JPH04321508A - Production of hydroxyapatite powder - Google Patents
Production of hydroxyapatite powderInfo
- Publication number
- JPH04321508A JPH04321508A JP1691891A JP1691891A JPH04321508A JP H04321508 A JPH04321508 A JP H04321508A JP 1691891 A JP1691891 A JP 1691891A JP 1691891 A JP1691891 A JP 1691891A JP H04321508 A JPH04321508 A JP H04321508A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- hap
- calcium
- tcp
- aqueous slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 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 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 74
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000019700 dicalcium phosphate Nutrition 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical class [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 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 4
- 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 abstract description 4
- 238000007731 hot pressing Methods 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-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
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、水酸化アパタイト粉末
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing hydroxyapatite powder.
【０００２】0002
【従来の技術】水酸化アパタイト［Ｃａ５ （ＰＯ４
）３ （ＯＨ）］（以下、ＨＡＰと記す）は、生体親和
性に優れ、かつ骨組織と直接結合する性質を有するため
、生体硬組織の代替材料として有用である。また、ＨＡ
Ｐのタンパク質の吸着性を利用して、クロマトグラフィ
ー用カラム充填材や細胞培養の担体、湿度センサ等にも
用いられている。[Prior art] Hydroxylated apatite [Ca5 (PO4
)3(OH)] (hereinafter referred to as HAP) has excellent biocompatibility and has the property of directly bonding with bone tissue, so it is useful as a substitute material for biological hard tissue. Also, H.A.
Utilizing the protein adsorption properties of P, it is also used in chromatography column packing materials, cell culture carriers, humidity sensors, etc.
【０００３】このような各種用途に応じてＨＡＰの特性
を制御することは、ＨＡＰ粉末の形態を制御することに
より達成される。例えば、タンパク質の吸着性は、ＨＡ
Ｐの結晶面で異なるとされている。[0003] Controlling the properties of HAP according to such various uses is achieved by controlling the form of HAP powder. For example, protein adsorption is HA
It is said that it differs depending on the crystal plane of P.
【０００４】従来、粉末の形態を制御してＨＡＰ粉末を
製造する方法としては、原料粉末を水の存在下で加圧・
加熱処理する、いわゆる水熱処理による方法が知られて
いる。例えば、湿式合成したＨＡＰ粉末を水熱処理して
アスペクト比３程度の柱状粒子よりなる粉末を得る方法
や、β−リン酸三カルシウム［Ｃａ３（ＰＯ４ ）２
］（以下、β−ＴＣＰと記す）の粉末に水熱処理を施し
てＨＡＰに転化させる方法が知られている。このような
水熱処理によるＨＡＰの製造方法によれば、粉末に形態
的な特性を付与することができる。[0004] Conventionally, as a method for manufacturing HAP powder by controlling the powder form, raw material powder was pressurized in the presence of water.
A method using heat treatment, so-called hydrothermal treatment, is known. For example, a method of hydrothermally treating wet-synthesized HAP powder to obtain a powder consisting of columnar particles with an aspect ratio of about 3, and a method of obtaining a powder consisting of columnar particles with an aspect ratio of about 3,
] (hereinafter referred to as β-TCP) is subjected to hydrothermal treatment to convert it into HAP. According to the method for producing HAP using such hydrothermal treatment, morphological characteristics can be imparted to the powder.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、湿式合
成したＨＡＰ粉末を水熱処理して得たＨＡＰ粉末の粒子
は、アスペクト比が３〜４の柱状粒子のものしか得られ
ていない。また、β−ＴＣＰを原料とした場合、β−Ｔ
ＣＰからＨＡＰへの転化率を９０％以上にするためには
、２００℃、２ＭＰａ以上の厳しい反応条件を５時間以
上保持することが必要である。また、得られる粉末粒子
の形態も多種混合、不定形のものである。[Problems to be Solved by the Invention] However, HAP powder particles obtained by hydrothermally treating wet-synthesized HAP powder are only columnar particles with an aspect ratio of 3 to 4. In addition, when β-TCP is used as a raw material, β-T
In order to achieve a conversion rate of CP to HAP of 90% or more, it is necessary to maintain severe reaction conditions of 200° C. and 2 MPa or more for 5 hours or more. Moreover, the morphology of the obtained powder particles is also a mixture of various types and irregular shapes.
【０００６】本発明は、かかる点に鑑みてなされたもの
であり、従来に比べてより低温、低圧、短時間の水熱反
応条件でβ−ＴＣＰをＨＡＰへ転化できると共に、粉末
粒子の形態を容易に制御し得るＨＡＰ粉末の製造方法を
提供するものである。The present invention has been made in view of the above points, and it is possible to convert β-TCP to HAP under hydrothermal reaction conditions at lower temperature, lower pressure, and shorter time than in the past, and it also allows the morphology of powder particles to be changed. A method for producing HAP powder that can be easily controlled is provided.
【０００７】[0007]
【課題を解決するための手段】本発明は、炭酸カルシウ
ム粉末およびリン酸水素カルシウムまたはリン酸水素カ
ルシウム二水和物の粉末をカルシウムとリンのモル比が
１．４５〜１．６０になるように秤量し、純水を加えて
所定濃度の水性スラリーを得る工程と、ボールミルを使
用して前記水性スラリーを回転粉砕することにより前記
炭酸カルシウム粉末と前記リン酸水素カルシウムまたは
前記リン酸水素カルシウム二水和物の粉末をメカノケミ
カル的に反応させる工程と、メカノケミカル的に反応さ
せた水性スラリーを所定温度で完全に乾燥した後粉砕し
て粉末にする工程と、該粉末を所定温度で焼成してβ−
リン酸三カルシウム微粉末を得る工程と、該β−リン酸
三カルシウム微粉末に水の存在下で加圧・加熱処理を施
すことにより水酸化アパタイト粉末を得る工程とを具備
することを特徴とする水酸化アパタイト粉末の製造方法
である。[Means for Solving the Problems] The present invention provides calcium carbonate powder and calcium hydrogen phosphate or calcium hydrogen phosphate dihydrate powder in such a way that the molar ratio of calcium to phosphorus is 1.45 to 1.60. and adding pure water to obtain an aqueous slurry of a predetermined concentration; and rotary grinding of the aqueous slurry using a ball mill to form the calcium carbonate powder and the calcium hydrogen phosphate or the calcium hydrogen phosphate dihydrogen phosphate. A step of mechanochemically reacting the hydrate powder, a step of completely drying the mechanochemically reacted aqueous slurry at a predetermined temperature and then pulverizing it into powder, and firing the powder at a predetermined temperature. Teβ−
It is characterized by comprising a step of obtaining tricalcium phosphate fine powder, and a step of obtaining hydroxyapatite powder by applying pressure and heat treatment to the β-tricalcium phosphate fine powder in the presence of water. This is a method for producing hydroxyapatite powder.
【０００８】また、粒子径が１μｍ以下であり、かつカ
ルシウムとリンのモル比が１．４５〜１．６０であるβ
−リン酸三カルシウム微粉末に水の存在下で加圧・加熱
処理を施すことにより水酸化アパタイト粉末を得ること
を特徴とする水酸化アパタイト粉末の製造方法である。[0008] Further, β having a particle size of 1 μm or less and a molar ratio of calcium to phosphorus of 1.45 to 1.60 is also available.
- A method for producing hydroxyapatite powder, which is characterized in that hydroxyapatite powder is obtained by applying pressure and heat treatment to tricalcium phosphate fine powder in the presence of water.
【０００９】ここで、β−ＴＣＰ微粉末のカルシウムと
リンのモル比を、１．４５〜１．６０の範囲内に限定し
たのは、β−ＴＣＰ微粉末のカルシウムとリンのモル比
を１．４５未満にすると、目的としないピロリン酸カル
シウムが生成し易くなるためであり、１．６０を越える
と、ＨＡＰ粉末の形態制御性が低下するためである。Here, the molar ratio of calcium to phosphorus in the β-TCP fine powder was limited to a range of 1.45 to 1.60 because the molar ratio of calcium to phosphorus in the β-TCP fine powder was 1. If it is less than .45, undesired calcium pyrophosphate is likely to be produced, and if it exceeds 1.60, the shape controllability of the HAP powder will deteriorate.
【００１０】0010
【作用】本発明の水酸化アパタイトの製造方法によれば
、原料の水性スラリーを、ボールミルで回転粉砕して、
炭酸カルシウム粉末とリン酸水素カルシウムまたは前記
リン酸水素カルシウム二水和物の粉末をメカノケミカル
的に反応させ、これを乾燥後粉砕して得た粉末を焼成す
る、いわゆるメカノケミカル法（湿式摩砕法）により、
粒子径が１μｍ以下でかつカルシウムとリンのモル比が
１．４５〜１．６０であるβ−ＴＣＰ微粉末を得ている
。このようなβ−ＴＣＰ微粉末は、比表面積が大きく、
焼結特性に優れているため、以後の水熱処理工程におい
てＨＡＰの核生成と結晶成長が速やかに進行する。
これにより、β−ＴＣＰからＨＡＰの転化が容易になる
と共に、ＨＡＰ粉末の形態を容易に制御できる。[Operation] According to the method for producing hydroxyapatite of the present invention, the raw material aqueous slurry is rotary pulverized in a ball mill.
The so-called mechanochemical method (wet milling method) involves mechanochemically reacting calcium carbonate powder with calcium hydrogen phosphate or calcium hydrogen phosphate dihydrate powder, drying and pulverizing the resulting powder, and firing the resulting powder. ),
A β-TCP fine powder having a particle size of 1 μm or less and a calcium to phosphorus molar ratio of 1.45 to 1.60 is obtained. Such β-TCP fine powder has a large specific surface area,
Since it has excellent sintering properties, HAP nucleation and crystal growth proceed rapidly in the subsequent hydrothermal treatment process. This facilitates the conversion of β-TCP to HAP and allows easy control of the form of the HAP powder.
【００１１】[0011]
【実施例】以下、本発明の実施例について詳細に説明す
る。[Examples] Examples of the present invention will be described in detail below.
【００１２】〔実施例１〕初めに、メカノケミカル法に
従ってβ−ＴＣＰ粉末を次のように製造した。まず、カ
ルシウムおよびリンのモル比（以下、Ｃａ／Ｐ比と記す
）が１．５０となるように炭酸カルシウム（ＣａＣＯ３
）０．０５０モルとリン酸水素カルシウム二水和物（
ＣａＨＰＯ４ ・２Ｈ２ Ｏ）０．１００モルを秤量す
る。次に、秤量した炭酸カルシウムおよびリン酸水素カ
ルシウム二水和物を、純水２００ｍｌと共にジルコニア
製ボールミルポットにより１日回転粉砕して水性スラリ
ーを得た。得られた水性スラリーを８０℃で１日乾燥し
た後、再び粉砕し７５０℃で１０時間焼成して粉末を得
た。この粉末をＸ線回折法により同定すると、β−ＴＣ
Ｐ粉末であることが確認された。このβ−ＴＣＰ微粉末
は粒子径が１μｍ以下であり、Ｃａ／Ｐ比が１．５０で
あった。[Example 1] First, β-TCP powder was produced according to the mechanochemical method as follows. First, calcium carbonate (CaCO3
) 0.050 mol and calcium hydrogen phosphate dihydrate (
Weigh out 0.100 mol of CaHPO4 .2H2 O). Next, the weighed calcium carbonate and calcium hydrogen phosphate dihydrate were rotary pulverized for one day in a zirconia ball mill pot with 200 ml of pure water to obtain an aqueous slurry. The resulting aqueous slurry was dried at 80° C. for one day, then ground again and calcined at 750° C. for 10 hours to obtain a powder. Identification of this powder by X-ray diffraction revealed that β-TC
It was confirmed that it was P powder. This β-TCP fine powder had a particle size of 1 μm or less and a Ca/P ratio of 1.50.
【００１３】このようにして得たβ−ＴＣＰ粉末２ｇを
純水１リットルと共にビーカーに入れてオートクレーブ
内に設置し、１３０℃、０．２７ＭＰａの反応条件下で
１時間保持して加圧・加熱処理を施した。処理後粉末を
分取し、８０℃で約１日乾燥させてＨＡＰ粉末を得た。2 g of the β-TCP powder thus obtained was placed in a beaker together with 1 liter of pure water, placed in an autoclave, and kept under reaction conditions of 130° C. and 0.27 MPa for 1 hour to pressurize and heat. Processed. After the treatment, the powder was collected and dried at 80° C. for about 1 day to obtain HAP powder.
【００１４】得られたＨＡＰ粉末を、粉末Ｘ線回折法に
より同定すると共に、ＳＥＭで該ＨＡＰ粉末の粒子形態
を観察した。その結果、粉末Ｘ線回析パターンは、主に
ＨＡＰ相が現われ、わずかにβ−ＴＣＰの残存を示すも
のであった。また、ＨＡＰとβ−ＴＣＰとの第１ピーク
のＸ線回折強度比から求めたＨＡＰ転化率は９０％であ
った。また、ＨＡＰ粉末は、図１に示す如く、針状粒子
からなることが確認された。ＨＡＰ粉末の粒子サイズは
、短径が０．５〜１μｍ、長径は３〜１５μｍであった
。The obtained HAP powder was identified by powder X-ray diffraction, and the particle morphology of the HAP powder was observed by SEM. As a result, the powder X-ray diffraction pattern mainly showed a HAP phase, with a slight amount of β-TCP remaining. Further, the HAP conversion rate determined from the X-ray diffraction intensity ratio of the first peak of HAP and β-TCP was 90%. Furthermore, it was confirmed that the HAP powder was composed of acicular particles as shown in FIG. The particle size of the HAP powder was 0.5 to 1 μm in the short axis and 3 to 15 μm in the long axis.
【００１５】さらに、得られたＨＡＰ粉末の粉末Ｘ線回
折パターンにおいて、第１ピークである（２１１）面の
回折強度を１００としたときの他のピーク強度比は、（
３００）面で９７、（００２）面で２４であり、ＡＳＴ
ＭのＨＡＰの標準パターンでは、（３００）面は６０、
（００２）面は４０となっている。これらを比較すると
、得られたＨＡＰ粒子の粉末Ｘ線回析パターンが（３０
０）面におけるピーク強度比に大きく偏っていることが
わかった。この結果、ＨＡＰ粒子の長軸方向は、結晶に
おけるＣ軸に相当していることが確認された。Furthermore, in the powder X-ray diffraction pattern of the obtained HAP powder, when the diffraction intensity of the (211) plane, which is the first peak, is taken as 100, the other peak intensity ratios are (
300) plane is 97, (002) plane is 24, and AST
In the standard HAP pattern of M, the (300) plane is 60,
The (002) plane is 40. When these are compared, the powder X-ray diffraction pattern of the obtained HAP particles is (30
It was found that the peak intensity ratio was largely biased toward the 0) plane. As a result, it was confirmed that the long axis direction of the HAP particles corresponded to the C axis in the crystal.
【００１６】以上のように、メカノケミカル法により製
造したＣａ／Ｐ比が１．５０であり、粒子径が１μｍ以
下であるβ−ＴＣＰ粉末は、比表面積が大きく、焼結特
性に優れている。このため、ＨＡＰの核生成や結晶生成
が速やかに進行するので、比較的低温、低圧、短時間の
水熱反応条件下でβ−ＴＣＰをＨＡＰに転化させること
ができる。この結果、オートクレーブのような簡易な装
置でも、β−ＴＣＰからＨＡＰへの転化反応を容易に行
うことができる。また、得られたＨＡＰ粉末は、形態的
に異方性の大きな針状粒子であった。このように、ＨＡ
Ｐ粉末の形態を容易に制御できることは、用途に応じて
ＨＡＰ粉末の特性を制御できるので有益である。As described above, the β-TCP powder produced by the mechanochemical method and having a Ca/P ratio of 1.50 and a particle size of 1 μm or less has a large specific surface area and excellent sintering properties. . Therefore, since nucleation and crystal formation of HAP proceed rapidly, β-TCP can be converted to HAP under hydrothermal reaction conditions at relatively low temperature, low pressure, and short time. As a result, even in a simple device such as an autoclave, the conversion reaction from β-TCP to HAP can be easily carried out. Moreover, the obtained HAP powder was acicular particles with large anisotropy in morphology. In this way, H.A.
Being able to easily control the morphology of the P powder is beneficial because it allows the properties of the HAP powder to be controlled depending on the application.
【００１７】〔実施例２〕炭酸カルシウム０．０５３モ
ル、リン酸水素カルシウム二水和物
（ＣａＨＰＯ４ ・２Ｈ２ Ｏ）０．１００モルを秤
量し、以下第１実施例と同様にして、Ｃａ／Ｐ比が１．
５３であるβ−ＴＣＰ粉末を製造した。得られた粉末は
、Ｘ線回折法で同定することによって、β−ＴＣＰに１
０％程度のＨＡＰを含むものであることが確認された。[Example 2] Calcium carbonate 0.053 mol, calcium hydrogen phosphate dihydrate
Weigh out 0.100 mol of (CaHPO4 .2H2 O), and proceed as in Example 1 until the Ca/P ratio is 1.
A β-TCP powder of No. 53 was produced. The obtained powder was identified by X-ray diffraction method, and it was determined that β-TCP had 1
It was confirmed that it contained approximately 0% HAP.
【００１８】このようにして得たβ−ＴＣＰ粉末２ｇを
、純水１ｌと共にビーカーに入れてオートクレーブ内に
配置し、１００℃、０．１０ＭＰａの反応条件下で１時
間保持して加圧・加熱処理を施した。処理後、粉末を分
取して８０℃で約１日乾燥してＨＡＰ粉末を得た。2 g of the β-TCP powder thus obtained was placed in a beaker together with 1 liter of pure water, placed in an autoclave, and held under reaction conditions of 100° C. and 0.10 MPa for 1 hour to pressurize and heat. Processed. After the treatment, the powder was collected and dried at 80° C. for about 1 day to obtain HAP powder.
【００１９】得られたＨＡＰ粉末を、実施例１と同様に
、粉末Ｘ線回折およびＳＥＭにより評価した。その結果
、第１実施例の反応条件よりも低温、低圧の水熱反応条
件にもかかわらず、得られた粉末のＸ線回折パターンは
、１００％ＨＡＰ相からなるものであり、β−ＴＣＰの
残存は認められなかった。また、得られたＨＡＰ粉末は
、図２に示す如く、１μｍ以下の微粒子からなり、その
粒子形態は針状、柱状、板状結晶等が混在していた。The obtained HAP powder was evaluated by powder X-ray diffraction and SEM in the same manner as in Example 1. As a result, despite the hydrothermal reaction conditions being lower temperature and lower pressure than the reaction conditions of the first example, the X-ray diffraction pattern of the obtained powder was composed of 100% HAP phase, indicating that of β-TCP. No residue was observed. Further, as shown in FIG. 2, the obtained HAP powder consisted of fine particles of 1 μm or less, and the particle morphology was a mixture of needle-like, columnar, and plate-like crystals.
【００２０】[0020]
【発明の効果】以上説明した如くに、本発明の水酸化ア
パタイト粉末の製造方法によれば、メカノケミカル法に
より製造した、所定のＣａ／Ｐ比を有するβ−ＴＣＰ粉
末を水熱処理することにより、従来よりも低温、低圧、
短時間の水熱反応条件でも容易にＨＡＰへ転化させるこ
とができる。また、Ｃａ／Ｐ比を適宜選択することによ
って、ＨＡＰ粉末の形態制御を容易に行うことができる
。この結果、ＨＡＰ粉末の特性を各種用途に応じて容易
に変更することができる等顕著な効果を有するものであ
る。As explained above, according to the method for producing hydroxyapatite powder of the present invention, β-TCP powder having a predetermined Ca/P ratio produced by a mechanochemical method is hydrothermally treated. , lower temperature and pressure than before,
It can be easily converted to HAP even under short-term hydrothermal reaction conditions. Further, by appropriately selecting the Ca/P ratio, the shape of the HAP powder can be easily controlled. As a result, it has remarkable effects such as the ability to easily change the properties of HAP powder according to various uses.
【図１】本発明の水酸化アパタイトの製造方法の第１の
実施例で得られた水酸化アパタイト粉末の粒子構造を示
す写真。FIG. 1 is a photograph showing the particle structure of hydroxyapatite powder obtained in a first example of the method for producing hydroxyapatite of the present invention.
【図２】本発明の水酸化アパタイトの製造方法の第２の
実施例で得られた水酸化アパタイト粉末の粒子構造を示
す写真。FIG. 2 is a photograph showing the particle structure of hydroxyapatite powder obtained in the second example of the method for producing hydroxyapatite of the present invention.
Claims (2)
カルシウムまたはリン酸水素カルシウム二水和物の粉末
をカルシウムとリンのモル比が１．４５〜１．６０にな
るように秤量し、純水を加えて所定濃度の水性スラリー
を得る工程と、ボールミルを使用して前記水性スラリー
を回転粉砕することにより前記炭酸カルシウム粉末と前
記リン酸水素カルシウムまたは前記リン酸水素カルシウ
ム二水和物の粉末をメカノケミカル的に反応させる工程
と、メカノケミカル的に反応させた水性スラリーを所定
温度で完全に乾燥した後粉砕して粉末にする工程と、該
粉末を所定温度で焼成してβ−リン酸三カルシウム微粉
末を得る工程と、該β−リン酸三カルシウム微粉末に水
の存在下で加圧・加熱処理を施すことにより水酸化アパ
タイト粉末を得る工程とを具備することを特徴とする水
酸化アパタイト粉末の製造方法。Claim 1: Weigh calcium carbonate powder and calcium hydrogen phosphate or calcium hydrogen phosphate dihydrate powder so that the molar ratio of calcium to phosphorus is 1.45 to 1.60, and add pure water. obtaining an aqueous slurry of a predetermined concentration using a ball mill; and rotary pulverizing the aqueous slurry using a ball mill to mechanochemically process the calcium carbonate powder and the calcium hydrogen phosphate or the calcium hydrogen phosphate dihydrate powder. a step of completely drying the mechanochemically reacted aqueous slurry at a predetermined temperature and then pulverizing it into a powder; and a step of baking the powder at a predetermined temperature to form a fine β-tricalcium phosphate. Hydroxylated apatite powder, comprising a step of obtaining a powder, and a step of obtaining a hydroxyapatite powder by applying pressure and heat treatment to the β-tricalcium phosphate fine powder in the presence of water. manufacturing method.
シウムとリンのモル比が１．４５〜１．６０であるβ−
リン酸三カルシウム微粉末に水の存在下で加圧・加熱処
理を施すことにより水酸化アパタイト粉末を得ることを
特徴とする水酸化アパタイト粉末の製造方法。2. β- particles having a particle size of 1 μm or less and a molar ratio of calcium to phosphorus of 1.45 to 1.60.
A method for producing hydroxyapatite powder, which comprises obtaining hydroxyapatite powder by pressurizing and heating tricalcium phosphate fine powder in the presence of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1691891A JPH04321508A (en) | 1991-01-18 | 1991-01-18 | Production of hydroxyapatite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1691891A JPH04321508A (en) | 1991-01-18 | 1991-01-18 | Production of hydroxyapatite powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04321508A true JPH04321508A (en) | 1992-11-11 |
Family
ID=11929513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1691891A Withdrawn JPH04321508A (en) | 1991-01-18 | 1991-01-18 | Production of hydroxyapatite powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04321508A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN112125290A (en) * | 2020-09-15 | 2020-12-25 | 上海摩漾生物科技有限公司 | Calcium-phosphorus microsphere material containing defect sites and preparation and application thereof |
-
1991
- 1991-01-18 JP JP1691891A patent/JPH04321508A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| KR100786312B1 (en) * | 2006-05-03 | 2007-12-17 | 박진우 | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN112125290A (en) * | 2020-09-15 | 2020-12-25 | 上海摩漾生物科技有限公司 | Calcium-phosphorus microsphere material containing defect sites and preparation and application thereof |
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