JPH01100048A - Production of calcium phosphate-based set material - Google Patents
Production of calcium phosphate-based set materialInfo
- Publication number
- JPH01100048A JPH01100048A JP62257939A JP25793987A JPH01100048A JP H01100048 A JPH01100048 A JP H01100048A JP 62257939 A JP62257939 A JP 62257939A JP 25793987 A JP25793987 A JP 25793987A JP H01100048 A JPH01100048 A JP H01100048A
- Authority
- JP
- Japan
- Prior art keywords
- citric acid
- polysaccharide
- phosphate
- ratio
- hydroxyapatite
- 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.)
- Granted
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 32
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 13
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 13
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000463 material Substances 0.000 title abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 22
- 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 abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 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 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 150000004676 glycans Chemical class 0.000 claims abstract description 11
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 11
- 239000005017 polysaccharide Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229920001661 Chitosan Polymers 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract 4
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 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 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229960003563 calcium carbonate Drugs 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
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003479 dental cement Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- -1 hydroxyapatite Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
Abstract
Description
【発明の詳細な説明】
「技術分野」
本発明は、例えば医科用あるいは歯科用セメントの材料
又は骨補填材として用いられるリン酸カルシウム系硬化
体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a calcium phosphate-based hardened material used, for example, as a material for medical or dental cement or as a bone grafting material.
「従来技術及びその問題点」
近年、種々のリン酸カルシウム系化合物、特にハイドロ
キシアパタイトは、生体適合性に優れた材料として注目
されている。ハイドロキシアパタイトが骨及び歯質を構
成する無機成分であることは周知のことであり、生体材
料としてこれらのリン酸カルシウム系化合物の使用が種
々検討されている。"Prior Art and its Problems" In recent years, various calcium phosphate compounds, particularly hydroxyapatite, have attracted attention as materials with excellent biocompatibility. It is well known that hydroxyapatite is an inorganic component constituting bones and teeth, and various uses of these calcium phosphate compounds as biomaterials have been investigated.
ところで、アパタイト以外のリン酸カルシウムは、加水
分解によりハイドロキシアパタイトに転化すると言われ
ているが、ある特定の条件下においては生成したハイド
ロキシアパタイトを硬化させることができることが見出
され、この性質を利用して歯科用あるいは医科用セメン
トとしてリン酸カルシウム粉末を用いることが盛んに研
究されている（例えば特開昭６２−１２７０５号、特開
昭６１−１６１２０６号、特開昭５９−１８２２６３号
、特開昭５９−８８３５１号公報等）。By the way, it is said that calcium phosphates other than apatite are converted to hydroxyapatite through hydrolysis, but it has been discovered that under certain conditions the generated hydroxyapatite can be hardened, and this property can be used to harden the hydroxyapatite. The use of calcium phosphate powder as dental or medical cement has been actively researched (for example, JP-A-62-12705, JP-A-61-161206, JP-A-59-182263, JP-A-59- 88351, etc.).
現在、このようなリン酸カルシウム系硬化体の原料とな
る活性なリン酸カルシウムとしては、α−リン酸三カル
シウム〔Ｃａ、（ＰＯ４）２〕、リン酸四カルシウムＣ
Ｃａａ （Ｐｏｔ） ｚＯ）及びこれらの２種の混合物
が知られている。その製法としては、α−リン酸三カル
シウムについては、炭酸カルシウムとピロリン酸カルシ
ウムを混合して１２５０℃で焼成する方法、リン酸四カ
ルシウムについては、炭酸カルシウムとピロリン酸カル
シウムを摩砕混合し、１５００℃で焼成する方法、また
、これらの混合物については、上記方法で製造された三
者を摩砕混合する方法が採られている。Currently, the active calcium phosphates used as raw materials for such hardened calcium phosphate products include α-tricalcium phosphate [Ca, (PO4)2], tetracalcium phosphate C
Caa (Pot) zO) and mixtures of the two are known. As for the manufacturing method, for α-tricalcium phosphate, calcium carbonate and calcium pyrophosphate are mixed and fired at 1250°C, and for tetracalcium phosphate, calcium carbonate and calcium pyrophosphate are ground and mixed and heated at 1500°C. As for the mixture thereof, a method is adopted in which the three materials produced by the above method are ground and mixed.
しかしながら、これらの製法は、いずれも固相反応であ
るために、得られる粉剤の組成は均一性を欠くものであ
った。このため、硬化時において反応が均一に進行せず
、硬化体の強度を低下させる原因の一つとなっていた。However, since all of these production methods involve solid-phase reactions, the composition of the powders obtained lacks uniformity. For this reason, the reaction does not proceed uniformly during curing, which is one of the causes of lowering the strength of the cured product.
また・、焼成温度が高いために、得られる粉剤の活性を
低いものとしてしまい、硬化時間の長時間化や不完全硬
化による硬化体強度の低下を招くものとなっていた。In addition, the high firing temperature lowers the activity of the resulting powder, leading to longer curing times and lower strength of the cured product due to incomplete curing.
また、このようにして得られたリン酸カルシウムよりな
る粉剤と混練される硬化液としては、混練物のｐＨを低
下させ、中性領域において硬化反応を進行させることが
生体組織への為害性をなくす面から望まれることであり
、従来はこのような点からクエン酸水溶液が最良のもの
とされてきた。In addition, for the hardening liquid to be kneaded with the powder made of calcium phosphate obtained in this way, it is necessary to lower the pH of the kneaded material and allow the hardening reaction to proceed in a neutral region in order to eliminate harm to living tissues. From this point of view, a citric acid aqueous solution has traditionally been considered the best solution.
しかし、この硬化液についても、なお改良の余地が残っ
ている。殊に、従来、広範に用いられていたアクリルセ
メント等と比べると、練和時に混練物の展延性がなく、
成形性が悪いという欠点があった。However, there is still room for improvement regarding this curing liquid. In particular, compared to acrylic cement, which has been widely used in the past, the kneaded material is not spreadable during kneading.
It had the disadvantage of poor moldability.
「発明の目的」
本発明の目的は、硬化反応を中性領域において均一かつ
充分に進行させ、練和時に優れた成形性を示し、硬化後
は、高い強度を有し、生体組織為害性のない硬化体を得
るリン酸カルシウム系硬化体の製造方法を提供すること
にある。"Objective of the Invention" The object of the present invention is to allow the curing reaction to proceed uniformly and sufficiently in the neutral region, to exhibit excellent formability during kneading, to have high strength after curing, and to be non-toxic to living tissues. It is an object of the present invention to provide a method for producing a calcium phosphate-based cured product, which produces a cured product that is free from the above.
「発明の構成」
本発明によるリン酸カルシウム系硬化体の製造方法は、
Ｃａ／Ｐ比が１．５を超え、１．８以下であるハイドロ
キシアパタイトを１１５０〜１４５０℃の温度で減圧条
件下で焼成して得られたα−リン酸三カルシウムとリン
酸四カルシウムの混合物よりなる粉剤と、クエン酸水溶
液に多糖類を溶解させてなる液剤とを混練することによ
って硬化させることを特徴とするものである。"Structure of the Invention" The method for producing a calcium phosphate cured product according to the present invention includes:
A mixture of α-tricalcium phosphate and tetracalcium phosphate obtained by calcining hydroxyapatite with a Ca/P ratio of more than 1.5 and less than 1.8 at a temperature of 1150 to 1450°C under reduced pressure conditions. This method is characterized in that it is hardened by kneading a powder made of the following and a liquid prepared by dissolving a polysaccharide in an aqueous citric acid solution.
このように本発明の製造方法においては、湿式法により
容易に合成できるＣａ／Ｐ比が１．５を超え、１．８以
下であるハイドロキシアパタイト原料組成物を１１５０
〜１４５０℃の温度で減圧下で焼成し、ハイドロキンア
パタイトを熱分解させてα−リン酸三カルシウムとリン
酸四カルシウムを生成させることにより得られたα−リ
ン酸三カルシウムとリン酸四カルシウムの混合物を粉剤
として用いるものであるから、得られる混合物における
組成は均一となり、また、従来のリン酸カルシウムの製
法と比較して焼成温度が１１５０〜１４５０℃と比較的
低いために、得られる粉剤の活性をより高いものとする
ことができる。As described above, in the production method of the present invention, a hydroxyapatite raw material composition having a Ca/P ratio of more than 1.5 and 1.8 or less, which can be easily synthesized by a wet method, is
α-Tricalcium phosphate and tetracalcium phosphate obtained by calcining under reduced pressure at a temperature of ~1450°C to thermally decompose hydroquinapatite to produce α-tricalcium phosphate and tetracalcium phosphate. Since a mixture of the following is used as a powder, the composition of the resulting mixture is uniform, and since the firing temperature is relatively low at 1150 to 1450°C compared to conventional calcium phosphate production methods, the activity of the resulting powder is improved. can be made higher.
従って、このようにして得られたα−リン酸三カルシウ
ムとリン酸四カルシウムの混合物を粉剤として用いれば
、硬化反応を均一かつ充分に進行させ、硬化強度の高い
硬化体が得られることが予想される。Therefore, it is expected that if the mixture of α-tricalcium phosphate and tetracalcium phosphate obtained in this way is used as a powder, the curing reaction will proceed uniformly and sufficiently, and a cured product with high curing strength will be obtained. be done.
ところが、この粉剤を硬化液としてのクエン酸水溶液と
混練したときに、混練物は展延性がなく、成形性が悪い
ので、混練物に成形性を付与するため鋭意研究を進めた
。その結果、クエン酸水溶液に多ｆＲ類を溶解させたも
のを液剤として用いると、練和時に混練物が展延性のあ
るガム状となり、硬化前に容易に任意の形状に成形が可
能となることを見出した。本発明はこのような知見に基
づいて完成されたものである。However, when this powder was kneaded with an aqueous citric acid solution as a hardening liquid, the kneaded product had no spreadability and had poor moldability, so intensive research was carried out in order to impart moldability to the kneaded product. As a result, when multi-fRs dissolved in citric acid aqueous solution is used as a liquid agent, the kneaded material becomes a spreadable gum-like product during kneading, and can be easily molded into any shape before hardening. I found out. The present invention was completed based on such knowledge.
以下、本発明をより詳細に説明する。The present invention will be explained in more detail below.
本発明のリン酸カルシウム系硬化体の製造方法において
用いられる粉剤は、Ｃａ／Ｐ比が１．５を超え、１．８
以下であるハイドロキシアパタイトを、１１５０〜１４
５０℃の温度で減圧条件下に焼成して得られる。The powder used in the method for producing a calcium phosphate-based cured product of the present invention has a Ca/P ratio of more than 1.5 and 1.8.
The following hydroxyapatite is 1150~14
It is obtained by firing at a temperature of 50° C. under reduced pressure conditions.
この粉剤の調製において原料として用いられるハイドロ
キシアパタイトは、リン酸水溶液と水酸化カルシウム懸
濁液とを公知方法によって反応させる湿式法により容易
に合成できるが、そのＣａ／Ｐ比は１．５を超え、１．
８以下である範囲にあることが必要であり、より好まし
くは１．６〜１．８の範囲にあるものとされる。すなわ
ち、Ｃａ／Ｐ比が１．５では、目的とする化合物の一つ
であるα−リン酸三カルシウムそのものとなってしまい
、Ｃａ／Ｐ比が１．８を超えるものであると、焼成時に
生体に対して悪影響を及ぼす酸化カルシウムが生成し、
好ましくないためである。Hydroxyapatite, which is used as a raw material in the preparation of this powder, can be easily synthesized by a wet method in which an aqueous phosphoric acid solution and a suspension of calcium hydroxide are reacted by a known method, but the Ca/P ratio exceeds 1.5. , 1.
It needs to be in a range of 8 or less, and more preferably in a range of 1.6 to 1.8. In other words, when the Ca/P ratio is 1.5, it becomes α-tricalcium phosphate itself, which is one of the target compounds, and when the Ca/P ratio exceeds 1.8, it becomes Calcium oxide, which has a negative effect on living organisms, is produced,
This is because it is not desirable.
原料とするハイドロキシアパタイトのＣａ／Ｐ比は、製
造工程において反応させる水酸化カルシウムとリン酸と
の比率を変えることによって変化させることができる。The Ca/P ratio of hydroxyapatite used as a raw material can be changed by changing the ratio of calcium hydroxide and phosphoric acid reacted in the manufacturing process.
そして、原料とするハイドロキシアパタイトのＣａ／Ｐ
比を変化させることにより、最終的に生成するα−リン
酸三カルシウムとリン酸四カルシウムの比率を所望のも
のに変化させることができる。And Ca/P of hydroxyapatite used as raw material
By changing the ratio, the ratio of α-tricalcium phosphate and tetracalcium phosphate finally produced can be changed to a desired value.
また、原料とするハイドロキシアパタイトは、例えば湿
式法により合成した後、５濾過、遠心分離、噴霧乾燥等
の手段により粉末化することが望ましく、更には、後の
工程で焼成して熱分解する前に５００〜７００℃程度の
温度で仮焼するなどして充分に乾燥させ、水分をできる
だけ除去することが望ましい。Hydroxyapatite used as a raw material is desirably synthesized by a wet method, for example, and then pulverized by means such as filtration, centrifugation, or spray drying. It is desirable to thoroughly dry the material by calcining it at a temperature of about 500 to 700°C to remove as much moisture as possible.
本発明の製造方法においては、上記のようなハイドロキ
シアパタイトを原料とし、１１５０〜１４５０℃の温度
で減圧条件下で焼成する。これは、１１５０℃未満の温
度では圧力を下げても、分解反応が起こらず、一方、１
４５０℃の温度を超えると、得られるα−リン酸三カル
シウムとリン酸四カルシウムの混合物の活性を低下させ
てしまうためであり、また、減圧条件下とするのは、こ
れにより焼成温度を低下させることが可能となるため、
生成物の活性を高くすることができ、更に工程の簡略化
及び製造コストの低下を図ることができるためである。In the manufacturing method of the present invention, hydroxyapatite as described above is used as a raw material and fired at a temperature of 1150 to 1450°C under reduced pressure conditions. This is because at temperatures below 1150°C, no decomposition reaction occurs even if the pressure is lowered;
This is because if the temperature exceeds 450°C, the activity of the resulting mixture of α-tricalcium phosphate and tetracalcium phosphate will be reduced, and the reason for reducing the pressure is that this lowers the calcination temperature. Because it is possible to
This is because the activity of the product can be increased, and furthermore, the process can be simplified and the manufacturing cost can be reduced.
なお、減圧条件は、１０Ｐａ以下であるのが好ましくは
、更には１０−”Ｐａ以下であるのが好ましい。Note that the reduced pressure condition is preferably 10 Pa or less, more preferably 10-''Pa or less.
このようにして調製されたα−リン酸三カルシウムとリ
ン酸四カルシウムの混合物は、必要に応じて機械的粉砕
等の手段により粉剤とされる。The mixture of α-tricalcium phosphate and tetracalcium phosphate thus prepared is made into a powder by mechanical crushing or the like, if necessary.
一方、本発明の製造方法において上記のようにして調製
された粉剤を硬化させるために用いられる液剤としては
、クエン酸水溶液に多ｍＨを溶解させたものが用いられ
る。この液剤において、クエン酸濃度は、好ましくは３
０重量％以上、より好ましくは４０〜５５重量％であり
、多糖類は好ましくは０．０５重量％以上の濃度でクエ
ン酸水溶液に溶解させる。すなわち、クエン酸濃度が３
０重量％未満であると、硬化体の強度を弱（してしまう
虞があり、また、多Ｉｌｌの濃度が０．０５重重量未満
であると、添加効果が認められない。On the other hand, in the production method of the present invention, the liquid agent used for curing the powder agent prepared as described above is a solution prepared by dissolving multi-mH in an aqueous citric acid solution. In this liquid preparation, the citric acid concentration is preferably 3
The polysaccharide is dissolved in the citric acid aqueous solution at a concentration of 0% by weight or more, more preferably 40 to 55% by weight, and the polysaccharide is preferably 0.05% by weight or more. That is, when the citric acid concentration is 3
If it is less than 0% by weight, there is a risk of weakening the strength of the cured product, and if the concentration of polyIll is less than 0.05% by weight, no effect of the addition will be observed.
また、多糖類としては、クエン酸に可溶性でかつ生体組
織為害性のないものであれば、任意のものであってよ（
、例えばキトサン、デンプン等が挙げられ、特にキトサ
ンが好ましい。In addition, any polysaccharide may be used as long as it is soluble in citric acid and is not harmful to living tissues.
Examples include chitosan, starch, etc., with chitosan being particularly preferred.
本発明の製造方法においては、上記のようにして調製さ
れた粉剤と液剤とを混練することにより、α−リン酸三
カルシウムとリン酸四カルシウムの加水分解反応を起こ
させてハイドロキシアパタイトを生成させ、硬化体を得
る。その際、粉剤と液剤の混練比は、液剤に対する粉剤
の配合量（Ｐ／Ｌ）が重量比で０．４〜２．５となるよ
うにすることが好ましい、すなわち、この比が０゜４未
満であると、固形分が少ないため、得られる硬化体の強
度が弱くなり、一方、２．５を超えると、粉剤と液剤の
均一な練和が困難となるためである。In the production method of the present invention, by kneading the powder and liquid prepared as described above, a hydrolysis reaction of α-tricalcium phosphate and tetracalcium phosphate is caused to produce hydroxyapatite. , to obtain a cured product. At that time, the kneading ratio of powder and liquid is preferably such that the amount of powder to liquid (P/L) is 0.4 to 2.5 by weight, that is, this ratio is 0.4 If it is less than 2.5, the strength of the cured product obtained will be weak due to the small solid content, while if it exceeds 2.5, it will be difficult to uniformly mix the powder and liquid.
「発明の実施例」
次に、実施例に基づいて本発明を詳述するが、本発明は
これに限定されるものではない。"Examples of the Invention" Next, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.
実施例１
リン酸水溶液と水酸化カルシウム懸濁液を公知方法で反
応させ、乾燥させてハイドロキシアパタイトを得た。得
られた生成物の確認は、Ｘ線回折によって行った。この
Ｘ線回折チャートを第１図に示す。また、得られたハイ
ドロキシアパタイトのＣａ／Ｐ比は、化学分析によって
１．６７と算定された。Example 1 A phosphoric acid aqueous solution and a calcium hydroxide suspension were reacted by a known method and dried to obtain hydroxyapatite. The obtained product was confirmed by X-ray diffraction. This X-ray diffraction chart is shown in FIG. Further, the Ca/P ratio of the obtained hydroxyapatite was calculated to be 1.67 by chemical analysis.
このハイドロキシアパタイトを温度１２００℃、圧力１
．３ Ｘ １ （Ｉ’Ｐａで１時間焼成した。得られた
生成物を上記と同様にＸ線回折により調べたところ、第
２図に示すようにα−リン酸三カルシウムのピークａと
リン酸四カルシウムのピークｂが発現し、ハイドロキシ
アパタイトの熱分解によりα−リン酸三カルシウムとリ
ン酸四カルシウムの混合物が生成したことが確認できた
。This hydroxyapatite was heated at a temperature of 1200℃ and a pressure of 1
．． The obtained product was examined by X-ray diffraction in the same manner as above, and as shown in Figure 2, peak a of α-tricalcium phosphate and peak a of phosphoric acid were found. A peak b of tetracalcium appeared, and it was confirmed that a mixture of α-tricalcium phosphate and tetracalcium phosphate was produced by thermal decomposition of hydroxyapatite.
このようにして得られたα−リン酸三カルシウムとリン
酸四カルシウムの混合物を粉剤とし、この粉剤２ｇと４
０％クエン酸水溶液１０ｇにキトサン（商品名フローナ
ックＮ、共和油脂工業■製）０．１ｇを溶解した液剤１
ｇを混練したところ、展延性のあるガム状練和物となり
、続いて約２分後に硬化し、高強度の硬化体となった。The mixture of α-tricalcium phosphate and tetracalcium phosphate thus obtained was made into a powder, and 2 g of this powder and 4 g of
Liquid agent 1 in which 0.1 g of chitosan (trade name Fronac N, manufactured by Kyowa Yushi Kogyo ■) was dissolved in 10 g of 0% citric acid aqueous solution.
When g was kneaded, it became a spreadable gum-like kneaded product, which subsequently hardened after about 2 minutes to become a high-strength hardened product.
比較例１
実施例１において、キトサンを添加しなかった液剤を用
いて粉剤と混練したところ、約２分後に硬化したが、硬
化前の練和物は展延性がなく、成形性が悪かった。Comparative Example 1 In Example 1, when a liquid agent to which chitosan was not added was kneaded with a powder agent, it hardened after about 2 minutes, but the kneaded product before hardening had no spreadability and poor moldability.
「発明の効果」
以上説明したように本発明によれば、α−リン酸三カル
シウムとリン酸四カルシウムの混合物からなる粉剤を硬
化液と混練したときに、混練物は優れた展延性を示し、
硬化前に任意の形状に容易に成形することができ、硬化
反応は均一かつ充分にしかも適度に温和に進行し、硬化
強度の高く、生体組織為害性のない硬化体を得ることが
できる。"Effects of the Invention" As explained above, according to the present invention, when a powder made of a mixture of α-tricalcium phosphate and tetracalcium phosphate is kneaded with a hardening liquid, the kneaded product exhibits excellent spreadability. ,
It can be easily molded into any shape before curing, the curing reaction proceeds uniformly, sufficiently, and moderately, and a cured product with high curing strength and no harm to living tissues can be obtained.
従って、本発明方法は歯科及び医科用セメントの製造の
ため有用であり、骨欠損部への補填材を製造するために
も好適に適用することができる。Therefore, the method of the present invention is useful for producing dental and medical cement, and can also be suitably applied to producing a filling material for bone defects.
第１図は実施例において合成したハイドロキシアパタイ
トのＸ＆ｉ１回折図、第２図は実施例において得られた
本発明に係る粉剤のＸ線回折図である。FIG. 1 is an X&i1 diffraction diagram of hydroxyapatite synthesized in Examples, and FIG. 2 is an X-ray diffraction diagram of powders according to the present invention obtained in Examples.
Claims (4)
イドロキシアパタイトを１１５０〜１４５０℃の温度で
減圧条件下で焼成して得られたα−リン酸三カルシウム
とリン酸四カルシウムの混合物よりなる粉剤と、クエン
酸水溶液に多糖類を溶解させてなる液剤とを混練するこ
とによって硬化させることを特徴とするリン酸カルシウ
ム系硬化体の製造方法。(1) α-Tricalcium phosphate and tetracalcium phosphate obtained by calcining hydroxyapatite with a Ca/P ratio of more than 1.5 and less than 1.8 at a temperature of 1150 to 1450°C under reduced pressure conditions. A method for producing a calcium phosphate-based cured product, which comprises curing by kneading a powder made of a mixture of calcium and a liquid prepared by dissolving a polysaccharide in an aqueous citric acid solution.
．５である特許請求の範囲第１項に記載の製造方法。(2) The weight ratio of powder to liquid is 0.4 to 2.
．． 5. The manufacturing method according to claim 1.
以上であり、多糖類の濃度が０．０５重量％以上である
特許請求の範囲第１項又は第２項に記載の製造方法。(3) The concentration of citric acid in the citric acid aqueous solution is 30% by weight
The manufacturing method according to claim 1 or 2, wherein the concentration of the polysaccharide is 0.05% by weight or more.
１項〜第３項に記載の製造方法。(4) The manufacturing method according to claims 1 to 3, wherein the polysaccharide is chitosan.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62257939A JP2563186B2 (en) | 1987-10-13 | 1987-10-13 | Method for producing calcium phosphate-based cured product |
| EP88110950A EP0298501B1 (en) | 1987-07-10 | 1988-07-08 | Composition for forming calcium phosphate type hardening material and process for producing such hardening material |
| DE3855611T DE3855611T2 (en) | 1987-07-10 | 1988-07-08 | Process for producing a calcium phosphate powder |
| DE8888110950T DE3869850D1 (en) | 1987-07-10 | 1988-07-08 | COMPOSITION FOR PRODUCING A HARDENABLE CALCIUM PHOSPHATE-LIKE MATERIAL AND METHOD FOR PRODUCING SUCH A MATERIAL. |
| EP91102716A EP0436499B1 (en) | 1987-07-10 | 1988-07-08 | A process for producing a calcium phosphate type powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62257939A JP2563186B2 (en) | 1987-10-13 | 1987-10-13 | Method for producing calcium phosphate-based cured product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01100048A true JPH01100048A (en) | 1989-04-18 |
| JP2563186B2 JP2563186B2 (en) | 1996-12-11 |
Family
ID=17313302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62257939A Expired - Fee Related JP2563186B2 (en) | 1987-07-10 | 1987-10-13 | Method for producing calcium phosphate-based cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2563186B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03128061A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| US5993535A (en) * | 1997-08-28 | 1999-11-30 | Ngk Spark Plug Co., Ltd. | Calcium phosphate cement and calcium phosphate cement composition |
| US6051061A (en) * | 1998-03-23 | 2000-04-18 | Ngk Spark Plug Co., Ltd. | Calcium phosphate cements and calcium phosphate cement compositions |
| KR20030006787A (en) * | 2001-07-16 | 2003-01-23 | 이승진 | Chitosan bead containing tricalcium phosphate for bone substitute |
| JP2005530525A (en) * | 2002-04-03 | 2005-10-13 | マシーズ メディツィナルテヒニク アクチエンゲゼルシャフト | Kneaded and moldable bone substitute |
| CN106552293A (en) * | 2016-11-24 | 2017-04-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
-
1987
- 1987-10-13 JP JP62257939A patent/JP2563186B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03128061A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| JPH0528627B2 (en) * | 1989-10-16 | 1993-04-26 | Kagaku Gijutsucho Mukizaishitsu Kenkyushocho | |
| US5993535A (en) * | 1997-08-28 | 1999-11-30 | Ngk Spark Plug Co., Ltd. | Calcium phosphate cement and calcium phosphate cement composition |
| US6051061A (en) * | 1998-03-23 | 2000-04-18 | Ngk Spark Plug Co., Ltd. | Calcium phosphate cements and calcium phosphate cement compositions |
| KR20030006787A (en) * | 2001-07-16 | 2003-01-23 | 이승진 | Chitosan bead containing tricalcium phosphate for bone substitute |
| JP2005530525A (en) * | 2002-04-03 | 2005-10-13 | マシーズ メディツィナルテヒニク アクチエンゲゼルシャフト | Kneaded and moldable bone substitute |
| JP4944363B2 (en) * | 2002-04-03 | 2012-05-30 | ジンテーズ ゲゼルシャフト ミト ベシュレンクテル ハフツング | Kneaded and moldable bone substitute |
| CN106552293A (en) * | 2016-11-24 | 2017-04-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
| CN106552293B (en) * | 2016-11-24 | 2019-11-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2563186B2 (en) | 1996-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5496399A (en) | Storage stable calcium phosphate cements | |
| US5281404A (en) | Composition for forming calcium phosphate type setting material and process for producing setting material | |
| DE60300666T2 (en) | Process for the preparation of porous calcium phosphate chips and granules from gelatine processing | |
| US5137534A (en) | Method for producing dental and medical bone prosthesis and bone prosthesis produced thereby | |
| JPH04135562A (en) | Hydraulic calcium phosphate cement | |
| GB2246770A (en) | Tetracalcium phosphate-based materials and processes for their preparation | |
| EP0298501B1 (en) | Composition for forming calcium phosphate type hardening material and process for producing such hardening material | |
| JP2563187B2 (en) | Method for producing calcium phosphate-based cured product | |
| EP0323632A1 (en) | Composition for forming calcium phosphate type setting material and process for producing setting material | |
| JPH01100048A (en) | Production of calcium phosphate-based set material | |
| KR100787526B1 (en) | Synthesis of spherical shaped hydroxyapatite, alpha-tricalcium phosphate and beta-tricalcium phosphate nano powders depending on the ph by microwave assisted process | |
| Hesaraki et al. | Investigation of an effervescent additive as porogenic agent for bone cement macroporosity | |
| JP3987220B2 (en) | Fast-setting calcium phosphate cement | |
| JPH0277261A (en) | Composite composition for producing cured body of calcium phosphate system and production of cured body | |
| JPH02275812A (en) | Liquid agent for hardened calcium phosphate and hardened material produced by using the agent | |
| JPH02102165A (en) | Production of calcium phosphate-based ceramic | |
| JPH0549618B2 (en) | ||
| JPH01301543A (en) | Curable composition | |
| JP2662984B2 (en) | Composite composition for producing calcium phosphate-based cured product and method for producing cured product | |
| JPH0244054A (en) | Self-curing composite bio-material having high strength and its preparation | |
| JPH04307067A (en) | Composite composition for manufacture of calcium phosphate based hardening body and manufacture of hardening body | |
| JP2000169199A (en) | Quick-hardening calcium phosphate cement | |
| JPH0536064B2 (en) | ||
| JPH06100410A (en) | Calcium phosphate-based filler | |
| JP3101999B2 (en) | Artificial bones and artificial teeth and their manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |