JPH03242364A - Production of calcium phosphate-based biomaterial - Google Patents
Production of calcium phosphate-based biomaterialInfo
- Publication number
- JPH03242364A JPH03242364A JP2035676A JP3567690A JPH03242364A JP H03242364 A JPH03242364 A JP H03242364A JP 2035676 A JP2035676 A JP 2035676A JP 3567690 A JP3567690 A JP 3567690A JP H03242364 A JPH03242364 A JP H03242364A
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- compound
- calcium
- apatite
- 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.)
- Pending
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 24
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 18
- 239000012620 biological material Substances 0.000 title claims abstract description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims description 7
- 235000011010 calcium phosphates Nutrition 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000292 calcium oxide Substances 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical group [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 abstract description 12
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 11
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims abstract description 11
- 235000019731 tricalcium phosphate Nutrition 0.000 claims abstract description 11
- 229940078499 tricalcium phosphate Drugs 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 9
- 229940043430 calcium compound Drugs 0.000 claims description 5
- 150000001674 calcium compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 235000011148 calcium chloride Nutrition 0.000 abstract description 3
- 239000001488 sodium phosphate Substances 0.000 abstract description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 17
- 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 17
- 239000011575 calcium Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 229960005069 calcium Drugs 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 238000000465 moulding Methods 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 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
- 229960002401 calcium lactate Drugs 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011008 sodium phosphates Nutrition 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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
- 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
- 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 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
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Dental Prosthetics (AREA)
- Compositions Of Oxide Ceramics (AREA)
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の医科用あるいは歯科用
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-based medical or dental 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及び
骨伝導性により人工歯根、人工骨など、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
ック状及び顆粒状の人工骨、人工歯根、人工耳小骨など
多岐にわたる。"Prior art and its problems" Due to its excellent biocompatibility and osteoconductivity, hydroxyapatite has been extensively studied for application to medical and dental biomaterials such as artificial tooth roots and artificial bones, and has been used in numerous applications. Something has 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.
ところで、以前は、化学量論組成のハイドロキシアパタ
イト〔化学式Ｃａ＋ｏ（Ｐ ０４）６（ＯＨ）！、Ｃａ
ＺＰ比＝ １．６７ ）を得ることは非常に難しいとさ
れており、これを克服するために数多くの研究がなされ
てきた。例えば、特開昭５３−８１４９９号公報には、
化学量論組成に比べて不足したカルシウムを加え、反応
させて化学量論組成のハイドロキシアパタイトを得るこ
とが開示されており、また、特開昭５９−２１５０９号
公報にはカルシウム塩とリン酸塩を摩砕しつつ反応させ
ることによりＣａ／Ｐ比＝１．６７に極めて近いハイド
ロキシアパタイトを得ることが開示されている。このよ
うな状況に伴い、化学量論組成のハイドロキシアパタイ
トの粉末を入手することは容易になってきた。By the way, previously, hydroxyapatite with stoichiometric composition [chemical formula Ca+o(P 04)6(OH)! , Ca
It is said that it is very difficult to obtain a ZP ratio of 1.67, and many studies have been conducted to overcome this problem. For example, in Japanese Patent Application Laid-Open No. 53-81499,
It is disclosed that hydroxyapatite with a stoichiometric composition is obtained by adding calcium that is insufficient compared to the stoichiometric composition and reacting. It is disclosed that hydroxyapatite having a Ca/P ratio very close to 1.67 can be obtained by reacting while grinding. Under these circumstances, it has become easier to obtain hydroxyapatite powder with a stoichiometric composition.
一方、従来、化学量論組成の純粋なハイドロキシアパタ
イトが生体材料には好ましいとされていたが、近年、用
途に応して特定の機能を付与するため、純粋なハイドロ
キシアパタイト以外の研究も行われるようになった。例
えば、本発明者は、特願平１２８４２０９号明細書にお
いて、カルシウム過剰アパタイトを９００°Ｃ以上の温
度で焼成して酸化カルシウムを分相させたものは、純粋
なハイドロキシアパタイトより骨伝導能に優れているこ
とを開示した。また、生体内非吸収性であるハイドロキ
シアパタイトに吸収性を付与するために、生体内で吸収
されるβ−リン酸三カルシウムを複合化させる研究もな
されている（例えば、第８２回日本補綴歯科学会学術大
会論文集、９４頁など）。On the other hand, pure hydroxyapatite with a stoichiometric composition has traditionally been considered preferable for biomaterials, but in recent years, research on materials other than pure hydroxyapatite has been conducted in order to impart specific functions depending on the application. It became so. For example, in Japanese Patent Application No. 1284209, the present inventor discovered that calcium-rich apatite fired at a temperature of 900°C or higher to phase separate calcium oxide has superior bone conductivity than pure hydroxyapatite. disclosed that In addition, in order to impart absorbability to hydroxyapatite, which is non-absorbable in the living body, research is being conducted to combine β-tricalcium phosphate, which is absorbed in the living body (for example, the 82nd Japan Prosthodontics Proceedings of academic conferences, 94 pages, etc.).
しかしながら、これらの原料粉末はいずれも合成段階か
らその都度特別に調製したものである。However, all of these raw material powders are specially prepared each time from the synthesis stage.
また、工業的規模で化学量論組成のハイドロキシアパタ
イトの生産が行われているメーカーでも、化学量論組成
のものを製造するために設定されている合成装置のパラ
メーターを変更しなければならず、さらに、その後の合
成品への夾雑を防止するために装置を洗浄する煩雑さを
考慮すると、合成工程から特定のＣａ／Ｐ比のアパタイ
トを得ようとすることは、非常に問題である。一方、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β−リン酸三カルシウム粉末を混合して
複合材料を得るのは、混合の均一性の点で問題がある。In addition, even manufacturers who produce hydroxyapatite with a stoichiometric composition on an industrial scale have to change the parameters of the synthesis equipment set to produce hydroxyapatite with a stoichiometric composition. Furthermore, trying to obtain apatite with a specific Ca/P ratio from the synthesis process is very problematic, considering the complexity of cleaning the equipment to prevent contamination in subsequent synthetic products. On the other hand, when a composite material is obtained by mixing commercially available stoichiometric hydroxyapatite powder with calcium oxide or β-tricalcium phosphate powder, there is a problem in the uniformity of the mixture.
「発明の目的」
本発明の目的は、市販のノ＼イドロキシアパタイト粉末
など、容易に入手できる原料を用いて、簡単な操作工程
でＣａ／Ｐ比が化学量論組成からはずれたリン酸カルシ
ウム系生体材料を効率よく製造する方法を提供すること
にある。"Objective of the Invention" The object of the present invention is to produce a calcium phosphate-based biological material whose Ca/P ratio deviates from the stoichiometric composition through a simple operation process using easily available raw materials such as commercially available nohydroxyapatite powder. The objective is to provide a method for efficiently manufacturing materials.
「発明の構成」
本発明ニよるリン酸カルシウム系生体材料の製造方法は
、焼成前のアパタイト成形体にカルシウム化合物又はリ
ン酸化合物の水溶液を含浸させ、焼成して酸化カルシウ
ム２〜６０重量％又はリン酸三カルシウムフル９０重量
％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-based biomaterial according to the present invention involves impregnating an apatite molded body before firing with an aqueous solution of a calcium compound or a phosphoric acid compound, and firing it to produce 2 to 60% by weight of calcium oxide or phosphoric acid. It is characterized by phase separation of 90% by weight of tricalcium.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
原料に用いるアパタイトは、容易に入手できるものであ
れば、どのようなものでもよい。その場合、化学量論組
成のものが最も好ましいが、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、化学量論組成から偏倚しているか）を分
析してあれば用いることができる。アパタイトとしては
、ハイドロキシアパタイトが最も好ましいが、フッ素ア
パタイト、塩素アパタイトを用いることもできる。Any apatite can be used as a raw material as long as it is easily available. In that case, it is most preferable to have a stoichiometric composition, but even if it deviates from the stoichiometric composition, it can be determined by chemical analysis, X-ray diffraction, etc. that it is non-stoichiometric (how much it deviates from the stoichiometric composition). It can be used if it has been analyzed. As the apatite, hydroxyapatite is most preferred, but fluoroapatite and chloroapatite can also be used.
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。本発明を実
施するには、■では圧粉体又は仮焼後の成形体（以下、
仮焼体という）、■及び■の方法では乾燥体及び仮焼体
のいずれでもよい。すなわち、本発明を実施する場合に
は、上記■〜■のいずれかの方法で製造した焼成前の成
形体にカルシウム化合物又はリン酸化合物の水溶液を含
浸させる。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. In order to carry out the present invention, in (1), a compacted powder body or a compacted body after calcination (hereinafter referred to as
(referred to as a calcined body), either a dried body or a calcined body may be used in methods (1) and (2). That is, when carrying out the present invention, an aqueous solution of a calcium compound or a phosphoric acid compound is impregnated into a pre-fired molded article produced by any of the methods (1) to (2) above.
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
う観点から水溶性のものが好ましい。また、ここで、ア
パタイトとしてハイドロキシアパタイトを適用する際に
、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、酢酸力ルシラム、乳酸カ
ルシウムなどを用いるか、又は本発明者が特願昭６３−
２４７２３６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。Examples of the calcium compound include calcium carbonate, calcium hydroxide, calcium chloride, calcium nitrate, calcium acetate, and calcium lactate, but water-soluble compounds are preferred from the viewpoint of uniform mixing. In addition, when applying hydroxyapatite as apatite, for example, if calcium chloride is used, chlorine will not volatilize during the firing process, but will be incorporated into the crystal structure, and there is a risk that some of the hydroxyapatite will become chloroapatite. Therefore, if this becomes a problem, use luciram acetate, calcium lactate, etc., or the inventor proposed
Preferably, the calcium sol proposed in No. 247236 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溶解度の高いものが好
ましい。また、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、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。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, for the same reason as calcium, those with high solubility are preferred. In addition, when using sodium phosphate or potassium phosphate, the sodium or potassium may not volatilize and may remain as an impurity in the apatite, so if this becomes a problem, use phosphoric acid, ammonium phosphate, Phosphate esters should be used.
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。Additionally, phosphoric acid and some phosphoric acid esters are highly acidic and may dissolve some apatite, so if these are a problem, avoid using such compounds. It is.
本発明の方法において含浸させる水溶性カルシウム化合
物又はリン酸化合物の量は、焼成により分相させたい量
に応じて適宜決定することができる。本発明においては
、焼結体中に酸化カルシウムを２〜６０重量％重量％分
易か又はリン酸三カルシウムを７〜９０重量％重量％分
易ことが必要である。酸化カルシウムが２重量％未満で
あると、骨伝導能が充分に改善されず、酸化カルシウム
が６０重量％を超えると、結晶形、収縮率の違いから、
焼結体が崩壊するおそれがある。また、リン酸三カルシ
ウムが７重量％未満であると、生体吸収性が低く、９０
重量％を超えると、吸収性はリン酸三カルシウムに等し
くなる。The amount of the water-soluble calcium compound or phosphoric acid compound to be impregnated in the method of the present invention can be appropriately determined depending on the amount of phase separation desired by firing. In the present invention, it is necessary to contain 2 to 60% by weight of calcium oxide or 7 to 90% by weight of tricalcium phosphate in the sintered body. If the calcium oxide content is less than 2% by weight, bone conduction ability will not be sufficiently improved, and if the calcium oxide content exceeds 60% by weight, due to differences in crystal shape and shrinkage rate,
There is a risk that the sintered body will collapse. Furthermore, if tricalcium phosphate is less than 7% by weight, bioabsorption is low and 90%
Above the weight percent, the absorbency is equal to tricalcium phosphate.
なお、酸化カルシウム又はリン酸三カルシウムの分相量
は、Ｘ線回折分析により求めることができる。Note that the amount of phase separation of calcium oxide or tricalcium phosphate can be determined by X-ray diffraction analysis.
上記のように、成形体を含浸した後、乾燥し、焼成する
。焼成は、常法で行うことができる。After impregnating the molded body as described above, it is dried and fired. Firing can be performed by a conventional method.
［発明の実施例ｊ
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。[Example j 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
公知の過酸化水素発泡法で作製したハイドロキシアパタ
イト多孔質乾燥体１．３ｇに水２ｇとリン酸水素二アン
モニウム０．０２ ｇから調製した水溶液をスポイトで
滴下、含浸させた後、１１００°Ｃで１時間焼成し、焼
結体を作製した。得られた焼結体を粉砕し、Ｘ線回折を
行ったところ、第１図に示すＸ線回折図が得られた。第
１図において、ａはリン酸三カルシウムのピークを示す
。この図から、得られた焼結体がハイドロキシアパタイ
トとリン酸三カルシウムの混合物であり、リン酸三カル
シウムの量は約９重量％であることが分かった。Example 1 An aqueous solution prepared from 2 g of water and 0.02 g of diammonium hydrogen phosphate was added dropwise to 1.3 g of a dried porous hydroxyapatite body prepared by a known hydrogen peroxide foaming method using a dropper to impregnate it. It was fired at °C for 1 hour to produce a sintered body. When the obtained sintered body was crushed and subjected to X-ray diffraction, the X-ray diffraction diagram shown in FIG. 1 was obtained. In FIG. 1, a indicates the peak of tricalcium phosphate. From this figure, it was found that the obtained sintered body was a mixture of hydroxyapatite and tricalcium phosphate, and the amount of tricalcium phosphate was about 9% by weight.
実施例２
公知の過酸化水素発泡法で作製したハイドロキシアパタ
イト多孔質乾燥体１．５ｇに水２ｇと酢酸カルシウム０
．０７ ｇから調製した水溶液をスポイトで滴下、含浸
させた後、１１００°Ｃで１時間焼成し、焼結体を作製
した。得られた焼結体を粉砕し、Ｘ線回折を行ったとこ
ろ、第２図に示すＸ線回折図が得られた。第２図におい
て、ｂは酸化カルシウムのピークを示す。この図から、
得られた焼結体がハイドロキシアパタイトと酸化カルシ
ウムの混合物であり、酸化カルシウムの量は約３重量％
であることが分かった。Example 2 2 g of water and 0 calcium acetate were added to 1.5 g of dried porous hydroxyapatite produced by a known hydrogen peroxide foaming method.
．． After dripping an aqueous solution prepared from 0.07 g with a dropper to impregnate it, it was fired at 1100°C for 1 hour to produce a sintered body. When the obtained sintered body was crushed and subjected to X-ray diffraction, the X-ray diffraction diagram shown in FIG. 2 was obtained. In FIG. 2, b indicates the peak of calcium oxide. From this figure,
The obtained sintered body is a mixture of hydroxyapatite and calcium oxide, and the amount of calcium oxide is about 3% by weight.
It turned out to be.
「発明の効果」
本発明の方法によれば、市販のハイドロキシアパタイト
粉末など、容易に入手できる原料を用いて、Ｃａ／Ｐ比
が化学量論組成から偏倚したリン酸カルシウム系生体材
料を簡単な操作で効率よく製造することができる。"Effects of the Invention" According to the method of the present invention, calcium phosphate biomaterials with a Ca/P ratio that deviates from the stoichiometric composition can be prepared using easily available raw materials such as commercially available hydroxyapatite powder. It can be manufactured efficiently.
第１図は実施例１で得られた焼結体のＸ線回折図、第２
図は実施例２で得られた焼結体のＸ線回折図である。
符号の説明
ａ・・・リン酸三カルシウムのピーク
ｂ・・・酸化カルシウムのピークFigure 1 is an X-ray diffraction diagram of the sintered body obtained in Example 1,
The figure is an X-ray diffraction diagram of the sintered body obtained in Example 2. Explanation of symbols a: Tricalcium phosphate peak b: Calcium oxide peak
Claims (2)
リン酸化合物の水溶液を含浸させ、焼成して酸化カルシ
ウム２〜６０重量％又はリン酸三カルシウム７〜９０重
量％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。1. A calcium phosphate system characterized by impregnating an apatite molded body before firing with an aqueous solution of a calcium compound or a phosphoric acid compound and firing it to phase separate 2 to 60% by weight of calcium oxide or 7 to 90% by weight of tricalcium phosphate. Method for producing biomaterials.
記載のリン酸カルシウム系生体材料の製造方法。2. Claim 1: The molded body is a green compact, a dried body or a calcined body.
The method for producing the described calcium phosphate biomaterial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2035676A JPH03242364A (en) | 1990-02-16 | 1990-02-16 | Production of calcium phosphate-based biomaterial |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2035676A JPH03242364A (en) | 1990-02-16 | 1990-02-16 | Production of calcium phosphate-based biomaterial |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03242364A true JPH03242364A (en) | 1991-10-29 |
Family
ID=12448486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2035676A Pending JPH03242364A (en) | 1990-02-16 | 1990-02-16 | Production of calcium phosphate-based biomaterial |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03242364A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047334A1 (en) * | 1996-06-14 | 1997-12-18 | Bioland | Method for preparing an implantable composite material, resulting material, implant including said material, and kit therefor |
-
1990
- 1990-02-16 JP JP2035676A patent/JPH03242364A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047334A1 (en) * | 1996-06-14 | 1997-12-18 | Bioland | Method for preparing an implantable composite material, resulting material, implant including said material, and kit therefor |
| FR2749756A1 (en) * | 1996-06-14 | 1997-12-19 | Bioland | PROCESS FOR THE PREPARATION OF AN IMPLANTABLE COMPOSITE MATERIAL, MATERIAL OBTAINED, IMPLANT COMPRISING SUCH MATERIAL, AND IMPLEMENTATION KIT |
| US6018095A (en) * | 1996-06-14 | 2000-01-25 | Bioland | Method for preparing an implantable composite material, resulting material, implant including said material, and kit therefor |
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