JPH02311309A - Production of fibrous hydroxyapatite - Google Patents
Production of fibrous hydroxyapatiteInfo
- Publication number
- JPH02311309A JPH02311309A JP1133490A JP13349089A JPH02311309A JP H02311309 A JPH02311309 A JP H02311309A JP 1133490 A JP1133490 A JP 1133490A JP 13349089 A JP13349089 A JP 13349089A JP H02311309 A JPH02311309 A JP H02311309A
- Authority
- JP
- Japan
- Prior art keywords
- hap
- fibrous
- hydrolyzed
- production
- buffer solution
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims description 5
- 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 title claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 abstract description 5
- 229910000391 tricalcium phosphate Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 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 5
- 235000019731 tricalcium phosphate Nutrition 0.000 description 5
- 230000012010 growth Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 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 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、繊維状ヒドロキシアパタイトの製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing fibrous hydroxyapatite.
ヒドロキシアパタイト（以下、ＨＡｐという）は、近年
、人工骨や人工歯根等の生体材料として注１」されるよ
うになっている。In recent years, hydroxyapatite (hereinafter referred to as HAp) has come to be used as a biomaterial for artificial bones, artificial tooth roots, and the like.
従来、ＨＡｐの製造方法としては、特公昭６２−４３２
５号公報又は特開昭６２−４６９０８号公報記載の方法
が知られている。Conventionally, the method for producing HAp was
The method described in Publication No. 5 or Japanese Patent Application Laid-Open No. 62-46908 is known.
前者のＨＡｐの製造方法は、Ｃａ ＨＰ Ｏ４（第ニリ
ン酸カルシウム、リン酸水素カルシウム）又はＣａＨＰ
Ｏ・２Ｈ２０（第二リン酸カルシウムの２水塩）と水の
スラリー溶液に、反応温度５−１００℃でＣａ／ｐモル
比１，６まてｐＨを１０以下に保ちなからＣａ （ＯＨ
） ２ （水酸化カルシウム）を添加し反応を行イっ
せ、微粒子針状粉末のＨＡｐを得る方法であり、後者の
ＨＡｐの製造方法は、ＣａＨＰＯ４，ＣａＨＰＯ４”、
２Ｈ２０又はα型Ｃａ （ＰＯ４）２ （第三リン酸カ
ルシウム、リン酸三カルシウム）の難水溶性リン酸カル
シウムを塩基性水溶液中で加水分解させて、Ｃａ／ｐの
モル比が１．６７より小さい非化学量論性のＨＡｐとな
し、これに、塩基性水溶液の下でカルシウムイオンを添
加してモル比を１．６７までの任意の比まで増加させ、
出発原料の粉末形状を継承した粒状粉末のＨＡｐを得る
方法である。The former method for producing HAp uses CaHP O4 (calcium diphosphate, calcium hydrogen phosphate) or CaHP
Add Ca (OH
) 2 (calcium hydroxide) is added and the reaction is carried out to obtain HAp in the form of fine needle-like powder.
2H20 or α-type Ca (PO4)2 (tertiary calcium phosphate, tricalcium phosphate), which is a poorly water-soluble calcium phosphate, is hydrolyzed in a basic aqueous solution to produce a non-stoichiometric amount with a Ca/p molar ratio of less than 1.67. of HAp, to which calcium ions are added under basic aqueous solution to increase the molar ratio to any ratio up to 1.67;
This is a method for obtaining granular powder HAp that inherits the powder shape of the starting material.
しかしながら、上記従来の製造方法により得られるＨＡ
ｐは、微粒子針状粉末又は粒状粉末の形体であるため、
糸、綿布、織布の原料としては不一 ９ −
適当である。However, HA obtained by the above conventional manufacturing method
Since p is in the form of fine needle-like powder or granular powder,
It is suitable as a raw material for yarn, cotton cloth, and woven cloth.
又、ＨＡｐ構造中のＯＨ基が生体との適合性に深く関与
していると言われているが、粒状粉末では結晶成長の方
向性がな（、結晶表面のＯＨ基が少なくなってしまう問
題がある。In addition, it is said that the OH groups in the HAp structure are deeply involved in compatibility with living organisms, but in granular powder, the crystal growth is not directional (there is a problem that the number of OH groups on the crystal surface decreases). There is.
更に、従来、ＨＡｐ焼結体は、骨、歯等に利用するには
、強度、靭性が不足している。Furthermore, conventional HAp sintered bodies lack strength and toughness to be used for bones, teeth, and the like.
このため、ＨＡｐを繊維状とし、糸、綿布、織布の原料
としたり、ＨＡｐ緻密体の強化剤として強度の向上を図
ること、成長方向の結晶表面にＯＨ基を多くして生体適
合性を増すことが望まれている。For this reason, it is possible to make HAp into a fibrous form and use it as a raw material for yarn, cotton cloth, or woven fabric, or to improve its strength by using it as a reinforcing agent for HAp dense bodies, and to improve its biocompatibility by increasing the number of OH groups on the crystal surface in the growth direction. It is hoped that this will increase.
そこで、本発明は、上記要望を可能とする繊維状ＨＡｐ
の製造方法の提供を目的とする。Therefore, the present invention provides fibrous HAp that can meet the above requirements.
The purpose is to provide a manufacturing method for.
前記課題を解決するため、本発明は、β型Ｃａ （ＰＯ
４）２を塩基性緩衝液中で加水分解する方法である。In order to solve the above problems, the present invention provides β-type Ca (PO
4) A method in which 2 is hydrolyzed in a basic buffer.
上記手段においては、低温型のβ型Ｃａ５（ＰＯ４）２
（以下、ＴＣＰという）は、三方晶系で、単斜晶系の高
温型のα型ＴＣＰより構造的にＨＡｐｊ六方品系）との
類似性が低く、α型ＴＣＰより反応性が低い。このため
、構造変化（分子の再配列）を伴い、次の反応式に示す
ようにＨＡｐへ加水分解される。In the above means, low-temperature β-type Ca5(PO4)2
(hereinafter referred to as TCP) is a trigonal system, has a lower structural similarity to HApj (hexagonal system) than the monoclinic high-temperature type α-TCP, and has lower reactivity than α-TCP. Therefore, it undergoes a structural change (molecular rearrangement) and is hydrolyzed to HAp as shown in the following reaction formula.
（１０−ｘ） Ｃａ （ＰＯ） ＋ ｆ３（２−ｘ）
＋３ｎｌ Ｈ２Ｏ→３ Ｃａ ｔｏ−ｘ（ＨＰ ０４）
ｘ（ＰＯ４）６−ｘ（ＯＨ）２−ｘ−ｎ Ｈ２０十２
（］−ｘ） Ｈａ Ｐ ０４
そして、上記構造変化の際に、形体の変化、すなわち繊
維長の伸びを伴って結晶成長が起こる。(10-x) Ca (PO) + f3(2-x)
+3nl H2O→3 Ca to-x (HP 04)
x(PO4)6-x(OH)2-x-n H2012
(]-x) Ha P 04 Then, during the above structural change, crystal growth occurs accompanied by a change in shape, that is, an elongation of the fiber length.
緩衝液は、ｐｌ（９〜１４が好ましく、特にｐＨ１２以
上であることが好ましい。ｐＨ９未満であると、ＨＡｐ
への加水分解反応の進行が著しく遅（なる。The buffer solution has a pH of pl (preferably 9 to 14, particularly preferably 12 or more. If the pH is less than 9, HAp
The progress of the hydrolysis reaction to is extremely slow.
又、緩衝液としては、Ｎ ａ ＯＨ−Ｋ Ｃａ （１）
１１１２〜１３） 、Ｎａ ＨＰＯ４−ＮａＯＨ（ｐ
ｌ（１１〜１２）又はＮ ａ ＨＣＯａ Ｎ ａ Ｏ
Ｈ（ｐｌ（９，ｅ〜Ｉｆ）が用いられる。In addition, as a buffer solution, N a OH-K Ca (1)
1112-13), Na HPO4-NaOH (p
l(11-12) or N a HCOa N a O
H(pl(9,e~If) is used.
反応温度は、４０〜３００℃、特に６０〜１５０℃とす
ることか好ましく、更に、１１０〜１４０℃がより好ま
しい。４０℃未満であると加水分解反応が進みにくく、
１５０℃を超えると合成装置が高価で複雑となり、又、
操作も複雑となる。The reaction temperature is preferably 40 to 300°C, particularly 60 to 150°C, and more preferably 110 to 140°C. If the temperature is below 40°C, the hydrolysis reaction will not proceed easily;
If the temperature exceeds 150°C, the synthesis equipment becomes expensive and complicated, and
Operation is also complicated.
以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.
実施例 １〜３
β型ＴＣＰ粉末（粒径０．２〜０．５ｔ１ｍ、 Ｃａ
／ ｐモル比１．５０）を出発原料とし、それぞれを緩
衝液であるＮａ０Ｈ−ＫＣ，ｉｌｌによりｐＨ１３とし
て第１表に示す反応温度と反応時間の下で撹拌しながら
加水分解した後、生成物をろ過、水洗、乾燥したところ
、ＨＡｐの生成率と反応温度及び時間との関係は第１図
に示すようになり、又、生成物の生成相、形体及びＣａ
／ｐモル比は、α型ＴＣＰを出発原料とした従来例を併
記する第１表のようになった。Examples 1-3 β-type TCP powder (particle size 0.2-0.5t1m, Ca
/ p molar ratio 1.50) as starting materials, each was hydrolyzed with stirring at the reaction temperature and reaction time shown in Table 1 at pH 13 using Na0H-KC,ill, which is a buffer solution, and the product was obtained. After filtering, washing with water, and drying, the relationship between the production rate of HAp and the reaction temperature and time is shown in Figure 1, and the formation phase, shape, and Ca
/p molar ratio is as shown in Table 1, which also includes conventional examples using α-type TCP as a starting material.
なお、成長相は、Ｘ線回折、ＩＲ分析によって評価し、
形体はＳＥＭ（走査形電子顕微鏡）によって観察したも
のであり、実施例今によって得られた生成物の電子顕微
鏡写真を第２図に示す。The growth phase was evaluated by X-ray diffraction and IR analysis.
The shape was observed by SEM (scanning electron microscope), and an electron micrograph of the product obtained in Example 2 is shown in FIG.
以上のように本発明によれば、β型ＴＣＰは、α型ＴＣ
Ｐより反応性が低いため、構造変化を伴ってＨＡｐへ加
水分解され、この構造変化の際に、形体の変化、すなわ
ち繊維長の伸びを伴って結晶成長が起こるので、繊維状
のＨＡｐを得ることかでき、かつその成長方向によりＯ
Ｈ基か結晶表面にならび、生体適合性を増すことができ
る。As described above, according to the present invention, β-type TCP is
Since it has lower reactivity than P, it is hydrolyzed to HAp with a structural change, and during this structural change, crystal growth occurs with a change in shape, that is, an elongation of the fiber length, resulting in fibrous HAp. O
H groups can be aligned with the crystal surface to increase biocompatibility.
又、繊維状ＨＡｐが得られることにより、ＨＡｐ糸の紡
糸、ＨＡｐ織布の作製か可能となると共に、ＨＡｐの多
孔体やフィルターを得ることが可能となる。又、クロマ
トグラフィーの充填剤としても利用でき、かつウィスカ
ーのように繊維状ＨＡｐを配向させて焼結することによ
ってＨＡｐ緻密体の強度、靭性の向上か可能となる。Furthermore, by obtaining fibrous HAp, it becomes possible to spin HAp yarns and produce HAp woven fabrics, and it also becomes possible to obtain porous bodies and filters of HAp. It can also be used as a filler in chromatography, and by sintering fibrous HAp in a whisker-like orientation, it is possible to improve the strength and toughness of the HAp dense body.
第１図はＨＡｐ生成率と反応時間との関係を示す相関図
、第２図は実施例４によって得られた生成物の形体を示
す電子顕微鏡写真である。
出 願 人 東芝セラミックス株式会社出 願 人
株式会社ニス・ティー・ケー・セラミックス研究所
手 続 ネ甫 正 書 （自発）
平成元年７月１９日
２．８．。２６“”“１“゛”３３４９０’ｉ。
繊維状ヒドロキシアパタイトの製造方法事件との関係
特許出願人
住 所 東京都新宿区西新宿１丁目２６番地２号東
芝セラミツ゛クス株式会社 （外１名）４、代理人 〒
１０３
住 所 東京都中央区日本橋本町２丁目５番７号、
・ 日康ビル 電話（２４１）７２６８号明細書の発明
の詳細な説明の柵。
６、補正の内容FIG. 1 is a correlation diagram showing the relationship between HAp production rate and reaction time, and FIG. 2 is an electron micrograph showing the morphology of the product obtained in Example 4. Applicant Toshiba Ceramics Corporation Applicant
Niss TK Ceramics Research Institute Procedures Written by Masaru Neho (self-motivated) July 19, 1989 2.8. . 26"""1"゛"33490'i.Relationship with the fibrous hydroxyapatite manufacturing method incident
Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Toshiba Ceramics Corporation (1 other person) 4, Agent:
103 Address: 2-5-7, Nihonbashi Honmachi, Chuo-ku, Tokyo.
- Nikko Building Telephone (241) 7268 Detailed description of the invention fence. 6. Contents of correction
Claims (1)
で加水分解することを特徴とする繊維状ヒドロキシアパ
タイトの製造方法。(1) A method for producing fibrous hydroxyapatite, which comprises hydrolyzing β-type Ca_3(PO_4)_2 in a basic buffer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1133490A JPH02311309A (en) | 1989-05-27 | 1989-05-27 | Production of fibrous hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1133490A JPH02311309A (en) | 1989-05-27 | 1989-05-27 | Production of fibrous hydroxyapatite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02311309A true JPH02311309A (en) | 1990-12-26 |
Family
ID=15105988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1133490A Pending JPH02311309A (en) | 1989-05-27 | 1989-05-27 | Production of fibrous hydroxyapatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02311309A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2693716A1 (en) * | 1992-07-20 | 1994-01-21 | Toulouse Inst Nat Polytech | Process for obtaining phosphocalcic hydroxyapatite, applications for bone or dental filling, or molding of parts, and products used. |
| WO2001002294A1 (en) * | 1999-07-05 | 2001-01-11 | Rhodia Chimie | Novel mineral compositions for use as hydroxyapatite precursors, use for reinforcing concrete |
| GB2433257A (en) * | 2005-12-19 | 2007-06-20 | Accentus Plc | Preparation of hydroxyapatite |
-
1989
- 1989-05-27 JP JP1133490A patent/JPH02311309A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2693716A1 (en) * | 1992-07-20 | 1994-01-21 | Toulouse Inst Nat Polytech | Process for obtaining phosphocalcic hydroxyapatite, applications for bone or dental filling, or molding of parts, and products used. |
| WO2001002294A1 (en) * | 1999-07-05 | 2001-01-11 | Rhodia Chimie | Novel mineral compositions for use as hydroxyapatite precursors, use for reinforcing concrete |
| FR2796061A1 (en) * | 1999-07-05 | 2001-01-12 | Bouygues Travaux Publics | NOVEL MINERAL COMPOSITIONS AS HYDROXYAPATITE PRECURSORS - CONCRETE REINFORCING APPLICATION |
| GB2433257A (en) * | 2005-12-19 | 2007-06-20 | Accentus Plc | Preparation of hydroxyapatite |
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