JPH03210271A - Production of biomaterial of calcium phosphate system - Google Patents
Production of biomaterial of calcium phosphate systemInfo
- Publication number
- JPH03210271A JPH03210271A JP2005859A JP585990A JPH03210271A JP H03210271 A JPH03210271 A JP H03210271A JP 2005859 A JP2005859 A JP 2005859A JP 585990 A JP585990 A JP 585990A JP H03210271 A JPH03210271 A JP H03210271A
- Authority
- JP
- Japan
- Prior art keywords
- calcium
- slurry
- phosphoric acid
- phase
- 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 38
- 239000012620 biological material Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000001506 calcium phosphate Substances 0.000 title claims description 22
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims description 14
- 235000011010 calcium phosphates Nutrition 0.000 title claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 5
- 229940043430 calcium compound Drugs 0.000 claims description 10
- 150000001674 calcium compounds Chemical class 0.000 claims description 10
- -1 phosphoric acid compound Chemical class 0.000 claims description 10
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 8
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 8
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 5
- 239000011575 calcium Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 23
- 238000000465 moulding Methods 0.000 abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 8
- 229910052586 apatite Inorganic materials 0.000 abstract description 7
- 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 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract 3
- 229910000394 calcium triphosphate Inorganic materials 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 2
- RFWLACFDYFIVMC-UHFFFAOYSA-D pentacalcium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O RFWLACFDYFIVMC-UHFFFAOYSA-D 0.000 abstract 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 18
- 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 description 18
- 239000000843 powder Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229960005069 calcium Drugs 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000316 bone substitute Substances 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 210000003094 ear ossicle Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「利用分野」
本発明は、リン酸カルシウム系生体材料の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of Application The present invention relates to a method for producing calcium phosphate biomaterials.
「従来技術及びその問題点」
ハイドロキシアパタイトは、その優れた生体親和性、骨
誘導性により人工骨、人工歯根、骨補填材などの医科用
あるいは歯科用生体材料への応用が広範に検討されてお
り、数多くのものが既に商品化されている。その製品形
態は、ブロック状及び顆粒状人工骨、人工歯根、人工耳
小骨など多岐にわたっている。"Prior art and its problems" Due to its excellent biocompatibility and osteoinductivity, hydroxyapatite has been extensively studied for application to medical and dental biomaterials such as artificial bones, artificial tooth roots, and bone replacement materials. Many of them have already been commercialized. The products come in a wide variety of forms, including block-shaped and granular artificial bones, artificial tooth roots, and artificial ear ossicles.
また、最近には、Ｃａ／Ｐ比＝１．６７の化学量論組成
のハイドロキシアパタイトよりＣａＯが分相したハイド
ロキシアパタイト、すなわちＣａ／Ｐ比＞ １．６７の
リン酸カルシウムは新生骨形成性に優れており（特願平
１−２８４２０９号明細書）、また、リン酸三カルシウ
ムが分相したハイドロキシアパタイト、すなわちＣａ／
Ｐ比＜ １．６７のリン酸カルシウムは骨置換性に優れ
ていることが報告され（第８２回日本補綴歯科学会学術
大会論文集、９４頁）、さらに、１．５＜Ｃａ／Ｐ＜１
．６７のものはリン酸三カルシウム（Ｃａ／ Ｐ ＝
１．５ ）より吸収を遅くすることができ、骨置換速度
を制御できることが分かっている。In addition, recently, hydroxyapatite with a CaO phase separation, that is, calcium phosphate with a Ca/P ratio of >1.67, has superior new bone formation properties than hydroxyapatite with a stoichiometric composition of Ca/P ratio of 1.67. (Japanese Patent Application No. 1-284209), and also hydroxyapatite with phase separation of tricalcium phosphate, that is, Ca/
It has been reported that calcium phosphate with a P ratio < 1.67 has excellent bone replacement properties (Proceedings of the 82nd Japanese Society of Prosthodontics, p. 94), and furthermore, calcium phosphate with a P ratio of 1.5 < Ca/P < 1
．． 67 is tricalcium phosphate (Ca/P =
1.5) It has been shown that resorption can be made slower and the rate of bone replacement can be controlled.
特定のＣａＺＰ比のリン酸カルシウムを調製する方法と
しては、特定のＣａ／Ｐ比となるように原料のリン酸化
合物とカルシウム化合物とを混合し、湿式合成し、焼成
させる方法が知られている。As a method for preparing calcium phosphate with a specific CaZP ratio, a method is known in which a phosphoric acid compound and a calcium compound as raw materials are mixed so as to have a specific Ca/P ratio, wet synthesis is performed, and then calcined.
しかし、特定のＣａ／Ｐ比のリン酸カルシウムを製造す
るため、その都度リン酸カルシウム系化合物の合成の段
階からＣａ／Ｐ比を特別に調整することは、極めて困難
である０例えば、合成装置のパラメーターをその都度変
更しなければならず、さらにその後の合成品の汚染を避
けるために、装置を洗浄する煩雑さなどを考慮すると、
合成の段階でＣａ／Ｐ比を特別に調整することには、非
常に問題がある。However, in order to produce calcium phosphate with a specific Ca/P ratio, it is extremely difficult to specifically adjust the Ca/P ratio from the stage of synthesizing the calcium phosphate compound each time. Considering that it has to be changed each time, and that it is complicated to clean the equipment to avoid contamination of the synthesized product afterwards,
Special adjustment of the Ca/P ratio during the synthesis stage is very problematic.
さらに、市販の化学量論組成のハイドロキシアパタイト
粉末と酸化カルシウム又はリン酸三カルシウム粉末を混
合して特定のＣａ／Ｐ比のリン酸カルシウムを調製する
方法があるが、この方法では生成物の均一性に問題があ
る。Furthermore, there is a method of preparing calcium phosphate with a specific Ca/P ratio by mixing commercially available stoichiometric hydroxyapatite powder with calcium oxide or tricalcium phosphate powder, but this method does not affect the uniformity of the product. There's a problem.
「発明の目的」
本発明は、市販のハイドロキシアパタイト粉末など、容
易に入手しうる原料を用いて、均一性に優れたＣａ／Ｐ
比＞ １．６７又はＣａ／Ｐ比＜ １．６７のリン酸カ
ルシウム焼結体から成る生体材料を極めて簡単に製造し
うる方法を提供することを目的とする。``Object of the Invention'' The present invention aims to produce a Ca/P powder with excellent uniformity using easily available raw materials such as commercially available hydroxyapatite powder.
It is an object of the present invention to provide a method for extremely easily producing a biomaterial made of a calcium phosphate sintered body having a Ca/P ratio>1.67 or a Ca/P ratio<1.67.
「発明の構成」
本発明によるリン酸カルシウム系生体材料の製造方法は
、ハイドロキシアパタイト粉末のスラリーにカルシウム
化合物又はリン酸化合物を含有させ、湿式成形した後、
焼成することにより固相反応により酸化カルシウム又は
リン酸三カルシウムを分相させることを特徴とする。"Structure of the Invention" The method for producing a calcium phosphate biomaterial according to the present invention includes adding a calcium compound or a phosphate compound to a slurry of hydroxyapatite powder, wet-molding the slurry, and then wet-molding the slurry.
The method is characterized in that calcium oxide or tricalcium phosphate is phase-separated by solid-phase reaction by firing.
本発明において、原料のハイドロキシアパタイト粉末は
、容易に入手しうるちのであればどのようなものでもよ
く、市販品を用いることができる。In the present invention, the raw material hydroxyapatite powder may be of any type as long as it is easily available, and commercially available products can be used.
この場合、化学量論組成（Ｃａ／Ｐ比＝ １．６７ ）
のものが好ましいが、化学量論組成からはずれたもので
も、化学分析、Ｘ線回折などにより非化学量論性（どれ
くらい化学量論組成からはずれているか）を分析してあ
れば用いることができる。In this case, the stoichiometric composition (Ca/P ratio = 1.67)
Although it is preferable that the composition deviates from the stoichiometric composition, it can be used as long as the non-stoichiometric nature (how much it deviates from the stoichiometric composition) has been analyzed by chemical analysis, X-ray diffraction, etc. .
このような原料から生体材料を製造する方法としては、
通常、以下の３方法がある。すなわち、■粉末のまま乾
式成形（プレス）により圧粉体を作製しく多孔質焼結体
を製造する場合には、ここで焼失性物質を混合する）、
焼成し、緻密質又は多孔質焼結体を得る方法、■粉末を
水に分散させ、バインダー、必要に応じて発泡剤、界面
活性剤などを加え、湿式成形用原料スラリーとし、各種
湿式成形に付した後、焼成することにより緻密質又は多
孔質焼結体を得る方法、■前述の■の原料スラリーをウ
レタンフオームなどの焼失性三次元網状構造体にコーテ
ィングし、加熱によりこれを消失させ、さらに焼成する
ことにより多孔質焼結体を得る方法がある。本発明の方
法は、上記の■及び■の方法に好適に適用できる。Methods for producing biomaterials from such raw materials include:
Generally, there are three methods: In other words, ■ When producing a porous sintered body by dry molding (pressing) the powder, a burnable substance is mixed here),
How to obtain a dense or porous sintered body by firing: ■ Disperse the powder in water, add a binder, a blowing agent, a surfactant, etc. as necessary, and make a raw material slurry for wet molding, which can be used for various wet moldings. A method of obtaining a dense or porous sintered body by attaching the slurry to a burnable three-dimensional network structure such as urethane foam, and burning it off by heating. There is a method of obtaining a porous sintered body by further firing. The method of the present invention can be suitably applied to methods (1) and (2) above.
本発明の方法においては、まず、上記のようなハイドロ
キシアパタイト粉末を用いて湿式成形用原料スラリーを
作製するが、ここで添加しうるカルシウム化合物として
は、炭酸カルシウム、水酸化カルシウム、塩化カルシウ
ム、硝酸カルシウム、酢酸カルシウム、乳酸カルシウム
などがあるが、均一な混合という観点から水溶性ものも
のが好ましい。また、ハイドロキシアパタイトスラリー
を調製してからカルシウム化合物を添加してもよいが、
カルシウム化合物を含む水溶液にアパタイト粉末を添加
してスラリーを調製することが好ましい、さらに、ここ
で、例えば塩化カルシウムを用いると、焼成工程でも塩
素は揮発せず、結晶構造中に取り込まれ、ハイドロキシ
アパタイトが一部塩素アパタイトになるおそれがあるの
で、これが問題となる場合には、酢酸カルシウム、乳酸
カルシウムなどを用いるか、本発明者が特願昭６３−２
４７２３６号明細書で提案したカルシウムゾルを用いる
のが好ましい。In the method of the present invention, first, a raw material slurry for wet molding is prepared using the hydroxyapatite powder as described above. Calcium compounds that can be added here include calcium carbonate, calcium hydroxide, calcium chloride, nitric acid. Calcium, calcium acetate, calcium lactate, etc. are available, but water-soluble ones are preferred from the viewpoint of uniform mixing. Alternatively, the calcium compound may be added after preparing the hydroxyapatite slurry.
It is preferable to prepare a slurry by adding apatite powder to an aqueous solution containing a calcium compound.Furthermore, if calcium chloride is used here, chlorine will not volatilize during the firing process and will be incorporated into the crystal structure, forming hydroxyapatite. However, if this becomes a problem, calcium acetate, calcium lactate, etc. may be used, or the present inventor proposed the patent application No.
Preferably, the calcium sol proposed in No. 47236 is used.
また、リン酸化合物としては、正リン酸（以下、リン酸
と略記する）、リン酸ナトリウム、リン酸水素カリウム
、リン酸アンモニウム、リン酸マグネシウム、トリエチ
ルホスフェート等のリン酸エステル類などが挙げられる
が、カルシウムと同様な理由から水溶性のものが好まし
く、また、リン酸化合物を含む水溶液にアパタイト粉末
を添加してスラリーとするのが好ましい。さらに、リン
酸ナトリウムやリン酸カリウムを用いた場合、ナトリウ
ムやカリウムが揮発せず、ハイドロキシアパタイト中に
不純物として残ってしまうおそれがあるので、これが問
題となる場合には、リン酸、リン酸アンモニウム、リン
酸エステル類を用いるべきである。また、リン酸、一部
のリン酸エステルの中には酸性が強く、一部ハイドロキ
シアパタイトを溶解してしまうおそれもあるので、これ
らが問題となる場合には、このような化合物の使用を避
けるべきである。Examples of phosphoric acid compounds include phosphoric acid esters such as orthophosphoric acid (hereinafter abbreviated as phosphoric acid), sodium phosphate, potassium hydrogen phosphate, ammonium phosphate, magnesium phosphate, and triethyl phosphate. However, water-soluble ones are preferable for the same reasons as calcium, and it is preferable to add apatite powder to an aqueous solution containing a phosphoric acid compound to form a slurry. Furthermore, when using sodium phosphate or potassium phosphate, sodium or potassium may not volatilize and may remain as an impurity in hydroxyapatite, so if this becomes a problem, use phosphoric acid or ammonium phosphate. , phosphoric acid esters should be used. Additionally, phosphoric acid and some phosphoric acid esters are highly acidic and may dissolve some hydroxyapatite, so if these are a problem, avoid using such compounds. Should.
本発明の方法において、添加する水溶性カルシウム化合
物又はリン酸化合物の量は、所望のＣａ／Ｐ比に比べて
不足のカルシウム量又はリン酸量の当量又はそれより少
し多い量とする。In the method of the present invention, the amount of the water-soluble calcium compound or phosphoric acid compound to be added is equivalent to or slightly larger than the insufficient amount of calcium or phosphoric acid compared to the desired Ca/P ratio.
本発明の方法を実施するには、上記のようにアパタイト
と水溶性カルシウム化合物又はリン酸化合物を含む湿式
成形用スラリーを調製し、湿式成形し、焼成すればよい
。焼成は９００〜１３００°Ｃの温度で常圧で行うこと
ができる。この焼成の過程で、スラリーに含まれる水溶
性カルシウム化合物又はリン酸化合物とアパタイトとの
間で固相反応が起こり、酸化カルシウム又はリン酸三カ
ルシウムが分相する。分相する酸化カルシウム又はリン
酸三カルシウムの量は、主として水溶性カルシウム化合
物又はリン酸化合物の添加量に依存するが、焼成温度、
焼成時間などの焼成条件によっても多少変動するので、
焼成条件を適切に決定することが好ましい。In order to carry out the method of the present invention, a slurry for wet molding containing apatite and a water-soluble calcium compound or a phosphoric acid compound may be prepared as described above, wet molded, and fired. Firing can be performed at a temperature of 900 to 1300°C and normal pressure. During this firing process, a solid phase reaction occurs between the water-soluble calcium compound or phosphate compound contained in the slurry and apatite, and calcium oxide or tricalcium phosphate undergoes phase separation. The amount of calcium oxide or tricalcium phosphate that undergoes phase separation mainly depends on the amount of water-soluble calcium compound or phosphoric acid compound added, but depends on the firing temperature,
It will vary slightly depending on firing conditions such as firing time, so
It is preferable to appropriately determine firing conditions.
また、本発明の方法により多孔質生体材料を製造するこ
ともでき、この場合には、湿式成形用スラリーに過酸化
水素、焼失性物質等を混入することができる。Furthermore, porous biomaterials can also be produced by the method of the present invention, in which case hydrogen peroxide, burnout substances, etc. can be mixed into the slurry for wet molding.
「発明の実施例」
次に、実施例に基づいて本発明をさらに詳しく説明する
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 more detail based on Examples, but the present invention is not limited thereto.
実施例１
旭光学工業■製ハイドロキシアパタイト粉末（商品名Ｈ
Ｐ−２０）Ｉｇ（この粉末を１１００°Ｃで熱処理した
もののＸ線回折図を第１図に示す。Example 1 Hydroxyapatite powder manufactured by Asahi Optical Industry ■ (trade name H
P-20) Ig (Figure 1 shows the X-ray diffraction pattern of this powder heat-treated at 1100°C.
これはハイドロキシアパタイトの単一相からなることを
示している。）をリン酸水素二アンモニウム０．２ｇと
水１０ｇから成る水溶液にマグネチックスターラーで撹
拌下に分散させた。得られたスラリー全量をアルミナ製
ルツボに入れ、灰化炉で蒸発乾固させた後、１１００℃
で熱処理した。得られた固体を乳鉢で粉砕した後、Ｘ線
回折分析を行い、第２図に示すＸ線回折図を得た。この
回折図は、得られた粉末がハイドロキシアパタイトとリ
ン酸三カルシウム（約７０重量％）との混合物であるこ
とを示す。This indicates that it consists of a single phase of hydroxyapatite. ) was dispersed in an aqueous solution consisting of 0.2 g of diammonium hydrogen phosphate and 10 g of water under stirring using a magnetic stirrer. The entire amount of the obtained slurry was put into an alumina crucible, evaporated to dryness in an ashing furnace, and heated to 1100°C.
heat treated with After pulverizing the obtained solid in a mortar, it was subjected to X-ray diffraction analysis, and the X-ray diffraction diagram shown in FIG. 2 was obtained. The diffractogram shows that the powder obtained is a mixture of hydroxyapatite and tricalcium phosphate (approximately 70% by weight).
なお、第１図においてＨはハイドロキシアパタイトの主
ピークを示し、第２図においてＨはハイドロキシアパタ
イト、αＴはα−リン酸三カルシウム、βＴはβ−リン
酸三カルシウムの主ピークを示す。In FIG. 1, H indicates the main peak of hydroxyapatite, in FIG. 2, H indicates hydroxyapatite, αT indicates α-tricalcium phosphate, and βT indicates the main peak of β-tricalcium phosphate.
実施例２
純粋なハイドロキシアパタイトから成る人工歯根を作製
するために製造したハイドロキシアパタイト粉末１ｇ（
この粉末を１１００°Ｃで熱処理したもののＸ線回折図
を第３図に示す、第３図は、粉末がハイドロキシアパタ
イトの単一相から成ることを示している。）を酢酸カル
シウム０．２ｇと水１０ｇから成る水溶液にマグネチッ
クスクーラーで攪拌下に分散させた。得られたスラリー
全量をアルミナ製ルツボに入れ、灰化炉で蒸発乾固させ
た後、１１００℃で熱処理した。得られた固体を乳鉢で
粉砕した後、Ｘ線回折分析を行い、第４図に示すＸ線回
折図を得た。この回折図は、得られた粉末がハイドロキ
シアパタイトと酸化カルシウム（約１０重量％）との混
合物であることを示す。Example 2 1 g of hydroxyapatite powder manufactured to create an artificial tooth root made of pure hydroxyapatite (
The X-ray diffraction pattern of this powder heat-treated at 1100° C. is shown in FIG. 3. FIG. 3 shows that the powder consists of a single phase of hydroxyapatite. ) was dispersed in an aqueous solution consisting of 0.2 g of calcium acetate and 10 g of water with stirring using a magnetic cooler. The entire amount of the obtained slurry was put into an alumina crucible, evaporated to dryness in an ashing furnace, and then heat-treated at 1100°C. After pulverizing the obtained solid in a mortar, X-ray diffraction analysis was performed to obtain the X-ray diffraction diagram shown in FIG. The diffractogram shows that the powder obtained is a mixture of hydroxyapatite and calcium oxide (approximately 10% by weight).
なお、第３図においてＨはハイドロキシアパタイトの主
ピークを示し、第４図においてＨはハイドロキシアパタ
イト、Ｃは酸化カルシウムの主ピークを示す。In addition, in FIG. 3, H shows the main peak of hydroxyapatite, and in FIG. 4, H shows the main peak of hydroxyapatite, and C shows the main peak of calcium oxide.
「発明の効果」
本発明の方法によれば、市販のアパタイトを使用して骨
新生性あるいは骨置換性に優れた所望のＣａ／Ｐ比のリ
ン酸カルシウム系生体材料を極めて簡単に製造すること
ができる。本発明の方法によれば、粉末同士を混合する
方法とは異なり、湿式法で混合及び成形を行うので、均
一な生成物が得られる。また、反応条件の設定に関して
は焼成条件を選択するだけですむので、均一な生成物を
容易に得ることができる。"Effects of the Invention" According to the method of the present invention, a calcium phosphate biomaterial with a desired Ca/P ratio and excellent osteogenic or bone replacement properties can be produced extremely easily using commercially available apatite. . According to the method of the present invention, unlike a method in which powders are mixed together, mixing and molding are performed by a wet method, so that a uniform product can be obtained. Moreover, since it is sufficient to select the firing conditions in setting the reaction conditions, a uniform product can be easily obtained.
第１図は実施例１に使用した原料ハイドロキシアパタイ
ト粉末のＸ線回折図、第２図は実施例１により得られた
粉末のＸ線回折図、第３図は実施例２に使用した原料ハ
イドロキシアパタイト粉末のＸ線回折図、第４図は実施
例２により得られた粉末のＸ線回折図である。
符号の説明 う
Ｈ・・・・ハイドロキシアパタイトの主ピークαＴ・・
・α−リン酸三カルシウムの主ピークβＴ・・・β−リ
ン酸三カルシウムの主ピークＣ・・・・酸化カルシウム
の主ピークFigure 1 is an X-ray diffraction diagram of the raw material hydroxyapatite powder used in Example 1, Figure 2 is an X-ray diffraction diagram of the powder obtained in Example 1, and Figure 3 is an X-ray diffraction diagram of the raw material hydroxyapatite powder used in Example 2. X-ray diffraction diagram of apatite powder. FIG. 4 is an X-ray diffraction diagram of the powder obtained in Example 2. Explanation of symbols UH...Main peak αT of hydroxyapatite...
・Main peak of α-tricalcium phosphate βT Main peak of β-tricalcium phosphate C Main peak of calcium oxide
Claims (1)
ム化合物又はリン酸化合物を含有させ、湿式成形した後
、焼成することにより固相反応により酸化カルシウム又
はリン酸三カルシウムを分相させることを特徴とするリ
ン酸カルシウム系生体材料の製造方法。 ２、ハイドロキシアパタイト粉末が市販品である請求項
１記載のリン酸カルシウム系生体材料の製造方法。[Claims] 1. A slurry of hydroxyapatite powder containing a calcium compound or a phosphoric acid compound, wet-molded, and then fired to cause phase separation of calcium oxide or tricalcium phosphate through a solid phase reaction. A method for producing a characteristic calcium phosphate biomaterial. 2. The method for producing a calcium phosphate biomaterial according to claim 1, wherein the hydroxyapatite powder is a commercially available product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005859A JPH03210271A (en) | 1990-01-12 | 1990-01-12 | Production of biomaterial of calcium phosphate system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005859A JPH03210271A (en) | 1990-01-12 | 1990-01-12 | Production of biomaterial of calcium phosphate system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03210271A true JPH03210271A (en) | 1991-09-13 |
| JPH0536064B2 JPH0536064B2 (en) | 1993-05-28 |
Family
ID=11622700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005859A Granted JPH03210271A (en) | 1990-01-12 | 1990-01-12 | Production of biomaterial of calcium phosphate system |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03210271A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408111C (en) * | 2006-06-21 | 2008-08-06 | 四川大学 | Method for preparing porous structure ceramic artificial bone |
| JP2015516982A (en) * | 2012-04-27 | 2015-06-18 | スティッチング フェーウー—フェーウーエムセー | Protection of materials by sphingosine compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654841A (en) * | 1979-10-08 | 1981-05-15 | Mitsubishi Mining & Cement Co | Bone broken portion and filler for void portion and method of treating bone of animal using said filler |
| JPS59232960A (en) * | 1983-06-13 | 1984-12-27 | 科学技術庁無機材質研究所長 | Manufacture of apatite hydroxide sintered body |
| JPS61168364A (en) * | 1985-01-18 | 1986-07-30 | 太平化学産業株式会社 | Production of living body hard tissue prosthetic material |
-
1990
- 1990-01-12 JP JP2005859A patent/JPH03210271A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654841A (en) * | 1979-10-08 | 1981-05-15 | Mitsubishi Mining & Cement Co | Bone broken portion and filler for void portion and method of treating bone of animal using said filler |
| JPS59232960A (en) * | 1983-06-13 | 1984-12-27 | 科学技術庁無機材質研究所長 | Manufacture of apatite hydroxide sintered body |
| JPS61168364A (en) * | 1985-01-18 | 1986-07-30 | 太平化学産業株式会社 | Production of living body hard tissue prosthetic material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408111C (en) * | 2006-06-21 | 2008-08-06 | 四川大学 | Method for preparing porous structure ceramic artificial bone |
| JP2015516982A (en) * | 2012-04-27 | 2015-06-18 | スティッチング フェーウー—フェーウーエムセー | Protection of materials by sphingosine compounds |
| US11273113B2 (en) | 2012-04-27 | 2022-03-15 | Stichting Vu | Protection of materials by sphingosine based compounds |
| US11944701B2 (en) | 2012-04-27 | 2024-04-02 | Stichting Vu | Protection of materials by sphingosine based compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536064B2 (en) | 1993-05-28 |
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