the immersion environment in the liquid of the (alpha) -TCP molded object in the said melt | dissolution precipitation reaction is stationary.
(4) The manufacturing method of the porous body of the calcium-phosphate type molded object in any one of said (1)-(3) using the liquid in which the alpha-TCP molded object can melt | dissolve as a liquid used for the said melt | dissolution precipitation reaction.
(5) The fragile site that appears due to the dissolution and precipitation reaction of the liquid exposed portion of the α-TCP molded body is one of MCPM, DCP, DCPD, OCP, or a mixture thereof, X-ray or morphologically. The manufacturing method of the porous body of the calcium-phosphate type molded object in any one of said (1)-(4).
(6) The method for producing a porous body of a calcium phosphate-based molded body according to any one of (1) to (5), wherein the α-TCP molded body is a wet product, a dried product, or a fired product.
(7) The calcium phosphate-based porous body according to any one of (1) to (6), wherein part or all of the formed body is converted to β-TCP by controlling the heat treatment temperature and / or the heat treatment time. Production method.
(8) The method for promoting the dissolution and precipitation reaction is a method for controlling or changing temperature or pH, wherein the temperature is controlled or changed in the range of 0-200 ° C., and the pH is controlled or changed in the range of pH 1-9. The manufacturing method of the porous body of the calcium-phosphate type molded object in any one of 1)-(7).
(9) A calcium phosphate-based porous body obtained by firing an α-TCP molded body after dissolution and precipitation treatment,
It has a coral-like node-strut structure with a fragile site decomposition residue and an expanded pore structure formed by sintering of the α-TCP molded body and decomposition of the fragile site formed by dissolution and precipitation reaction. A calcium phosphate-based molded article characterized by achieving a relatively high porosity, water absorption, and practical strength compared to an untreated fired product with increased strength due to bonding and expanded pore diameter. Porous body.
(10) The porous body of a calcium phosphate-based molded article according to (8), wherein the calcium phosphate is α-TCP, β-TCP, or hydroxyapatite.
(11) A calcium phosphate-based molded body containing hydroxyapatite or hydroxyapatite obtained by hydrothermal treatment of a porous body of a calcium phosphate-based molded body obtained by firing the α-TCP molded body according to (9) Porous body.
(12) A calcium phosphate porous body member comprising the porous body of the calcium phosphate-based molded body according to any one of (9) to (11).
次に、本発明について更に詳細に説明する。
本発明は、下記２ステップによりα−ＴＣＰからなるリン酸カルシウム系成形体の多孔体を製造する方法であって、液体中で多孔化対象のα−ＴＣＰ成形体の液体暴露部の溶解析出反応を促し、熱で分解しやすい脆弱部位の部分を設け、該成形体を熱処理することにより、上記脆弱部位を分解、除去し、成形体構成粒子同士を焼結すると共に、成形体構成粒子の間隙を拡張する、ことを特徴とするものである。
Next, the present invention will be described in more detail.
The present invention is a method for producing a calcium phosphate-based porous body made of α-TCP by the following two steps, which promotes the dissolution and precipitation reaction in the liquid exposed portion of the α-TCP molded body to be made porous in liquid. By providing a portion of the fragile part that is easily decomposed by heat and heat-treating the molded body, the fragile part is decomposed and removed, the molded body constituent particles are sintered, and the gap between the molded body constituent particles is expanded. It is characterized by that.
本発明では、溶解析出反応が、多孔化対象のα−ＴＣＰ成形体の液体中への浸漬による浸漬溶液中のリン、カルシウムの濃度上昇とｐＨ上昇により、成形体の表面及び微小気孔にリン酸カルシウムを析出させる反応であること、また、溶解析出反応におけるα−ＴＣＰ成形体の液体中への浸漬環境が静置であること、を好ましい実施の態様としている。上記溶液反応に用いる液体としては、α−ＴＣＰ成形体が溶解しうる液体を用いることができ、例えば、ｐＨ１．５〜５の塩酸水溶液、コハク酸水溶液、クエン酸水溶液、酢酸水溶液、若しくは、純水、超純水が例示される。 In the present invention, the dissolution and precipitation reaction is performed by adding calcium phosphate to the surface and micropores of the molded body by increasing the concentration and pH of phosphorus and calcium in the immersion solution by immersing the α-TCP molded body to be porous in the liquid. It is a preferred embodiment that the reaction is a precipitation reaction and that the environment in which the α-TCP molded body is immersed in the liquid in the dissolution precipitation reaction is stationary. As the liquid used in the solution reaction, a liquid in which the α-TCP molded body can be dissolved can be used. For example, a hydrochloric acid aqueous solution having a pH of 1.5 to 5, a succinic acid aqueous solution, a citric acid aqueous solution, an acetic acid aqueous solution, or a pure Water and ultrapure water are exemplified.
本発明では、液体中でα−ＴＣＰ成形体に、振盪、撹拌等の操作を加えることにより、溶解析出反応をより促進することができる。また、本発明では、α−ＴＣＰ成形体の溶解析出により出現する脆弱部位は、Ｘ線的、或いは形態的に、ＭＣＰＭ、ＤＣＰ、ＤＣＰＤ、ＯＣＰのいずれか、若しくはそれらの混合物であること、α−ＴＣＰ成形体は、湿潤物、乾燥物、乃至焼成物であること、熱処理温度及び／又は熱処理時間の制御により、成形体の一部若しくは全部をβ−ＴＣＰ化すること、が好適である。 In this invention, melt | dissolution precipitation reaction can be accelerated | stimulated more by adding operation, such as shaking and stirring, to (alpha) -TCP molded object in a liquid. In the present invention, the fragile site that appears due to dissolution and precipitation of the α-TCP molded body is X-ray or morphologically any of MCPM, DCP, DCPD, OCP, or a mixture thereof, α It is preferable that the TCP molded body is a wet product, a dried product, or a fired product, and part or all of the molded product is converted to β-TCP by controlling the heat treatment temperature and / or the heat treatment time.
また、本発明は、溶解析出処理後のα−ＴＣＰ成形体を焼成して得られる多孔質リン酸カルシウム系焼結体であって、α−ＴＣＰ成形体の焼結と脆弱部位の分解によりできた、脆弱部位の分解残渣を伴ったサンゴ様のｎｏｄｅ−ｓｔｒｕｔ構造と拡張した気孔構造を有し、焼結で強度が上がり、かつ気孔径が拡張した、無処理の焼成品と比べて、比較的高い気孔率、吸水性、及び実用的な強度を実現していること、リン酸カルシウムが、α−ＴＣＰ、β−ＴＣＰ、又は水酸アパタイトであること、が好適である。 In addition, the present invention is a porous calcium phosphate-based sintered body obtained by firing the α-TCP molded body after the dissolution and precipitation treatment, and was obtained by sintering the α-TCP molded body and decomposing the fragile site. It has a coral-like node-strut structure with a fragile residue decomposition residue and an expanded pore structure, and its strength is increased by sintering, and it is relatively high compared to an untreated fired product with an expanded pore diameter. It is preferable that the porosity, water absorption, and practical strength are realized, and that the calcium phosphate is α-TCP, β-TCP, or hydroxyapatite.
本発明における成形体の主要成分であるα−ＴＣＰ（α−ｔｒｉｃａｌｃｉｕｍ ｐｈｏｓｐｈａｔｅ）は、Ｃａ３（ＰＯ４）２の化学組成を持つリン酸カルシウムであり、例えば、“α−リン酸三カルシウム”と呼ばれている。 Α-TCP (α-tricalcium phosphate), which is a main component of the molded body in the present invention, is calcium phosphate having a chemical composition of Ca 3 (PO 4 ) 2 , and is called, for example, “α-tricalcium phosphate”. ing.
本発明において、α−ＴＣＰは、目的に応じて適宜の形状に成形して用いられるが、例えば、直径１ｍｍ程度の球形状に成形する場合、α−ＴＣＰ原料粉体とアルギン酸ナトリウム水溶液よりなるα−ＴＣＰスラリーを、凝固液に滴下することにより、球状に成形して、α−ＴＣＰ湿潤ゲルビーズにする。このとき、スラリー中のα−ＴＣＰ粒径は、好適には、５μｍ以下であることが、この後に続く多孔化処理の観点から、望ましい。しかし、これらに制限されるものではない。 In the present invention, α-TCP is used after being molded into an appropriate shape according to the purpose. For example, when forming into a spherical shape having a diameter of about 1 mm, α-TCP is made of α-TCP raw material powder and sodium alginate aqueous solution. -Drop the TCP slurry into the coagulation liquid to form a spherical shape into α-TCP wet gel beads. At this time, the α-TCP particle size in the slurry is preferably 5 μm or less from the viewpoint of the subsequent porous treatment. However, it is not limited to these.
成形したα−ＴＣＰを、適宜の液体に浸漬する。α−ＴＣＰ成形体は、湿潤状態、若しくは乾燥状態、焼成状態のいずれでもよい。適宜の液体は、α−ＴＣＰ成形体の浸漬によりｐＨが上昇する液体であればよく、例えば、ｐＨ１．５〜５の塩酸水溶液、コハク酸水溶液、クエン酸水溶液、酢酸水溶液、若しくは、純水、超純水が例示される。しかし、これらに制限されるものではなく、これらと実質的に同効のもの、或いはこれらと類似のものであれば同様に使用することができる。 The molded α-TCP is immersed in an appropriate liquid. The α-TCP molded body may be in a wet state, a dry state, or a fired state. The appropriate liquid may be a liquid whose pH is increased by immersion of the α-TCP molded body. For example, a hydrochloric acid aqueous solution having a pH of 1.5 to 5, a succinic acid aqueous solution, a citric acid aqueous solution, an acetic acid aqueous solution, or pure water, Ultrapure water is exemplified. However, the present invention is not limited to these, and any one having substantially the same effect as these or those similar to these can be used in the same manner.
α−ＴＣＰ成形体は、浸漬液中で徐々に溶解し、浸漬液中のリン、カルシウム濃度を高め、浸漬液のｐＨ上昇をもたらし、その結果、成形体上に析出物を生じるに至る（溶解析出反応）（図１の左参照）。成形体が緻密でない場合、浸漬液は、成形体構成粒子の間隙に浸潤するため、上記の溶解析出反応は、成形体の最表面だけでなく、成形体構成粒子の間隙近傍でも起こる。 The α-TCP molded body dissolves gradually in the immersion liquid, increases the phosphorus and calcium concentration in the immersion liquid, and raises the pH of the immersion liquid, resulting in the formation of precipitates on the molded body (dissolution) (Precipitation reaction) (See the left in FIG. 1). When the molded body is not dense, the immersion liquid infiltrates into the gaps between the molded body constituent particles, and thus the dissolution and precipitation reaction occurs not only on the outermost surface of the molded body but also in the vicinity of the gaps between the molded body constituent particles.
従って、上記溶解析出反応の結果、成形体表面及び構成粒子の間隙に析出物を従えた酸処理α−ＴＣＰ成形体としてのα−ＴＣＰ成形体を得る。析出物は、浸漬液のｐＨと温度、圧力により制御される。 Therefore, as a result of the dissolution precipitation reaction, an α-TCP molded body is obtained as an acid-treated α-TCP molded body in which the precipitates follow the molded body surface and the gaps between the constituent particles. The precipitate is controlled by the pH, temperature and pressure of the immersion liquid.
例えば、α−ＴＣＰ成形体を、ｐＨ２以上の浸漬液に４０℃、常圧で２４時間浸漬することにより、α−ＴＣＰ成形体上にＯＣＰ様の結晶を析出させることができる。また、例えば、α−ＴＣＰ成形体を、ｐＨ２未満の浸漬液に、４℃、常圧で２４時間浸漬することにより、α−ＴＣＰ成形体上にＤＣＰＤ結晶を析出させることができる。 For example, an OCP-like crystal can be deposited on the α-TCP molded body by immersing the α-TCP molded body in an immersion liquid having a pH of 2 or higher at 40 ° C. and normal pressure for 24 hours. Further, for example, the DCPD crystal can be deposited on the α-TCP molded body by immersing the α-TCP molded body in an immersion liquid having a pH of less than 2 at 4 ° C. and normal pressure for 24 hours.
上記のように調製した酸処理α−ＴＣＰ成形体を焼成する。このとき、析出物が分解、除去され、その結果、成形体構成粒子の間隙が拡張した多孔化α−ＴＣＰ成形体としてのα−ＴＣＰ成形体を得る（図１の右参照）。多孔化α−ＴＣＰ成形体は、理想的には、数ミクロンの細孔を持つサンゴ様のｎｏｄｅ−ｓｔｒｕｔ構造になる。 The acid-treated α-TCP molded body prepared as described above is fired. At this time, precipitates are decomposed and removed, and as a result, an α-TCP molded body is obtained as a porous α-TCP molded body in which the gaps between the molded body constituent particles are expanded (see the right in FIG. 1). The porous α-TCP molded body ideally has a coral-like node-strut structure having pores of several microns.
析出物は、例えば、ＭＣＰＭ、ＤＣＰ、ＤＣＰＤ、乃至ＯＣＰのように、α−ＴＣＰよりも熱安定性が低いものであることが望ましい。焼成温度を１１５０〜１４００℃とすると、成形体構成粒子同士はしっかり焼結しながらも、成形体構成粒子の間隙が拡張した、高強度且つ多孔質のα−ＴＣＰ成形体を得ることができる。 Desirably, the precipitate has a lower thermal stability than α-TCP, such as MCPM, DCP, DCPD, or OCP. When the firing temperature is 1150 to 1400 ° C., it is possible to obtain a high-strength and porous α-TCP molded body in which the gap between the molded body constituent particles is expanded while the molded body constituent particles are firmly sintered.
また、焼成温度を８００〜１１５０℃とすると、一部若しくは全部がβ−ＴＣＰ化した多孔質成形体を得ることができる。更に、上記のように調製した多孔化α−ＴＣＰ成形体を水熱処理することにより、一部若しくは全部がＨＡ化した多孔質成形体を得ることができる。 Moreover, when a calcination temperature is set to 800 to 1150 ° C., a porous molded body in which a part or the whole is β-TCP can be obtained. Furthermore, a porous molded body partially or wholly made HA can be obtained by hydrothermally treating the porous α-TCP molded body prepared as described above.
本発明によるリン酸カルシウム系成形体の多孔化方法によれば、サンゴ様構造と数ミクロンの流路幅を持つ細孔を、発泡法や骨材焼失法を用いることなく、α−ＴＣＰ成形体に付与することができる。数ミクロンの細孔は、成形体の比表面積を増大させ、液性成分との親和性を向上し、成形体の溶解性を比較的高くすることができる。 According to the method for making a calcium phosphate-based molded body according to the present invention, a coral-like structure and a pore having a flow path width of several microns are imparted to an α-TCP molded body without using a foaming method or an aggregate burning method. can do. The pores of several microns can increase the specific surface area of the molded body, improve the affinity with the liquid component, and relatively increase the solubility of the molded body.
また、通常、焼結により構成粒子の間隙は縮小するが、そのような常識に反して、本発明では、多孔化処理にもかかわらず、構成粒子同士のしっかりした焼結により高強度化が起こるので、成形体の強度低下が少なく、しかも構成粒子の間隙は拡張される。 In addition, although the gap between the constituent particles is usually reduced by sintering, contrary to such common knowledge, in the present invention, high strength occurs due to the solid sintering of the constituent particles despite the porous treatment. Therefore, the strength reduction of the molded body is small, and the gap between the constituent particles is expanded.
更に、本多孔化処理によれば、α−ＴＣＰ成形体をスタート成形体として、例えば、多孔化後のα−ＴＣＰ成形体を水熱処理することにより、スタート成形体と類似の気孔構造を持つ水酸アパタイト成形体としたり、熱処理温度制御により、スタート成形体と類似の気孔構造を持つβ−ＴＣＰ成形体とすることができる。 Furthermore, according to the present porous treatment, the α-TCP molded body is used as a start molded body, and for example, water having a pore structure similar to that of the start molded body is obtained by hydrothermal treatment of the porous α-TCP molded body. An acid apatite molded body or a β-TCP molded body having a pore structure similar to that of the start molded body can be obtained by controlling the heat treatment temperature.
本発明は、溶解析出反応により、α−ＴＣＰ成形体の構成粒子の間隙近傍に分解しやすい脆弱部位の部分を設け、該部分を熱分解除去することにより、構成粒子の間隙を拡張することで特徴付けられる、多孔質リン酸カルシウム系焼結体及びその製造方法を提供するものである。本発明では、数ミクロンの流路（細孔）幅を持つサンゴ様構造を、発泡法や骨材焼失法を用いることなく、α−ＴＣＰ成形体に付与することが可能である。 The present invention provides a brittle portion portion that is easily decomposed in the vicinity of the gap between the constituent particles of the α-TCP molded body by dissolution and precipitation reaction, and expands the gap between the constituent particles by thermally removing the portion. A porous calcium phosphate-based sintered body and a method for producing the same are characterized. In the present invention, a coral-like structure having a flow path (pore) width of several microns can be imparted to an α-TCP molded body without using a foaming method or an aggregate burning method.
本発明のサンゴ様構造は、成形体の比表面積を増大させ、液性成分との親和性を向上し、成形体の溶解性を比較的高くすることができ、多孔化処理にもかかわらず、成形体の強度低下が少ない。本発明では、α−ＴＣＰ成形体をスタート成形体として、例えば、多孔化後のα−ＴＣＰ成形体を水熱処理することにより、スタート成形体と類似の気孔構造を持つ水酸アパタイト成形体とすることが可能である。 The coral-like structure of the present invention can increase the specific surface area of the molded body, improve the affinity with the liquid component, and can relatively increase the solubility of the molded body. There is little decrease in strength of the molded body. In the present invention, the α-TCP molded body is used as a start molded body. For example, the porous α-TCP molded body is hydrothermally treated to form a hydroxyapatite molded body having a pore structure similar to that of the start molded body. It is possible.
本発明のリン酸カルシウム系成形体の多孔化方法は、熱処理温度制御により、スタート成形体と類似の気孔構造を持つβ−ＴＣＰ成形体とすることができ、例えば、人工骨、薬剤担体、触媒担体、フィルターなどを製造するための手段として好適に利用することが可能である。 The method for making a calcium phosphate-based molded body of the present invention porous can be a β-TCP molded body having a pore structure similar to the start molded body by heat treatment temperature control. For example, artificial bone, drug carrier, catalyst carrier, It can be suitably used as a means for producing a filter or the like.
本発明により、次のような格別の作用効果が奏される。
（１）溶解析出反応により、α−ＴＣＰ成形体の構成粒子の間隙近傍に分解しやすい脆弱部位の部分を設け、該部分を熱分解除去することにより、構成粒子同士を焼結、高強度化すると共に、構成粒子の間隙を拡張した、多孔質人工骨を製造し、提供することができる。
（２）数ミクロンの流路（細孔）幅を持つサンゴ様構造を、発泡法や骨材焼失法を用いることなく、α−ＴＣＰ成形体に付与することができる。
（３）サンゴ様構造は、成形体の比表面積を増大させ、液性成分との親和性を向上し、成形体の溶解性を比較的高くすることができる。
（４）多孔化処理にもかかわらず、成形体の強度低下が少ない。
（５）α−ＴＣＰ成形体をスタート成形体として、例えば、多孔化後のα−ＴＣＰ成形体を水熱処理することにより、スタート成形体と類似の気孔構造を持つ水酸アパタイト成形体としたり、熱処理温度制御によりスタート成形体と類似の気孔構造を持つβ−ＴＣＰ成形体とすることができる。
（６）本発明の多孔化方法は、例えば、人工骨、薬剤担体、触媒担体、フィルターなどを製造するための手段として好適に利用しうるものとして有用である。
According to the present invention, the following special effects are achieved.
(1) By the dissolution and precipitation reaction, a portion of a fragile portion that is easily decomposed is provided in the vicinity of the gap between the constituent particles of the α-TCP molded body, and the constituent particles are sintered and increased in strength by removing the portion by thermal decomposition. At the same time, it is possible to manufacture and provide a porous artificial bone having an expanded gap between constituent particles.
(2) A coral-like structure having a flow path (pore) width of several microns can be imparted to an α-TCP molded body without using a foaming method or an aggregate burning method.
(3) The coral-like structure can increase the specific surface area of the molded body, improve the affinity with the liquid component, and relatively increase the solubility of the molded body.
(4) Despite the porous treatment, there is little decrease in strength of the molded body.
(5) The α-TCP molded body as a start molded body, for example, by hydrothermal treatment of the porous α-TCP molded body, a hydroxyapatite molded body having a pore structure similar to the start molded body, A β-TCP molded body having a pore structure similar to the start molded body can be obtained by controlling the heat treatment temperature.
(6) The porous method of the present invention is useful, for example, as a means that can be suitably used as a means for producing artificial bones, drug carriers, catalyst carriers, filters, and the like.
以下、本発明を実施例に基づいて具体的に説明するが、本発明は、これらによって何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these.
α−ＴＣＰ粉体と１％アルギン酸ナトリウム水溶液を混合し、４０％α−ＴＣＰスラリーを調製した。上記α−ＴＣＰスラリーを、１％塩化カルシウム水溶液に滴下することにより、α−ＴＣＰゲルビーズを作製した。上記α−ＴＣＰゲルビーズを、６０℃、２４時間乾燥することにより、α−ＴＣＰ乾燥ビーズを作製した。乾燥α−ＴＣＰビーズの空隙率及び空隙メジアン径は、５８．７８％、０．６９０５μｍであった。 α-TCP powder and 1% sodium alginate aqueous solution were mixed to prepare a 40% α-TCP slurry. The α-TCP slurry was dropped into a 1% calcium chloride aqueous solution to prepare α-TCP gel beads. The α-TCP gel beads were dried at 60 ° C. for 24 hours to prepare α-TCP dry beads. The porosity and median diameter of the dry α-TCP beads were 58.78% and 0.6905 μm.
α−ＴＣＰ乾燥ビーズをｐＨ２．５の塩酸酸性水溶液に浸漬し、４０℃、２４時間静置した。上記処理により、α−ＴＣＰ乾燥ビーズの一部が溶解し、溶液中のｐＨを上昇させ、その結果として、α−ＴＣＰ乾燥ビーズ上に析出物が形成された。α−ＴＣＰ乾燥ビーズ上の析出物は、ＯＣＰ様のモルフォロジーを呈した（図２）。酸処理α−ＴＣＰビーズの空隙率及び空隙メジアン径は、５５．２７％、０．０４２０μｍであった。 The α-TCP dried beads were immersed in an acidic aqueous hydrochloric acid solution having a pH of 2.5 and allowed to stand at 40 ° C. for 24 hours. By the said process, a part of (alpha) -TCP dry bead melt | dissolved and the pH in a solution was raised, As a result, the deposit was formed on the (alpha) -TCP dry bead. The precipitate on the α-TCP dry beads exhibited an OCP-like morphology (FIG. 2). The porosity and median diameter of the acid-treated α-TCP beads were 55.27% and 0.0420 μm.
上記酸処理後のα−ＴＣＰビーズを、水洗、乾燥後、１４００℃で焼成することにより、ビーズ上の析出物を分解し、サンゴ様構造を持つ多孔質α−ＴＣＰビーズを得た（図３）。多孔化α−ＴＣＰビーズの空隙率及び空隙メヂアン径は、４２．０７％、１．６９２μｍであり、気孔径の拡張が確認できた。 The acid-treated α-TCP beads were washed with water, dried, and then fired at 1400 ° C. to decompose precipitates on the beads to obtain porous α-TCP beads having a coral-like structure (FIG. 3). ). The porosity and void median diameter of the porous α-TCP beads were 42.07% and 1.692 μm, and expansion of the pore diameter was confirmed.
粉砕したα−ＴＣＰ粉体を用いて、実施例１と同様の多孔化処理を行うことにより、よりサンゴ様構造が顕著なα−ＴＣＰ多孔体を得ることができた（図４）。 Using the pulverized α-TCP powder, the same porous treatment as in Example 1 was performed, and an α-TCP porous body with a more remarkable coral-like structure could be obtained (FIG. 4).
実施例１と同様の方法で、α−ＴＣＰ乾燥ビーズを作製した。α−ＴＣＰ乾燥ビーズをｐＨ１．５の塩酸酸性水溶液に浸漬し、４℃、２４時間静置した。上記処理により、α−ＴＣＰ乾燥ビーズの一部が溶解し、溶液中のｐＨを上昇させ、その結果として、α−ＴＣＰ乾燥ビーズ上に、ＤＣＰＤの析出物が形成された。（図５）。上記酸処理後のα−ＴＣＰビーズを、水洗、乾燥後、１４００℃で焼成することにより、ビーズ上の析出物を分解し、多孔質α−ＴＣＰビーズを得た（図６）。 Α-TCP dry beads were produced in the same manner as in Example 1. The α-TCP dry beads were immersed in an acidic aqueous hydrochloric acid solution having a pH of 1.5 and allowed to stand at 4 ° C. for 24 hours. By the said process, a part of alpha-TCP dry bead melt | dissolved and the pH in a solution was raised, As a result, the deposit of DCPD was formed on the alpha-TCP dry bead. (FIG. 5). The α-TCP beads after the acid treatment were washed with water, dried and then fired at 1400 ° C. to decompose precipitates on the beads to obtain porous α-TCP beads (FIG. 6).
実施例１で作製した多孔化α−ＴＣＰビーズを、１５０℃、５日間水熱処理することにより、ＨＡ化多孔化α−ＴＣＰビーズを作製することができた（図７）。 The porous α-TCP beads prepared in Example 1 were hydrothermally treated at 150 ° C. for 5 days, whereby HA-modified porous α-TCP beads could be prepared (FIG. 7).
比較例１
実施例１において、塩酸処理を行わずに、α−ＴＣＰビーズを１４００℃で焼成した。ただα−ＴＣＰビーズを１４００℃で焼成しただけでは、サンゴ様構造はできなかった（図８）。無処理α−ＴＣＰビーズの空隙率及び空隙メジアン径は、２３．２３％、０．６６８６μｍであった。
Comparative Example 1
In Example 1, α-TCP beads were baked at 1400 ° C. without performing hydrochloric acid treatment. However, a coral-like structure could not be obtained only by firing α-TCP beads at 1400 ° C. (FIG. 8). The porosity and median diameter of the untreated α-TCP beads were 23.23% and 0.6686 μm.
実施例１と同様の方法で、α−ＴＣＰスラリーを３０％として作製したα−ＴＣＰ乾燥ビーズを、５００ｍｇずつ、ｐＨ２．５の塩酸酸性水溶液２５ｍｌに浸漬し、４０℃のインキュベーターシェイカーで、１、３，５，１５，２４，４８時間、５０ｒｐｍで、振盪して、溶解析出反応を促進することにより、α−ＴＣＰ乾燥ビーズ上に、析出物を形成した。上記酸処理中の処理液ｐＨは、各経過時間において、６．４、６．３７５、６．３０１、６．１４８、５．８６７、５．６８２となった。酸処理１時間のｐＨ上昇は、α−ＴＣＰ乾燥ビーズの溶解を、その後のｐＨ下降は、処理液からのリン酸カルシウムの析出を、それぞれ示唆している。 In the same manner as in Example 1, α-TCP dried beads prepared with 30% α-TCP slurry were immersed in 25 ml of an acidic aqueous hydrochloric acid solution having a pH of 2.5, and 1 in a 40 ° C. incubator shaker. The precipitate was formed on the α-TCP dry beads by accelerating the dissolution precipitation reaction by shaking at 50 rpm for 3, 5, 15, 24, 48 hours. The treatment solution pH during the acid treatment was 6.4, 6.375, 6.301, 6.148, 5.867, 5.682 at each elapsed time. An increase in pH during 1 hour of acid treatment suggests dissolution of α-TCP dry beads, and a subsequent decrease in pH suggests precipitation of calcium phosphate from the treatment solution.
以上詳述したように、本発明は、溶解析出反応により、α−ＴＣＰ成形体の構成粒子の間隙近傍に分解しやすい脆弱部位の部分を設け、該部分を熱分解除去することにより、構成粒子の間隙を拡張することを特徴とした、多孔質リン酸カルシウム系焼結体及びその製造方法に係るものであり、本発明により、数ミクロンの流路（細孔）幅を持つサンゴ様構造を、発泡法や骨材焼失法を用いることなく、α−ＴＣＰ成形体に付与することができる。本発明のサンゴ様構造は、成形体の比表面積を増大させ、液性成分との親和性を向上し、成形体の溶解性を比較的高くすることができる。 As described above in detail, the present invention provides a constituent particle by providing a portion of a fragile portion that is easily decomposed in the vicinity of a gap between constituent particles of the α-TCP molded body by dissolution and precipitation, and thermally decomposing and removing the portion. According to the present invention, a coral-like structure having a flow path (pore) width of a few microns is foamed, which relates to a porous calcium phosphate sintered body and a method for producing the same. It can be applied to the α-TCP molded body without using the method or the aggregate burning method. The coral-like structure of the present invention can increase the specific surface area of the molded body, improve the affinity with the liquid component, and relatively increase the solubility of the molded body.
多孔化処理にもかかわらず、成形体の強度低下が少ない。本発明では、α−ＴＣＰ成形体をスタート成形体として、例えば、多孔化後のα−ＴＣＰ成形体を水熱処理することにより、スタート成形体と類似の気孔構造を持つ水酸アパタイト成形体としたり、熱処理温度制御により、スタート成形体と類似の気孔構造を持つβ−ＴＣＰ成形体とすることができる。本発明のリン酸カルシウム系成形体の多孔化方法は、例えば、人工骨、薬剤担体、触媒担体、フィルターなどを製造するための手段として好適に利用しうるものとして有用である。 Despite the porous treatment, there is little decrease in strength of the molded body. In the present invention, the α-TCP molded body is used as a start molded body. For example, by hydrothermally treating the porous α-TCP molded body, a hydroxyapatite molded body having a pore structure similar to that of the start molded body can be obtained. The β-TCP molded body having a pore structure similar to that of the start molded body can be obtained by controlling the heat treatment temperature. The method for making a calcium phosphate-based molded body of the present invention porous is useful, for example, as a means that can be suitably used as a means for producing artificial bones, drug carriers, catalyst carriers, filters, and the like.
Claims (12)
１）液体中で多孔化対象のα−ＴＣＰ成形体の液体暴露部の溶解析出反応を促し、熱で分解しやすい脆弱部位の部分を設け、
２）該成形体を熱処理することにより、上記脆弱部位を分解、除去し、構成粒子同士を焼結すると共に、成形体構成粒子の間隙を拡張する、
ことを特徴とする、リン酸カルシウム系成形体の多孔体の製造方法。 A method for producing a porous body of a calcium phosphate-based molded body by the following two steps,
1) Promote dissolution and precipitation reaction of the liquid exposed portion of the α-TCP molded body to be made porous in the liquid, and provide a portion of a fragile portion that is easily decomposed by heat.
2) By heat-treating the molded body, the fragile site is decomposed and removed, the constituent particles are sintered with each other, and the gap between the molded body constituent particles is expanded.
The manufacturing method of the porous body of the calcium-phosphate type molded object characterized by the above-mentioned.
α−ＴＣＰ成形体の焼結と、溶解析出反応で形成された脆弱部位の分解によりできた、脆弱部位の分解残渣を伴ったサンゴ様のｎｏｄｅ−ｓｔｒｕｔ構造と拡張した気孔構造を有し、焼結で強度が上がり、かつ気孔径が拡張した、無処理の焼成品と比べて比較的高い気孔率、吸水性、及び実用的な強度を実現していることを特徴とするリン酸カルシウム系成形体の多孔体。 It is a porous body of a calcium phosphate-based molded body obtained by firing an α-TCP molded body after dissolution and precipitation treatment,
It has a coral-like node-strut structure with a fragile site decomposition residue and an expanded pore structure formed by sintering of the α-TCP molded body and decomposition of the fragile site formed by dissolution and precipitation reaction. A calcium phosphate-based molded article characterized by achieving a relatively high porosity, water absorption, and practical strength compared to an untreated fired product with increased strength due to bonding and expanded pore diameter. Porous body.
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| JP2020503109A (en) * | 2016-12-23 | 2020-01-30 | サンスター スイス エスエー | Bone graft substitute |
| JP2023072636A (en) * | 2021-11-12 | 2023-05-24 | ▲フ▼派海洋生技股▲分▼有限公司 | Porous tricalcium phosphate material, pharmaceutical composition for bone healing containing the same, and method for producing the same |
| JP7483782B2 (en) | 2016-12-23 | 2024-05-15 | コラジェン マトリックス，インク． | Bone graft substitutes |
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| JP2005067966A (en) * | 2003-08-26 | 2005-03-17 | Makoto Kitamura | Calcium phosphate ceramics porous material and its manufacturing method |
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| JP2020503109A (en) * | 2016-12-23 | 2020-01-30 | サンスター スイス エスエー | Bone graft substitute |
| JP2022088628A (en) * | 2016-12-23 | 2022-06-14 | コラジェン マトリックス，インク． | Bone transplant substitute |
| JP7197483B2 (en) | 2016-12-23 | 2022-12-27 | コラジェン マトリックス，インク． | bone graft substitute |
| JP7483782B2 (en) | 2016-12-23 | 2024-05-15 | コラジェン マトリックス，インク． | Bone graft substitutes |
| JP2023072636A (en) * | 2021-11-12 | 2023-05-24 | ▲フ▼派海洋生技股▲分▼有限公司 | Porous tricalcium phosphate material, pharmaceutical composition for bone healing containing the same, and method for producing the same |
| JP7419422B2 (en) | 2021-11-12 | 2024-01-22 | ▲フ▼派海洋生技股▲分▼有限公司 | Porous tricalcium phosphate material, pharmaceutical composition for bone healing containing the same, and method for producing the same |
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