JPS63176347A - Manufacture of apatite porous body - Google Patents

Manufacture of apatite porous body

Info

Publication number
JPS63176347A
JPS63176347A JP62004637A JP463787A JPS63176347A JP S63176347 A JPS63176347 A JP S63176347A JP 62004637 A JP62004637 A JP 62004637A JP 463787 A JP463787 A JP 463787A JP S63176347 A JPS63176347 A JP S63176347A
Authority
JP
Japan
Prior art keywords
apatite
porous body
powder
porosity
porous
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.)
Granted
Application number
JP62004637A
Other languages
Japanese (ja)
Other versions
JPH0214311B2 (en
Inventor
英毅 門間
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute for Research in Inorganic Material
Original Assignee
National Institute for Research in Inorganic Material
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National Institute for Research in Inorganic Material filed Critical National Institute for Research in Inorganic Material
Priority to JP62004637A priority Critical patent/JPS63176347A/en
Publication of JPS63176347A publication Critical patent/JPS63176347A/en
Publication of JPH0214311B2 publication Critical patent/JPH0214311B2/ja
Granted legal-status Critical Current

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  • Dental Preparations (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。
(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 産業上の利用分野 本発明はアパタイト多孔体の製造方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for manufacturing a porous apatite body.

アパタイト多孔体及びその焼成物は生体内の歯。Apatite porous bodies and their fired products are teeth in living organisms.

骨の主成分に近似した化学組成を有し、歯、骨修復材料
として、また生体高分子や生体有害有機物または無機質
イオンの吸着剤としてを用なものである。
It has a chemical composition similar to the main component of bone, and is used as a tooth and bone repair material, and as an adsorbent for biopolymers, biohazardous organic substances, and inorganic ions.

従来技術 従来の水硬性リン酸カルシウムには、リン酸四カルシウ
ムとリン酸三カルシウムとが知られている。これらの水
硬化性を利用して(硬化物はアパタイト多孔体)覆髄材
、裏装材として歯科治療に使用されている。
Prior Art Tetracalcium phosphate and tricalcium phosphate are known as conventional hydraulic calcium phosphates. Utilizing these water-curing properties (the cured product is a porous apatite), it is used in dental treatment as pulp capping material and lining material.

しかし、リン酸三カルシウム、リン酸四カルシウムは、
ピロリン酸カルシウム(CatPtOt)粉末とカルシ
ウム塩粉末との混合物を1200℃以上での焼成による
固相反応、その後急冷、粉砕して製造されるので、非常
に高価なものとなる欠点があった。
However, tricalcium phosphate and tetracalcium phosphate
Since it is produced by solid phase reaction by firing a mixture of calcium pyrophosphate (CatPtOt) powder and calcium salt powder at 1200° C. or higher, followed by rapid cooling and pulverization, it has the disadvantage of being very expensive.

発明の目的 本発明は従来法のような高価なリン酸三カルシウム、リ
ン酸四カルシウムを使用することなく、安価にアパタイ
ト多孔体を得る方法を提供するにある。
OBJECTS OF THE INVENTION The present invention provides a method for obtaining a porous apatite material at low cost without using expensive tricalcium phosphate or tetracalcium phosphate as in conventional methods.

発明の構成 本発明は前記目的を達成すべく鋭意研究の結果、リン酸
水素カルシウム2永和物またはその無水物に炭酸カルシ
ウム粉末を混和すると、炭酸カルシウムがpH緩衝材と
して作用し、水硬化し得られ、容易にアパタイト多孔体
が得られる新しい知見を得た。この知見に基づいて本発
明を完成した。
Structure of the Invention The present invention has been made as a result of intensive research to achieve the above object. When calcium carbonate powder is mixed with calcium hydrogen phosphate dihydrate or its anhydride, the calcium carbonate acts as a pH buffering material and can be water-cured. We obtained new knowledge that allows easy production of apatite porous materials. The present invention was completed based on this knowledge.

本発明の要旨は、リン酸水素カルシウム2水和物または
その無水水和物にCa/Pモル比で1.50〜1.67
になる割合で炭酸カルシウム粉末を配合し、これに水を
加えて水和反応させることを特徴とするアパタイト多孔
体の製造方法にある。リン酸水素カルシウム2水和物(
CaHPOa・2)1.0)およびその無水和物(Ca
HPOa)は、次のような水和反応でアパタイトへ変化
する。
The gist of the present invention is to provide calcium hydrogen phosphate dihydrate or its anhydrous hydrate with a Ca/P molar ratio of 1.50 to 1.67.
A method for producing an apatite porous material is provided, which comprises blending calcium carbonate powder in a proportion as follows, adding water to the powder, and causing a hydration reaction. Calcium hydrogen phosphate dihydrate (
CaHPOa・2)1.0) and its anhydrate (Ca
HPOa) changes into apatite through the following hydration reaction.

CaHPO4・2HtOまたはCaHPOa+ (4−
Z )H,PO4 (但し、0≦n≦2.5.0≦Z≦1を表わす)この水
和反応は弱酸性から塩基性の範囲(6〈pH<9)でよ
く進行する。従って、反応進行に伴って生ずるH3P0
aによるpH降下を緩衝しなければ反応は進行しない。
CaHPO4・2HtO or CaHPOa+ (4-
Z ) H, PO4 (0≦n≦2.5.0≦Z≦1) This hydration reaction proceeds well in the weakly acidic to basic range (6<pH<9). Therefore, H3P0 generated as the reaction progresses
The reaction will not proceed unless the pH drop caused by a is buffered.

そのために、これまではpH緩衝液を予め反応系に入れ
ておくか、あるいは消石灰またはアンモニア水等の塩基
性物質を逐次添加してきた。このような方法では反応系
を常に攪拌しなければならなかった。この攪拌のため得
られるものは粉末状のものとなり、硬化したアパタイト
多孔体を得ることはできなかった。
To this end, until now, a pH buffer solution has been added to the reaction system in advance, or a basic substance such as slaked lime or aqueous ammonia has been successively added. In such a method, the reaction system had to be constantly stirred. Due to this stirring, the product obtained was in the form of powder, and a hardened porous apatite material could not be obtained.

本発明のように、CaHPO4・2HioまたはCaH
PO4の粉末に固体pHtl衝材であるCaC0z粉末
を混合しておくと、水和反応に伴うpH降下をCaC0
z粉末により緩衝し得られ、攪拌を必要とせず、静置状
態で水和反応を進行し得られ、同時に反応生成物は互い
にからみ合ったアパタイト多孔体として得られる。
As in the present invention, CaHPO4.2Hio or CaH
If CaC0z powder, which is a solid pHtl buffer, is mixed with PO4 powder, the pH drop caused by the hydration reaction can be suppressed by CaC0.
It is obtained by buffering with Z powder, and the hydration reaction can proceed in a stationary state without stirring, and at the same time, the reaction product is obtained as a porous apatite body entangled with each other.

固体pH緩衝材としてはCaC0,以外にBaC0,。Solid pH buffering materials include CaC0 and BaC0.

5rCOsなどがあるが、これらの金属成分は生体異物
であるので、CaC0,であることが好ましい。
5rCOs, etc., but since these metal components are xenobiotics, CaCO is preferable.

CaCO3粉末のCaHPOa・2HzOまたはCaH
POa粉末への混合割合はCa/Pモル比で1.50〜
1.67である。
CaCO3 powder CaHPOa・2HzO or CaH
The mixing ratio to POa powder is Ca/P molar ratio of 1.50~
It is 1.67.

Ca/Pモル比が1.50未満では未反応のCaHPO
t ’ 2HzOまたはCaHPO4が残留するので、
焼成するとCa=(PO4)zとビロリン酸カルシウム
(CaHPO4)との混合相からなるセラミック多孔体
となる。また1゜67を超えると遊離のCaC0,が混
合してき、これを焼成するとCaOとなり、高アルカリ
性となり、生体には使用し難くなる。
If the Ca/P molar ratio is less than 1.50, unreacted CaHPO
t' 2HzO or CaHPO4 remains, so
When fired, it becomes a ceramic porous body consisting of a mixed phase of Ca=(PO4)z and calcium birophosphate (CaHPO4). Moreover, when the temperature exceeds 1°67, free CaC0 is mixed in, and when this is calcined, it becomes CaO, which becomes highly alkaline and difficult to use for living organisms.

この混合物に水を加えてスラリー化してから型に流し込
み、これを100℃未満で加温するとアパタイトが生じ
て硬化する。その基本反応を示すと次の通りである。
Water is added to this mixture to form a slurry, which is then poured into a mold and heated at less than 100°C to form apatite and harden. The basic reaction is shown below.

CaHPOt ・2HzOまたはCaHPOa+(4−
Z )H3PO4 生じたHzPOaはCaC0、によって次のように中和
されてアパタイトに転化する。
CaHPOt ・2HzO or CaHPOa+ (4-
Z ) H3PO4 The generated HzPOa is neutralized by CaC0 and converted into apatite as follows.

6HffPO,+(10−Z )CaCO++ 88z
O+)bC(h ” (9−Z)C(h(但し、0≦n
≦2.5.0≦2≦1を表わす)得られたアパタイト水
硬多孔体を1ooo〜1350℃で焼成すると気孔率が
低下し、強度の高まったリン酸カルシウムセラミック多
孔体が得られる。
6HffPO, +(10-Z)CaCO++ 88z
O+)bC(h ” (9-Z)C(h (however, 0≦n
≦2.5.0≦2≦1) When the obtained apatite hydraulic porous body is fired at 100° C. to 1350° C., the porosity is reduced and a calcium phosphate ceramic porous body with increased strength is obtained.

該多孔体はアパタイト単一組(Z=0の場合)、あるい
はアパタイトとCa3(POt)i (0<Z ≦1の
場合)の種々割合の混合相のものとなる。
The porous body is a single apatite group (when Z=0) or a mixed phase of apatite and Ca3(POt)i (when 0<Z≦1) in various proportions.

この焼成温度が1000℃未満では焼結し難く、135
0℃を超えるとアパタイトが分解し初めるので、焼成に
際しては前記の温度であることが必要である。焼成の反
応式を示すと次の通りである。
If the firing temperature is less than 1000°C, sintering will be difficult and 135
If the temperature exceeds 0° C., the apatite will begin to decompose, so it is necessary to keep the above-mentioned temperature during firing. The reaction formula for calcination is as follows.

Ca+ o−g(HPO4)z(PO4)6−11(O
H) z−z ・n)lzO−” (1−Z )Ca+
o(Pot)6(OH)z+3Zca*(POt)z+
(Z+n)HzO 但し、0<2≦1を表わす。
Ca+ o-g(HPO4)z(PO4)6-11(O
H) z−z ・n)lzO−” (1−Z )Ca+
o(Pot)6(OH)z+3Zca*(POt)z+
(Z+n)HzO However, 0<2≦1.

実施例1゜ CaHPOt 42HzO粉末にCaC0,粉末をCa
/Pモル比が1.67になるように配合し、この混合物
を水でスラリー化してパイレックス管に流し込み、ふた
をして50℃で16時間加温して硬化させた。得られた
未反応原料粉末を含むアパタイト水硬多孔体は気孔率7
1〜74%、ダイアメトラル引張り強さ15〜12kg
/am”であった。
Example 1゜CaHPOt 42HzO powder with CaC0, powder with Ca
/P molar ratio was 1.67, this mixture was slurried with water, poured into a Pyrex tube, covered with a lid, and heated at 50° C. for 16 hours to cure. The resulting apatite hydraulic porous body containing unreacted raw material powder has a porosity of 7.
1-74%, diametral tensile strength 15-12kg
/am”.

実施例2゜ 実施例1において、50℃で16時間を80℃で22時
間に変えて行ったところ、気孔率71〜76%、ダイア
メトラル引張り強さ17〜8 kg/co+”の未反応
原料粉末を含むアパタイト水硬多孔体が得られた。
Example 2 In Example 1, 16 hours at 50°C was changed to 22 hours at 80°C, resulting in an unreacted raw material powder with a porosity of 71-76% and a diametral tensile strength of 17-8 kg/co+''. An apatite hydraulic porous material was obtained.

これを1250℃で3時間焼成した。気孔率は45〜5
0%に減少し、ダイアメトラル引張り強さは48〜19
 kg/c+a”に増大したアパタイト単一組のセラミ
ック多孔体が得られた。
This was baked at 1250°C for 3 hours. Porosity is 45-5
0% and the diametral tensile strength is 48-19
A ceramic porous body with a single set of apatite increased to kg/c+a'' was obtained.

実施例3゜ 実施例1において、CaHPOa・2820に変えてC
aHPO4を用いて、80℃で40時間加温して硬化さ
せると、気孔率79〜81%、ダイアメトラル引張り強
さ4〜2 kg/cm”のアパタイト単一組の水硬多孔
体が得られた。
Example 3 In Example 1, instead of CaHPOa 2820, C
When aHPO4 was used and cured by heating at 80°C for 40 hours, a single set of apatite hydraulic porous material with a porosity of 79-81% and a diametral tensile strength of 4-2 kg/cm was obtained. .

実施例4゜ Ca1(PO* ・2H冨0粉末にCaC01粉末をC
a/Pモル比が1.57になるように混合し、この混合
物を水でスラリー化してからパイレックス管に流し込み
、ふたをして80℃で16時間加温して硬化させた。得
られたアパタイト単一組からなる水硬多孔体の気孔率は
72〜80%、ダイアメトラル引張り強さは2〜1kg
/am”であった。
Example 4゜CaC01 powder was added to Ca1(PO*・2H-0 powder)
The mixture was mixed so that the a/P molar ratio was 1.57, and this mixture was slurried with water, poured into a Pyrex tube, covered with a lid, and heated at 80° C. for 16 hours to cure. The resulting hydraulic porous body consisting of a single set of apatite has a porosity of 72 to 80% and a diametral tensile strength of 2 to 1 kg.
/am”.

これを1250℃で3時間焼成すると、気孔率は46〜
47%に減少し、ダイアメトラル引張り強さは5〜4 
kg/cm”に増大したアパタイトとリン酸三カルシウ
ムとの混合相からなるセラミック多孔体が得られた。
When this is fired at 1250℃ for 3 hours, the porosity is 46~
47%, and the diametral tensile strength is 5-4
A ceramic porous body consisting of a mixed phase of apatite and tricalcium phosphate, which increased in size to 100 kg/cm'', was obtained.

比較例 実施例4において、Ca/Pモル比が1.33になるよ
うにして硬化させた。得られた未反応原料を含むアパタ
イト水硬多孔体の気孔率は77〜80%、ダイアメトラ
ル引張り強さは8〜3 kg/am2であった。
Comparative Example In Example 4, curing was performed such that the Ca/P molar ratio was 1.33. The resulting apatite hydraulic porous body containing unreacted raw materials had a porosity of 77 to 80% and a diametral tensile strength of 8 to 3 kg/am2.

これを実施例4と同様に焼成すると、気孔率は60〜6
1%に減少し、ダイアメトラル引張り強さは14〜11
 kg/cn”に増大したリン酸三カルシウムとビロリ
ン酸カルシウムとの混合相からなるセラミック多孔体が
得られた。
When this was fired in the same manner as in Example 4, the porosity was 60 to 6.
1%, and the diametral tensile strength is 14-11
A ceramic porous body consisting of a mixed phase of tricalcium phosphate and birocalcium phosphate, which increased in weight to kg/cn'', was obtained.

発明の効果 本発明の方法によると、従来法におけるような高価なリ
ン酸三カルシウム、リン酸四カルシウムを使用すること
なく、安価に得られるリン酸水素カルシウム・2水和物
またはその無水和物から容易にアパタイト多孔体が得ら
れ、その気孔率も高範囲に制御し得られる優れた効果を
奏し得られる。
Effects of the Invention According to the method of the present invention, calcium hydrogen phosphate dihydrate or its anhydrate can be obtained at low cost without using expensive tricalcium phosphate or tetracalcium phosphate as in conventional methods. An apatite porous body can be easily obtained from the above, and the porosity can be controlled within a high range, resulting in excellent effects.

Claims (1)

【特許請求の範囲】[Claims] リン酸水素カルシウム2水和物またはその無水和物にC
a/Pモル比で1.50〜1.67になる割合で炭酸カ
ルシウム粉末を配合し、これを水を加えて水和反応させ
ることを特徴とするアパタイト多孔体の製造方法。
Calcium hydrogen phosphate dihydrate or its anhydrate with C
A method for producing an apatite porous body, which comprises blending calcium carbonate powder in an a/P molar ratio of 1.50 to 1.67, and adding water to cause a hydration reaction.
JP62004637A 1987-01-12 1987-01-12 Manufacture of apatite porous body Granted JPS63176347A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62004637A JPS63176347A (en) 1987-01-12 1987-01-12 Manufacture of apatite porous body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62004637A JPS63176347A (en) 1987-01-12 1987-01-12 Manufacture of apatite porous body

Publications (2)

Publication Number Publication Date
JPS63176347A true JPS63176347A (en) 1988-07-20
JPH0214311B2 JPH0214311B2 (en) 1990-04-06

Family

ID=11589514

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62004637A Granted JPS63176347A (en) 1987-01-12 1987-01-12 Manufacture of apatite porous body

Country Status (1)

Country Link
JP (1) JPS63176347A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008501643A (en) * 2004-05-06 2008-01-24 イノフォス インコーポレーテッド Novel hydroxyapatite calcium phosphate, its preparation and use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010140634A1 (en) * 2009-06-02 2010-12-09 日鉄鉱業株式会社 Tube-shaped calcium phosphate and process for production thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008501643A (en) * 2004-05-06 2008-01-24 イノフォス インコーポレーテッド Novel hydroxyapatite calcium phosphate, its preparation and use

Also Published As

Publication number Publication date
JPH0214311B2 (en) 1990-04-06

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