JPH0461807B2 - - Google Patents
Info
- Publication number
- JPH0461807B2 JPH0461807B2 JP61094634A JP9463486A JPH0461807B2 JP H0461807 B2 JPH0461807 B2 JP H0461807B2 JP 61094634 A JP61094634 A JP 61094634A JP 9463486 A JP9463486 A JP 9463486A JP H0461807 B2 JPH0461807 B2 JP H0461807B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- wet
- drying
- calcium
- hydroxyapatite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 18
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 230000000887 hydrating effect Effects 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 102100036850 C-C motif chemokine 23 Human genes 0.000 description 6
- 101000713081 Homo sapiens C-C motif chemokine 23 Proteins 0.000 description 6
- 239000001506 calcium phosphate Substances 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Dental Preparations (AREA)
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は高純度でCa/Pのモル比が理論値1.67
に極めて近似した値を有する粒子状の水酸アパタ
イトの製造方法に関する。[Detailed description of the invention] (Industrial application field) The present invention has high purity and a theoretical value of Ca/P molar ratio of 1.67.
The present invention relates to a method for producing particulate hydroxyapatite having a value extremely close to .
(従来の技術)
従来、水酸アパタイトはCa10(PO4)6(OH)2の
化学式であつて、化学量論的なCa/Pのモル比
は1.67の値を有し、その合成方法としてはカルシ
ウム成分とりん酸成分とを水中での反応による湿
式法と高温下の固相反応による乾式法とがあるが
何れの方法によつてもCa/Pのモル比が1.67の水
酸アパタイトが得られなかつた。そのため、従来
法としては先ずりん酸成分とカルシウム成分とを
反応せしめてCa/Pモルが1.65近辺の微結晶のり
ん酸カルシウムを製造した後不足のカルシウム成
分を更に添加反応させてCa/Pモル比1.67近似の
ものを得る方法(例えば特開昭53−110999号、特
開昭53−111000号、特公昭59−13443号等参照)
やCa/Pモル比1.6まではPHを10以下に保ちなが
らCaHPO4またはCaHPO4・2H2OとCa(OH)2と
を反応させる方法(特開昭60−5009号公報参照)
等の方法があるが、これらの方法はカルシウム成
分を2段階に分けて行うため、反応のコントロー
ルが煩瑣であつたり、或は反応条件が過酷である
等の欠点があつた。他方、カルシウム成分の水溶
液又は懸濁液にりん酸成分の水溶液又は懸濁液を
摩砕させながら反応させる方法(特開昭59−
21509号公報参照)があり、この方法は1段階で
カルシウム成分とりん酸成分とを反応させる長所
を有するが反応中に摩砕操作を行うため反応熱が
上がり過ぎて得られた微結晶りん酸カルシウムの
Ca/P比が1.67からかなりずれることがある、等
の欠点があり、必ずしも満足すべき方法とは云え
なかつた。(Prior art) Hydroxyapatite has a chemical formula of Ca 10 (PO 4 ) 6 (OH) 2 and a stoichiometric Ca/P molar ratio of 1.67. There are two methods: a wet method in which a calcium component and a phosphoric acid component are reacted in water, and a dry method in which a solid phase reaction is performed at high temperatures. was not obtained. Therefore, the conventional method is to first react the phosphoric acid component and the calcium component to produce microcrystalline calcium phosphate with a Ca/P mole of around 1.65, and then add and react the insufficient calcium component to produce Ca/P mole. A method to obtain a ratio approximating 1.67 (for example, see Japanese Patent Application Laid-Open No. 53-110999, Japanese Patent Application Publication No. 53-111000, Japanese Patent Publication No. 59-13443, etc.)
A method of reacting CaHPO 4 or CaHPO 4.2H 2 O with Ca(OH) 2 while keeping the pH below 10 for Ca/P molar ratios up to 1.6 (see JP-A-60-5009).
However, since these methods involve dividing the calcium component into two stages, they have drawbacks such as complicated reaction control and harsh reaction conditions. On the other hand, there is a method in which an aqueous solution or suspension of a phosphoric acid component is reacted with an aqueous solution or suspension of a calcium component while being ground (Japanese Patent Application Laid-open No. 1983-1992).
(Refer to Publication No. 21509), which has the advantage of reacting the calcium component and the phosphoric acid component in one step, but since the grinding operation is performed during the reaction, the heat of reaction rises too much, resulting in the formation of microcrystalline phosphoric acid. of calcium
This method had drawbacks such as the Ca/P ratio sometimes deviating considerably from 1.67, and could not necessarily be said to be a satisfactory method.
(解決しようとする問題点)
本発明者らはこれらの欠点を改良し、反応操作
が容易にしてCa/Pのモル1.67に近似した値を有
する水酸アパタイトの製造する方法について種々
検討した結果、本発明を完成するに至つたもの
で、本発明の目的は高純度でCa/Pモル比が1.67
に極めて近似した値を有する粒子状の水酸アパタ
イトを製造する方法を提供するにある。(Problems to be Solved) The inventors of the present invention have investigated various methods for producing hydroxyapatite having a Ca/P mole value close to 1.67 by improving these drawbacks and by facilitating reaction operations. This led to the completion of the present invention, and the purpose of the present invention is to obtain high purity Ca/P molar ratio of 1.67.
The object of the present invention is to provide a method for producing particulate hydroxyapatite having a value very close to .
(問題点を解決するための手段)
すなわち、本発明者らはカルシウム成分の懸濁
液にりん酸を滴下すると、第5図に示すようにPH
12まで平衡状態を保ち、PH11以下になると急激な
変化を生じ、またPH11まではカルシウム成分に対
してりんの量が不足しているため空気中の炭酸ガ
スを吸い込み炭酸カルシウムになりやすく、更に
PH11付近においてあまり濃度の高いりん酸を使用
すると部分的にPHが下がり過ぎてブルツシヤイト
或はりん酸三カルシウムになる等の知見より本発
明の反応条件を見出したのである。すなわち、本
発明は水酸化カルシウムの懸濁液に撹拌下市販の
りん酸(85%)を2〜4倍に希釈したりん酸水溶
液を滴下しPH11付近にした後、約5倍以上に、好
ましくは8倍以上、好適には10倍以上に希釈した
りん酸水溶液を更に滴下してPH10〜9に調整し、
得られた沈殿を乾燥することを特徴とする水酸ア
パタイトの湿式合成法であつて、本発明で使用す
る出発原料である水酸化カルシウムとしては市販
の水酸化カルシウムをそのまま使用しうるが、炭
酸カルシウムを800℃以上の高温で焼成したのち
水和して得た水酸化カルシウムを使用することが
好ましく、また、懸濁液の濃度としては通常この
種水酸アパタイト湿式合成法で使用する濃度でよ
く、大体10%前後であり、反応温度としては50℃
を越えてはならない。しかして、乾燥条件として
は約60〜80℃の低温で20〜30時間乾燥後、更に高
温の100〜200℃で20〜30時間乾燥させることが好
ましく特に70℃で24時間後120℃で24時間乾燥す
るのが最適である。すなわち、低温下での乾燥で
は長時間を要し、また最初より100℃以上の高温
で加熱すると水酸基が分解しCa/Pモル比に変
化きたし目的とする理論値に極めて近似した値の
水酸アパタイトが得られないからである。(Means for Solving the Problems) That is, when the present inventors dropped phosphoric acid into a suspension of calcium components, the pH changed as shown in Figure 5.
It maintains an equilibrium state until the pH reaches 12, but when the pH drops below 11, a sudden change occurs.Also, until the pH reaches 11, the amount of phosphorus is insufficient compared to the calcium component, so it easily absorbs carbon dioxide gas from the air and becomes calcium carbonate.
The reaction conditions of the present invention were discovered based on the knowledge that if phosphoric acid with a too high concentration at a pH around 11 is used, the pH partially drops too much, resulting in bruschite or tricalcium phosphate. That is, in the present invention, a phosphoric acid aqueous solution prepared by diluting commercially available phosphoric acid (85%) 2 to 4 times is added dropwise to a suspension of calcium hydroxide under stirring to bring the pH to around 11, and then the pH is preferably increased to about 5 times or more. further dropwise a phosphoric acid aqueous solution diluted 8 times or more, preferably 10 times or more to adjust the pH to 10 to 9,
This is a wet synthesis method for hydroxyapatite characterized by drying the obtained precipitate. Commercially available calcium hydroxide can be used as it is as the starting material calcium hydroxide used in the present invention, but carbonate It is preferable to use calcium hydroxide obtained by calcining calcium at a high temperature of 800°C or higher and then hydrating it, and the concentration of the suspension is usually the same as that used in this type of hydroxyapatite wet synthesis method. Generally, it is around 10%, and the reaction temperature is 50℃.
Must not exceed. Therefore, as for drying conditions, it is preferable to dry at a low temperature of about 60 to 80°C for 20 to 30 hours, and then further dry at a high temperature of 100 to 200°C for 20 to 30 hours, especially after 24 hours at 70°C and 24 hours at 120°C. It is best to dry for hours. In other words, drying at a low temperature takes a long time, and heating at a high temperature of 100°C or higher will decompose the hydroxyl group and change the Ca/P molar ratio, resulting in a hydroxyl acid with a value very close to the desired theoretical value. This is because apatite cannot be obtained.
次に実施例を以つて本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例
水酸化カルシウム100gを1の水に懸濁させ
撹拌器(東京理化器械;EYELA.MINI D、C
STIRRER)にて撹拌混合液中に、市販のりん
酸(85%)を3倍希釈したりん酸をマイクロチユ
ーブポンプ(東京理化器械;MIP−3)にて、
連続的に滴下した。PH11より市販のりん酸(85
%)を10倍希釈したりん酸を同様のマイクロチユ
ーブポンプにて徐々に滴下しPH9〜10にした。Example: Suspend 100 g of calcium hydroxide in 1 water using a stirrer (Tokyo Rika Kikai; EYELA.MINI D, C)
Using a microtube pump (Tokyo Rika Kikai; MIP-3), add phosphoric acid (3 times diluted commercially available phosphoric acid (85%)) into the stirred mixture using a microtube pump (Tokyo Rika Kikai; MIP-3).
Dropped continuously. Commercially available phosphoric acid (85
%) was gradually diluted 10 times using the same microtube pump to adjust the pH to 9-10.
この沈殿として得られた試料を口過し、70℃、
24時間乾燥した後、120℃、24時間乾燥したもの
をX線回折にて結晶構造の同定をした結果を第2
a図にしめす。これは、微結晶りん酸カルシウム
である。この試料を、結晶化させるために800℃
で1時間焼成し、X線回折にて、結晶構造の同定
をしたところ第2b図の様になり水酸アパタイト
の単一相のX線解析パターンを示す。また、走査
型電子顕微鏡写真(20000倍)で観察した結果を
第1図として示す。この写真より得られた水酸ア
パタイトは、約0.1μmの粒子状の粉体である。 The sample obtained as this precipitate was passed through the mouth and heated to 70°C.
After drying for 24 hours, the crystal structure was identified by X-ray diffraction after drying at 120℃ for 24 hours.
Shown in figure a. This is microcrystalline calcium phosphate. This sample was heated to 800℃ to crystallize it.
After firing for 1 hour, the crystal structure was identified by X-ray diffraction, as shown in Figure 2b, which shows the X-ray analysis pattern of a single phase of hydroxyapatite. Furthermore, the results of observation using a scanning electron microscope photograph (20,000 times) are shown in FIG. The hydroxyapatite obtained from this photograph is a granular powder with a diameter of approximately 0.1 μm.
比較例 1
水酸カルシウム100gを1の水に懸濁させ撹
拌器(東京理化器械;EYELA.MINI D、C
STIRRER)にて撹拌混合液中に、市販のりん酸
(85%)を10倍希釈したりん酸をマイクロチユー
ブポンプ(東京理化器械;MIP−3)にて、連
続的に滴下し、PH9〜10にした。この沈殿として
得られた試料を口過し、70℃、24時間乾燥後、
120℃、24時間乾燥したものを、X線回折にて、
結晶構造の同定をした(第3図参照)。ここで見
られる(1)は、炭酸カルシウムの(104)面の結晶
ピークで水酸アパタイトの単一相は得られない。Comparative Example 1 100g of calcium hydroxide was suspended in 1 water using a stirrer (Tokyo Rika Kikai; EYELA.MINI D, C
Using a microtube pump (Tokyo Rika Kikai; MIP-3), phosphoric acid (commercially available phosphoric acid (85%) diluted 10 times) was continuously added dropwise into the stirred mixture using a microtube pump (Tokyo Rika Kikai; MIP-3). I made it. The sample obtained as this precipitate was passed through the mouth, and after drying at 70°C for 24 hours,
After drying at 120℃ for 24 hours, X-ray diffraction revealed that
The crystal structure was identified (see Figure 3). The (1) seen here is the crystal peak of the (104) plane of calcium carbonate, and a single phase of hydroxyapatite cannot be obtained.
比較例 2
水酸カルシウム100gを1の水に懸濁させ撹
拌器(東京理化器械;EYELA.MINI D、C
STIRRER)にて撹拌混合液中に、市販のりん酸
(85%)を3倍希釈したりん酸をマイクロチユー
ブポンプ(東京理化器械;MIP−3)にて、連
続的に滴下し、PH9〜10にした。この沈殿として
得られた試料を口過し、70℃、24時間乾燥後、
120℃、24時間乾燥し、1200℃、1時間焼成し、
X線回折にて、結晶構造の同定をした(第4図参
照)。ここで見られる(2)は、りん酸三カルシウム
の(217)面の結晶ピークで水酸アパタイトの単
一相はえられない。(乾燥後のX線解析パターン
は実験例の乾燥後のX線解析パターンと同様のも
のを示した。)
(効 果)
以上述べたように、本発明においてはりん酸水
溶液を先に述べたような条件において添加すると
いう極めて容易な走査によりCa/Pの理論値に
極めて近似した値を有する水酸アパタイトを粒状
として合成することが出来る等の効果を奏するも
のである。Comparative Example 2 100g of calcium hydroxide was suspended in 1 water using a stirrer (Tokyo Rika Kikai; EYELA.MINI D, C
Using a microtube pump (Tokyo Rika Kikai; MIP-3), phosphoric acid (commercially available phosphoric acid (85%) diluted 3 times) was continuously added dropwise into the stirring mixture using a microtube pump (Tokyo Rika Kikai; MIP-3). I made it. The sample obtained as this precipitate was passed through the mouth, and after drying at 70°C for 24 hours,
Dry at 120℃ for 24 hours, bake at 1200℃ for 1 hour,
The crystal structure was identified by X-ray diffraction (see Figure 4). (2) seen here is the crystal peak of the (217) plane of tricalcium phosphate, and a single phase of hydroxyapatite cannot be obtained. (The X-ray analysis pattern after drying was similar to the X-ray analysis pattern after drying in the experimental example.) (Effects) As stated above, in the present invention, the phosphoric acid aqueous solution was It is possible to synthesize granular hydroxyapatite having a Ca/P value extremely close to the theoretical value by an extremely easy scanning operation in which addition is performed under such conditions.
第1図は本発明の実施例1によつて得た水酸ア
パタイトの結晶の構造の電子顕微鏡写真であり、
第2図はX線図であり、第3図及び第4図は比較
例1及び2によつて得た水酸アパタイトのX線図
である。第5図は水酸化カルシウム1mol懸濁液
中に10%りん酸水溶液を滴下した時のPH値の変化
を示す。
第2図〜第4図における横軸は角度、縦軸は強
度であり第5図における横軸はりん酸水溶液の滴
下、縦軸はPH値である。
FIG. 1 is an electron micrograph of the crystal structure of hydroxyapatite obtained in Example 1 of the present invention;
FIG. 2 is an X-ray diagram, and FIGS. 3 and 4 are X-ray diagrams of hydroxyapatite obtained in Comparative Examples 1 and 2. Figure 5 shows the change in PH value when a 10% aqueous phosphoric acid solution was dropped into a 1 mol calcium hydroxide suspension. In FIGS. 2 to 4, the horizontal axis is the angle, the vertical axis is the intensity, and in FIG. 5, the horizontal axis is the dropping of the phosphoric acid aqueous solution, and the vertical axis is the PH value.
Claims (1)
液を滴下反応させて水酸アパタイトを湿式合成す
る方法において、PH11付近に至るまで市販の約85
%程度のりん酸を使用し、これを2〜4倍に希釈
したりん酸水溶液を滴下し、しかるのち約5倍以
上に希釈したりん酸水溶液を滴下してPH10〜9に
調節し、得られた沈澱物を乾燥することを特徴と
する水酸アパタイトを湿式合成する方法。 2 水酸化カルシウムが炭酸カルシウム又は酸化
カルシウムを高温焼成した後水和した水酸化カル
シウムである特許請求の範囲第1項記載の水酸ア
パタイトを湿式合成する方法。 3 反応温度が50℃以下である特許請求の範囲第
1項記載の水酸アパタイトを湿式合成する方法。 4 低温乾燥後、更に高温乾燥する特許請求の範
囲第1項記載の水酸アパタイトを湿式合成する方
法。[Claims] 1. In a method of wet-synthesizing hydroxyapatite by dropping a stirred phosphoric acid aqueous solution into a calcium hydroxide suspension, commercially available
% of phosphoric acid, dropwise add a phosphoric acid aqueous solution diluted 2 to 4 times, and then dropwise add a phosphoric acid aqueous solution diluted approximately 5 times or more to adjust the pH to 10 to 9. A method for wet-synthesizing hydroxyapatite, which comprises drying the precipitate obtained by drying the precipitate. 2. The method for wet-synthesizing hydroxyapatite according to claim 1, wherein the calcium hydroxide is calcium hydroxide obtained by hydrating calcium carbonate or calcium oxide after being calcined at a high temperature. 3. A method for wet-synthesizing hydroxyapatite according to claim 1, wherein the reaction temperature is 50°C or lower. 4. A method for wet-synthesizing hydroxyapatite according to claim 1, which comprises drying at a low temperature and then drying at a high temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9463486A JPS62252307A (en) | 1986-04-25 | 1986-04-25 | Wet synthesis of hydroxy apatite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9463486A JPS62252307A (en) | 1986-04-25 | 1986-04-25 | Wet synthesis of hydroxy apatite |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62252307A JPS62252307A (en) | 1987-11-04 |
JPH0461807B2 true JPH0461807B2 (en) | 1992-10-02 |
Family
ID=14115697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9463486A Granted JPS62252307A (en) | 1986-04-25 | 1986-04-25 | Wet synthesis of hydroxy apatite |
Country Status (1)
Country | Link |
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JP (1) | JPS62252307A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2629761B2 (en) * | 1987-12-23 | 1997-07-16 | 住友化学工業株式会社 | Method for forming hydroxyapatite film |
CA2783723C (en) * | 2009-12-11 | 2019-01-15 | Arun Wagh | Inorganic phosphate compositions and methods |
US20130139930A1 (en) | 2009-12-18 | 2013-06-06 | Latitude 18, Inc. | Inorganic phosphate corrosion resistant coatings |
MY169686A (en) * | 2011-01-27 | 2019-05-13 | Sirim Berhad | A method of converting limestone into tri-calcium phosphate and tetra-calcium phosphate powder simultaneously |
JPWO2023209788A1 (en) * | 2022-04-26 | 2023-11-02 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5645814A (en) * | 1979-09-25 | 1981-04-25 | Kureha Chem Ind Co Ltd | Hydroxyapatite, its ceramic material and its manufacture |
-
1986
- 1986-04-25 JP JP9463486A patent/JPS62252307A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5645814A (en) * | 1979-09-25 | 1981-04-25 | Kureha Chem Ind Co Ltd | Hydroxyapatite, its ceramic material and its manufacture |
Also Published As
Publication number | Publication date |
---|---|
JPS62252307A (en) | 1987-11-04 |
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