JPH04175212A - Method for wet synthesis of hydroxyapatite - Google Patents
Method for wet synthesis of hydroxyapatiteInfo
- Publication number
- JPH04175212A JPH04175212A JP30547990A JP30547990A JPH04175212A JP H04175212 A JPH04175212 A JP H04175212A JP 30547990 A JP30547990 A JP 30547990A JP 30547990 A JP30547990 A JP 30547990A JP H04175212 A JPH04175212 A JP H04175212A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- calcium hydroxide
- phosphoric acid
- water
- reaction
- 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
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 46
- 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 abstract description 46
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000000034 method Methods 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 42
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 239000012620 biological material Substances 0.000 abstract description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910052586 apatite Inorganic materials 0.000 abstract 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 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 101001077535 Emericella nidulans (strain FGSC A4 / ATCC 38163 / CBS 112.46 / NRRL 194 / M139) Nicotinate hydroxylase hnxS Proteins 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、水酸アパタイトの湿式合成法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a wet synthesis method for hydroxyapatite.
〔従来の技術］
化学式〇 ａ １ｏ （Ｐ ０４） （ＯＨ）２で表示
される水酸アパタイトは人工骨等の生体材料として注目
されている物質であり、種々の合成法が提案されている
。[Prior Art] Hydroxyapatite, which is represented by the chemical formula 〇 a 1o (P 04) (OH) 2, is a substance that is attracting attention as a biomaterial for artificial bones and the like, and various synthesis methods have been proposed.
その中の一つとして、例えば特開昭６２−２５２３０７
号公報に開示されている水酸アパタイトの湿式合成法で
は、水酸化カルシウム懸濁液に撹拌下、ＰＨＩＩ付近に
至るまで２〜４倍に希釈したリン酸水溶液を滴下し、こ
の後、約５倍以上に希釈したリン酸水溶液を滴下してＰ
ＨＩＯ〜９に調節し、得られた沈澱物を乾燥することに
より、水酸アパタイトの合成を行っている。As one of them, for example, JP-A-62-252307
In the wet synthesis method of hydroxyapatite disclosed in the publication, a phosphoric acid aqueous solution diluted 2 to 4 times to around PHII is added dropwise to a calcium hydroxide suspension under stirring, and then about 5 Drop a phosphoric acid aqueous solution diluted more than twice as much as P.
Hydroxyapatite is synthesized by adjusting the HIO to ~9 and drying the obtained precipitate.
［発明が解決しようとする課題］
ところが、上記従来の構成では、反応条件とし７ｐＨ１
０〜９を保つために、水酸化カルシウム懸濁液に約５倍
以上に希釈した低濃度のリン酸水溶液を徐々に滴下して
いるので、合成に非常に長い時間を要するという問題点
を有している。[Problems to be Solved by the Invention] However, in the above conventional configuration, the reaction condition is 7pH1.
In order to maintain the pH between 0 and 9, a low concentration phosphoric acid aqueous solution diluted approximately 5 times or more is gradually dropped into the calcium hydroxide suspension, which poses the problem of requiring a very long time for synthesis. are doing.
〔課題を解決するための手段］
請求項第１項の発明に係る水酸アパタイトの湿式合成法
は、上記の課題を解決するために、撹拌下、水酸化カル
シウム懸濁液に水酸アパタイトを分散させる水溶性高分
子分散剤を加えた後、リン酸水溶液をｐＨ９〜１１にな
るまで加えることを特徴としている。[Means for solving the problem] In order to solve the above problem, the wet synthesis method of hydroxyapatite according to the invention of claim 1 involves adding hydroxyapatite to a calcium hydroxide suspension under stirring. The method is characterized in that after adding a water-soluble polymer dispersant to be dispersed, an aqueous phosphoric acid solution is added until the pH reaches 9 to 11.
請求項第２項の発明に係る水酸アパタイトの湿式合成法
は、上記の課題を解決するために、撹拌下、反応温度を
５〜５０℃に保ちながら、水酸化カルシウム懸濁液にリ
ン酸水溶液をｐＨ９〜１１になるまで加えた後、水酸ア
パタイトを分散させる水溶性高分子分散剤を加えること
を特徴としている。In order to solve the above-mentioned problems, the wet synthesis method of hydroxyapatite according to the invention of claim 2 is provided by adding phosphoric acid to a calcium hydroxide suspension while stirring and keeping the reaction temperature at 5 to 50°C. The method is characterized in that after adding an aqueous solution until the pH becomes 9 to 11, a water-soluble polymer dispersant for dispersing hydroxyapatite is added.
請求項第１項の構成によれば、撹拌下、水酸化カルシウ
ム懸濁液に水酸アパタイトを分散させる水溶性高分子分
散剤を加えた後、リン酸水溶液をｐＨ９〜１１になるま
で加えるので、水酸化カルシウムとリン酸との反応によ
り生成した水酸アパタイト粒子によって水酸化カルシウ
ム粒子表面が覆われて反応が妨げられることが少なくな
る。これにより、水酸アパタイトの生成反応が速やかに
進行する。According to the structure of claim 1, a water-soluble polymer dispersant for dispersing hydroxyapatite is added to a calcium hydroxide suspension under stirring, and then an aqueous phosphoric acid solution is added until the pH becomes 9 to 11. The surface of the calcium hydroxide particles is covered with hydroxyapatite particles generated by the reaction between calcium hydroxide and phosphoric acid, and the reaction is less likely to be hindered. As a result, the hydroxyapatite production reaction progresses rapidly.
請求項第２項の構成によれば、撹拌下、反応温度を５〜
５０℃に保ちながら、水酸化カルシウム懸濁液に水酸ア
パタイトを分散させる水溶性高分子分散剤を加えた後、
リン酸水溶液をｐＨ９〜１１になるまで加えるので、水
酸化カルシウムとリン酸との反応により生成した水酸ア
パタイト粒子によって水酸化カルシウム粒子表面が覆わ
れて反応が妨げられることが少なくなる。これにより、
水酸アパタイトの生成反応が速やかに進行する。According to the structure of claim 2, the reaction temperature is set to 5 to 5 while stirring.
After adding a water-soluble polymer dispersant for dispersing hydroxyapatite to the calcium hydroxide suspension while maintaining the temperature at 50°C,
Since the phosphoric acid aqueous solution is added until the pH reaches 9 to 11, the surface of the calcium hydroxide particles is less likely to be covered with hydroxyapatite particles generated by the reaction between calcium hydroxide and phosphoric acid, thereby preventing the reaction from being hindered. This results in
The reaction for producing hydroxyapatite proceeds rapidly.
しかも、反応温度を５〜５０℃に保っているので、水溶
性高分子分散剤の重合反応が起こりにくくなり、粘度の
低いスラリーが得られる。Furthermore, since the reaction temperature is maintained at 5 to 50°C, the polymerization reaction of the water-soluble polymer dispersant is less likely to occur, and a slurry with low viscosity can be obtained.
〔実施例１〕
２００Ｉ！、のステンレス製タンクに１５０１のイオン
交換水を注入し、攪拌機（佐竹化学機械工業社製Ａ５１
０）にて攪拌しながら、以下の操作を行った。[Example 1] 200I! Pour 1501 ion-exchanged water into a stainless steel tank and use a stirrer (A51 manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.).
The following operations were performed while stirring at 0).
まず、２０ｋｇの水酸化カルシウム（日本石灰工業社製
ＣＨ−２Ｎ）を加えることにより、水酸化カルシウム懸
濁液を得た。この水酸化カルシウム懸濁液に水溶性高分
子分散剤として、アクリル酸のＨ＋イオンがＮＨ，”イ
オンに置換されている、分子量約１万のアクリル系−Ｎ
Ｈ，（第一工業製薬社製Ｄ−１３４）を加えて、アクリ
ル系−ＮＨ，を０．５％含む水酸化カルシウム懸濁液を
調製し、これにリン酸水溶液として８５％リン酸（ラサ
工業社製食品添加用）をｐａｔ Ｏになるまで一気に加
えることにより、数１０分間でスラリーが得られた。First, 20 kg of calcium hydroxide (CH-2N manufactured by Nippon Lime Industries Co., Ltd.) was added to obtain a calcium hydroxide suspension. In this calcium hydroxide suspension, as a water-soluble polymer dispersant, acrylic -N with a molecular weight of about 10,000 is used, in which the H+ ions of acrylic acid are replaced with NH,'' ions.
H, (D-134 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to prepare a calcium hydroxide suspension containing 0.5% of acrylic-NH, and to this was added 85% phosphoric acid (Rasa) as an aqueous phosphoric acid solution. A slurry was obtained in several tens of minutes by adding pat O (for food additives manufactured by Kogyo Co., Ltd.) at once until it reached pat O.
なお、上記リン酸を加えた当初、スラリーの粘度は低か
ったが、反応熱による温度の上昇と共に高くなり、５０
’Ｃを越えた時点から、スラリーの粘度は増大してヨー
グルト状になり、溶液表面がほとんど枝打たない程度に
なった。この粘度の増大は温度の上昇に伴う上記分散剤
の重合に依るものと考えられる。The viscosity of the slurry was low when the phosphoric acid was added, but it increased as the temperature rose due to the heat of reaction, and the viscosity increased to 50%.
From the point at which the slurry exceeded 'C', the viscosity of the slurry increased and became yogurt-like, to such an extent that the surface of the solution was hardly plucked. This increase in viscosity is thought to be due to polymerization of the dispersant as the temperature rises.
上記スラリーを凍結乾燥機（セントラル科学貿易社製Ｆ
Ｄ−２０−５５−ＭＰ）にて乾燥させることにより粉末
状の試料が得られた。粉末Ｘ線回折法により生成物の同
定を行った結果、この試料は水酸アパタイトの単一相か
らなることが分かった。また、走査電子顕微鏡写真によ
り粒子径を調べた結果、粒径が０．１μｍ以下の球状微
粒子からなることが分かった。The above slurry was dried using a freeze dryer (F manufactured by Central Kagaku Trading Co., Ltd.).
A powdered sample was obtained by drying with D-20-55-MP). The product was identified by powder X-ray diffraction, and it was found that this sample consisted of a single phase of hydroxyapatite. Further, as a result of examining the particle size using scanning electron micrographs, it was found that the particles were composed of spherical fine particles with a particle size of 0.1 μm or less.
なお、スラリーの粘度の高低は上記結果には影響を与え
なかった。また、上記水酸化カルシウム懸濁液に加える
アクリル系−ＮＨ，の濃度を０゜１〜２０％の範囲で変
えた場合も上記と同様の結果が得られた。Note that the viscosity of the slurry did not affect the above results. Similar results were also obtained when the concentration of acrylic-NH added to the calcium hydroxide suspension was varied within the range of 0.1 to 20%.
また、リン酸を加える際、ｐＨ１１よりも大きくなると
炭酸カルシウムが生じやすく、ｐＨ９よりも小さくなる
とβ−リン酸三カルシウム［Ｃａ。Furthermore, when adding phosphoric acid, if the pH is higher than 11, calcium carbonate is likely to be produced, and if the pH is lower than 9, β-tricalcium phosphate [Ca] is likely to be produced.
（ＰＯ４）Ｚ］が生じてしまうので、ｐＨ９〜１１にす
ることが単一な水酸アパタイトを製造する上で好ましい
。(PO4)Z] is generated, so it is preferable to adjust the pH to 9 to 11 in order to produce a single hydroxyapatite.
また、水酸化カルシウム懸濁液における水酸化カルシウ
ム濃度は１０〜３０％程度であることが、単一な水酸ア
パタイトを効率良く製造する上で適当である。Further, it is appropriate that the calcium hydroxide concentration in the calcium hydroxide suspension is about 10 to 30% in order to efficiently produce a single hydroxyapatite.
〔実施例２］
前記実施例１において、水溶性高分子分散剤として、分
子量約１万のアクリル系−ＮＨ４（第一工業製薬社製Ｄ
−１３４）の代わりに、分子量約２万のアクリル系−Ｎ
Ｈ４（第一工業製薬社製Ｄ−１０２）を用いた場合も、
前記実施例１と同様の結果が得られた。[Example 2] In Example 1, acrylic-NH4 (Daiichi Kogyo Seiyaku Co., Ltd., D
-134), acrylic-N with a molecular weight of approximately 20,000
Even when using H4 (D-102 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
The same results as in Example 1 were obtained.
［実施例３］
前記実施例１において、水溶性高分子分散剤として、分
子量約１万のアクリル系−ＮＨ，（第一工業製薬社製Ｄ
−１３４）の代わりに、分子量約１万のアクリル系−Ｈ
（第一工業製薬社製Ｄ−１３４Ａ）を用いた場合も、前
記実施例１と同様の結果が得られた。[Example 3] In Example 1, acrylic-NH having a molecular weight of about 10,000 (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the water-soluble polymer dispersant.
-134), acrylic-H with a molecular weight of approximately 10,000
(D-134A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) also used, the same results as in Example 1 were obtained.
〔実施例４〕
前記実施例１において、水溶性高分子分散剤として、分
子量約１万のアクリル系−ＮＨ，（第一工業製薬社製Ｄ
−１３４）の代わりに、無水マレイン酸系（第一工業製
薬社製Ｄ−１１４）を用いた場合も、前記実施例１と同
様の結果が得られた。[Example 4] In Example 1, acrylic-NH having a molecular weight of about 10,000 (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the water-soluble polymer dispersant.
The same results as in Example 1 were obtained when maleic anhydride (D-114 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used instead of -134).
〔実施例５〕
反応温度を５０℃以下に保つために冷却槽付きの３００
ｉのステンレス製タンクに１５０１！、のイオン交換水
を注入し、攪拌ｍ（佐竹化学機械工業社製Ａ５１０）に
て攪拌しながら、以下の操作を行った。[Example 5] In order to keep the reaction temperature below 50°C, a 300
1501 in i stainless steel tank! , and the following operations were performed while stirring with a stirring m (A510 manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.).
マス、２０ｋｇの水酸化カルシウム（日本石灰工業社製
ＣＨ−２Ｎ）を加えることにより、水酸化カルシウム懸
濁液を得た。この水酸化カルシウム懸濁液に８５％リン
酸（ラサ工業社製食品添加用）をｐＨ１０になるまで一
気に加えた。その後、水溶性高分子分散剤として、分子
量約１万のアクリル系−ＮＨ，（第一工業製薬社製Ｄ−
１３４）をその濃度が０．５％になるように加えること
により、数分間で市販の牛乳程度にさらさらした粘度の
スラリーが得られ、攪拌も容易であった。A calcium hydroxide suspension was obtained by adding mass and 20 kg of calcium hydroxide (CH-2N manufactured by Nippon Lime Industries Co., Ltd.). To this calcium hydroxide suspension, 85% phosphoric acid (manufactured by Rasa Kogyo Co., Ltd. for food addition) was added all at once until the pH reached 10. Thereafter, as a water-soluble polymer dispersant, acrylic-NH having a molecular weight of approximately 10,000, (D-Daiichi Kogyo Seiyaku Co., Ltd.)
By adding 134) to a concentration of 0.5%, a slurry with a viscosity comparable to that of commercially available milk was obtained in a few minutes and was easily stirred.
これは、反応温度を５０″Ｃ以下に保ったために、上記
分散剤の重合があまり進まなかったためと考えられる。This is considered to be because the polymerization of the dispersant did not proceed much because the reaction temperature was kept below 50''C.
上記スラリーを凍結乾燥機（セントラル科学貿易社製Ｆ
Ｄ−２０−５５−ＭＰ）にて乾燥させることにより粉末
状の試料が得られた。粉末Ｘ線回折法により生成物の同
定を行った結果、この試料は水酸アパタイトの単一相か
らなることが分かった。また、走査電子顕微鏡写真によ
り粒子径を調べた結果、粒径が０．１μｍ以下の球状微
粒子からなることが分かった。The above slurry was dried using a freeze dryer (F manufactured by Central Kagaku Trading Co., Ltd.).
A powdered sample was obtained by drying with D-20-55-MP). The product was identified by powder X-ray diffraction, and it was found that this sample consisted of a single phase of hydroxyapatite. Further, as a result of examining the particle size using scanning electron micrographs, it was found that the particles were composed of spherical fine particles with a particle size of 0.1 μm or less.
なお、反応温度が低すぎると、水酸アパタイトの反応速
度が小さくなり過ぎ、合成に時間を要することになるの
で、５℃以上に反応温度を保つことが望ましい。Note that if the reaction temperature is too low, the reaction rate of hydroxyapatite will be too low and the synthesis will take time, so it is desirable to keep the reaction temperature at 5° C. or higher.
〔比較例］
２００１のステンレス製タンクに１５０１のイオン交換
水を注入し、攪拌機（佐竹化学機械工業社製Ａ５１０）
にて攪拌しながら、以下の操作を行った。[Comparative example] 1501 ion-exchanged water was poured into a 2001 stainless steel tank, and a stirrer (A510 manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.) was used.
The following operations were performed while stirring.
まず、２０ｋｇの水酸化カルシウム（日本石灰工業社製
ＣＭ−２Ｎ）を加えることにより、水酸化カルシウム懸
濁液を得た。この水酸化カルシウム懸濁液に８５％リン
酸（ラサ工業社製食品添加用）をＰＨＩＯになるまで一
気に加えたが、その途端、かなりの発熱が起こると共に
、粘度が上昇して上記攪拌機による攪拌が不能になった
。First, a calcium hydroxide suspension was obtained by adding 20 kg of calcium hydroxide (CM-2N manufactured by Nippon Lime Industries Co., Ltd.). 85% phosphoric acid (manufactured by Rasa Kogyo Co., Ltd. for food additive use) was added to this calcium hydroxide suspension all at once until it reached PHIO. Stirring became impossible.
上記スラリーを凍結乾燥機（セントラル科学貿易社製Ｆ
Ｄ−２０−５５−ＭＰ）にて乾燥させることにより粉末
状の試料が得られた。粉末Ｘ線回折法により生成物の同
定を行った結果、この試料は水酸アパタイトの単一相か
らなるのではなく、水酸アパタイト、β−リン酸三カル
シウム〔Ｃａ３（ＰＯ４）Ｚ ）及び未反応の水酸化カ
ルシウムの混合相からなることが分かった。The above slurry was dried using a freeze dryer (F manufactured by Central Kagaku Trading Co., Ltd.).
A powdered sample was obtained by drying with D-20-55-MP). As a result of product identification using powder X-ray diffraction, it was found that this sample did not consist of a single phase of hydroxyapatite, but instead consisted of hydroxyapatite, β-tricalcium phosphate [Ca3(PO4)Z] and The reaction was found to consist of a mixed phase of calcium hydroxide.
以上の実施例１〜５では、水溶性高分子分散剤としてア
クリル系の分散剤を挙げたが、水酸化カルシウム粒子表
面に存在して、水酸化カルシウムとリン酸との過度の反
応を抑制すると共に、水酸化カルシウムとリン酸との反
応で生成した水酸アパタイト粒子を水酸化カルシウム粒
子表面から分散させる働きをし、かつ、生成した水酸ア
パタイトを溶解しないものであれば、いかなる水溶性高
分子分散剤であってもよく、ポリアクリル酸塩以外にも
例えば、ニトロフミン酸塩、リグニンスルフォン酸塩、
スチレン−無水マレイン酸共重合体等の分散剤が用いら
れる。In Examples 1 to 5 above, acrylic dispersants were used as water-soluble polymer dispersants, but they exist on the surface of calcium hydroxide particles to suppress excessive reaction between calcium hydroxide and phosphoric acid. In addition, any highly water-soluble material can be used as long as it works to disperse the hydroxyapatite particles produced by the reaction between calcium hydroxide and phosphoric acid from the surface of the calcium hydroxide particles and does not dissolve the hydroxyapatite produced. It may be a molecular dispersant, and in addition to polyacrylates, for example, nitrofumates, lignin sulfonates,
A dispersant such as a styrene-maleic anhydride copolymer is used.
このような水溶性高分子分散剤の存在下では、水酸化カ
ルシウム懸濁液に高濃度のリン酸を一気に加えても水酸
化カルシウムとリン酸との反応による発熱がある程度抑
えられ、しかも、生成した水酸アパタイト粒子により水
酸化カルシウム粒子表面が覆われて反応が妨げられるこ
とが少なくなるため、本実施例のように水酸アパタイト
の生成反応が速やかに進行すると考えられる。In the presence of such a water-soluble polymer dispersant, even if high-concentration phosphoric acid is added all at once to a calcium hydroxide suspension, the heat generated by the reaction between calcium hydroxide and phosphoric acid can be suppressed to some extent, and the generation of Since the surface of the calcium hydroxide particles is covered by the hydroxyapatite particles and the reaction is less likely to be hindered, it is thought that the hydroxyapatite production reaction proceeds quickly as in this example.
請求項第１項の発明に係る水酸アパタイトの湿式合成法
は、以上のように、撹拌下、水酸化カルシウム懸濁液に
水酸アパタイトを分散させる水溶性高分子分散剤を加え
た後、リン酸水溶液をｐＨ９〜１１になるまで加えるの
で、水酸化カルシウムとリン酸との反応により生成した
水酸アパタイト粒子によって水酸化力ルンウム粒子表面
が覆われて反応が妨げられることが少なくなる。これに
より、水酸アパタイトの生成反応が速やかに進行するの
で、短時間で大量の水酸アパタイトを合成できるという
効果を奏する。The wet synthesis method of hydroxyapatite according to the invention of claim 1 is as described above, after adding a water-soluble polymer dispersant for dispersing hydroxyapatite to a calcium hydroxide suspension under stirring. Since the phosphoric acid aqueous solution is added until the pH reaches 9 to 11, the surface of the hydroxyapatite particles generated by the reaction between calcium hydroxide and phosphoric acid is less likely to cover the surface of the hydroxide particles and hinder the reaction. This allows the hydroxyapatite production reaction to proceed rapidly, resulting in the effect that a large amount of hydroxyapatite can be synthesized in a short period of time.
請求項第２項の発明に係る水酸アパタイトの湿式合成法
は、以上のように、撹拌下、反応温度を５〜５０℃に保
ちながら、水酸化カルシウム懸濁液に水酸アパタイトを
分散させる水溶性高分子分散剤を加えた後、リン酸水溶
液をｐＨ９〜１１になるまで加えるので、水酸化カルシ
ウムとリン酸との反応により生成した水酸アパタイト粒
子によって水酸化カルシウム粒子表面が覆われて反応が
妨げられることが少なくなる。これにより、水酸アパタ
イトの生成反応が速やかに進行するので、短時間で大量
の水酸アパタイトを合成できるという効果を奏する。し
かも、反応温度を５〜５０℃に保っているので、水溶性
高分子分散剤の重合反応が起こりにくくなり、粘度の低
いスラリーが得られる。このため、攪拌が容易になると
いう効果も併せて奏する。As described above, the wet synthesis method for hydroxyapatite according to the invention of claim 2 involves dispersing hydroxyapatite in a calcium hydroxide suspension while stirring and maintaining the reaction temperature at 5 to 50°C. After adding the water-soluble polymer dispersant, an aqueous phosphoric acid solution is added until the pH reaches 9 to 11, so the surface of the calcium hydroxide particles is covered with hydroxyapatite particles generated by the reaction between calcium hydroxide and phosphoric acid. The reaction is less likely to be disturbed. As a result, the hydroxyapatite production reaction proceeds rapidly, resulting in the effect that a large amount of hydroxyapatite can be synthesized in a short period of time. Furthermore, since the reaction temperature is maintained at 5 to 50°C, the polymerization reaction of the water-soluble polymer dispersant is less likely to occur, and a slurry with low viscosity can be obtained. Therefore, it also has the effect of making stirring easier.
Claims (1)
を分散させる水溶性高分子分散剤を加えた後、リン酸水
溶液をｐＨ９〜１１になるまで加えることを特徴とする
水酸アパタイトの湿式合成法。 ２、撹拌下、反応温度を５〜５０℃に保ちながら、水酸
化カルシウム懸濁液にリン酸水溶液をｐＨ９〜１１にな
るまで加えた後、水酸アパタイトを分散させる水溶性高
分子分散剤を加えることを特徴とする水酸アパタイトの
湿式合成法。[Claims] 1. A water-soluble polymer dispersant for dispersing hydroxyapatite is added to a calcium hydroxide suspension under stirring, and then an aqueous phosphoric acid solution is added until the pH becomes 9 to 11. Wet synthesis method of hydroxyapatite. 2. While stirring and keeping the reaction temperature at 5 to 50°C, add an aqueous phosphoric acid solution to the calcium hydroxide suspension until the pH becomes 9 to 11, then add a water-soluble polymer dispersant to disperse the hydroxyapatite. A wet synthesis method of hydroxyapatite characterized by the addition of hydroxyapatite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30547990A JPH0825730B2 (en) | 1990-11-09 | 1990-11-09 | Wet synthesis of hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30547990A JPH0825730B2 (en) | 1990-11-09 | 1990-11-09 | Wet synthesis of hydroxyapatite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04175212A true JPH04175212A (en) | 1992-06-23 |
| JPH0825730B2 JPH0825730B2 (en) | 1996-03-13 |
Family
ID=17945655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30547990A Expired - Fee Related JPH0825730B2 (en) | 1990-11-09 | 1990-11-09 | Wet synthesis of hydroxyapatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825730B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263415A (en) * | 1993-03-11 | 1994-09-20 | Taihei Kagaku Sangyo Kk | Production of spherical hydroxyapatite particle aggregate |
| USRE39196E1 (en) | 1997-01-16 | 2006-07-18 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| EP1132431A4 (en) * | 1998-11-13 | 2007-05-02 | Mitsui Chemicals Inc | Organic polymer/fine inorganic particle aqueous dispersion with excellent dispersion stability and use thereof |
-
1990
- 1990-11-09 JP JP30547990A patent/JPH0825730B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263415A (en) * | 1993-03-11 | 1994-09-20 | Taihei Kagaku Sangyo Kk | Production of spherical hydroxyapatite particle aggregate |
| USRE39196E1 (en) | 1997-01-16 | 2006-07-18 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| USRE41584E1 (en) | 1997-01-16 | 2010-08-24 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| USRE43661E1 (en) | 1997-01-16 | 2012-09-18 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| USRE44820E1 (en) | 1997-01-16 | 2014-04-01 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and methods of their production |
| USRE46275E1 (en) | 1997-01-16 | 2017-01-17 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| EP1132431A4 (en) * | 1998-11-13 | 2007-05-02 | Mitsui Chemicals Inc | Organic polymer/fine inorganic particle aqueous dispersion with excellent dispersion stability and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0825730B2 (en) | 1996-03-13 |
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