JPH0324405B2 - - Google Patents
Info
- Publication number
- JPH0324405B2 JPH0324405B2 JP27207084A JP27207084A JPH0324405B2 JP H0324405 B2 JPH0324405 B2 JP H0324405B2 JP 27207084 A JP27207084 A JP 27207084A JP 27207084 A JP27207084 A JP 27207084A JP H0324405 B2 JPH0324405 B2 JP H0324405B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hap
- ratio
- temperature
- cahpo
- 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
Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 32
- 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 32
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Materials For Medical Uses (AREA)
Description
〔産業上の利用分野〕
本発明はヒドロキシアパタイト（HAp）の製
造法に関する。
近年、生体材料としてりん酸化合物、特に
HApが注目され人工骨、人工歯などに用いられ
ている。これはHApが生体内に埋入された場合
安全かつ化学的に安定でありしかもそれが生体内
で拒否反応を起こすことなく自然骨と結合治瘉し
やすいからである。
その他HApの用途としては高級な磁器の一種
である骨灰磁器いわゆるボーンチヤイナの原料、
あるいはクロマトグラフイー用充填剤等がある。
〔従来技術〕
一般にHApの合成法としては、高温下の固相
反応による乾式法と大気圧下での水溶液反応ある
いは水熱反応による湿式法が知られているが、高
温下での固相反応は1000℃以上の高温で長時間の
焼成が必要であり、装置も高価となるため工業的
な方法とは言い難い。
また、湿式法のうち、水熱反応による方法とし
て、CaHPO4・2H2O（又はCaHPO4）とCa
（OH）2の反応による方法が知られている（特開
昭53−111000号）。この方法はそれぞれの原料を
固体混合し、この混合物をオートクレーブを用い
て、100〜500℃、１〜500気圧の熱水条件下で水
熱反応させることにより結晶性HApを製造する
ものである。
しかし、この方法は反応条件が過酷なため反応
装置が高価となり、エネルギーコストも高いとい
う欠点を有している。
一方、水溶液法によるHApの製造方法として
は、リン酸の中和による方法があるが、反応速度
が大きく、得られる沈澱物がコロイド状になり、
取扱や操作の面で不便である。またHApの主た
る用途である生体材料として用いる場合において
は例えば鉄、亜鉛、鉛などがある程度以上含まれ
ているとこれらのイオンが生体内で溶出するおそ
れがあることから、不純物の極めて少ないものが
要求されるため、粗リン酸を原料とする場合に
は、不純物除去が極めてやつかいなものである。
以上の方法とは全く異つた極めて工業的な方法
として、本発明者らは既にCaHPO4・2H2Oと水
のスラリーにCa（OH）2を添加し、大気圧下で反
応をおこなう水溶液法を提案している（特開昭60
−5009号）。この方法はCa（OH）2の添加をCa／Ｐ
モル比1.6（理論添加量の90％）まではPH10以下に
保つように徐々におこなうことにより、容易に、
且つ短時間で高純度のHApを製造し得るもので
ある。
〔従来技術の問題点〕
従来提案されたHApの製造法のうち、乾式法
および水熱反応による方法はいずれも装置が高価
となり、エネルギー的にも不利なものであつた。
また、水溶液法のうちリン酸の中和による方法
は、生成物の取扱いに問題があると同時に高純度
のHAp製造には不適であつた。一方本発明者ら
が既に提案した前記の方法においては、一旦反応
により生成したHApのCa／Ｐモル比が、濾過洗
浄の操作中に変動することがあり、再現性よく所
望のCa／Ｐモル比のHApを得ることが必ずしも
満足するものではなかつた。
〔発明が解決しようとする問題点〕
本発明は前記の従来技術の問題点を解決するた
めのものであり、また特願昭58−110947号の方法
において再現性よく所望のCa／Ｐ比のHApを得
ることを目的とするものである。
〔問題点を解決するための手段〕
すなわち本発明はCaHPO4・2H2Oと水とのス
ラリーにCaOおよび／またはCa（OH）2を添加し、
ヒドロキシアパタイトを製造する方法において、
温度５〜70℃でCa／Ｐモル比1.54まではPHを10以
下に保ちながらCaOおよび／またはCa（OH）2を
加え、次いで残量を加えた後反応液スラリーを65
℃以上で0.5時間以上熟成することを特徴とする
ヒドロキシアパタイトの製造法である。
本発明をさらに詳しく説明するとCaHPO4・
2H2OとCa源としてCa（OH）2を用いた場合の基
本反応式は下記のように示される。
6CaHPO4・2H2O＋4Ca（OH）2
→Ca10（PO4）6（OH）2↓＋18H2O
この場合、CaHPO4・2H2Oと水のスラリー溶液
に温度100℃以下で当量のCa（OH）2を一挙に投入
しても反応は極めて遅くHApは生成し難い。し
かしながらCaHPO4・2H2Oスラリーに各反応速
度を超えない範囲でCa（OH）2を連続的または断
続的に供給する場合、具体的には反応液のPH値が
特定の値以上にならないように調節しながらCa
（OH）2溶液を供給すれば、反応は容易に進行し、
完結する。本反応はPHの制御が大きな要素で、例
えば、反応温度50℃においてはCa／Ｐモル比1.58
まではPH10以下、好ましくはPH9.0以下の領域で
反応させる。その後はPH９以上で反応をおこない
理論Ca／Ｐ比1.67のHApを合成する。また、仕
込みCa／Ｐ比が若干1.67を超えても後段の洗浄に
よりCa（OH）2を除去することができるので、容
易にCa／Ｐ比1.67のHApを得ることができる。
本反応は、反応時のPHが極めて重要な因子であ
り、反応を完結させるためにはPH制御に十分留意
する必要があり、PHを10以下に保たない場合には
未反応のCaHPO4・2H2Oが残存し、HApが得ら
れないものである。
反応温度は通常５〜70℃であるが、反応を速く
進行させるためには30〜70℃が好ましい。５℃以
下においては反応の進行が遅くなり好ましくな
い。また70℃以上ではCaHPO4・2H2Oが
CaHPO4に転移するため避けるべきである。
また、生成物HApのCa／Ｐ比はCa（OH）2供給
量（仕込みCa／Ｐ比）を変えることにより、
Ca／Ｐ比1.48〜1.67のHApを容易に得ることが
できる。このようにして生成したHApはこのま
までは不安定であり、後段での洗浄により、
Ca／Ｐ比が変動するため、本発明においては、
反応終了後熟成をおこなうものである。反応液ス
ラリーの熟成の条件としては、熟成温度を65℃以
上、より好ましくは90℃以上とするものであり、
熟成時間は温度にもよるが100℃で少くとも0.5時
間以上、65℃では少くとも一昼夜の熟成が必要で
ある。従つて、効率的に熟成をおこなうために
は、より高温で熟成をおこなう方がよい。
かかる熟成をおこなつたのち、濾過等の常用手
段で固形分を分離し、過剰量のCa（OH）2を洗浄
除去する。
このようにして、所望のCa／Ｐ比のHApを再
現性よく得ることができ、HApの理論Ca／Ｐ比
である1.67のHApを得るには特に優れた方法で
ある。
本発明において使用するCa（OH）2は粉末、ス
ラリーどちらで供給しても構わない。またCa
（OH）2のかわりにCaOを用いても勿論構わない。
さらに生成物HApへのCO2- 3イオンの混入をでき
るだけ低く押えたい場合には、不活性ガス（例え
ばN2など）雰囲気下で反応させることが望まし
い。
本発明で得られるHApは微粒子板状粉末であ
りそのまま若しくはその他のセルロース、コラー
ゲン等の有機物と共に成型焼結して又は有機マト
リツクスとの複合体として生体材料として使用で
きるほか、クロマトグラフイー充填剤としての用
途にも十分使用できる。
以下実施例により本発明を詳細に説明する。
実施例１〜７、比較例１、２
温水ジヤケツトを施したSUS304製の蓋つき60
反応装置に撹拌機、PH計、温度計、還流冷却器
をセツトし、内部にCaHPO4・2H2Oを水と共に
仕込んだのち加温し、所定の温度となつた時点で
別に設けた撹拌機つき石灰乳タンクから温水ジヤ
ケツトにより予熱された10％石灰乳をポンプで反
応装置に供給し、反応をおこなつた。反応終了後
所定の温度で熟成し、固形分を濾別し、水で過剰
Ca（OH）2を洗浄除去し、乾燥した。
反応条件、熟成条件および結果を第１表に示
す。また実施例１の各反応時間でのPH、Ca
（OH）2の添加率の関係を第１図に、得られた生
成物のＸ線回折パターンを第２図に示す。
[Industrial Field of Application] The present invention relates to a method for producing hydroxyapatite (HAp). In recent years, phosphoric acid compounds, especially
HAp has attracted attention and is used in artificial bones, artificial teeth, etc. This is because HAp is safe and chemically stable when implanted in a living body, and it also easily fuses with natural bone without causing a rejection reaction in the living body. Other uses of HAp include raw materials for bone ash porcelain, a type of high-grade porcelain,
Alternatively, there are packing materials for chromatography, etc. [Prior art] In general, there are two known methods for synthesizing HAp: a dry method using a solid-phase reaction at high temperatures, and a wet method using an aqueous solution reaction or hydrothermal reaction at atmospheric pressure. It is difficult to call this an industrial method because it requires firing at a high temperature of 1000°C or more for a long time, and the equipment is expensive. In addition, among the wet methods, there is a method using hydrothermal reaction, in which CaHPO 4 2H 2 O (or CaHPO 4 ) and Ca
A method based on the reaction of (OH) 2 is known (Japanese Patent Application Laid-open No. 111000/1983). In this method, crystalline HAp is produced by mixing the respective raw materials in solid form and subjecting this mixture to a hydrothermal reaction using an autoclave under hydrothermal conditions of 100 to 500°C and 1 to 500 atm. However, this method has the disadvantage that the reaction conditions are harsh, the reaction equipment is expensive, and the energy cost is also high. On the other hand, as a method for producing HAp using an aqueous solution method, there is a method using phosphoric acid neutralization, but the reaction rate is high and the resulting precipitate becomes colloidal.
It is inconvenient in terms of handling and operation. In addition, when using HAp as a biological material, which is the main use of HAp, if it contains more than a certain amount of iron, zinc, lead, etc., these ions may be eluted in the living body. Therefore, when crude phosphoric acid is used as a raw material, it is extremely difficult to remove impurities. As an extremely industrial method that is completely different from the above methods, the present inventors have already developed an aqueous solution method in which Ca(OH) 2 is added to a slurry of CaHPO 4 2H 2 O and water and the reaction is carried out under atmospheric pressure. (Japanese Unexamined Patent Application Publication No. 1983)
-5009). This method involves the addition of Ca(OH) 2 to Ca/P
Up to a molar ratio of 1.6 (90% of the theoretical addition amount), by gradually maintaining the pH below 10, it is easy to
Moreover, highly pure HAp can be produced in a short time. [Problems with the Prior Art] Among the methods for producing HAp that have been proposed so far, both the dry method and the hydrothermal reaction method require expensive equipment and are disadvantageous in terms of energy.
Furthermore, among the aqueous solution methods, the method using phosphoric acid neutralization has problems in handling the product and is not suitable for producing high-purity HAp. On the other hand, in the above-mentioned method already proposed by the present inventors, the Ca/P molar ratio of HAp once generated by the reaction may change during the filtration and washing operation, and the desired Ca/P molar ratio can be achieved with good reproducibility. Obtaining the ratio HAp was not always satisfactory. [Problems to be Solved by the Invention] The present invention is intended to solve the above-mentioned problems of the prior art, and also to achieve a desired Ca/P ratio with good reproducibility using the method of Japanese Patent Application No. 110947/1983. The purpose is to obtain HAp. [Means for solving the problem] That is, the present invention adds CaO and/or Ca(OH) 2 to a slurry of CaHPO 4 2H 2 O and water,
In a method for producing hydroxyapatite,
Add CaO and/or Ca(OH) 2 while keeping the pH below 10 at a temperature of 5 to 70°C up to a Ca/P molar ratio of 1.54, then add the remaining amount and mix the reaction slurry at 65°C.
This is a method for producing hydroxyapatite, which is characterized by aging at a temperature of 0.5 hours or more at a temperature of ℃ or higher. To explain the present invention in more detail, CaHPO4・
The basic reaction formula when using 2H 2 O and Ca(OH) 2 as a Ca source is shown below. 6CaHPO 4・2H 2 O＋4Ca(OH) 2 → Ca 10 (PO 4 ) 6 (OH) 2 ↓＋18H 2 O In this case, an equivalent amount of Ca ( Even if OH) 2 is added all at once, the reaction is extremely slow and it is difficult to generate HAp. However, when Ca(OH) 2 is supplied continuously or intermittently to the CaHPO 4 2H 2 O slurry within a range that does not exceed each reaction rate, it is necessary to ensure that the PH value of the reaction solution does not exceed a specific value. Ca while adjusting to
If (OH) 2 solution is supplied, the reaction will proceed easily,
Complete. Controlling the pH is a major factor in this reaction; for example, at a reaction temperature of 50°C, the Ca/P molar ratio is 1.58.
The reaction is carried out at a pH of 10 or less, preferably 9.0 or less. Thereafter, the reaction is carried out at a pH of 9 or higher to synthesize HAp with a theoretical Ca/P ratio of 1.67. Further, even if the charged Ca/P ratio slightly exceeds 1.67, Ca(OH) 2 can be removed by subsequent washing, so HAp with a Ca/P ratio of 1.67 can be easily obtained. In this reaction, the pH during the reaction is an extremely important factor, and in order to complete the reaction, it is necessary to pay sufficient attention to pH control.If the pH is not kept below 10, unreacted CaHPO4 . 2H 2 O remains and HAp cannot be obtained. The reaction temperature is usually 5 to 70°C, preferably 30 to 70°C in order to speed up the reaction. If the temperature is below 5°C, the reaction progresses slowly, which is not preferable. Moreover, at temperatures above 70°C, CaHPO 4 2H 2 O
It metastasizes to CaHPO4 and should be avoided. In addition, the Ca/P ratio of the product HAp can be adjusted by changing the amount of Ca(OH) 2 supplied (the charged Ca/P ratio).
HAp with a Ca/P ratio of 1.48 to 1.67 can be easily obtained. HAp generated in this way is unstable as it is, and washing in the subsequent stage
Since the Ca/P ratio varies, in the present invention,
Aging is performed after the reaction is completed. The conditions for aging the reaction liquid slurry are that the aging temperature is 65°C or higher, more preferably 90°C or higher,
The aging time depends on the temperature, but at 100°C it is at least 0.5 hours, and at 65°C it is at least one day and night. Therefore, in order to ripen efficiently, it is better to ripen at a higher temperature. After such aging, the solid content is separated by conventional means such as filtration, and excess Ca(OH) 2 is washed away. In this way, HAp with a desired Ca/P ratio can be obtained with good reproducibility, and this is a particularly excellent method for obtaining HAp with a theoretical Ca/P ratio of 1.67. Ca(OH) 2 used in the present invention may be supplied in either powder or slurry form. Also Ca
Of course, CaO may be used instead of (OH) 2 .
Furthermore, if it is desired to suppress the incorporation of CO 2-3 ions into the product HAp as low as possible, it is desirable to carry out the reaction under an inert gas (for example, N 2 etc.) atmosphere. The HAp obtained in the present invention is a fine particle plate-like powder and can be used as a biomaterial as it is or by molding and sintering with other organic substances such as cellulose and collagen, or as a composite with an organic matrix, and can also be used as a chromatography filler. It can also be used for many purposes. The present invention will be explained in detail below with reference to Examples. Examples 1 to 7, Comparative Examples 1 and 2 60 with lid made of SUS304 with hot water jacket
A stirrer, a PH meter, a thermometer, and a reflux condenser are set in the reaction apparatus, and CaHPO 4 2H 2 O is charged inside with water and then heated. When the predetermined temperature is reached, a separate stirrer is installed. 10% lime milk preheated by a hot water jacket was supplied from the lime milk tank to the reactor using a pump, and the reaction was carried out. After the reaction is completed, ripen at a specified temperature, remove solids by filtration, and add excess water.
Ca(OH) 2 was washed away and dried. The reaction conditions, aging conditions and results are shown in Table 1. In addition, PH and Ca at each reaction time in Example 1
The relationship between the addition rate of (OH) 2 is shown in Figure 1, and the X-ray diffraction pattern of the obtained product is shown in Figure 2.
本発明によれば、生体材料等として有用なヒド
ロキシアパタイトを容易に得ることができ、しか
も再現性よく所望のCa／Ｐ比とすることができ
るものである。
According to the present invention, hydroxyapatite, which is useful as a biomaterial, can be easily obtained, and a desired Ca/P ratio can be obtained with good reproducibility.
第１図は実施例１における各反応時間でのPH、
Ca（OH）2添加率の関係を示すグラフである。第
２図および第３図はそれぞれ実施例１及び比較例
３のＸ線回折パターンである。
Figure 1 shows the pH at each reaction time in Example 1,
It is a graph showing the relationship between Ca(OH) 2 addition rate. FIG. 2 and FIG. 3 are X-ray diffraction patterns of Example 1 and Comparative Example 3, respectively.
Claims (1)
よび／またはCa（OH）2を添加し、ヒドロキシア
パタイトを製造する方法において、温度５〜70℃
でCa／Ｐモル比1.54まではPHを10以下に保ちなが
らCaOおよび／またはCa（OH）2を加え、次いで
残量を加えた後反応液スラリーを65℃以上で0.5
時間以上熟成することを特徴とするヒドロキシア
パタイトの製造法。1. A method for producing hydroxyapatite by adding CaO and/or Ca(OH) 2 to a slurry of CaHPO 4 2H 2 O and water at a temperature of 5 to 70°C.
Add CaO and/or Ca(OH) 2 while keeping the PH below 10 until the Ca/P molar ratio is 1.54, then add the remaining amount and stir the reaction slurry at 65°C or higher to 0.5
A method for producing hydroxyapatite characterized by aging for more than an hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27207084A JPS61151010A (en) | 1984-12-25 | 1984-12-25 | Production of hydroxy apatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27207084A JPS61151010A (en) | 1984-12-25 | 1984-12-25 | Production of hydroxy apatite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61151010A JPS61151010A (en) | 1986-07-09 |
| JPH0324405B2 true JPH0324405B2 (en) | 1991-04-03 |
Family
ID=17508674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27207084A Granted JPS61151010A (en) | 1984-12-25 | 1984-12-25 | Production of hydroxy apatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61151010A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0832552B2 (en) * | 1990-05-21 | 1996-03-29 | 三菱マテリアル株式会社 | Hydroxyapatite fine single crystal and method for producing the same |
| JP3981725B2 (en) * | 2002-10-23 | 2007-09-26 | 独立行政法人産業技術総合研究所 | Apatite hydrogel complexed with protein, solidified body thereof, and production method thereof |
-
1984
- 1984-12-25 JP JP27207084A patent/JPS61151010A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61151010A (en) | 1986-07-09 |
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