JPH0214311B2 - - Google Patents
Info
- Publication number
- JPH0214311B2 JPH0214311B2 JP62004637A JP463787A JPH0214311B2 JP H0214311 B2 JPH0214311 B2 JP H0214311B2 JP 62004637 A JP62004637 A JP 62004637A JP 463787 A JP463787 A JP 463787A JP H0214311 B2 JPH0214311 B2 JP H0214311B2
- Authority
- JP
- Japan
- Prior art keywords
- apatite
- powder
- cahpo
- porous body
- porosity
- 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
- 229910052586 apatite Inorganic materials 0.000 claims description 25
- 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 claims description 25
- 239000000843 powder Substances 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 description 8
- 239000001506 calcium phosphate Substances 0.000 description 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000019731 tricalcium phosphate Nutrition 0.000 description 6
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 6
- 229940078499 tricalcium phosphate Drugs 0.000 description 6
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 4
- 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 3
- 229940043256 calcium pyrophosphate Drugs 0.000 description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 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
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004068 calcium phosphate ceramic Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002676 xenobiotic agent Substances 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアパタイト多孔体の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a porous apatite body.
アパタイト多孔体及びその焼成物は生体内の
歯、骨の主成分に近似した化学組成を有し、歯、
骨修復材料として、また生体高分子や生体有害有
機物または無機質イオンの吸着剤として有用なも
のである。 Apatite porous bodies and fired products thereof have chemical compositions similar to the main components of teeth and bones in living organisms, and
It is useful as a bone repair material and as an adsorbent for biopolymers, biohazardous organic substances, or inorganic ions.
従来技術
従来の水硬性リン酸カルシウムには、リン酸四
カルシウムとリン酸三カルシウムとが知られてい
る。これらの水硬化性を利用して（硬化物はアパ
タイト多孔体）覆髄材、裏装材として歯科治療に
使用されている。Prior Art Tetracalcium phosphate and tricalcium phosphate are known as conventional hydraulic calcium phosphates. Utilizing these water-curing properties (the cured product is a porous apatite), it is used in dental treatment as pulp capping material and lining material.
しかし、リン酸三カルシウム、リン酸四カルシ
ウムは、ピロリン酸カルシウム（Ca2P2O7）粉末
とカルシウム塩粉末との混合物を1200℃以上での
焼成による固相反応、その後急冷、粉砕して製造
されるので、非常に高価なものとなる欠点があつ
た。 However, tricalcium phosphate and tetracalcium phosphate are produced by solid phase reaction by firing a mixture of calcium pyrophosphate (Ca 2 P 2 O 7 ) powder and calcium salt powder at 1200°C or higher, followed by rapid cooling and pulverization. The drawback was that it was very expensive.
発明の目的
本発明は従来法のような高価なリン酸三カルシ
ウム、リン酸四カルシウムを使用することなく、
安価にアパタイト多孔体を得る方法を提供するに
ある。Purpose of the invention The present invention does not use expensive tricalcium phosphate or tetracalcium phosphate as in conventional methods.
The object of the present invention is to provide a method for obtaining a porous apatite material at low cost.
発明の構成
本発明は前記目的を達成すべく鋭意研究の結
果、リン酸水素カルシウム２水和物またはその無
水物に炭酸カルシウム粉末を混和すると、炭酸カ
ルシウムがPH緩衝材として作用し、水硬化し得ら
れ、容易にアパタイト多孔体が得られる新しい知
見を得た。この知見に基づいて本発明を完成し
た。Structure of the Invention The present invention has been made as a result of extensive research to achieve the above object. When calcium carbonate powder is mixed with calcium hydrogen phosphate dihydrate or its anhydride, the calcium carbonate acts as a PH buffering material, causing water hardening. We have obtained new knowledge that allows a porous apatite to be easily obtained. The present invention was completed based on this knowledge.
本発明の要旨は、リン酸水素カルシウム２水和
物またはその無水水和物にCa／Ｐモル比で1.50〜
1.67になる割合で炭酸カルシウム粉末を配合し、
これに水を加えて水和反応させることを特徴とす
るアパタイト多孔体の製造方法にある。リン酸水
素カルシウム２水和物（CaHPO4・2H2O）およ
びその無水和物（CaHPO4）は、次のような水和
反応でアパタイトへ変化する。 The gist of the present invention is to provide calcium hydrogen phosphate dihydrate or its anhydrous hydrate with a Ca/P molar ratio of 1.50 to 1.50.
Contains calcium carbonate powder at a ratio of 1.67,
A method for producing a porous apatite is characterized by adding water to the porous apatite and causing a hydration reaction. Calcium hydrogen phosphate dihydrate (CaHPO 4 .2H 2 O) and its anhydrate (CaHPO 4 ) are transformed into apatite through the following hydration reaction.
CaHPO4・2H2OまたはCaHPO4水中
――→
Ca10-z（HPO4）z（PO4）6-z（OH）2-z・nH2O
＋（４−Ｚ）H3PO4
（但し、０ｎ2.5、０Ｚ１を表わす）
この水和反応は弱酸性から塩基性の範囲（６＜
PH＜９）でよく進行する。従つて、反応進行に伴
つて生ずるH3PO4によるPH降下を緩衝しなけれ
ば反応は進行しない。CaHPO 4・2H 2 O or CaHPO 4 in water---→ Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2-z・nH 2 O + (4-Z)H 3 PO 4 ( However, this represents 0n2.5, 0Z1) This hydration reaction ranges from weak acidity to basicity (6<
It progresses well with pH<9). Therefore, the reaction will not proceed unless the PH drop due to H 3 PO 4 that occurs as the reaction progresses is buffered.
そのために、これまではPH緩衝液を予め反応系
に入れておくか、あるいは消石灰またはアンモニ
ア水等の塩基性物質を逐次添加してきた。このよ
うな方法では反応系を常に撹拌しなければならな
かつた。この撹拌のため得られるものは粉末状の
ものとなり、硬化したアパタイト多孔体を得るこ
とはできなかつた。 To this end, until now, a PH buffer solution has been added to the reaction system in advance, or a basic substance such as slaked lime or aqueous ammonia has been successively added. In such a method, the reaction system had to be constantly stirred. Due to this stirring, the product obtained was in the form of powder, and a hardened porous apatite material could not be obtained.
本発明のように、CaHPO4・2H2Oまたは
CaHPO4の粉末に固体PH緩衝材であるCaCO3粉末
を混合しておくと、水和反応に伴うPH降下を
CaCO3粉末により緩衝し得られ、撹拌を必要と
せず、静置状態で水和反応を進行し得られ、同時
に反応生成物は互いにからみ合つたアパタイト多
孔体として得られる。 As in the present invention, CaHPO4.2H2O or
By mixing CaHPO 4 powder with CaCO 3 powder, which is a solid PH buffer, the PH drop caused by the hydration reaction can be suppressed.
It is obtained by buffering with CaCO 3 powder, and the hydration reaction can proceed in a stationary state without stirring, and at the same time, the reaction product is obtained as a porous apatite body that is entangled with each other.
固体PH緩衝材としてはCaCO3以外にBaCO3、
SrCO3などがあるが、これらの金属成分は生体異
物であるので、CaCO3であることが好ましい。 In addition to CaCO 3 , BaCO 3 ,
There are SrCO 3 and the like, but since these metal components are xenobiotics, CaCO 3 is preferable.
CaCO3粉末のCaHPO4・2H2OまたはCaHPO4
粉末への混合割合はCa／Ｐモル比で1.50〜1.67で
ある。Ca／Ｐモル比が1.50未満では未反応の、
CaHPO4・2H2OまたはCaHPO4が残留するので、
焼成するとCa3（PO4）2とピロリン酸カルシウム
（Ca2P2O7）との混合相からなるセラミツク多孔
体となる。また1.67を超えると遊離のCaCO3が混
合してき、これを焼成するとCaOとなり、高アル
カリ性となり、生体には使用し難くなる。 CaCO3 powder CaHPO4・2H2O or CaHPO4
The mixing ratio in the powder is a Ca/P molar ratio of 1.50 to 1.67. If the Ca/P molar ratio is less than 1.50, unreacted
Since CaHPO 4 2H 2 O or CaHPO 4 remains,
When fired, it becomes a ceramic porous body consisting of a mixed phase of Ca 3 (PO 4 ) 2 and calcium pyrophosphate (Ca 2 P 2 O 7 ). Moreover, when it exceeds 1.67, free CaCO 3 is mixed in, and when this is calcined, it becomes CaO, which becomes highly alkaline and difficult to use for living organisms.
この混合物に水を加えてスラリー化してから型
に流し込み、これを100℃未満で加温するとアパ
タイトが生じて硬化する。その基本反応を示すと
次の通りである。 Add water to this mixture to form a slurry, pour it into a mold, and heat it below 100°C to form apatite and harden. The basic reaction is shown below.
CaHPO4・2H2OまたはCaHPO4水中
――→
Ca10-z（HPO4）z（PO4）6-z（OH）2-z・nH2O
＋（４−Ｚ）H3PO4
生じたH3PO4はCaCO3によつて次のように中
和されてアパタイトに転化する。CaHPO 4・2H 2 O or CaHPO 4 in water---→ Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2-z・nH 2 O + (4-Z)H 3 PO 4 produced The H 3 PO 4 is neutralized by CaCO 3 and converted into apatite as follows.
6H3PO4＋（10−Ｚ）CaCO3水中
――→
――→
Ca10-z（HPO4）z（PO4）6-z（OH）2-z・nH2O＋8H2O＋
H2CO3
＋（９−Ｚ）CO3
（但し、０ｎ2.5、０Ｚ１を表わす）
得られたアパタイト水硬多孔体を1000〜1350℃
で焼成すると気孔率が低下し、強度の高まつたリ
ン酸カルシウムセラミツク多孔体が得られる。6H 3 PO 4 + (10−Z) CaCO 3 in water --→ --→ Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2-z・nH 2 O+8H 2 O+
H 2 CO 3 + (9-Z) CO 3 (represents 0n2.5, 0Z1) The obtained apatite hydraulic porous body was heated to 1000-1350°C.
When fired, a calcium phosphate ceramic porous body with reduced porosity and increased strength can be obtained.
該多孔体はアパタイト単一相（Ｚ＝０の場合）、
あるいはアパタイトとCa3（PO4）2（０＜Ｚ１の
場合）の種々割合の混合相のものとなる。 The porous body is apatite single phase (when Z=0),
Alternatively, it is a mixed phase of apatite and Ca 3 (PO 4 ) 2 (in the case of 0<Z1) in various proportions.
この焼成温度が1000℃未満では焼結し難く、
1350℃を超えるとアパタイトが分解し初めるの
で、焼成に際しては前記の温度であることが必要
である。焼成の反応式を示すと次の通りである。 If the firing temperature is less than 1000℃, it will be difficult to sinter.
If the temperature exceeds 1350°C, the apatite will begin to decompose, so it is necessary to maintain the above-mentioned temperature during firing. The reaction formula for calcination is as follows.
Ca10-z（HPO4）z（PO4）6-z（OH）2-z・nH2O
→（１−Ｚ）Ca10（PO4）6（OH）2＋3ZCa3（PO4）2＋
（Ｚ＋ｎ）H2O
但し、０＜Ｚ１を表わす。Ca 10-z (HPO 4 ) z (PO 4 ) 6-z (OH) 2-z・nH 2 O → (1-Z) Ca 10 (PO 4 ) 6 (OH) 2 +3ZCa 3 (PO 4 ) 2 +
(Z+n)H 2 O However, 0<Z1.
実施例 １
CaHPO4・2H2O粉末にCaCO3をCa／Ｐモル比
が1.67になるように配合し、この混合物を水でス
ラリー化してパイレツクス管に流し込み、ふたを
して50℃で16時間加温して硬化させた。得られた
未反応原料粉末を含むアパタイト水硬多孔体は気
孔率71〜74％、ダイアメトラル引張り強さ15〜12
Kg／cm2であつた。Example 1 CaCO 3 was blended with CaHPO 4 2H 2 O powder so that the Ca/P molar ratio was 1.67, this mixture was made into a slurry with water, poured into a Pyrex tube, covered and heated at 50°C for 16 hours. It was heated and hardened. The resulting apatite hydraulic porous body containing unreacted raw material powder has a porosity of 71-74% and a diametral tensile strength of 15-12.
It was Kg/ cm2 .
実施例 ２
実施例１において、50℃で16時間を80℃で22時
間に変えて行つたところ、気孔率71〜76％、ダイ
アメトラル引張り強さ17〜８Kg／cm2の未反応原料
粉末を含むアパタイト水硬多孔体が得られた。Example 2 In Example 1, 16 hours at 50°C was changed to 22 hours at 80°C, and the result was that the powder contained unreacted raw material powder with a porosity of 71-76% and a diametral tensile strength of 17-8 Kg/ cm2. An apatite hydraulic porous body was obtained.
これを1250℃で３時間焼成した。気孔率は45〜
50％に減少し、ダイアメトラル引張り強さは48〜
19Kg／cm2に増大したアパタイト単一相のセラミツ
ク多孔体が得られた。 This was baked at 1250°C for 3 hours. Porosity is 45~
Reduced to 50%, diametral tensile strength is 48 ~
A ceramic porous body with a single apatite phase increased in weight to 19 kg/cm 2 was obtained.
実施例 ３
実施例１において、CaHPO4・2H2Oに変えて
CaHPO4を用いて、80℃で40時間加温して硬化さ
せると、気孔率79〜81％、ダイアメトラル引張り
強さ４〜２Kg／cm2のアパタイト単一相の水硬多孔
体が得られた。Example 3 In Example 1, instead of CaHPO 4 2H 2 O
When CaHPO 4 was used and cured by heating at 80°C for 40 hours, an apatite single-phase hydraulic porous body with a porosity of 79-81% and a diametral tensile strength of 4-2 Kg/cm 2 was obtained. .
実施例 ４
CaHPO4・2H2O粉末にCaCO3粉末をCa／Ｐモ
ル比が1.57になるよう混合し、この混合物を水で
スラリー化してからパイレツクス管に流し込み、
ふたをして80℃で16時間加温して硬化させた。得
られたアパタイト単一相からなる水硬多孔体の気
孔率は72〜80％、ダイアメトラル引張り強さは２
〜１Kg／cm2であつた。Example 4 CaHPO 4 2H 2 O powder was mixed with CaCO 3 powder so that the Ca/P molar ratio was 1.57, this mixture was slurried with water and then poured into a Pyrex tube.
The mixture was covered with a lid and heated at 80°C for 16 hours to cure. The resulting hydraulic porous body consisting of a single phase of apatite has a porosity of 72 to 80% and a diametral tensile strength of 2.
It was ~1Kg/ cm2 .
これを1250℃で３時間焼成すると、気孔率は46
〜47％に減少し、ダイアメトラル引張り強さは５
〜４Kg／cm2に増大したアパタイトとリン酸三カル
シウムとの混合相からなるセラミツク多孔体が得
られた。 When this is fired at 1250℃ for 3 hours, the porosity is 46
~47% and the diametral tensile strength is 5
A ceramic porous body consisting of a mixed phase of apatite and tricalcium phosphate, which increased to ~4 kg/cm 2 , was obtained.
比較例
実施例４において、Ca／Ｐモル比が1.33になる
ようにして硬化させた。得られた未反応原料を含
むアパタイト水硬多孔体の気孔率は77〜80％、ダ
イアメトラル引張り強さは８〜３Kg／cm2であつ
た。Comparative Example In Example 4, curing was performed such that the Ca/P molar ratio was 1.33. The resulting apatite hydraulic porous body containing unreacted raw materials had a porosity of 77 to 80% and a diametral tensile strength of 8 to 3 Kg/cm 2 .
これを実施例４と同様に焼成すると、気孔率は
60〜61％に減少し、ダイアメトラル引張り強さは
14〜11Kg／cm2に増大したリン酸三カルシウムとピ
ロリン酸カルシウムとの混合相からなるセラミツ
ク多孔体が得られた。 When this was fired in the same manner as in Example 4, the porosity was
The diametral tensile strength decreased to 60-61%
A ceramic porous body consisting of a mixed phase of tricalcium phosphate and calcium pyrophosphate with an increased weight of 14 to 11 kg/cm 2 was obtained.
発明の効果
本発明の方法によると、従来法におけるような
高価なリン酸三カルシウム、リン酸四カルシウム
を使用することなく、安価に得られるリン酸水素
カルシウム・２水和物またはその無水物から容易
にアパタイト多孔体が得られ、その気孔率も高範
囲に制御し得られる優れた効果を奏し得られる。Effects of the Invention According to the method of the present invention, calcium hydrogen phosphate dihydrate or its anhydride, which can be obtained at low cost, is used without using expensive tricalcium phosphate or tetracalcium phosphate as in conventional methods. An apatite porous body can be easily obtained, and its porosity can be controlled within a high range, resulting in excellent effects.
Claims (1)
水和物にCa／Ｐモル比で1.50〜1.67になる割合で
炭酸カルシウム粉末を配合し、これを水を加えて
水和反応させることを特徴とするアパタイト多孔
体の製造方法。1. Calcium carbonate powder is blended with calcium hydrogen phosphate dihydrate or its anhydrate at a Ca/P molar ratio of 1.50 to 1.67, and water is added to cause a hydration reaction. A method for producing an apatite porous body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62004637A JPS63176347A (en) | 1987-01-12 | 1987-01-12 | Manufacture of apatite porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62004637A JPS63176347A (en) | 1987-01-12 | 1987-01-12 | Manufacture of apatite porous body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63176347A JPS63176347A (en) | 1988-07-20 |
| JPH0214311B2 true JPH0214311B2 (en) | 1990-04-06 |
Family
ID=11589514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62004637A Granted JPS63176347A (en) | 1987-01-12 | 1987-01-12 | Manufacture of apatite porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63176347A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010140634A1 (en) * | 2009-06-02 | 2010-12-09 | 日鉄鉱業株式会社 | Tube-shaped calcium phosphate and process for production thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2869893B1 (en) * | 2004-05-06 | 2006-07-28 | Rhodia Chimie Sa | NOVEL CALCIUM PHOSPHATE GRANULES OF THE HYDROXYAPATITE TYPE, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS |
-
1987
- 1987-01-12 JP JP62004637A patent/JPS63176347A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010140634A1 (en) * | 2009-06-02 | 2010-12-09 | 日鉄鉱業株式会社 | Tube-shaped calcium phosphate and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63176347A (en) | 1988-07-20 |
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| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |