JPS59107912A - Manufacture of hydroxyapatite containing carbonate - Google Patents
Manufacture of hydroxyapatite containing carbonateInfo
- Publication number
- JPS59107912A JPS59107912A JP57217842A JP21784282A JPS59107912A JP S59107912 A JPS59107912 A JP S59107912A JP 57217842 A JP57217842 A JP 57217842A JP 21784282 A JP21784282 A JP 21784282A JP S59107912 A JPS59107912 A JP S59107912A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- calcium
- c0ap
- water
- 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
Landscapes
- Dental Preparations (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、炭酸含有ヒドロキシアパタイトの新しい製造
方法の発明である。DETAILED DESCRIPTION OF THE INVENTION The present invention is a new method for producing carbonic acid-containing hydroxyapatite.
一般に、アパタイトとは、一般式Ｍ２＋ 、ｏ＜ｚＯ−
）６百 で表わされる化合物を言い、この式でＭは、Ｃ
ａ％Ｐｂ％Ｂａ、 Ｓｒ、 Ｍｇ、 Ｎｉ％Ｎａ％に１
Ｆｅ１Ａｌその他金属原子を、
ｚＯ４は、ＰＯ４、Ａ３０４ ％ ＶＯ４、Ｓ０４．５
ｉ０４、Ｃ０３その他の酸根を、
Ｙは、Ｆ、 ＯＨ，ＣＩ、 Ｂｒ、 ＝Ｏ１＝ＣＯ３そ
の他の陰イオン性原子（団）を示す広範囲な化合物群の
総称である。Generally, apatite has the general formula M2+, o<zO-
)600 In this formula, M is C
a%Pb%Ba, Sr, Mg, Ni%Na%1
Fe1Al and other metal atoms, zO4 is PO4, A304% VO4, S04.5
i04, C03 and other acid radicals; Y is a general term for a wide range of compounds representing F, OH, CI, Br, =O1=CO3 and other anionic atoms (groups);
本発明においては、上記一般式においてＭが実質的にＣ
ａであ’）、ｚＯ４が実質的にＰＯ４であシＹが実質的
にＯＨである化合物をヒドロキシアパタイトと呼ぶ。そ
して、ここでｚＯ４又は／及びＹの一部が−ＣＯ３で置
換されたものを炭酸含有ヒドロキシアパタイトと呼ぶ。In the present invention, M in the above general formula is substantially C
a'), a compound in which zO4 is substantially PO4 and Y is substantially OH is called hydroxyapatite. Here, the material in which zO4 and/or Y is partially substituted with -CO3 is called carbonate-containing hydroxyapatite.
ヒドロキシアパタイト（以下ＨＡｐと略記する。）は、
天然歯Ｙ天然骨と同じ化学組成を持つ無機化合物である
所から、バイオセラミックスの原料として注目され、人
工歯や人工骨等への適用が検討されている。Hydroxyapatite (hereinafter abbreviated as HAp) is
Natural teeth Y: Because it is an inorganic compound with the same chemical composition as natural bone, it has attracted attention as a raw material for bioceramics, and its application to artificial teeth and bones is being considered.
ヤ
他方、天然歯／天然骨は、ＨＡｐが約７０％、コラーゲ
ンなどの有機物が約３０％よりなる複合体機を含有して
いるという事実である。ＨＡｐを合成するにあたｐ、Ｈ
Ａｐに数パーセントの炭酸根を含有させ、バイオセラミ
ックスの原料として炭酸根を含有するＨＡｐ （以下炭
酸根を含有するＨＡｐをＣ０Ａｐと略記する）の使用が
注目されている。すＮ′
なわち天然歯ノ天然骨と化学組成が近いＣ０Ａｐをイン
ブラント材として使用すると、生体に対する親和性が増
し、天然歯Ｘ天然骨への順化スピードが早くなり、拒絶
反応を減らすなどの多くの利点が予想される。On the other hand, it is a fact that natural teeth/natural bones contain a composite material consisting of about 70% HAp and about 30% organic matter such as collagen. When synthesizing HAp, p, H
Ap contains several percent of carbonate radicals, and the use of HAp containing carbonate radicals (hereinafter HAp containing carbonate radicals will be abbreviated as C0Ap) is attracting attention as a raw material for bioceramics. In other words, when C0Ap, which has a chemical composition similar to that of natural teeth and natural bone, is used as an implant material, it increases its affinity for living organisms, accelerates the acclimatization speed to natural teeth and natural bone, and reduces rejection reactions. Many benefits are expected.
ＨＡｐについては古くから多くの文献や特許などにその
製造方法が知られてい”る。主要なものとして次の様な
ものがある。Regarding HAp, methods for producing it have been known in many documents and patents for a long time.The following are the main methods.
（１）オートクレーブ中で無水リン酸水素カルシウムと
リン酸を１００〜５００℃、１〜５００気圧の条件下で
約４８時間反応させる水熱合成法。(1) A hydrothermal synthesis method in which anhydrous calcium hydrogen phosphate and phosphoric acid are reacted in an autoclave under conditions of 100 to 500°C and 1 to 500 atm for about 48 hours.
（２）９００〜１３００℃の高温でリン酸三カルシウム
と酸化カルシウムを水蒸気気流下約３時間反応させる乾
式合成法。(2) A dry synthesis method in which tricalcium phosphate and calcium oxide are reacted at a high temperature of 900 to 1300°C for about 3 hours under a stream of steam.
（３）水溶性のリン酸塩とカルシウム塩とを水溶液′中
３７℃、ｐＨ７〜８で２０日以上反応させ、化学量論比
に近ずける湿式合成法。(3) A wet synthesis method in which a water-soluble phosphate and a calcium salt are reacted in an aqueous solution at 37° C. and pH 7 to 8 for 20 days or more to bring the ratio close to the stoichiometric ratio.
しかしながら上記（１）の方法も（２）の方法も共に高
温や高圧で反応を行なう為装置が高価なものとなシ、さ
らに装置の操作も複雑かつ消費するエネルギーも莫大な
ものである。しかも得られるＨＡｐには炭酸根が含壕れ
難い不安定性がある。（３）の方法においては僅かな条
件の違いによシ生成物の組成が大きく影響され、さらに
化学量論比組成のＨＡｐを得るには２０日以上という凡
そ産業的実施には考えられない時間を要するので、取扱
いや操作が煩雑となシ結果の再現性もよくない。この方
法でもＣ０Ａｐを得ることができるが化学量論比の制御
が困難である。However, both method (1) and method (2) require expensive equipment because the reaction is carried out at high temperature and pressure, and furthermore, the equipment is complicated to operate and consumes a huge amount of energy. Moreover, the obtained HAp is unstable, making it difficult for carbonate roots to be entrapped. In method (3), the composition of the product is greatly affected by slight differences in conditions, and it takes more than 20 days to obtain HAp with a stoichiometric composition, which is unthinkable for industrial implementation. This requires complicated handling and operation, and the reproducibility of the results is also poor. C0Ap can also be obtained with this method, but it is difficult to control the stoichiometric ratio.
これらのことから従来の方法では品質の優れたＨＡｐ特
にＣ０Ａｐを実用的な量定量的に合成する事は非常に困
難であった。それ故にＨＡｐ特にＣ０Ａｐはその優れた
性質が知られているにも拘わらず、製造上の難点から高
価なものとなシ用途開発が他の無機材料に比較して遅れ
ている。For these reasons, it has been extremely difficult to synthesize high-quality HAp, particularly COAp, in a practical quantitative manner using conventional methods. Therefore, although HAp, particularly COAp, is known for its excellent properties, it is expensive due to manufacturing difficulties, and its application development has been delayed compared to other inorganic materials.
本発明者等はかかる状況に鑑みて品位の優れたＨＡｐ特
にＣ０Ａｐを多量に簡便に得る方法を鋭意研究した結果
、本発明に到達したものである即ち本発明は、炭酸含有
ヒドロキシアノくタイトの製造方法であって、その技術
的特徴は特許請求の範囲に記載の通りであシ、有機溶媒
の一種以上を含む反応媒体とさらに必要に応じて適当量
の水を反応時に存在させて、リン酸又は／及びそのカル
シウム塩と炭酸カルシウムとを反応させる技術に関し、
この技術によれば常圧下の比較的低温度で、しかも短時
間に再現性良く結晶性に優れた粉末のＣ０Ａｐを得る事
が可能である。In view of this situation, the inventors of the present invention have conducted intensive research on a method for easily obtaining a large amount of high-quality HAp, particularly C0Ap, and have arrived at the present invention. A production method, the technical characteristics of which are as described in the claims, wherein a reaction medium containing one or more organic solvents and, if necessary, an appropriate amount of water are present during the reaction to produce phosphorus. Regarding the technology of reacting an acid or/and its calcium salt with calcium carbonate,
According to this technique, it is possible to obtain powdered COAp with excellent crystallinity with good reproducibility in a relatively low temperature under normal pressure and in a short time.
本発明を実施するにあたっては、リン酸又は／及びその
カルシウムと炭酸カルシウムを所望のＣａ／Ｐ比に予め
反応槽内に仕込み、適度の水を添加しスラリーとする。In carrying out the present invention, phosphoric acid or/and its calcium and calcium carbonate are charged in advance into a reaction tank at a desired Ca/P ratio, and an appropriate amount of water is added to form a slurry.
次にこのスラリーに有機溶媒を加え加熱還流する。還流
時間としては約２時間もあれば十分である。なお加熱還
流時間及び反応槽への有機溶媒を含む原料の仕込順序は
通常上記の通シ実施されるが必ずしもこれに限定する必
要はない。Next, an organic solvent is added to this slurry and heated to reflux. A reflux time of about 2 hours is sufficient. The heating reflux time and the order of charging raw materials containing organic solvents to the reaction tank are generally carried out as described above, but are not necessarily limited thereto.
加熱終了後は生成したＣ０Ａｐが析出しスラリー状とな
っているのでこれを分離すればよい。分離方法は通常実
施される戸別のみによる方法と、水を有機溶媒と共に蒸
発させた後にＣ０Ａｐを戸別する方法が適用できる。特
に後者では留出した水と有機溶媒に相当する容量の有機
溶媒を加えながら脱水を行い、脱水が終了した後有機溶
媒とＣ０Ａｐを炉別により分離する方法である。Ｃ０Ａ
ｐの脱水を完全に行いうる点では後者の方法が好ましい
。After the heating is completed, the generated C0Ap precipitates and becomes a slurry, which can be separated. As the separation method, the usual door-to-door method or the door-to-door separation method after evaporating water together with an organic solvent can be applied. Particularly in the latter method, dehydration is carried out while adding an organic solvent in a volume equivalent to the distilled water and the organic solvent, and after the dehydration is completed, the organic solvent and C0Ap are separated in a separate furnace. C0A
The latter method is preferred in that p can be completely dehydrated.
本発明において原料とされるリン酸又は／及びそのカル
シウム塩としては、Ｈ３ＰＯ４、Ｃａ （Ｈ２Ｐ ０４
）２・Ｈｚ０、Ｃａ（ＰＯ３）２、ＣａＨＰＯ４、Ｃａ
ＨＰＯ４・２Ｈ２０、（：ａ２Ｐ２０７、Ｃａ３（ＰＯ
４）２、Ｃａｇ、Ｈｚ（ＰＯ４）６ ・５Ｈ２０等が使
用可能である。しかしながらこれらの化合物は本発明に
おいて使用可能力原料の一部であってこれらに限定する
必要はない。炭酸カルシウムと上記の化合物の１種類以
上を適宜選択してカルシウムとリンの原子比（Ｃａ／Ｐ
）が１．３０乃至１．９０となる様に原料を配合すれば
好条件で本発明を実施することが出来る。Phosphoric acid and/or its calcium salt used as raw materials in the present invention include H3PO4, Ca (H2P 04
)2・Hz0, Ca(PO3)2, CaHPO4, Ca
HPO4・2H20, (:a2P207, Ca3(PO
4) 2, Cag, Hz (PO4)6 ・5H20, etc. can be used. However, these compounds are part of the raw materials that can be used in the present invention, and there is no need to limit them thereto. Calcium carbonate and one or more of the above compounds are appropriately selected to adjust the atomic ratio of calcium to phosphorus (Ca/P).
) is 1.30 to 1.90, the present invention can be carried out under favorable conditions.
使用する原料の純度が高い程、純度の高い製品が得易く
好ましいが、本発明の実施に特に純度の高い原料を求め
られるものではなく目的物について要求される純度に応
じて適当な純度の原料を選択するとよい。なお生体材料
とする場合にはＦｅ。The higher the purity of the raw materials used, the easier it is to obtain a product with high purity, which is preferable, but the practice of the present invention does not require particularly high purity raw materials, and raw materials of appropriate purity can be used depending on the purity required for the target product. It is recommended to select . In addition, when it is used as a biomaterial, Fe is used.
Ｎｉ、 Ｚｎなどの不純物や重金属その他の生体有害物
の含有量の低い原料を選択することが好ましい。It is preferable to select a raw material with a low content of impurities such as Ni and Zn, heavy metals, and other biologically harmful substances.
一般的には工業グレードの原料でも充分に使用できる。In general, industrial grade raw materials can be used satisfactorily.
本発明において反応時のカルシウムとリンとの仕込量を
Ｃａ／Ｐの原子比で１．３０乃至１．９０の範囲、好ま
しくは１．４５乃至１・７５の範囲とすると１得られる
Ｃ０Ａｐの結晶性が良好でかつ未反応成分が殆んどなく
なる利点がある。目的とするＣ０Ａｐの原子比（Ｃａ／
Ｐ）は、理論的には５／３であるのでカルシウムとリン
の反応時における原子比も５／３が最適であるはずであ
るが、実際の反応に際しては、原子比が上記の範囲内で
あれば好条件にＣ０Ａｐを合成することができる。さら
に、Ｃａ／Ｐの原子比が１．３０以下乃至１．９０以上
の場合セあってもＣ０Ａｐの用途の一部、例えば水処理
用やイオン交換体等に用いる場合は、十分な性能のＣ０
Ａｐが得られる事も確認されている。In the present invention, when the amount of calcium and phosphorus charged during the reaction is in the range of 1.30 to 1.90 in Ca/P atomic ratio, preferably in the range of 1.45 to 1.75, 1 C0Ap crystal is obtained. It has the advantage of good properties and almost no unreacted components. Target atomic ratio of C0Ap (Ca/
P) is theoretically 5/3, so the optimal atomic ratio during the reaction between calcium and phosphorus should be 5/3, but in actual reaction, the atomic ratio should be within the above range. If so, C0Ap can be synthesized under favorable conditions. Furthermore, even if the Ca/P atomic ratio is 1.30 or less to 1.90 or more, if the C0Ap is used for some purposes, such as water treatment or ion exchangers, sufficient performance of the
It has also been confirmed that Ap can be obtained.
状態変数の選択によシ上記の有機溶媒の適否が異なる場
合もちシうるが、一般的に本発明の実施に好都合な有機
溶媒としてはベンゼン、トルエン、キシレン、ペンタン
、ヘキサン、ヘプタン、オクタン、デカン、各種石油ナ
フサや工業ガソリン等の芳香族及び脂肪族炭化水素類、
１ｓｏ−ブタノール、ｎ−７ミルアルコ一ル等ノアルコ
ール類、トリエチルアミン、トリブチルアミン等のアミ
ン類、エチルエーテル、エチルブチルエーテルや各種セ
ルンルブ類、カルピトール類等のエーテル類、メチルエ
チルケトン、メチルイソブチルケトン等のケトン類が挙
げられる。これらは本発明において使用可能な有機溶媒
の一例にすぎない。Although the suitability of the above organic solvents may vary depending on the selection of state variables, organic solvents that are generally convenient for carrying out the present invention include benzene, toluene, xylene, pentane, hexane, heptane, octane, and decane. , aromatic and aliphatic hydrocarbons such as various petroleum naphthas and industrial gasoline,
Alcohols such as 1so-butanol and n-7 methylalcohol, amines such as triethylamine and tributylamine, ethers such as ethyl ether, ethyl butyl ether, various cernlubes, calpitols, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. can be mentioned. These are just examples of organic solvents that can be used in the present invention.
有機溶媒の添加量はその種類、反応時の原料の種類、反
応時の攪拌条件などによシそれぞれ適正値が異なるが、
いずれの条件においてもスラリー濃度として５０％以下
となる量を添加することが好ましい。またＣ０Ａｐ中の
炭酸根は有機溶媒の種類、スラリー濃度及び原料の種類
とその時の仕込割合に付随する炭酸カルシウムの量によ
シコントロールすることが可能であシ、天然歯、天然骨
と同程度の炭酸根含有量を上記の方法でコントロールす
ることができる。この方法で行なうと７．ＯＭ量％以下
の範囲で炭酸根の含有量をコントロールすることができ
る。The appropriate amount of the organic solvent to be added varies depending on the type of organic solvent, the type of raw materials during the reaction, the stirring conditions during the reaction, etc.
Under any conditions, it is preferable to add the amount such that the slurry concentration is 50% or less. In addition, the carbonate content in C0Ap can be controlled by the type of organic solvent, slurry concentration, type of raw materials, and the amount of calcium carbonate associated with the charging ratio at that time, and is at the same level as natural teeth and bones. The carbonate radical content of can be controlled by the above method. If you do it this way, 7. The content of carbonate radicals can be controlled within the range of OM amount% or less.
既述の様に従来のＣ０Ａｐの製造方法が再現性に乏しい
上に高温、高圧、長時間、最適ｐＨ値の調メ
整を要する等によるエネルギ゛−の莫膚な消費、及び、
煩雑な操作、高価な装置を必要とするのに対し、本発明
では有機溶媒を共存させ、低温で反応させて、得られた
結晶を戸別、乾燥する方法のみであるので、熱エネルギ
ーの消費も極めて少なく、また製造装置も簡素でかつ安
価なものですみ、通常のガラスまたはステンレス製の材
質でも充分である。As mentioned above, the conventional method for producing COAp has poor reproducibility, requires high temperature, high pressure, long time, and adjustment of the optimum pH value, which consumes a huge amount of energy.
In contrast to this method, which requires complicated operations and expensive equipment, the present invention uses only a method in which an organic solvent is allowed to coexist, the reaction is carried out at low temperatures, and the obtained crystals are dried door to door, thereby reducing the consumption of thermal energy. The number of parts is extremely small, and the manufacturing equipment is simple and inexpensive, and ordinary glass or stainless steel materials are sufficient.
以上のように従来法では簡便には困難であった結晶性Ｈ
Ａｐ１特にはＣ０Ａｐを、本発明では安価に再現性よく
定量的に製造する事を可能にしたもので工業的に大きな
価値がある。As mentioned above, crystalline H
The present invention makes it possible to quantitatively produce Ap1, particularly C0Ap, at low cost and with good reproducibility, which is of great industrial value.
以下実施例によシ本発明をさらに明確に説明する。The present invention will be explained more clearly using Examples below.
実施例１
リン酸水素カルシウム・２水塩（リン酸２カルシウム・
２水塩） １０３．２１、炭酸カルシウム３８、Ｏｒ、
水６０ｆ、ｎ−ペンタン４００ｆを１ｔのフラスコに仕
込み、攪拌しながら昇温させ還流温度（３５℃）以下で
約２時間加熱した後、反応系内の水分とｎ−ペンタンを
蒸発させ、留出したｎ−ペンタンと水に相当する容量の
ｎ−ペンタンを系内に加えながら脱水を行なった。脱水
が進行するに従って内温か上昇し内温か３６℃を越えた
時点で加熱を中止して、冷却後生成物（沈殿）を溶媒よ
シ炉別しこれを乾燥して白色の粉末を得た。この粉末の
Ｘ線回折図を第１図、赤外吸収スペクトルを第２図にそ
れぞれ示す。Example 1 Calcium hydrogen phosphate dihydrate (dicalcium phosphate
dihydrate) 103.21, calcium carbonate 38, Or,
60 f of water and 400 f of n-pentane were charged into a 1 t flask, heated while stirring, and heated below the reflux temperature (35°C) for about 2 hours. Water and n-pentane in the reaction system were evaporated and distilled. Dehydration was carried out while adding a volume of n-pentane corresponding to the amount of n-pentane and water into the system. As the dehydration progressed, the internal temperature rose, and when the internal temperature exceeded 36° C., heating was stopped, and after cooling, the product (precipitate) was filtered out of the solvent and dried to obtain a white powder. The X-ray diffraction pattern and infrared absorption spectrum of this powder are shown in FIG. 1 and FIG. 2, respectively.
第１図よシ明らかなように回折角度２θ＝３１．７．３
２．２．３２．８に主ピークを有し、ＡＳＴＭカード９
−４３２に記載のＨＡｐの特性回折ピークと一致・した
。As is clear from Figure 1, the diffraction angle 2θ = 31.7.3
ASTM card 9 with main peak at 2.2.32.8
The peak was consistent with the characteristic diffraction peak of HAp described in -432.
また第２図よシ明らかなように、１４．００ ｃｍ−’
付近にＩ（Ａｐ 中に含まれる炭酸根に特有の数本に
***した吸収帯がある。これより得られたＨＡｐは炭酸
を含有していることが確認された。Also, as is clear from Figure 2, 14.00 cm-'
There is an absorption band in the vicinity that is split into several parts, which is characteristic of the carbonate roots contained in I(Ap).It was confirmed that the HAp obtained from this contains carbonic acid.
実施例７２〜４
無水リン酸２カルシウム、リン酸１カルシウム・１水温
、無水リン酸３カルシウム、炭酸カルシウム、水、有機
溶媒を第１表に示した条件で仕込み、第１表以外の条件
については実施例−１と同様な操作によシ本発明のＣ０
Ａｐを得た。Examples 72-4 Anhydrous dicalcium phosphate, monocalcium phosphate/1 water temperature, anhydrous tricalcium phosphate, calcium carbonate, water, and organic solvent were prepared under the conditions shown in Table 1, and for conditions other than Table 1. C0 of the present invention was prepared by the same operation as in Example-1.
Got Ap.
第１表には実施例−１についても併記したようをコント
ロールして、短時間でＣ０Ａｐを定量的に得た。In Table 1, C0Ap was quantitatively obtained in a short period of time by controlling as shown in Example-1 as well.
比較例
リン酸水素カルシウム・２水塩１０３．２０４、水酸化
カルシウム２９．６０ｔ１水６０１、メチルインブチル
ケトン４００ｔを１ｔのフラスコに仕込み、攪拌しなが
ら昇温させ還流温度（８９℃）以下で約２時間加熱した
後反応系内の水分とメチルイノブチルケトンを蒸発させ
、留出したメチルインブチルケトンと水に相当する容量
のソルインブチルクトｙを系内に加えながら脱水を行な
った。脱水が進行するに従って内温か上昇し内温か１１
７℃を越えた時点で加熱を中止して脱水を止め、冷却後
生成物（沈殿）を溶媒より戸別しこれを乾燥して白色の
粉末を得た。Comparative Example 103.204 t of calcium hydrogen phosphate dihydrate, 29.60 t of calcium hydroxide, 601 t of water, and 400 t of methyl imbutyl ketone were charged into a 1 t flask, and the temperature was raised with stirring to bring the temperature to about 200 ml below the reflux temperature (89°C). After heating for 2 hours, water and methyl imbutyl ketone in the reaction system were evaporated, and dehydration was carried out while adding sol in butyl ketone in a volume equivalent to the distilled methyl im butyl ketone and water to the system. As dehydration progresses, the internal temperature rises and the internal temperature reaches 11.
When the temperature exceeded 7°C, heating was stopped to stop dehydration, and after cooling, the product (precipitate) was removed from the solvent and dried to obtain a white powder.
この実験結果も第１表に併記した。The results of this experiment are also listed in Table 1.
格子定数測定による炭酸根の存在の証明実験をび焼成後
の化学分析及び格子定数の桓１１定結果を第２表に示し
た。また原料を第２１ノン酸カルシウム・２水塩と水酸
化カルシウムで反応させて得られは、Ｃｏｎｗａｙの微
量拡散分析装置を用いてイ１なった。Table 2 shows the chemical analysis and lattice constant results of the experiment to prove the existence of carbonate radicals by measuring the lattice constant. Further, the raw material obtained by reacting the 21st calcium nonate dihydrate with calcium hydroxide was analyzed using a Conway microdiffusion analyzer.
第２表 曇空気中、１３００℃、ｌｈｒ焼成。Table 2 Firing at 1300℃ in cloudy air for 1 hour.
゛第２表よシ実施例Ｌ１によシ得られたＣ０Ａｐは１焼
成前では４％はど炭酸根を含んでいる事がわかる。焼成
後はＣ０Ａｐの結晶の成長に伴い炭酸根が飛散し、炭酸
根含有率も低下している。さらにこの事実は粉末Ｘ線回
折により求めた格子定数にも認められ、焼成前のものに
ついては炭酸根がＣ０Ａｐの格子間にとシこまれ、それ
によシ格子不整をおこしａ軸、ａ軸ともにＡＳＴＭ ９
−４３２の格子定数よりも大きくなったと思われる。さ
らには、焼成後の格子定数がＡＳＴＭ９−４３２とほぼ
同程度の値を示しているが、これは炭酸根が格子間よシ
飛散し、格子不整がなくなった為と思われる。また比い
る事がよシ明確に証明された。It can be seen from Table 2 that the C0Ap obtained in Example L1 contains 4% carbonate radicals before one firing. After firing, the carbonate roots are scattered as the C0Ap crystals grow, and the carbonate root content is also reduced. Furthermore, this fact is also confirmed in the lattice constant determined by powder X-ray diffraction, and in the case of the unfired carbonate radical is inserted between the lattices of C0Ap, which causes lattice misalignment, and both the a-axis and the a-axis ASTM 9
It seems that the lattice constant is larger than that of −432. Furthermore, the lattice constant after firing is approximately the same as that of ASTM9-432, which is thought to be because the carbonate radicals are scattered between the lattices and lattice irregularities are eliminated. Again, the comparison was clearly proven.
第１図及び第２図は、本発明の実施（実施例−１）によ
って得られたＣ０ＡｐＯＸ線回折図及び赤外吸収スペク
トル図をそのままトレースしたもの８である。
手 続 補 正 書（自発）
昭和５８年１０月２６日
特許庁長官 若 杉 和 夫 殿
１、事件の表示
昭和５７年特許願第２１７８４２号
２、発明の名称
炭酸含有ヒドロキシアパタイトの製造方法３、補正をす
る者
明細書の「発明の詳細な説明」の欄
５、補正の内容
Ｈ４Ｆ、０７、ＨＰＯＢＳＰａＯｙ、ＰＣＩ、、ＰＣＩ
ｇ、Ｃａ（ＨｔＰＯ４）・Ｈｌｏ」と訂正する。
以上1 and 2 are traces 8 of the C0ApOX-ray diffraction diagram and infrared absorption spectrum diagram obtained by implementing the present invention (Example-1). Procedural amendment (spontaneous) October 26, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case: Patent Application No. 217842, filed in 19822, Name of the invention: Process for producing carbonic acid-containing hydroxyapatite3, Column 5 of “Detailed Description of the Invention” in the specification of the person making the amendment H4F, 07, HPOBSPaOy, PCI, PCI
g, Ca(HtPO4)・Hlo”. that's all
Claims (2)
のカルシウム塩と炭酸カルシウムとを反応させる事を特
徴とする炭酸含有ヒドロキシアパタイトの製造方法。(1) A method for producing carbonic acid-containing hydroxyapatite, which comprises reacting phosphoric acid or/and its calcium salt with calcium carbonate in a reaction medium containing an organic solvent.
１・３０乃至１．９０の範囲で行なう事を特徴とする特
許請求の範囲第１項に記載の方法。(2) The method according to claim 1, characterized in that the atomic ratio of calcium and phosphorus (Ca/P) is in the range of 1.30 to 1.90.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57217842A JPS59107912A (en) | 1982-12-14 | 1982-12-14 | Manufacture of hydroxyapatite containing carbonate |
| US06/544,361 US4481175A (en) | 1982-12-14 | 1983-10-21 | Process for preparing apatite |
| GB08328249A GB2132991B (en) | 1982-12-14 | 1983-10-21 | Process for preparing apatite |
| FR8317298A FR2537558B1 (en) | 1982-12-14 | 1983-10-28 | PROCESS FOR THE MANUFACTURE OF APATITIS |
| DE19833339232 DE3339232A1 (en) | 1982-12-14 | 1983-10-28 | METHOD FOR PRODUCING A CALCIUM PHOSPHORUS APATIT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57217842A JPS59107912A (en) | 1982-12-14 | 1982-12-14 | Manufacture of hydroxyapatite containing carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59107912A true JPS59107912A (en) | 1984-06-22 |
Family
ID=16710607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57217842A Pending JPS59107912A (en) | 1982-12-14 | 1982-12-14 | Manufacture of hydroxyapatite containing carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59107912A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015086097A (en) * | 2013-10-30 | 2015-05-07 | 三菱製紙株式会社 | (carbonate) calcium apatite containing strontium and method of producing fine particle of the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58190807A (en) * | 1982-04-28 | 1983-11-07 | Mitsui Toatsu Chem Inc | Manufacture of calcium-phosphorus type apatite |
-
1982
- 1982-12-14 JP JP57217842A patent/JPS59107912A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58190807A (en) * | 1982-04-28 | 1983-11-07 | Mitsui Toatsu Chem Inc | Manufacture of calcium-phosphorus type apatite |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015086097A (en) * | 2013-10-30 | 2015-05-07 | 三菱製紙株式会社 | (carbonate) calcium apatite containing strontium and method of producing fine particle of the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4481175A (en) | Process for preparing apatite | |
| CA1297656C (en) | Process of preparing hydroxylapatite | |
| Graham et al. | Reactions of octacalcium phosphate to form hydroxyapatite | |
| US4448758A (en) | Hydroxyapatite, ceramic material and process for preparing thereof | |
| Gibson et al. | Preparation and characterization of magnesium/carbonate co-substituted hydroxyapatites | |
| EP1042222B1 (en) | Process for the preparation of magnesium and carbonate substituted hydroxyapatite | |
| US20050226939A1 (en) | Production of nano-sized hydroxyapatite particles | |
| Glazov et al. | Calcium phosphate apatites: wet formation, thermal transformations, terminology, and identification | |
| JPH0369844B2 (en) | ||
| WO1999032401A1 (en) | Method for the preparation of carbonated hydroxyapatite compositions | |
| JPS5951485B2 (en) | Production method of CaO-P↓2O↓5-based apatite | |
| JPS59107912A (en) | Manufacture of hydroxyapatite containing carbonate | |
| JP3880090B2 (en) | Preparation method of non-stoichiometric witrockite by liquid phase reaction | |
| Salahi et al. | Synthesis and thermal behaviour of β tricalcium phosphate precipitated from aqueous solutions | |
| Wahyudi et al. | Synthesis and phase transformation of hydroxyapatite from Indonesian natural sources | |
| JPS6344683B2 (en) | ||
| RU2629079C1 (en) | Method for producing calcium pyrophosphate powder | |
| JP2572793B2 (en) | Method for producing hydroxyapatite fine particles | |
| CN110203900B (en) | Preparation method of porous flaky apatite with good biocompatibility | |
| JPH06122510A (en) | Method for producing hexacalcium phosphate | |
| JPH0940407A (en) | Production of tetracalcium phosphate | |
| WO2000068144A1 (en) | Method for the preparation of carbonated hydroxyapatite compositions | |
| JPS605009A (en) | Preparation of hydroxy apatite | |
| JP2989260B2 (en) | Method for producing hydroxyapatite | |
| JPS6343322B2 (en) |