JPH0313162B2 - - Google Patents
Info
- Publication number
- JPH0313162B2 JPH0313162B2 JP60185150A JP18515085A JPH0313162B2 JP H0313162 B2 JPH0313162 B2 JP H0313162B2 JP 60185150 A JP60185150 A JP 60185150A JP 18515085 A JP18515085 A JP 18515085A JP H0313162 B2 JPH0313162 B2 JP H0313162B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- reaction
- cahpo
- molar ratio
- calcium phosphate
- 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
- 239000011575 calcium Substances 0.000 claims description 44
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims 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 claims description 27
- 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 claims description 13
- 239000001506 calcium phosphate Substances 0.000 claims description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 8
- 235000011010 calcium phosphates Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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製造方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for producing hydroxyapatite.
水酸アパタイトは一般式
Ca10-Z（HPO4）Z（PO4）6-Z（OH）2-Z・nH2O
ただし、ｎは２〜2.5，ｚは０〜１を表わす）
の化学組成を有し、生体内の歯骨の主成分と近似
したもので、人工歯根，人工骨，あるいはそれら
の充填材として有用なものである。また生体高分
子や生体有害有機質あるいは無機質イオンの吸着
剤としても作用するものである。 Hydroxyapatite has the general formula Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z・nH 2 O (where n represents 2 to 2.5 and z represents 0 to 1)
It has a chemical composition similar to the main component of in-vivo dental bone, and is useful as an artificial tooth root, artificial bone, or a filling material therefor. It also acts as an adsorbent for biopolymers, biohazardous organic substances, or inorganic ions.
従来技術 従来の水酸アパタイトの製造方法としては、 (1) 固相反応法 (2) 水熱反応法 (3) 沈殿反応法 (4) 加水分解法が知られている。Conventional technology The conventional method for producing hydroxyapatite is (1) Solid phase reaction method (2) Hydrothermal reaction method (3) Precipitation reaction method (4) Hydrolysis method is known.
(1)の固相反応法は1000℃以上の高温で水蒸気共
存下で焼成する方法であり、また(2)の水熱反応法
も密封耐圧容器と高圧下で行うため、いずれも反
応装置が高価となり、かつ得られる水酸アパタイ
ト粉末は、前記用途に適されない不利な面を持つ
ている欠点があつた。 The solid phase reaction method (1) involves firing in the coexistence of water vapor at a high temperature of 1000°C or higher, and the hydrothermal reaction method (2) is also carried out in a sealed pressure-resistant container and under high pressure, so in both cases the reaction equipment is It is expensive and the resulting hydroxyapatite powder has disadvantages that make it unsuitable for the above-mentioned uses.
(3)の沈殿反応法は、得られる水酸アパタイト粉
末は高活性で易焼結性であるが、沈殿物がコロイ
ド状となるため、取扱いが不便であると共に不純
物イオンの洗浄除去が困難であり、かつ化学組成
の再現性が悪い欠点がある。 In the precipitation reaction method (3), the obtained hydroxyapatite powder is highly active and easily sintered, but since the precipitate is colloidal, it is inconvenient to handle and it is difficult to wash and remove impurity ions. However, it also has the disadvantage of poor reproducibility of chemical composition.
(4)の加水分解法は前記(3)の方法を改良した方法
であり、例えば、CaHPO4またはCaHPO4・
2H2Oと水のスラリー溶液を、PH10以下の塩基性
に保ちながらCa（OH）2を連続的または断続的に
供給する方法が知られている。しかしながら、こ
の方法では反応温度50℃で40時間以上という長時
間を要する欠点があつた（特開昭60−5009号公
報）。また、この場合、ｎ−ペンタンやtert−ブ
タノール等の有機溶媒の共存下においては、Ca
（OH）2の添加を２時間に短縮し得られるが（特
開昭58−190807号，特開昭59−217610号）、有機
溶媒を必要とし、その後処理も面倒となる欠点が
あつた。 The hydrolysis method (4) is an improved method of the above method (3), for example, CaHPO 4 or CaHPO 4 .
A method is known in which Ca(OH) 2 is continuously or intermittently supplied while maintaining a slurry solution of 2H 2 O and water at a basic pH of 10 or less. However, this method had the drawback of requiring a long reaction time of 40 hours or more at a reaction temperature of 50° C. (Japanese Patent Application Laid-Open No. 60-5009). In this case, in the coexistence of organic solvents such as n-pentane and tert-butanol, Ca
Although the addition of (OH) 2 can be shortened to 2 hours (Japanese Patent Application Laid-open No. 58-190807, JP-A No. 59-217610), it has the disadvantage that an organic solvent is required and subsequent processing is troublesome.
発明の目的
本発明は前記(4)の加水分解法における欠点を解
消すべくなされたもので、その目的は有機溶媒を
使用することなく、短時間に所望のCa／Ｐモル
比を有する水酸アパタイトを製造する方法を提供
するにある。Purpose of the Invention The present invention was made in order to solve the drawbacks of the hydrolysis method (4) above, and its purpose is to produce hydroxyl which has a desired Ca/P molar ratio in a short period of time without using an organic solvent. The present invention provides a method for manufacturing apatite.
発明の構成
本発明者らは前記目的を達成すべく、難水溶性
リン酸カルシウムの加水分解による水酸アパタイ
トの生成反応機構を調べた結果、第１段階に
Ca／Ｐモル比が1.67より小さい水酸アパタイトが
生成し、第２段階としてこの水酸アパタイトが
Caを吸収してCa／Ｐモル比が1.67へと変化して
行くことを究明した。従つて、先ず難水溶性リン
酸カルシウムを加水分解した後に、これにCaを
添加してCa／Ｐモル比を増加させると、水酸ア
パタイトは短時間に容易に製造し得られることが
分つた。この知見に基いて本発明を完成した。Structure of the Invention In order to achieve the above object, the present inventors investigated the reaction mechanism for producing hydroxyapatite by hydrolysis of poorly water-soluble calcium phosphate, and as a result, the first step was
Hydroxyapatite with a Ca/P molar ratio smaller than 1.67 is generated, and in the second step, this hydroxyapatite is
It was determined that the Ca/P molar ratio changes to 1.67 as Ca is absorbed. Therefore, it has been found that hydroxyapatite can be easily produced in a short time by first hydrolyzing poorly water-soluble calcium phosphate and then adding Ca to it to increase the Ca/P molar ratio. The present invention was completed based on this knowledge.
本発明の要旨は難水溶性リン酸カルシウムを、
カルシウムイオンを含まない塩基性水溶液中で加
水分解させて、Ca／Ｐのモル比が1.67より小さい
非化学量論性の水酸アパタイトとなし、これに、
塩基性水溶液の下でカルシウムイオンを添加して
Ca／Ｐモル比を1.67までの任意の比まで増加させ
ることを特徴とする水酸アパタイトの製造方法に
ある。 The gist of the present invention is to use poorly water-soluble calcium phosphate,
Hydrolyzed in a basic aqueous solution containing no calcium ions to form non-stoichiometric hydroxyapatite with a Ca/P molar ratio of less than 1.67, which
Adding calcium ions under basic aqueous solution
A method for producing hydroxyapatite characterized by increasing the Ca/P molar ratio to an arbitrary ratio up to 1.67.
難水溶性リン酸カルシウムとしては、例えば
CaHPO4・2H2O，CaHPO4，Ca3（PO4）2が挙げ
られる。しかし、これに限定されるものではな
い。 Examples of poorly water-soluble calcium phosphate include
Examples include CaHPO 4 .2H 2 O, CaHPO 4 and Ca 3 (PO 4 ) 2 . However, it is not limited to this.
本発明の製造方法の第一段階におけるこれら難
水溶性リン酸カルシウムの加水分解の基本反応式
を示すと次の通りである。 The basic reaction formula for the hydrolysis of poorly water-soluble calcium phosphate in the first step of the production method of the present invention is as follows.
（10−ｚ）CaHPO4・2H2O＋｛（２−ｚ）＋ｎ｝
H2O
→Ca10-Z（HPO4）Z（PO4）6-Z（OH）2-Z・nH2O
＋（４−ｚ）H3PO4＋２（10−ｚ）H2O
（10−ｚ）CaHPO4＋｛（２−ｚ）＋ｎ｝H2O
→Ca10-Z（HPO4）Z（PO4）6-Z（OH）2-Z・nH2O
＋（４−ｚ）H3PO4
（10−ｚ）Ca3（PO4）2＋｛３（２−ｚ）＋3n｝H2O
→3Ca10-Z（HPO4）Z（PO4）6-Z（OH）2-Z・
nH2O
＋２（１−ｚ）H3PO4
この場合、Ca2の共存またはPHが高すぎても低
すぎても水酸アパタイトの生成は起こり難い。例
えば、40℃、３時間後では、第１図および第２図
に示すように、PH９以上ではアパタイトの生成は
なく、PH７以下ではアパタイト以外の副生成物が
混在するようになる。従つて、第１段階では、
Ca2は添加せず、また、PHは最適値を選んで加水
分解させる。PHの最適値としては、例えば、
CaHPO4・2H2Oの40℃の場合でPH8.0±0.5の範
囲、CaHPO4の80℃の場合でPH9.0±0.5の範囲、
α−TCPの80℃の場合でPH９±１の範囲あるい
は初期PH８〜10に設定する。反応の終点は、反応
進行に伴うPH低下を補償して各最適PH範囲を保つ
ための塩基性物質の滴下が不必要になる時点とし
て検出できる。(10−z)CaHPO 4・2H 2 O+{(2−z)+n}
H 2 O → Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z・nH 2 O + (4-z) H 3 PO 4 +2 (10-z) H 2 O ( 10-z) CaHPO 4 + {(2-z) + n}H 2 O → Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z・nH 2 O + (4-z )H 3 PO 4 (10-z)Ca 3 (PO 4 ) 2 +{3(2-z)+3n}H 2 O →3Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z・
nH 2 O + 2 (1-z) H 3 PO 4 In this case, the formation of hydroxyapatite is unlikely to occur even if Ca 2 coexists or the pH is too high or too low. For example, after 3 hours at 40°C, as shown in Figures 1 and 2, at pH 9 or higher, no apatite is produced, and at pH 7 or lower, by-products other than apatite are mixed. Therefore, in the first stage,
Hydrolysis is carried out without adding Ca 2 and by selecting the optimum pH value. For example, the optimal value of PH is:
PH8.0±0.5 range at 40℃ for CaHPO4・2H2O , PH9.0±0.5 range at 80℃ for CaHPO4 ,
In the case of α-TCP at 80℃, set the pH to a range of 9±1 or an initial pH of 8 to 10. The end point of the reaction can be detected as the point at which it is no longer necessary to add a basic substance dropwise to compensate for the decrease in pH as the reaction progresses and maintain the respective optimum pH range.
第２段階において、Ca2+を添加して吸収反応
させる。その反応式を示すと次の通りである。 In the second step, Ca 2+ is added to cause an absorption reaction. The reaction formula is as follows.
Ca10-Z（HPO4）Z（PO4）6-Z（OH）2-Z・nH2O＋
zCa2+
＋zOH-→Ca10（PO4）6（OH2）＋zH+＋
nH2O
この場合、PHを高くする程Ca2+は良く吸収さ
れる（第３図参照）ので、PH９以上であることが
よい。 Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z・nH 2 O+
zCa 2+ +zOH - →Ca 10 (PO 4 ) 6 (OH 2 ) + zH + +
nH 2 O In this case, the higher the pH, the better the absorption of Ca 2+ (see Figure 3), so the pH is preferably 9 or higher.
第１段階および第２段階でPHを調節する塩基性
物質としては、例えばNaOH，KOH，Ca
（OH）2，NH3，NH4OH，NH2C（CH2OH）3，
（CH3）4NOH等が挙げられる。 Basic substances that adjust PH in the first and second stages include, for example, NaOH, KOH, Ca
(OH) 2 , NH 3 , NH 4 OH, NH 2 C(CH 2 OH) 3 ,
Examples include (CH 3 ) 4 NOH.
第２段階に用いるCa2源としては、例えば、Ca
（OH）2，CaCl2・2H2O，CaO，CaF2，CaCO3，
（CH3COO）2Ca等が挙げられる。 As the Ca 2 source used in the second stage, for example, Ca
(OH) 2 , CaCl 2・2H 2 O, CaO, CaF 2 , CaCO 3 ,
(CH 3 COO) 2 Ca etc.
第１段階での加水分解反応は原料の難水溶性リ
ン酸カルシウムに適度の水を加え、上記のCa2を
含まない塩基性物質でアルカリ性となした後、加
熱還流する。加熱還流数時間にしてCa／Ｐ＝1.50
程度の非化学量論的な水酸アパタイトに転化され
る。 In the first step, the hydrolysis reaction involves adding an appropriate amount of water to the poorly water-soluble raw material calcium phosphate, making it alkaline with the above-mentioned Ca 2 -free basic substance, and then heating and refluxing. Ca/P=1.50 after heating under reflux for several hours
is converted to non-stoichiometric hydroxyapatite.
その後、第２段階としてCa2を添加し、更に塩
基性物質を加えて加熱還流を続ける。この時
Ca2+の添加量及び反応時間を制御することによ
りCa／Ｐが1.50〜1.67までの水酸アパタイトが得
られる。この時のPHは出来るだけ高い方が反応時
間が速いので、通常はPH９以上（第３図参照）で
あるのがよい。加熱還流によりCa／Ｐ＝1.67に転
化した水酸アパタイトを分離する。例えば過
し、洗浄することによつて高純度の水酸アパタイ
トが得られる。 Then, in the second step, Ca 2 is added, and then a basic substance is added, and heating and refluxing is continued. At this time
By controlling the amount of Ca 2+ added and the reaction time, hydroxyapatite with a Ca/P of 1.50 to 1.67 can be obtained. At this time, the reaction time is faster if the pH is as high as possible, so it is usually better to set the pH to 9 or higher (see Figure 3). The hydroxyapatite converted to Ca/P=1.67 by heating under reflux is separated. For example, by filtering and washing, highly pure hydroxyapatite can be obtained.
実施例 １
CaHPO4・2H2O2ｇ，水200mlをビーカーに仕
込み、撹拌しながら加熱して40℃に昇温し、
NH4OHでPHを８に保ち約３時間反応させた。こ
の時ビーカー内の粉末はCa／Ｐ＝1.50の水酸アパ
タイトに転化していた。これにCaCl2・2H2O2ｇ
を加えてNH4OHでPHを10とし、更に反応を進め
た。３時間後ビーカー内の液を別し、乾燥し
た。得られたものは白色のCa／Ｐ＝1.67の水酸ア
パタイト粉末であつた。Example 1 Put CaHPO 4・2H 2 O2g and 200ml of water into a beaker, heat while stirring to raise the temperature to 40℃,
The pH was maintained at 8 with NH 4 OH and the reaction was carried out for about 3 hours. At this time, the powder in the beaker had been converted to hydroxyapatite with Ca/P=1.50. Add CaCl 2・2H 2 O2g to this
was added, the pH was adjusted to 10 with NH 4 OH, and the reaction was further advanced. After 3 hours, the liquid in the beaker was separated and dried. What was obtained was white hydroxyapatite powder with Ca/P=1.67.
実施例 ２
CaHPO45ｇ，水150mlをビーカーに仕込み、撹
拌しながら加熱して80℃に昇温させた。これに
NH4OHを添加してPHを９とし、約１時間反応さ
せた。その後CaCl2・2H2Oを５ｇ加えて、
NH4OHでPHを９にし反応を進めた。２時間後
別して乾燥し白色粉末を得た。この粉末はCa／
Ｐ＝1.62の水酸アパタイトであつた。Example 2 5 g of CaHPO 4 and 150 ml of water were placed in a beaker and heated while stirring to raise the temperature to 80°C. to this
NH 4 OH was added to adjust the pH to 9, and the reaction was allowed to proceed for about 1 hour. After that, add 5g of CaCl 2.2H 2 O,
The pH was adjusted to 9 with NH 4 OH and the reaction proceeded. After 2 hours, it was separated and dried to obtain a white powder. This powder is Ca/
It was hydroxyapatite with P=1.62.
実施例 ３
α−TCP（Ca3（PO4）2）５ｇ，水150mlをビーカ
ーに仕込み、撹拌しながら加熱し80℃に昇温し
た。これにNH4OHを添加してPHを10に保ち約２
時間反応させた。その後、CaCl2・2H2Oを1.5ｇ
加え、NH4OHでPHを９にして、反応を進めた。
約２時間後別し乾燥して白色粉末を得た。この
粉末はCa／Ｐ＝1.67の水酸アパタイトであつた。Example 3 5 g of α-TCP (Ca 3 (PO 4 ) 2 ) and 150 ml of water were placed in a beaker and heated while stirring to raise the temperature to 80°C. Add NH 4 OH to this and keep the pH at 10, about 2
Allowed time to react. Then add 1.5g of CaCl 2 2H 2 O
In addition, the pH was adjusted to 9 with NH 4 OH to proceed with the reaction.
After about 2 hours, it was separated and dried to obtain a white powder. This powder was hydroxyapatite with Ca/P=1.67.
発明の効果 本発明は次のような優れた効果を有する。Effect of the invention The present invention has the following excellent effects.
(1) 従来の非有機溶媒系における沈殿法に比べ
て、製造時間は約1/10ですみ、しかも容易に安
定してCa／Ｐ＝1.67の水酸アパタイトを製造す
ることができる。(1) Compared to conventional precipitation methods using non-organic solvents, the production time is approximately 1/10, and hydroxyapatite with Ca/P = 1.67 can be produced easily and stably.
(2) 従来の固相反応法や水熱反応におけるような
高温で耐圧容器を必要とせず、100℃以下の低
温で短時間に水酸アパタイトを製造することが
できる。(2) Hydroxyapatite can be produced in a short time at a low temperature of 100°C or less, without requiring a high-temperature and pressure-resistant container like in conventional solid-phase reaction methods or hydrothermal reactions.
(3) Ca2+イオンの供給量及びその反応時間を制
御することにより、Ca／Ｐのモル比を1.50〜
1.67の任意組成の水酸アパタイトとなし得る。(3) By controlling the supply amount of Ca 2+ ions and its reaction time, the Ca/P molar ratio can be adjusted to 1.50~
It can be made into hydroxyapatite of any composition of 1.67.
(4) 出発原料の粉末形状を継承した水酸アパタイ
トになり易いため、過・洗浄も容易で高純度
のものとなし得る。(4) Since it easily becomes hydroxyapatite that inherits the powder shape of the starting material, it can be easily filtered and washed and can be made into a highly pure product.
第１図はCaHPO4・2H2Oの加水分解における
PH（アンモニア水使用）と水酸アパタイトの生成
率との関係図、第２図はCaHPO4・2H2Oの加水
分解生成物（40℃、３時間後）のＸ線回折図、第
３図はCa2+吸収反応におけるPHと生成水酸アパ
タイトのCa／Ｐモル比との関係図を示す。
Figure 1 shows the hydrolysis of CaHPO 4 2H 2 O.
Relationship diagram between PH (using ammonia water) and hydroxyapatite production rate, Figure 2 is an X-ray diffraction diagram of the hydrolysis product of CaHPO 4 2H 2 O (40℃, 3 hours later), Figure 3 shows a diagram of the relationship between the pH in the Ca 2+ absorption reaction and the Ca/P molar ratio of the produced hydroxyapatite.
Claims (1)
オンを含まない塩基性水溶液中で加水分解させ
て、Ca／Ｐのモル比が1.67より小さい非化学量論
性の水酸アパタイトとなし、これに、塩基性水溶
液の下でカルシウムイオンを添加してCa／Ｐモ
ル比を1.67までの任意の比まで増加させることを
特徴とする水酸アパタイトの製造方法。 ２ 難水溶性リン酸カルシウムが、CaHPO4，
CaHPO4・2H2O，Ca3（PO4）2である特許請求の
範囲第１項記載の水酸アパタイトの製造方法。[Claims] 1. Hydrolyzing poorly water-soluble calcium phosphate in a basic aqueous solution containing no calcium ions to form non-stoichiometric hydroxyapatite with a Ca/P molar ratio of less than 1.67; A method for producing hydroxyapatite, which comprises adding calcium ions to the hydroxyapatite in a basic aqueous solution to increase the Ca/P molar ratio to an arbitrary ratio up to 1.67. 2 Slightly water-soluble calcium phosphate is CaHPO 4 ,
The method for producing hydroxyapatite according to claim 1, which is CaHPO 4 .2H 2 O, Ca 3 (PO 4 ) 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18515085A JPS6246908A (en) | 1985-08-23 | 1985-08-23 | Production of hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18515085A JPS6246908A (en) | 1985-08-23 | 1985-08-23 | Production of hydroxyapatite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6246908A JPS6246908A (en) | 1987-02-28 |
| JPH0313162B2 true JPH0313162B2 (en) | 1991-02-21 |
Family
ID=16165733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18515085A Granted JPS6246908A (en) | 1985-08-23 | 1985-08-23 | Production of hydroxyapatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6246908A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07115850B2 (en) * | 1989-10-31 | 1995-12-13 | 積水化成品工業株式会社 | Method for producing hydroxyapatite and method for producing modified tricalcium phosphate |
| FR2857658B1 (en) * | 2003-07-16 | 2006-09-22 | Rhodia Chimie Sa | NOVEL CALCIUM PHOSPHATE GRANULES OF THE HYDROXYAPATITE TYPE, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS |
| GB2433257A (en) * | 2005-12-19 | 2007-06-20 | Accentus Plc | Preparation of hydroxyapatite |
| JP5248848B2 (en) * | 2007-12-11 | 2013-07-31 | 山八歯材工業株式会社 | Implant manufacturing method and artificial tooth root manufacturing method |
| JP7100615B2 (en) * | 2019-11-01 | 2022-07-13 | ＨＯＹＡ Ｔｅｃｈｎｏｓｕｒｇｉｃａｌ株式会社 | Production method and hydroxyapatite particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS605009A (en) * | 1983-06-22 | 1985-01-11 | Central Glass Co Ltd | Preparation of hydroxy apatite |
-
1985
- 1985-08-23 JP JP18515085A patent/JPS6246908A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS605009A (en) * | 1983-06-22 | 1985-01-11 | Central Glass Co Ltd | Preparation of hydroxy apatite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6246908A (en) | 1987-02-28 |
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