JPS63159207A - Production of hydroxyapatite - Google Patents
Production of hydroxyapatiteInfo
- Publication number
- JPS63159207A JPS63159207A JP30379686A JP30379686A JPS63159207A JP S63159207 A JPS63159207 A JP S63159207A JP 30379686 A JP30379686 A JP 30379686A JP 30379686 A JP30379686 A JP 30379686A JP S63159207 A JPS63159207 A JP S63159207A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- calcium
- powder
- slurry
- temperature
- 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.)
- Pending
Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 title abstract description 27
- 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 title abstract description 27
- 238000004519 manufacturing process Methods 0.000 title description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000019700 dicalcium phosphate Nutrition 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 150000004683 dihydrates Chemical class 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004811 liquid chromatography Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 10
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000001506 calcium phosphate Substances 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- VOAQDGKNFNLTHL-UHFFFAOYSA-L calcium phosphoric acid dihydroxide hydrate Chemical compound O.[OH-].[OH-].[Ca+2].OP(O)(O)=O VOAQDGKNFNLTHL-UHFFFAOYSA-L 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- -1 for example Chemical compound 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 210000003094 ear ossicle Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003973 paint 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
- 239000006187 pill Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は水酸アパタイトの改良された製造方法に関する
ものである。さらに詳しくいえば、本発明は、人工骨材
料、人工歯根材料、耳小骨材料などの生体材料をはじめ
、液体クロマトグラフィー用カラム充てん剤、肥料、湿
度センサーなどに有用な水散アパタイトを、穏やかな条
件で短時間に工業的有利に製造する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing hydroxyapatite. More specifically, the present invention provides water-dispersible apatite, which is useful for biological materials such as artificial bone materials, artificial tooth root materials, and ear ossicular materials, as well as column packing materials for liquid chromatography, fertilizers, humidity sensors, etc. The present invention relates to an industrially advantageous manufacturing method in a short period of time under certain conditions.
従来の技術
近年、医療技術の発展に伴い、人工関節、人工骨、人工
歯根などを生体内に埋入し、失われた生体の一部や機能
を回復させる治療方法が開発され、広く行われている。Conventional technology In recent years, with the development of medical technology, treatment methods have been developed and widely used to restore lost parts and functions of the body by implanting artificial joints, artificial bones, artificial tooth roots, etc. ing.
これらの人工骨材の素材としては、骨や歯などの生体無
機質の組成と近似し、生体に対して毒性がなく、かつ骨
との結合性や新生骨との置換性などに優れたものが好ま
しいとされ、このような要件を満たすものとして、水酸
アパタイトやβ−リン酸三カルシウムなどの生体親和性
リン酸カルシウムが注目され、これらの材料を用いて人
工歯根ｔ−調調製ることが提案されている（例えば特開
昭５６−５４８１号公報参照）。The materials for these artificial aggregates are those that have a composition similar to that of biological inorganic materials such as bones and teeth, are non-toxic to living organisms, and have excellent bonding properties with bone and ability to replace new bone. Biocompatible calcium phosphates such as hydroxyapatite and β-tricalcium phosphate have attracted attention as preferred materials that meet these requirements, and it has been proposed to prepare artificial tooth roots using these materials. (See, for example, Japanese Patent Laid-Open No. 56-5481).
ところで、水酸アパタイトやβ−リン酸三カルシウムの
製造法には、乾式法と湿式法とがあり、例えば水酸アパ
タイトの乾式製造法として、リン酸水素カルシウムと過
剰の酸化カルシウムとを９００〜１３００℃の高温下に
おいて水蒸気気流中で反応させて、水酸アパタイトを製
造する方法が知られている。しかしながら、この方法は
操作が複雑である上に、装置費が高くつき、製造コスト
の上昇を免れないという欠点を有している。By the way, there are dry methods and wet methods for producing hydroxyapatite and β-tricalcium phosphate. For example, in the dry method for producing hydroxyapatite, calcium hydrogen phosphate and excess calcium oxide are mixed at A method is known in which hydroxyapatite is produced by reacting in a steam stream at a high temperature of 1300°C. However, this method has disadvantages in that the operation is complicated, the equipment cost is high, and manufacturing costs are inevitably increased.
また、生体温度３７℃、生理的ｐＨ７，１〜７．４の条
件下で、０．５モル／ｌのカルシウムとリン酸水溶液と
を反応させる湿式法によって、水酸アパタイトヲ裂遺し
うろことも知られている。しかしながら、この湿式法は
、温度及びｐＨを厳密にコントロールする必要がある上
に、水酸アパタイトの生成に長時間を要するなどの問題
があって、実用的な方法とはいえない。It is also known that hydroxyapatite can be cleaved by a wet method in which 0.5 mol/l calcium is reacted with an aqueous phosphoric acid solution under conditions of a biological temperature of 37°C and a physiological pH of 7.1 to 7.4. It is being However, this wet method requires strict control of temperature and pH, and also requires a long time to produce hydroxyapatite, so it cannot be considered a practical method.
一方、β−リン酸三カルシウムの展進方法としては、例
えばリン酸水素カルシウムを８００〜１０００℃の温度
で仮焼してβ−ピロリン酸カルシウム（β−ｃａ２ｐ２
０７）に転化し、これと炭酸カルシウムと？約１：ｌの
モル比で、ボットミルやボールミルなどを用いて湿式混
合し、次いでこの混合粉末’ｉ １０００〜−１００℃
の範囲の温度で焼成して、β−リン酸三カルシウムを製
造する乾式法が知られている。しかしながら、この方法
においては、リン酸水素カルシウムの仮焼操作や、β−
ピロリン酸カルシウムと炭散カルシウムとの混合粉末の
焼成操作が必要であって、プロセスが複雑である上に、
装置費が高くつき、製造コストの上昇を免れない。On the other hand, as a method for developing β-tricalcium phosphate, for example, calcium hydrogen phosphate is calcined at a temperature of 800 to 1000°C to produce β-calcium pyrophosphate (β-ca2p2
07), and this and calcium carbonate? Wet mix using a bot mill, ball mill, etc. at a molar ratio of about 1:l, and then mix this mixed powder at a temperature of 1000 to -100°C.
A dry method is known in which β-tricalcium phosphate is produced by firing at a temperature in the range of . However, in this method, calcination operation of calcium hydrogen phosphate and β-
It is necessary to calcinate the mixed powder of calcium pyrophosphate and calcium charcoal, and the process is complicated.
Equipment costs are high and manufacturing costs inevitably rise.
また、β−リン酸三カルシウムの湿式製造方法として、
水酸カルシウムの水性スラリーとリン駿水溶液とを中和
反応させる方法や、硝酸カルシウム水溶液とリン酸水素
アンモニウム水溶液とを反応させる方法などが知られて
いる。しかしながら、前者の方法においては１反応熱が
大きくて、反応系の温度コントロールが困難である上に
、ｐＨを６〜７の一定に保持しないと、種々のカルシウ
ム／リン原子比をもつ粒子が生成して、均質な粒子が得
られないという問題があシ、また、後者の方法において
も、ｐＨや液温を一定に保持しないと種々のカルシウム
／リン原子比をもつ粒子が生成して不均質になるため、
そのコントロールに十分な注意が必要であるなどの問題
を有している。In addition, as a wet production method of β-tricalcium phosphate,
A method of neutralizing an aqueous slurry of calcium hydroxide and an aqueous phosphorus solution, a method of reacting an aqueous calcium nitrate solution and an aqueous ammonium hydrogen phosphate solution, and the like are known. However, in the former method, the heat of one reaction is large, making it difficult to control the temperature of the reaction system, and if the pH is not kept constant at 6 to 7, particles with various calcium/phosphorus atomic ratios are generated. In addition, even in the latter method, if the pH and temperature of the liquid are not kept constant, particles with various calcium/phosphorus atomic ratios will be generated and become non-uniform. In order to become
There are problems such as the need for sufficient care in its control.
発明が解決しようとする問題点
本発明は、このような従来の生体親和性リン酸カルシウ
ムの展進方法が有する欠点を改良し、複雑な装置を用い
ることなく、かつｐＨや温度の厳密なコントロールを必
要としない簡単な操作によって、穏やかな条件で短時間
に生体親和性リン酸カルシウムを製造する工業的に有利
な方法を提供することを目的としてなされたものである
。Problems to be Solved by the Invention The present invention improves the drawbacks of the conventional method for promoting biocompatible calcium phosphate, and solves the problem without using complicated equipment and requiring strict control of pH and temperature. The purpose of this invention is to provide an industrially advantageous method for producing biocompatible calcium phosphate in a short time under mild conditions using simple operations that do not require any nuisance.
問題点を解決するための手段
本発明者らは、生体親和性リン酸カルシウムを工業的有
利に製造する方法を開発するために鋭意研究を重ね比結
果、炭酸カルシウム粉末とリン酸水素カルシウム又はそ
の二水和物の粉末とを特定の割合で用いて水性スラリー
ｆｔ調裂し、次いでこのスラリーを特定の機械的条件で
摩砕しながら反応させることによシ、水酸アパタイトが
容易に得られることを見出し、この知見に基づいて本発
明を完成するに至り之。Means for Solving the Problems The present inventors have conducted extensive research in order to develop a method for industrially advantageous production of biocompatible calcium phosphate, and have found that calcium carbonate powder and calcium hydrogen phosphate or its dihydrate It has been shown that hydroxyapatite can be easily obtained by preparing an aqueous slurry using a specific proportion of powder and a specific proportion of hydroxyapatite, and then reacting this slurry while grinding it under specific mechanical conditions. Based on this finding, we have completed the present invention.
すなわち、本発明は、炭酸カルシウム粉末とリン酸水素
カルシウム又はその二水和物の粉末とを、カルシウム原
子のリン原子に対する原子比が１．５〜１．６７の範囲
になるような割合で用いて水性スラリーを調失し、次い
でこのスラリーを湿式粉砕機によシ摩砕混合しながら反
応させることを特徴とする水酸アバζイトの農道方法を
提供するものである。That is, the present invention uses calcium carbonate powder and calcium hydrogen phosphate or its dihydrate powder in a ratio such that the atomic ratio of calcium atoms to phosphorus atoms is in the range of 1.5 to 1.67. The present invention provides a farm road method for producing hydroxyl aba-Zite, which is characterized in that an aqueous slurry is prepared using a wet grinder, and then this slurry is subjected to a reaction while being ground and mixed in a wet grinder.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法においては、！ず原料として炭酸カルシウム
粉末とリン酸水素カルシウム又はその二水和物の粉末と
を、カルシウム原子のリン原子に対する原子比が１．５
〜１．６７の範囲になるような割合で用いて、水性スラ
リーを調製する。前記原子比が１．５未満では、生成物
中にβ−リン酸三カルシウムや未反応のリン酸水素カル
シウムの含有量が多くて、水酸アパタイトの純度が低く
、また１、６７を超えると生成物中に未反応の炭酸カル
シウムの含有量が多くなシ、水酸アパタイトの純度が低
下する。In the method of the present invention,! First, calcium carbonate powder and calcium hydrogen phosphate or its dihydrate powder are used as raw materials, and the atomic ratio of calcium atoms to phosphorus atoms is 1.5.
Aqueous slurries are prepared using proportions ranging from 1.67 to 1.67. When the atomic ratio is less than 1.5, the content of β-tricalcium phosphate and unreacted calcium hydrogen phosphate is high in the product, resulting in low purity of hydroxyapatite, and when it exceeds 1.67, If the product contains a large amount of unreacted calcium carbonate, the purity of the hydroxyapatite decreases.
また、スラリー濃度は１通常５〜４０重量％の範囲で選
ばれる。この濃度が５重量％禾満では濃度が低すぎて実
用的でなく、一方４０重量％を超えると反応性か低下す
るので好ましくない。Further, the slurry concentration is usually selected within the range of 5 to 40% by weight. If the concentration is less than 5% by weight, the concentration is too low to be practical, while if it exceeds 40% by weight, the reactivity will decrease, which is not preferred.
次に、このようにして調表された水性スラリーを、好ま
しくは２０〜５０℃の範囲の温度において、湿式粉砕機
により摩砕混合しながら反応させる。この際使用する摩
砕装置としては、例えばボールミル、レッドデビルミル
（ペイントコンディショナー）、振動ミル、コロイドミ
ルなどを用いることができる。湿式粉砕機を用いない摩
砕混合は反応がスムースに進行せず、かつ純度の高い均
質な水酸アパタイト力Ｉ得られない。Next, the aqueous slurry thus prepared is reacted while being ground and mixed using a wet grinder, preferably at a temperature in the range of 20 to 50°C. As the grinding device used in this case, for example, a ball mill, a red devil mill (paint conditioner), a vibration mill, a colloid mill, etc. can be used. In the case of grinding and mixing without using a wet grinder, the reaction does not proceed smoothly and a homogeneous hydroxyapatite with high purity cannot be obtained.
このような条件で摩砕することにより、リン酸水素カル
シウムと炭酸カルシウムは徐々に溶解し、あたかも均一
系反応のよりな状態が得られ、微細で均質な粒子の水酸
アパタイトが生成する。この際、従来の湿式法と異な夛
、ｐＨ調整を行う必要は全くない。ま友反応時間は反応
温度や剪断応力によって左右されるが、一般的には３０
分ないし５時間程度で十分である。By grinding under such conditions, calcium hydrogen phosphate and calcium carbonate are gradually dissolved, a more homogeneous reaction state is obtained, and fine, homogeneous particles of hydroxyapatite are produced. At this time, there is no need to perform pH adjustment, which is different from conventional wet methods. The Mayu reaction time depends on the reaction temperature and shear stress, but is generally 30
About 5 minutes to 5 hours is sufficient.
このようにして８反応させたのち、ろ過や遠心分離など
の手段によシ反応生成物をとり出し、好ましくは４０〜
２００℃の範囲の温度で乾燥することにより、微細で均
質な純度の高い水酸アパタイトの乾燥粉末が得られる。After 8 reactions in this manner, the reaction product is taken out by means such as filtration or centrifugation, and is preferably
By drying at a temperature in the range of 200° C., a fine, homogeneous and highly pure hydroxyapatite dry powder is obtained.
この乾燥粉末を６００〜１２００℃の範囲の温度で焼成
することにより、強度の良好な水酸アパタイト焼結体か
得られる。By firing this dry powder at a temperature in the range of 600 to 1200°C, a sintered hydroxyapatite body with good strength can be obtained.
発明の効果
本発明方法は、原料として炭酸カルシウム粉末と、リン
酸水素カルシウム又はその二水和物の粉末を用い、湿式
法で水酸アパタイトを製造する方法であって、この方法
によると、複雑な装置や。Effects of the Invention The method of the present invention is a method for producing hydroxyapatite by a wet method using calcium carbonate powder and powder of calcium hydrogen phosphate or its dihydrate as raw materials. A device.
ｐＨ及び温度の厳密なコントロールを必要とせず、極め
て簡単な操作によって、穏やかな条件で短時間に、微細
で均質な純度の高い水酸アパタイトが得られる。Fine, homogeneous, and highly pure hydroxyapatite can be obtained in a short time under mild conditions by an extremely simple operation without requiring strict control of pH and temperature.
本発明方法で得られた水酸アパタイトは１例えば人工骨
材料、人工歯根材料、耳小骨材料などの生体材料をはじ
め、液体クロマトグラフィー用カラム充てん剤、肥料、
湿度センサーなどに好適に用いられる。The hydroxyapatite obtained by the method of the present invention can be used for biological materials such as artificial bone materials, artificial tooth root materials, ear ossicle materials, column packing for liquid chromatography, fertilizers, etc.
Suitable for use in humidity sensors, etc.
実施例 次に実施例により本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
容量２５０−のポリ容器中に、径５ｆｍのアルミナボー
ルｚｏｏｒ、！Ｊン酸水素カルシウム・三水和物粉末１
８Ｆ、炭酸カルシウム粉末７ｆ及び水１００２を入れ、
レッドビルミルを用い、２５℃で１時間摩砕混合した。Example 1 An alumina ball zoor with a diameter of 5 fm was placed in a 250-capacity polyethylene container. Calcium hydrogen phosphate trihydrate powder 1
8F, add 7f of calcium carbonate powder and 1002ml of water,
The mixture was ground and mixed at 25° C. for 1 hour using a Redville mill.
なお、カルシウム／リン原子比は１．６７であった。Note that the calcium/phosphorus atomic ratio was 1.67.
次いで、スラリーをろ過して、固体生成物をとり出し、
１００℃で乾燥したのち、９００℃で６０分間焼成した
。このものは、 Ｘ！ｓ回折によシ水酸アパタイトであ
ることが確認された。このＸ線回折チャートを第１図に
示す。The slurry is then filtered to remove the solid product,
After drying at 100°C, it was fired at 900°C for 60 minutes. This thing is X! It was confirmed by s diffraction that it was hydroxyapatite. This X-ray diffraction chart is shown in FIG.
実施例２
実施ガニにおいて、水の量ｔ−６Ｏｆに変え、かつ焼成
温度を８００℃に変えた以外は、実施例１と全く同様な
操作を行った。得られたものはＸ線回折より水酸アパタ
イトであることが確認されに０このＸ線回折チャートを
＠２図に示す。Example 2 The same operation as in Example 1 was performed on the crab, except that the amount of water was changed to t-6Of and the firing temperature was changed to 800°C. The obtained product was confirmed to be hydroxyapatite by X-ray diffraction, and the X-ray diffraction chart is shown in Figure 2.
実施例３
容量２５０−のポリ容器中に、径５ ｘｍのアルミナボ
ール２００り、リン酸水素カルシウム・三水和物粉末１
８．４ｆ、炭酸カルシウム粉末６，６２及び水１００９
ｆ入れ、レッドピルミルを用い、２５℃で１時間摩砕
混合した。なお、カルシウム／す／原子比は１．６２で
あった。Example 3 In a 250-volume polyethylene container, 200 alumina balls with a diameter of 5 x m and 1 calcium hydrogen phosphate trihydrate powder were placed.
8.4f, calcium carbonate powder 6,62 and water 1009
The mixture was mixed by pulverization at 25° C. for 1 hour using a red pill mill. Note that the calcium/su/atomic ratio was 1.62.
次いで、スラリーヲろ過し、固体生成物をとり出し、１
３０℃で乾燥した。このものは、Ｘ線回折結果より、水
酸アパタイトであることが確認された。このＸ線回折チ
ャー）１第３図に示す。Next, the slurry was filtered, the solid product was taken out, and 1
It was dried at 30°C. This material was confirmed to be hydroxyapatite based on the results of X-ray diffraction. This X-ray diffraction chart is shown in FIG.
比較例
実施例３において、リン酸水素カルシウム・三水和物粉
末の量を１４．、Ｍ、炭酸カルシウム粉末の量を１０．
７ｆに変えた以外は、実施例３と全く同様な操作を行っ
た。得られたものは、Ｘ線回折結果より、水酸アパタイ
トと未反応炭酸カルシウムの混合物であることが確認さ
れ友。このＸ線チャートを第４図に示す。なお、カルシ
ウム／リン原子比は１．７５であった。Comparative Example In Example 3, the amount of calcium hydrogen phosphate trihydrate powder was 14. , M, the amount of calcium carbonate powder is 10.
The same operation as in Example 3 was performed except that the temperature was changed to 7f. The obtained product was confirmed to be a mixture of hydroxyapatite and unreacted calcium carbonate based on the results of X-ray diffraction. This X-ray chart is shown in FIG. Note that the calcium/phosphorus atomic ratio was 1.75.
第１図、第２図及び第３図は、それぞれ本発明の実施例
で得られた水酸アパタイトのｘｉ１回折チャート、第４
図は比較例で得られた水酸アパタイトと炭酸カルシウム
との混合物のＸ＠回折チャートである。Figures 1, 2 and 3 are the xi1 diffraction chart and the 4th diffraction chart of hydroxyapatite obtained in the example of the present invention, respectively.
The figure is an X@ diffraction chart of a mixture of hydroxyapatite and calcium carbonate obtained in a comparative example.
Claims (1)
の二水和物の粉末とを、カルシウム原子のリン原子に対
する原子比が１．５〜１．６７の範囲になるような割合
で用いて水性スラリーを調製し、次いでこのスラリーを
湿式粉砕機により摩砕混合しながら反応させることを特
徴とする水酸アパタイトの製造方法。1. Prepare an aqueous slurry by using calcium carbonate powder and calcium hydrogen phosphate or its dihydrate powder in a ratio such that the atomic ratio of calcium atoms to phosphorus atoms is in the range of 1.5 to 1.67. and then reacting this slurry while grinding and mixing using a wet grinder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30379686A JPS63159207A (en) | 1986-12-22 | 1986-12-22 | Production of hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30379686A JPS63159207A (en) | 1986-12-22 | 1986-12-22 | Production of hydroxyapatite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63159207A true JPS63159207A (en) | 1988-07-02 |
Family
ID=17925399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30379686A Pending JPS63159207A (en) | 1986-12-22 | 1986-12-22 | Production of hydroxyapatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63159207A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073357A (en) * | 1989-08-01 | 1991-12-17 | Toagosei Chemical Industry, Co., Ltd. | Process for producing hydroxylapatites |
| WO2000058209A1 (en) * | 1999-03-26 | 2000-10-05 | Nara Machinery Co., Ltd. | Method for synthesis of hydroxyapatite, and hydroxyapatite complex and method for preparing the same |
| WO2000058210A1 (en) * | 1999-03-26 | 2000-10-05 | Nara Machinery Co., Ltd. | Method for producing calcium phosphate powder |
| US7169372B1 (en) * | 2000-07-03 | 2007-01-30 | Zakrytoe Aktsionernoe Obschestvo “OSTIM” | Method for producing nano-sized crystalline hydroxyapatite |
| WO2008090648A1 (en) * | 2007-01-25 | 2008-07-31 | Meiji University | Cement material and cement |
| JP2012148903A (en) * | 2011-01-17 | 2012-08-09 | Mikimoto Pharmaceut Co Ltd | Method for manufacturing hydroxyapatite |
| JP2020521597A (en) * | 2017-06-02 | 2020-07-27 | ザ ユニバーシティ オブ ウェスタン オーストラリア | Method for producing calcified tissue substitute |
-
1986
- 1986-12-22 JP JP30379686A patent/JPS63159207A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073357A (en) * | 1989-08-01 | 1991-12-17 | Toagosei Chemical Industry, Co., Ltd. | Process for producing hydroxylapatites |
| WO2000058209A1 (en) * | 1999-03-26 | 2000-10-05 | Nara Machinery Co., Ltd. | Method for synthesis of hydroxyapatite, and hydroxyapatite complex and method for preparing the same |
| WO2000058210A1 (en) * | 1999-03-26 | 2000-10-05 | Nara Machinery Co., Ltd. | Method for producing calcium phosphate powder |
| US6592989B1 (en) | 1999-03-26 | 2003-07-15 | Nara Machinery Co., Ltd. | Method for synthesis of hydroxyapatite, and hydroxyapatite complex and method for preparing the same |
| US7169372B1 (en) * | 2000-07-03 | 2007-01-30 | Zakrytoe Aktsionernoe Obschestvo “OSTIM” | Method for producing nano-sized crystalline hydroxyapatite |
| WO2008090648A1 (en) * | 2007-01-25 | 2008-07-31 | Meiji University | Cement material and cement |
| US8172939B2 (en) | 2007-01-25 | 2012-05-08 | Meiji University | Material for cement, and cement |
| JP2012148903A (en) * | 2011-01-17 | 2012-08-09 | Mikimoto Pharmaceut Co Ltd | Method for manufacturing hydroxyapatite |
| JP2020521597A (en) * | 2017-06-02 | 2020-07-27 | ザ ユニバーシティ オブ ウェスタン オーストラリア | Method for producing calcified tissue substitute |
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