JPH0940408A - Production of hydroxyapatite platelike large-sized crystal - Google Patents
Production of hydroxyapatite platelike large-sized crystalInfo
- Publication number
- JPH0940408A JPH0940408A JP7192209A JP19220995A JPH0940408A JP H0940408 A JPH0940408 A JP H0940408A JP 7192209 A JP7192209 A JP 7192209A JP 19220995 A JP19220995 A JP 19220995A JP H0940408 A JPH0940408 A JP H0940408A
- Authority
- JP
- Japan
- Prior art keywords
- temp
- hydroxyapatite
- powder
- crystal
- platelike
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 24
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 12
- 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 12
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 6
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 abstract 4
- 235000019700 dicalcium phosphate Nutrition 0.000 abstract 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 3
- 235000010216 calcium carbonate Nutrition 0.000 abstract 3
- 239000000725 suspension Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000606 toothpaste Substances 0.000 description 4
- 229940034610 toothpaste Drugs 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- -1 humidity sensors Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Cosmetics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、人工骨や人工歯等
の素材として用いることのできる板状ヒドロキシアパタ
イトの大型結晶を製造する為の有用な方法に関するもの
である。また本発明によって得られる板状ヒドロキシア
パタイト大型結晶は、クロマトグラフィー用カラム充填
材、歯磨用基材、化粧品用原料等として有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a useful method for producing large crystals of plate-like hydroxyapatite that can be used as a material for artificial bones, artificial teeth and the like. Further, the large plate-shaped hydroxyapatite crystals obtained by the present invention are useful as a column packing material for chromatography, a base material for toothpaste, a raw material for cosmetics and the like.
【０００２】[0002]
【従来の技術】ＣａＯ−Ｐ2 Ｏ5 系アパタイトは主とし
て生体材料として開発されており、中でもヒドロキシア
パタイト［Ｃａ10（ＰＯ4 ）6 （ＯＨ2 ）2 、以下「Ｈ
ＡＰ」と略記することがある］は、人間の骨や歯の主要
構成物質であり、生体内に埋入された場合に生体との親
和性が良く、自然骨との化学結合性も極めて良好である
ので、人工骨や人工歯等の素材として用いられている。
また蛋白質との親和性が良好であることを利用してクロ
マトグラフィー用のカラム充填材としても用いられてい
る。その他、ＨＡＰは、肥料、湿度センサー、歯磨用基
材、化粧品用原料等、様々な分野で利用されている。 2. Description of the Related Art CaO-P 2 O 5 -based apatite has been mainly developed as a biomaterial. Among them, hydroxyapatite [Ca 10 (PO 4 ) 6 (OH 2 ) 2 , hereinafter referred to as "H
It may be abbreviated as "AP"], which is a major constituent of human bones and teeth, has a good affinity with the living body when implanted in the living body, and has an extremely good chemical bondability with natural bone. Therefore, it is used as a material for artificial bones and artificial teeth.
It is also used as a column packing material for chromatography due to its good affinity with proteins. In addition, HAP is used in various fields such as fertilizers, humidity sensors, base materials for toothpaste, and raw materials for cosmetics.
【０００３】ＣａＯ−Ｐ2 Ｏ5 系アパタイトを製造する
方法としては、例えば特開昭５３−８１４９９号、同５
３−１１０９９９号、同５３−１１１０００号等の技術
が提案されている。しかしながら、これらの方法では、
反応温度：１００〜５００℃、圧力：１〜５００気圧と
いう過酷な反応条件を必要とし、しかも特別の装置を必
要とするという欠点がある。こうした欠点を解消した方
法として、例えば特開昭６１−１５１０１１号や同６３
−１５９２０７号等には、比較的穏やかな条件で且つ特
別の装置を必要としないＨＡＰの製造方法が提案されて
いる。A method for producing CaO-P 2 O 5 -based apatite is disclosed in, for example, JP-A-53-81499 and JP-A-5-81499.
Technologies such as 3-110999 and 53-111000 have been proposed. However, with these methods,
It has a drawback that it requires harsh reaction conditions of a reaction temperature of 100 to 500 ° C. and a pressure of 1 to 500 atm and requires a special device. As a method for solving such a defect, for example, JP-A-61-151011 and JP-A-63-151011.
No. 159207 or the like proposes a method for producing HAP under relatively mild conditions and requiring no special equipment.
【０００４】[0004]
【発明が解決しようとする課題】ところで、ＨＡＰで
は、例えば化粧品用としては被覆力を向上させること、
歯磨用としては適度な研磨力を得ること、更にはクロマ
トグラフィー用としては、充填性に優れたものとする等
の観点から、板状で比較的大型の粒子を得ることが望ま
れているが、これまで提案された上記各種の技術では、
その様な希望形状のＨＡＰは得られていない。例えば上
記特開昭６１−１５１０１１号には、「ＣａＨＰＯ4 と
水のスラリーにＣａＣＯ3 ：２〜２５ｍｏｌ％含有する
Ｃａ（ＯＨ） 2 とＣａＣＯ3 との混合物をｐＨ１０以下
に保ちながら徐々に加え６０〜１００℃にて反応を行う
方法」について開示されているが、板状のＨＡＰの製造
を意図したものではなく、また基本的にＣａＨＰＯ4 を
原料としているので、後述する様にこの原料からは板状
のＨＡＰを製造することはできない。[Problems to be Solved by the Invention] By the way, with HAP
Is to improve the covering power for cosmetics, for example.
As a toothpaste, it must have an adequate polishing power,
For tography use, it should have excellent filling properties, etc.
From the viewpoint of, it is desirable to obtain plate-like and relatively large particles.
However, in the above various technologies proposed so far,
No HAP having such a desired shape has been obtained. For example above
JP-A-61-151011 describes "CaHPO.Four When
CaCO in water slurryThree : Contains 2 to 25 mol%
Ca (OH) 2 And CaCOThree PH of the mixture with 10 or less
Add gradually while maintaining the temperature at 60 to 100 ℃
Method ", but manufacture of plate-shaped HAP
Is not intended, and basically CaHPOFour To
Since it is used as a raw material, it will be plate-shaped from this raw material as described later.
HAP cannot be manufactured.
【０００５】一方、特開昭６３−１５９２０７号には、
「ＣａＣＯ3 粉末とＣａＨＰＯ4 またはその二水和物の
粉末を、Ｃａ原子のリン原子に対する原子比が１．５〜
１．６７の範囲になる様な割合で水性スラリーを調製
し、次いでこのスラリーを湿式粉砕機により摩砕混合し
ながら反応する方法」について開示されている。しかし
ながら、この方法においても、その製造工程で湿式粉砕
機を用いるものであるので、製造上から板状ＨＡＰの大
型結晶を得ることはできず、一次粒子が１μｍ以下の微
細粒子のＨＡＰしか得られていない。On the other hand, in Japanese Patent Laid-Open No. 63-159207,
“The CaCO 3 powder and CaHPO 4 or its dihydrate powder were used, and the atomic ratio of Ca atoms to phosphorus atoms was 1.5 to
A method of preparing an aqueous slurry in a ratio so as to be in the range of 1.67 and then reacting the slurry while milling and mixing with a wet mill is disclosed. However, even in this method, since a wet pulverizer is used in the manufacturing process, it is not possible to obtain a plate-like HAP large crystal from the viewpoint of manufacturing, and only primary particles of HAP having a fine particle size of 1 μm or less are obtained. Not not.
【０００６】本発明はこうした状況の下になされたもの
であって、その目的は、比較的穏やかな反応条件でしか
も特別の装置を必要とせず、板状ＨＡＰの大型結晶を製
造する為の方法を提供することにある。The present invention has been made under these circumstances, and an object thereof is a method for producing large crystals of plate-like HAP under relatively mild reaction conditions and without requiring special equipment. To provide.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成し得た本
発明とは、板状の結晶形態を有するＣａＨＰＯ4 ・２Ｈ
2 Ｏ粉末と、平均粒径：５μｍ以下のＣａＣＯ3 微粒子
粉末を、水懸濁状態で４０〜７０℃に加温・保持する点
に要旨を有する板状ＨＡＰ大型結晶の製造方法である。Means for Solving the Problems The present invention capable of achieving the above-mentioned object means that CaHPO 4 .2H having a plate-like crystal morphology.
2 O powder and CaCO 3 fine particle powder having an average particle size of 5 μm or less are heated and held at 40 to 70 ° C. in a water suspension state, which is a method for producing a plate-shaped HAP large crystal.
【０００８】[0008]
【発明の実施の形態】本発明者らは、上記目的を達成す
るべく様々な角度から検討した。そしてまず、原料とし
て用いられるＣａＨＰＯ4 ・２Ｈ2 Ｏ粉末が板状の大型
粒子（平均粒径５〜３０μｍ程度）として製造されるこ
とに着目し、この結晶形態を維持する様に反応させれ
ば、希望する形状のＨＡＰが得られるのではないかと考
えた。そして更に検討を重ねたところ、上記の様なＣａ
ＨＰＯ4 ・２Ｈ2 Ｏ粉末と、平均粒径を厳密に規定した
ＣａＣＯ3 粉末を水に懸濁させて水懸濁液とし、この水
懸濁液を所定の温度に保持して穏やかに反応させれば、
上記目的が見事に達成されることを見出し、本発明を完
成した。尚本発明において「板状」とは、外観の全体形
状の如何にかかわらず、平たいものであれば良く、例え
ば後記図２に示される形状も含むものである。また「大
型結晶」とは、平均粒径が５〜３０μｍ程度であること
を意味する。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have studied from various angles in order to achieve the above object. And first, paying attention to the fact that CaHPO 4 .2H 2 O powder used as a raw material is produced as plate-like large particles (average particle diameter of about 5 to 30 μm), and reacting so as to maintain this crystal form. I thought that the desired shape of HAP could be obtained. After further study, the above Ca
The HPO 4 .2H 2 O powder and the CaCO 3 powder whose average particle size is strictly defined are suspended in water to form an aqueous suspension, and this aqueous suspension is kept at a predetermined temperature and gently reacted. If
The present invention has been completed by finding that the above objects can be achieved brilliantly. In the present invention, the “plate shape” may be flat regardless of the overall appearance, and includes, for example, the shape shown in FIG. 2 described later. The term “large crystal” means that the average particle size is about 5 to 30 μm.
【０００９】本発明では板状の結晶形態を有するＣａＨ
ＰＯ4 ・２Ｈ2 Ｏ粉末を原料の一つとして用いる必要が
あるが、これは上記趣旨から明らかな様に、該粉末が有
している上記板状形態をＨＡＰの形態として残すためで
ある。こうした観点からして、無水物のＣａＨＰＯ4 粉
末は本発明の原料として使用できない。即ち、ＣａＨＰ
Ｏ4 粉末は、微細粉末として製造されるので、この様な
粉末を原料として用いて本発明の工程で反応させても、
原料粉末の結晶形態をＨＡＰの結晶形態に反映させるこ
とができず、希望する形状のＨＡＰは得られない。In the present invention, CaH having a plate-like crystal morphology
It is necessary to use the PO 4 .2H 2 O powder as one of the raw materials, and this is because the plate-like morphology of the powder remains as the HAP morphology, as is clear from the above-mentioned purpose. From this point of view, anhydrous CaHPO 4 powder cannot be used as a raw material of the present invention. That is, CaHP
Since the O 4 powder is produced as a fine powder, even if such a powder is used as a raw material and reacted in the process of the present invention,
The crystal form of the raw material powder cannot be reflected in the crystal form of HAP, and HAP having a desired shape cannot be obtained.
【００１０】本発明で用いるもう一方の原料のＣａＣＯ
3 は、その平均粒径が５μｍ以下の微粒子のものを用い
る必要がある。これはＣａＣＯ3 の平均粒径が５μｍを
超えると、本発明で規定する反応条件（４０〜７０℃）
において反応が進まず、生成物中に未反応のＣａＨＰＯ
4 ・２Ｈ2 Ｏ粉末やＣａＣＯ3 粉末が残留する。Another raw material used in the present invention, CaCO
For 3, it is necessary to use fine particles having an average particle diameter of 5 μm or less. This is because when the average particle size of CaCO 3 exceeds 5 μm, the reaction conditions specified in the present invention (40 to 70 ° C.)
Reaction does not proceed, and unreacted CaHPO in the product
4 · 2H 2 O powder and CaCO 3 powder remains.
【００１１】上記の様なＣａＨＰＯ4 ・２Ｈ2 Ｏ粉末と
ＣａＣＯ3 粉末は、水懸濁状態とされるが、このときの
両粉末の混合比率は従来技術にも示された様に（例え
ば、特開昭６３−１５９２０７号）、Ｃａ原子のリン原
子に対する原子比が１．５〜１．６７の範囲になる様な
割合とするのが適当である。The CaHPO 4 .2H 2 O powder and the CaCO 3 powder as described above are suspended in water, and the mixing ratio of both powders at this time is as shown in the prior art (for example, JP-A-63-159207), it is suitable to set the atomic ratio of Ca atoms to phosphorus atoms to be in the range of 1.5 to 1.67.
【００１２】水懸濁状態で加温・保持するときの温度
は、４０〜７０℃とする必要がある。この温度が４０℃
未満では反応速度が遅くなって、１０時間以上反応させ
ても生成物中に未反応のＣａＨＰＯ4 ・２Ｈ2 Ｏ粉末や
ＣａＣＯ3 粉末が残留する。It is necessary that the temperature for heating / holding in a water suspension state is 40 to 70 ° C. This temperature is 40 ℃
If it is less than this, the reaction rate becomes slow, and unreacted CaHPO 4 .2H 2 O powder or CaCO 3 powder remains in the product even after reacting for 10 hours or more.
【００１３】一方、７０℃を超える様な温度では、Ｃａ
ＨＰＯ4 ・２Ｈ2 Ｏに含まれる結晶水の脱離による結晶
崩壊が発生し、生成するＨＡＰは微細結晶になってしま
う。尚、加温・保持温度の好ましい範囲は５０〜６０℃
程度である。また加温・保持時間については特に限定さ
れるものではないが、上記の条件下では４〜６時間程度
で反応がほぼ終了する。On the other hand, when the temperature exceeds 70 ° C., Ca
Crystallization collapse occurs due to desorption of the water of crystallization contained in HPO 4 .2H 2 O, and the HAP produced becomes fine crystals. The preferred range of heating / holding temperature is 50-60 ° C.
It is a degree. The heating / holding time is not particularly limited, but under the above conditions, the reaction is almost completed in about 4 to 6 hours.
【００１４】本発明で規定する上記要件をいずれも満足
させることによって、下記（１）式に従って希望する形
態のＨＡＰが製造される。 ６ＣａＨＰＯ4 ・２Ｈ2 Ｏ＋４ＣａＣＯ3 →Ｃａ10（ＰＯ4 ）6 （ＯＨ）2 ＋１４Ｈ2 Ｏ＋４ＣＯ2 ↑ …（１）By satisfying all of the above requirements defined in the present invention, the desired form of HAP can be manufactured according to the following formula (1). 6CaHPO 4・ 2H 2 O + 4CaCO 3 → Ca 10 (PO 4 ) 6 (OH) 2 + 14H 2 O + 4CO 2 ↑ (1)
【００１５】以下本発明を実施例によって更に詳細に説
明するが、下記実施例は本発明を限定する性質のもので
はなく、前・後記の趣旨に徴して設計変更することはい
ずれも本発明の技術的範囲に含まれるものである。The present invention will be described in more detail with reference to the following examples, but the following examples are not intended to limit the present invention, and any modification of the design of the present invention can be made without departing from the spirit of the preceding and the following. It is included in the technical scope.
【００１６】[0016]
実施例１ ５リットルビーカーにイオン交換水３０００ｇを入れ、
デジタルミキサーで撹拌しつつ、ＣａＨＰＯ4 ・２Ｈ2
Ｏ粉末（太平化学産業株式会社製）２５８ｇと、平均粒
径：４μｍのＣａＣＯ3 粉末（カルシード株式会社製、
超高純度品）１００ｇを加えて水懸濁状態とした後、加
温して液温を６０℃に保ち、撹拌下に５時間反応させ
た。ヌッチェで反応沈殿物を濾別した後、１５０℃で３
時間乾燥し、反応生成物を２４８ｇ得た。Example 1 3000 g of ion-exchanged water was placed in a 5 liter beaker,
CaHPO 4・ 2H 2 while stirring with a digital mixer
258 g of O powder (manufactured by Taihei Chemical Industry Co., Ltd.) and CaCO 3 powder having an average particle diameter of 4 μm (manufactured by Calceed Co., Ltd.,
Ultrapure product) (100 g) was added to make a water suspension, and the mixture was heated to maintain the liquid temperature at 60 ° C. and reacted for 5 hours under stirring. After filtering off the reaction precipitate with a Nutsche,
After drying for an hour, 248 g of a reaction product was obtained.
【００１７】比較例１ ５リットルビーカーにイオン交換水３０００ｇを入れ、
デジタルミキサーで撹拌しつつ、ＣａＨＰＯ4 ・２Ｈ2
Ｏ粉末（太平化学産業株式会社製）２５８ｇと、平均粒
径：１４μｍのＣａＣＯ3 粉末（和光純薬工業株式会社
製、試薬特級）１００ｇを加えて水懸濁状態とした後、
加温して液温を６０℃に保ち、撹拌下に５時間反応させ
た。ヌッチェで反応沈殿物を濾別した後、１５０℃で３
時間乾燥し、反応生成物を２４５ｇ得た。Comparative Example 1 3000 g of ion-exchanged water was placed in a 5 liter beaker,
CaHPO 4・ 2H 2 while stirring with a digital mixer
After adding 258 g of O powder (manufactured by Taihei Chemical Industry Co., Ltd.) and 100 g of CaCO 3 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) having an average particle size of 14 μm, a water suspension state was obtained.
The mixture was heated to maintain the liquid temperature at 60 ° C. and reacted for 5 hours under stirring. After filtering off the reaction precipitate with a Nutsche,
After drying for an hour, 245 g of a reaction product was obtained.
【００１８】比較例２ 実施例１と同様にして、ＣａＨＰＯ4 ・２Ｈ2 Ｏ粉末と
ＣａＣＯ3 粉末を水懸濁状態とした後、加温して液温を
８０℃に保ち、撹拌下に５時間反応させた。ヌッチェで
反応沈殿物を濾別した後、１５０℃で３時間乾燥し、反
応生成物を２４７ｇ得た。Comparative Example 2 In the same manner as in Example 1, CaHPO 4 .2H 2 O powder and CaCO 3 powder were suspended in water and heated to maintain the liquid temperature at 80 ° C. Reacted for hours. The reaction precipitate was filtered off with a Nutsche and dried at 150 ° C. for 3 hours to obtain 247 g of a reaction product.
【００１９】比較例３ 実施例１と同様にして、ＣａＨＰＯ4 ・２Ｈ2 Ｏ粉末と
ＣａＣＯ3 粉末を水懸濁状態とした後、加温して液温を
３０℃に保ち、撹拌下に１０時間反応させた。ヌッチェ
で反応沈殿物を濾別した後、１５０℃で３時間乾燥し、
反応生成物を２４７ｇ得た。Comparative Example 3 In the same manner as in Example 1, CaHPO 4 .2H 2 O powder and CaCO 3 powder were made into a water suspension state and then heated to maintain the liquid temperature at 30 ° C. and stirred for 10 hours. Reacted for hours. After filtering off the reaction precipitate with a Nutsche, it was dried at 150 ° C. for 3 hours,
247 g of a reaction product was obtained.
【００２０】上記実施例１および比較例１〜３で得られ
た反応生成物について、Ｘ線回折装置（商品名「ＲＡＤ
−１Ａ」、理学電機株式会社製）を用いて同定すると共
に、レーザ回折式粒度分布測定器（商品名「ＳＡＬＤ−
１１００」、株式会社島津製作所製）を用いて平均粒径
を測定した。Regarding the reaction products obtained in Example 1 and Comparative Examples 1 to 3, an X-ray diffractometer (trade name "RAD
-1A "manufactured by Rigaku Denki Co., Ltd., and a laser diffraction particle size distribution analyzer (trade name" SALD- ").
1100 ", manufactured by Shimadzu Corporation) was used to measure the average particle size.
【００２１】その結果を、反応条件と共に、下記表１に
示す。尚表１において、「ａｍ−ＨＡＰ」は低結晶性ヒ
ドロキシアパタイトであることを示している。またＸ線
回折結果を図１に示す。The results are shown in Table 1 below together with the reaction conditions. In Table 1, "am-HAP" indicates low crystalline hydroxyapatite. The X-ray diffraction results are shown in FIG.
【００２２】[0022]
【表１】 [Table 1]
【００２３】これらの結果から明らかな様に、本発明で
規定する要件を満足する実施例１のものは、ＣａＣＯ3
が残留することなく大型結晶のＨＡＰが生成しているこ
とが分かる。また、実施例１および比較例２で得られた
反応生成物について、走査型電子顕微鏡（商品名「Ｓ−
２３００」、株式会社日立製作所製）によって、その結
晶の粒子構造を観察した。その結果を、夫々図２および
図３に示すが、実施例１で得られた反応生成物（図２）
は、板状で大型の粒子構造を有しているが、比較例２で
得られた反応生成物（図３）は微細な針状結晶のもので
あった。As is clear from these results, in Example 1 satisfying the requirements specified in the present invention, CaCO 3
It can be seen that large-scale HAP is generated without remaining. Further, with respect to the reaction products obtained in Example 1 and Comparative Example 2, a scanning electron microscope (trade name "S-
2300 ", manufactured by Hitachi, Ltd.), and the grain structure of the crystal was observed. The results are shown in FIG. 2 and FIG. 3, respectively. The reaction product obtained in Example 1 (FIG. 2)
Had a plate-like and large particle structure, but the reaction product obtained in Comparative Example 2 (FIG. 3) was fine needle-like crystals.
【００２４】[0024]
【発明の効果】本発明は以上の様に構成されており、板
状の大型結晶を有するヒドロキシアパタイトが、特別の
装置を必要とせず、しかも比較的穏やかな条件で製造す
ることができた。また本発明方法は、ヒドロキシアパタ
イトの大量生産も可能であり、板状の大型ヒドロキシア
パタイト結晶の工業的製法が確立できた。更に、本発明
によって得られるヒドロキシアパタイトは、人工骨、人
工歯根等の生体材料をはじめとして、液体クロマトグラ
フィー用カラム充填剤、肥料、湿度センサー、歯磨用基
材、化粧品原料として有用に利用できる。EFFECTS OF THE INVENTION The present invention is configured as described above, and hydroxyapatite having a plate-like large crystal can be produced under relatively mild conditions without requiring a special device. In addition, the method of the present invention enables mass production of hydroxyapatite, and an industrial production method of plate-like large hydroxyapatite crystals has been established. Further, the hydroxyapatite obtained by the present invention can be effectively used as a column packing material for liquid chromatography, a fertilizer, a humidity sensor, a toothpaste base material, and a cosmetic raw material, including biomaterials such as artificial bones and artificial tooth roots.
【図１】実施例１および比較例１〜３によって得られた
反応生成物におけるＸ線回折結果を示すチャートある。FIG. 1 is a chart showing the X-ray diffraction results of the reaction products obtained in Example 1 and Comparative Examples 1 to 3.
【図２】実施例１で得られた反応生成物の粒子構造を示
す図面代用顕微鏡写真である。2 is a drawing-substitute micrograph showing the particle structure of the reaction product obtained in Example 1. FIG.
【図３】比較例１で得られた反応生成物の粒子構造を示
す図面代用顕微鏡写真である。3 is a drawing-substitute micrograph showing the particle structure of the reaction product obtained in Comparative Example 1. FIG.
Claims (1)
２Ｈ2 Ｏ粉末と、平均粒径：５μｍ以下のＣａＣＯ3 微
粒子粉末を、水懸濁状態で４０〜７０℃に加温・保持す
ることを特徴とする板状ヒドロキシアパタイト大型結晶
の製造方法。1. CaHPO 4 · having a plate-like crystal morphology
A method for producing plate-like hydroxyapatite large crystals, which comprises heating 2H 2 O powder and CaCO 3 fine particle powder having an average particle size of 5 μm or less at 40 to 70 ° C. in a water suspension state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19220995A JP3641298B2 (en) | 1995-07-27 | 1995-07-27 | Method for producing plate-like hydroxyapatite large crystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19220995A JP3641298B2 (en) | 1995-07-27 | 1995-07-27 | Method for producing plate-like hydroxyapatite large crystals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0940408A true JPH0940408A (en) | 1997-02-10 |
| JP3641298B2 JP3641298B2 (en) | 2005-04-20 |
Family
ID=16287485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19220995A Expired - Fee Related JP3641298B2 (en) | 1995-07-27 | 1995-07-27 | Method for producing plate-like hydroxyapatite large crystals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3641298B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998029490A1 (en) * | 1996-12-27 | 1998-07-09 | Maruo Calcium Company Limited | Synthetic resin additive and synthetic resin composition |
| WO1999032401A1 (en) * | 1997-12-22 | 1999-07-01 | Abonetics Limited | Method for the preparation of carbonated hydroxyapatite compositions |
| WO1999058447A1 (en) * | 1998-05-08 | 1999-11-18 | Nof Corporation | Hydroxyapatite, composite, processes for producing these, and use of these |
| JP2004513973A (en) * | 2000-12-08 | 2004-05-13 | カールハヴエ ソシエテ アノニム | A delicate surface, especially an abrasive component for cleaning teeth |
| JP2005272439A (en) * | 2004-02-23 | 2005-10-06 | Kose Corp | Solid powdery cosmetic |
| FR2869893A1 (en) * | 2004-05-06 | 2005-11-11 | Rhodia Chimie Sa | NOVEL CALCIUM PHOSPHATE GRANULES OF THE HYDROXYAPATITE TYPE, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS |
| CN102167300A (en) * | 2011-03-10 | 2011-08-31 | 南京工业大学 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
| CN114684967A (en) * | 2022-04-06 | 2022-07-01 | 深圳大学 | Synergistic treatment method for calcareous solid waste and phosphorus-containing waste liquid and application of product thereof |
-
1995
- 1995-07-27 JP JP19220995A patent/JP3641298B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287530B1 (en) | 1996-12-27 | 2001-09-11 | Maruo Calcium Company Ltd. | Synthetic resin additive and synthetic resin composition containing particles of porous hydroxyapatite |
| WO1998029490A1 (en) * | 1996-12-27 | 1998-07-09 | Maruo Calcium Company Limited | Synthetic resin additive and synthetic resin composition |
| WO1999032401A1 (en) * | 1997-12-22 | 1999-07-01 | Abonetics Limited | Method for the preparation of carbonated hydroxyapatite compositions |
| US6582672B1 (en) | 1997-12-22 | 2003-06-24 | Apatech Limited | Method for the preparation of carbonated hydroxyapatite compositions |
| JP4254057B2 (en) * | 1998-05-08 | 2009-04-15 | 日油株式会社 | Method for producing hydroxyapatite and method for producing composite |
| WO1999058447A1 (en) * | 1998-05-08 | 1999-11-18 | Nof Corporation | Hydroxyapatite, composite, processes for producing these, and use of these |
| US6395037B1 (en) | 1998-05-08 | 2002-05-28 | Nof Corporation | Hydroxyapatite, composite, processes for producing these, and use of these |
| JP2004513973A (en) * | 2000-12-08 | 2004-05-13 | カールハヴエ ソシエテ アノニム | A delicate surface, especially an abrasive component for cleaning teeth |
| JP2005272439A (en) * | 2004-02-23 | 2005-10-06 | Kose Corp | Solid powdery cosmetic |
| FR2869893A1 (en) * | 2004-05-06 | 2005-11-11 | Rhodia Chimie Sa | NOVEL CALCIUM PHOSPHATE GRANULES OF THE HYDROXYAPATITE TYPE, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS |
| US7468172B2 (en) | 2004-05-06 | 2008-12-23 | Innophos, Inc. | Hydroxapatite calcium phosphates, their methods of preparation and their applications |
| US7767300B2 (en) | 2004-05-06 | 2010-08-03 | Innophos, Inc. | Hydroxyapatite calcium phosphates, their method of preparation and their applications |
| EP1753438A4 (en) * | 2004-05-06 | 2011-12-28 | Innophos Inc | NEW HYDROXYAPATITE-CALCIUM PHOSPHATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR APPLICATIONS |
| CN102167300A (en) * | 2011-03-10 | 2011-08-31 | 南京工业大学 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
| CN114684967A (en) * | 2022-04-06 | 2022-07-01 | 深圳大学 | Synergistic treatment method for calcareous solid waste and phosphorus-containing waste liquid and application of product thereof |
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