JP2629761B2 - Method for forming hydroxyapatite film - Google Patents
Method for forming hydroxyapatite filmInfo
- Publication number
- JP2629761B2 JP2629761B2 JP62327727A JP32772787A JP2629761B2 JP 2629761 B2 JP2629761 B2 JP 2629761B2 JP 62327727 A JP62327727 A JP 62327727A JP 32772787 A JP32772787 A JP 32772787A JP 2629761 B2 JP2629761 B2 JP 2629761B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- hydrosol
- hydroxyapatite
- aqueous solution
- substrate
- 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.)
- Expired - Fee Related
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00389—The prosthesis being coated or covered with a particular material
- A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
- A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は基体の表面にヒドロキシアパタイトの皮膜を
形成する方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for forming a hydroxyapatite film on a surface of a substrate.
ヒドロキシアパタイトは生体適合性に優れ、吸着能も
大きいことから種々の応用の検討がされてきた。特に生
体硬組織の置換あるいは修復用のインプラント材として
の利用は活発に研究が進められている。インプラント材
としては生体適合性のほかに生体力学的強度が要求され
る。しかしながらヒドロキシアパタイト自体は焼結体に
おいても強度の点で不十分である。したがって金属材
料、セラミックス、ガラス等を基体あるいは芯材として
その表面にヒドロキシアパタイトの皮膜を形成すること
が実用的に最も有望視されている。Hydroxyapatite has been studied for various applications because of its excellent biocompatibility and large adsorption capacity. In particular, research on the use as an implant material for replacement or repair of living hard tissue has been actively conducted. An implant material is required to have biomechanical strength in addition to biocompatibility. However, hydroxyapatite itself is insufficient in strength even in a sintered body. Therefore, forming a hydroxyapatite film on the surface of a metal or ceramics or glass as a substrate or core material is considered most practically most promising.
ヒドロキシアパタイトの皮膜を形成する方法として、
これまで種々の方法が提案されている。たとえば特開昭
52−82893号公報にはプラズマ溶射法、特開昭59−10904
9号公報にはスパッタリング法、特開昭59−111753号公
報にはPVD、CVD法、特開昭53−128190号公報には電気泳
動法、特開昭53−118411号公報には塗布法がそれぞれ開
示されている。As a method of forming a hydroxyapatite film,
Various methods have been proposed so far. For example,
JP-A-52-82893 discloses a plasma spraying method and JP-A-59-10904.
No. 9 discloses a sputtering method, JP-A-51-111753 discloses a PVD, CVD method, JP-A-53-128190 discloses an electrophoresis method, and JP-A-53-118411 discloses a coating method. Each is disclosed.
〔発明が解決しようとする問題点〕 ところが、プラズマ溶射法、スパッタリング法、CVD
法、PVD法においては多孔体の内部など複雑な形状をし
た基体表面には皮膜の形成が困難であり、電気泳動法に
おいては基体が非導電性のものには皮膜を形成できない
という問題点を有している。塗布法は操作も簡便であ
り、前記特開昭53−118411号公報には、アパタイトの微
粉末を水に懸濁させ、この懸濁液を基体の表面に塗布し
焼成する方法が開示されているが、微粉末をより細かい
粒子にすることが一般に難しく凝集粒が存在し易いこと
並びに分散している粒子の大きさが一般に0.5μｍを超
えていることなどのために基体表面へのアパタイトの付
着強度が弱く、剥離し易いという問題点を有している。[Problems to be solved by the invention] However, plasma spraying, sputtering, CVD
It is difficult to form a film on the surface of a substrate with a complicated shape such as the inside of a porous body in the PVD method and the PVD method, and it is not possible to form a film on a non-conductive substrate in the electrophoresis method. Have. The coating method is simple in operation, and JP-A-53-118411 discloses a method in which a fine powder of apatite is suspended in water, and this suspension is applied to the surface of a substrate and fired. However, it is generally difficult to make fine powder into finer particles, and it is difficult to form agglomerates, and the size of dispersed particles generally exceeds 0.5 μm. There is a problem that the adhesive strength is weak and the film is easily peeled.
かかる事情に鑑み本発明者らは塗布法により付着強度
の高い皮膜を形成するためには皮膜厚をクラックの発生
しない１〜２μｍ以下にすること、凝集のない微粒子を
分散した状態で塗布することが重要であるという構想の
下に鋭意検討した結果、ヒドロゾルを使用することによ
り良好なヒドロキシアパタイトの皮膜が形成できること
を見出し本発明を完成するに至った。In view of such circumstances, the inventors of the present invention set the film thickness to 1 to 2 μm or less, which does not cause cracks, to form a film having a high adhesion strength by a coating method, and apply in a state where fine particles having no aggregation are dispersed. As a result of intensive studies under the concept that is important, the present inventors have found that a good hydroxyapatite film can be formed by using a hydrosol, and have completed the present invention.
すなわち本発明は保護コロイドの存在下に水酸化カル
シウム水溶液とリン酸水溶液をCa/P＝1.50〜2.0（原子
比）の割合で混合し調整したヒドロゾルを基体に被覆し
た後、乾燥し不溶化処理することを特徴とするヒドロキ
シアパタイト皮膜の形成方法を提供するものである。That is, in the present invention, a calcium hydroxide aqueous solution and a phosphoric acid aqueous solution are mixed at a Ca / P ratio of 1.50 to 2.0 (atomic ratio) in the presence of a protective colloid, and the resulting hydrosol is coated on a substrate, and then dried and insolubilized. It is another object of the present invention to provide a method for forming a hydroxyapatite film.
以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
ここにヒドロゾルとは水を分散媒とするコロイドを称
するもので乳濁液や懸濁液に比較して分散している粒子
が小さいものである。一般にコロイド粒子の大きさは0.
1〜0.001μｍである。Here, the hydrosol refers to a colloid using water as a dispersion medium, and has smaller dispersed particles than an emulsion or a suspension. Generally, the size of colloid particles is 0.
1 to 0.001 μm.
ヒドロキシアパタイトのヒドロゾルの一般的な製法に
ついて次の文献、グメリンス ハンドブック デル ア
ンオーガニシェ ヘミー（Gmelins Handbuch der Anorg
anischen Chemie）第28巻Ｂ−３号、1158〜1159（196
1）に以下の３つの方法が開示されている。For a general description of the preparation of hydroxyapatite hydrosols, see Gmelins Handbuch der Anorg.
anischen Chemie) Vol. 28, No. B-3, 1158-1159 (196
The following three methods are disclosed in 1).
リン酸水溶液と水酸化カルシウム水溶液との混合によ
り生成した沈澱を母体と共に攪拌してヒドロキシアパタ
イトのヒドロゾルを製造する。The precipitate formed by mixing the aqueous phosphoric acid solution and the aqueous calcium hydroxide solution is stirred with the base to produce a hydroxyapatite hydrosol.
リン酸水溶液とカルシウム塩水溶液をCa/P＝1.50の割
合で混合して生成した第三リン酸カルシウムの沈澱物を
0.0008〜0.0016Nの濃度で複分解することによりヒドロ
キシアパタイトのヒドロゾルを製造する。The precipitate of tricalcium phosphate formed by mixing the aqueous solution of phosphoric acid and the aqueous solution of calcium salt at a ratio of Ca / P = 1.50
A hydrosol of hydroxyapatite is produced by metathesis at a concentration of 0.0008 to 0.0016N.
ゼラチンの存在下に塩化カルシウム溶液にリン酸三ナ
トリウム溶液を加えたときに生成するリン酸カルシウム
よりヒドロキシアパタイトのヒドロゾルを製造する。た
だし、この際リン酸カルシウムとゼラチンの濃度に依存
する。A hydroxyapatite hydrosol is produced from calcium phosphate generated when a trisodium phosphate solution is added to a calcium chloride solution in the presence of gelatin. However, this depends on the concentrations of calcium phosphate and gelatin.
しかるに本発明者らの実験によればゼラチンなどの保
護コロイドを添加せずに生成させた沈澱物は攪拌を続け
てもゾル化することなく上記、の方法は再現するこ
とが困難であった。またの方法はヒドロゾルを生成す
るが塩化ナトリウムが副生し、塩化ナトリウムの結晶が
大きいためにこのヒドロゾルを基体等に被覆した場合、
皮膜性状に悪影響を及ぼすことになり好ましくない。However, according to the experiments of the present inventors, it was difficult to reproduce the above-mentioned method without forming a sol even when stirring was continued without adding a protective colloid such as gelatin. Another method produces a hydrosol, but when sodium chloride is produced as a by-product and the crystal of sodium chloride is large, when this hydrosol is coated on a substrate or the like,
This is undesirable because it adversely affects the film properties.
本発明におけるヒドロゾルは保護コロイドの存在下に
水酸化カルシウム水溶液とリン酸水溶液をCa/P＝1.50〜
2.0（以下原子比を表わす）の割合で混合して調整され
る。特にCa/Pの割合は1.50〜1.67の範囲が好ましい。In the present invention, the hydrosol is prepared by adding an aqueous solution of calcium hydroxide and an aqueous solution of phosphoric acid in the presence of a protective colloid to Ca / P = 1.50-
It is adjusted by mixing at a ratio of 2.0 (hereinafter, representing the atomic ratio). In particular, the ratio of Ca / P is preferably in the range of 1.50 to 1.67.
Ca/P＝1.50未満の場合は第二リン酸カルシウムが生成
し、ヒドロキシアパタイトが生成せず、2.0を超えると
水酸化カルシウムの残留が過大となり、ヒドロキシアパ
タイトの生成割合が減少し好ましくない。When Ca / P is less than 1.50, dibasic calcium phosphate is generated and hydroxyapatite is not generated. When it is more than 2.0, the residual amount of calcium hydroxide becomes excessive, and the generation rate of hydroxyapatite decreases, which is not preferable.
Ca/P＝1.50〜1.67の範囲で水酸化カルシウム水溶液と
リン酸水溶液を混合した場合、母液のpHは最終的には６
〜８に推移する。一方、Ca/P＝1.67を超えると未反応の
水酸化カルシウムが母液中に残留することになり、反応
終了後も母液のpHは８〜11となる。この場合は必要に応
じて酸で中性化してもよい。When an aqueous solution of calcium hydroxide and an aqueous solution of phosphoric acid are mixed in the range of Ca / P = 1.50 to 1.67, the pH of the mother liquor finally becomes 6
８8. On the other hand, if Ca / P exceeds 1.67, unreacted calcium hydroxide will remain in the mother liquor, and the pH of the mother liquor will be 8 to 11 even after completion of the reaction. In this case, if necessary, the acid may be neutralized with an acid.
Ca/P＝1.50〜1.67の範囲で水酸化カルシウム水溶液と
リン酸水溶液を混合すれば反応当初は生成するリン酸カ
ルシウムが母液内に留まる。これを攪拌下あるいは攪拌
せずに保持すると母液中の水酸化カルシウムが次第に消
費され、リン酸カルシウムのCa/Pの値が増加し母液中の
pHは低下する。pHが６〜８に達したとき、ほとんどの水
酸化カルシウムは消費され、複分解反応が終結する。こ
の際リン酸カルシウムのCa/Pの割合は原料の混合割合に
等しくなる。さらに母液から回収し風乾後に得られた粉
末を粉末Ｘ線回折により分析したところ低結晶のヒドロ
キシアパタイトを示した。If an aqueous solution of calcium hydroxide and an aqueous solution of phosphoric acid are mixed in the range of Ca / P = 1.50 to 1.67, calcium phosphate generated at the beginning of the reaction stays in the mother liquor. If this is maintained with or without stirring, the calcium hydroxide in the mother liquor is gradually consumed, the Ca / P value of calcium phosphate increases, and
pH drops. When the pH reaches 6-8, most of the calcium hydroxide is consumed and the metathesis reaction is terminated. At this time, the ratio of Ca / P of calcium phosphate becomes equal to the mixing ratio of the raw materials. Further, the powder recovered from the mother liquor and obtained after air-drying was analyzed by powder X-ray diffraction. As a result, low-crystalline hydroxyapatite was shown.
本発明で使用する水酸化カルシウムは通常の方法で製
造されたものでよく、特に限定されるものではない。ま
た該水溶液の濃度は水酸化カルシウムの溶解度以下であ
れば特に限定されるものではないが、生成する皮膜厚み
が薄くなりすぎないように溶解度のおよそ1/100以上が
望ましい。The calcium hydroxide used in the present invention may be one produced by a usual method, and is not particularly limited. The concentration of the aqueous solution is not particularly limited as long as it is equal to or lower than the solubility of calcium hydroxide, but is preferably about 1/100 or more of the solubility so that the thickness of the formed film does not become too thin.
また本発明で使用するリン酸も通常の方法で製造され
たものでよく、特に限定されるものではない。該水溶液
中の濃度も特に限定されるものではないが、水酸化カル
シウムの濃度と同水準とした方が望ましい。Further, the phosphoric acid used in the present invention may be one produced by a usual method, and is not particularly limited. Although the concentration in the aqueous solution is not particularly limited, it is preferable that the concentration is the same as the concentration of calcium hydroxide.
本発明で使用する保護コロイドとしてゼラチン、アル
ブミン、アラビアゴム、ブロタルビン酸、リサルビン酸
など通常のものが使用されるが、ヒドロキシアパタイト
の皮膜形成後に不溶化処理し易いものを選べばよい。保
護コロイドは水酸化カルシウム水溶液またはリン酸水溶
液のいずれか一方あるいは両方に溶解することができ
る。保護コロイドの濃度は生成するヒドロキシアパタイ
トの重量の0.5〜10倍量を含有することが望ましい。10
倍量より多い場合は皮膜中のヒドロキシアパタイトの濃
度が希釈されるので連続したヒドロキシアパタイトの層
が形成され難く、0.5倍量よる少ない場合は保護コロイ
ドの作用効果が小さくヒドロゾルの形成が難しいので好
ましくない。As the protective colloid used in the present invention, conventional ones such as gelatin, albumin, gum arabic, brotalbic acid, and risarbic acid are used, but those which can be easily insolubilized after forming a hydroxyapatite film may be selected. The protective colloid can be dissolved in one or both of an aqueous solution of calcium hydroxide and an aqueous solution of phosphoric acid. The concentration of the protective colloid is desirably 0.5 to 10 times the weight of the hydroxyapatite to be produced. Ten
If the amount is more than twice, the concentration of hydroxyapatite in the film is diluted, so that a continuous layer of hydroxyapatite is difficult to be formed.If the amount is less than 0.5 times, the effect of the protective colloid is small, and it is difficult to form a hydrosol. Absent.
次に本発明により得られたヒドロゾルを基体に被覆す
る方法としては塗布、噴霧、浸漬等通常の方法が採用で
きる。Next, as a method for coating the substrate with the hydrosol obtained according to the present invention, ordinary methods such as coating, spraying, and dipping can be adopted.
用いる基体としては金属、セラミックス、ガラス等い
ずれも可能であるが、プラスチック等疎水性のものには
適用し難しいので表面処理をして親水性にしておいた方
が好ましい。As the substrate to be used, any of metal, ceramics, glass and the like can be used, but it is difficult to apply to a hydrophobic material such as plastic, so it is preferable that the surface is treated to be hydrophilic.
本発明は特に表面が複雑な形状をしている基体に適用
することができる。たとえば表面が多孔化されたインプ
ラント材に適用することができる。このようなインプラ
ント材としてはチタン合金などの金属、アルミナなどの
セラミックス、バイオガラスなどのガラスがある。The present invention is particularly applicable to a substrate having a complicated surface. For example, the present invention can be applied to an implant material having a porous surface. Examples of such implant materials include metals such as titanium alloys, ceramics such as alumina, and glasses such as bioglass.
基体に被覆したヒドロゾルは乾燥され、さらに不溶化
処理を施される。The hydrosol coated on the substrate is dried and further subjected to an insolubilization treatment.
該不溶化はヒドロキシアパタイトの皮膜をより強力な
ものとするために必要な処理である。具体的な不溶化処
理としては架橋剤等の不溶化薬剤、たとえばホルムアル
デヒド、グルタルアルデヒド、タンニン酸等を皮膜に塗
布あるいは噴霧することにより安定で強固な皮膜を製造
する方法、焼成して保護コロイドを除去し、強固な皮膜
のみとする方法がある。不溶化処理として焼成する場合
は焼成残渣が生じない保護コロイドを選択すればよい。
焼成条件は使用する保護コロイドの焼失温度、基体の耐
熱温度を考慮して決定すればよい。ただしヒドロキシア
パタイトは1200℃以上では熱分解が著しくなるのでこの
温度以下とするのが望ましい。The insolubilization is a necessary treatment for making the hydroxyapatite film stronger. As a specific insolubilization treatment, a method for producing a stable and strong film by applying or spraying an insolubilizing agent such as a cross-linking agent, for example, formaldehyde, glutaraldehyde, tannic acid, etc. on the film, and baking to remove the protective colloid. There is a method of forming only a strong film. When baking is performed as the insolubilization treatment, a protective colloid that does not generate a baking residue may be selected.
The firing conditions may be determined in consideration of the burning temperature of the protective colloid used and the heat resistant temperature of the substrate. However, since the thermal decomposition of hydroxyapatite is remarkable at 1200 ° C. or more, it is preferable to set the temperature to this temperature or less.
本発明によれば従来の塗布法よりも皮膜の付着強度が
強く、しかも複雑な表面形状をした基体に対しても容易
にヒドロキシアパタイトの皮膜を形成することが可能と
なり、さらに大面積の基体にも皮膜を形成でき、成膜速
度が早く安価な方法であり、得られた基体は種々の用途
に使用でき、特にインプラント材、吸着分離材、触媒と
して有用である。ADVANTAGE OF THE INVENTION According to this invention, the adhesion strength of a film is stronger than the conventional coating method, and also it is possible to easily form a hydroxyapatite film even on a substrate having a complicated surface shape. This is a low-cost method that can form a film, has a high film-forming speed, and can be used for various purposes, and is particularly useful as an implant material, an adsorption separation material, and a catalyst.
以下本発明を実施例により説明するが、本発明はこれ
らに限定されるものではない。Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.
なお実施例において用いる％は重量％を表わす。 The percentages used in the examples represent% by weight.
実施例１ 0.055％水酸化カルシウム水溶液500gに精製ゼラチン
1.0gを溶解し、攪拌しながら該液中に0.060％リン酸水
溶液365gを４分間で添加した。（Ca/P＝1.66）このとき
液のpHは最初12.3から11.2まで低下し、さらにこの液を
７日間静置したところpHは8.0まで低下した。その結果
沈澱物は全くなく、ヒドロゾルが生成した。Example 1 Purified gelatin in 500 g of 0.055% calcium hydroxide aqueous solution
1.0 g was dissolved, and 365 g of a 0.060% phosphoric acid aqueous solution was added to the solution with stirring over 4 minutes. (Ca / P = 1.66) At this time, the pH of the solution first decreased from 12.3 to 11.2, and when the solution was allowed to stand for 7 days, the pH dropped to 8.0. The result was no precipitate and a hydrosol formed.
このヒドロゾルを一部抜き取り、これに凝集剤である
硫酸ナトリウムを添加して凝集させ濾取した。得られた
スラリーを風乾後に粉末Ｘ線回折を行ったところ、第１
図に示すように低結晶性のヒドロキシアパタイトであっ
た。A part of this hydrosol was withdrawn, and sodium sulfate as a coagulant was added thereto to coagulate and filter. The obtained slurry was air-dried and then subjected to powder X-ray diffraction.
As shown in the figure, it was a low crystalline hydroxyapatite.
基体として縦25mm、横25mm、深さ1mmの凹部を有する
縦40mm、横40mm、厚さ5mmのアルミナ緻密焼結体（純度9
9.9％）の凹部内に直径1mmのアルミナビーズが一層接合
されたものを準備した。A dense alumina sintered body of 40 mm in length, 40 mm in width, and 5 mm in thickness having a concave part of 25 mm in length, 25 mm in width and 1 mm in depth (purity 9
(9.9%) was prepared in which alumina beads having a diameter of 1 mm were further joined in the concave portion of (9.9%).
基体の凹部内が完全に満たされるまで上記のヒドロゾ
ルを注入後、風乾し焼成した。焼成条件として室温から
800℃まで100℃/Hrで昇温し、800℃で１時間の保持をし
た。The above hydrosol was injected until the inside of the concave portion of the substrate was completely filled, and then air-dried and fired. From room temperature as firing conditions
The temperature was raised to 800 ° C. at 100 ° C./Hr, and the temperature was maintained at 800 ° C. for 1 hour.
焼成後の皮膜は光沢があり、干渉縞があった。 The fired film was glossy and had interference fringes.
皮膜の厚さを膜厚計にて測定した結果、その厚さは約
0.3μｍであった。As a result of measuring the thickness of the film with a film thickness meter, the thickness was approximately
0.3 μm.
得られた基体を生理食塩水に１週間浸漬したが、皮膜
は変化せず強固であった。When the obtained substrate was immersed in physiological saline for one week, the film was strong without any change.
実施例２ 0.060％リン酸水溶液405gを使用する以外は実施例１
と同様の試薬を用い同様の方法にてCa/P＝1.50のヒドロ
ゾルを調製した。調製時のpHは最初12.3から10.8まで低
下し、さらにこの液を７日間静置したところpHは8.0ま
で低下した。その結果沈澱物は全くなく、ヒドロゾルが
生成した。Example 2 Example 1 except that 405 g of a 0.060% phosphoric acid aqueous solution was used.
A hydrosol with Ca / P = 1.50 was prepared in the same manner using the same reagent as in Example 1. The pH at the time of preparation dropped from 12.3 to 10.8 at first, and when this solution was allowed to stand for 7 days, the pH dropped to 8.0. The result was no precipitate and a hydrosol formed.
このヒドロゾルを実施例１と同様の方法で確認したと
ころ、低結晶性のヒドロキシアパタイトであった。When this hydrosol was confirmed in the same manner as in Example 1, it was low-crystalline hydroxyapatite.
基体として表面粗さRa＝0.05μｍのアルミナ基板（純
度99.9％、縦10mm、横10mm、厚さ0.8mm）をアセトンで
洗浄したものを準備した。A substrate was prepared by washing an alumina substrate (purity 99.9%, length 10 mm, width 10 mm, thickness 0.8 mm) with acetone with a surface roughness Ra = 0.05 μm as acetone.
このアルミナ基板の表面に上記のヒドロゾルを滴下し
て厚さ1mmの液膜を形成した。その後、実施例１と同様
の方法、条件で風乾、焼成した。The above hydrosol was dropped on the surface of the alumina substrate to form a liquid film having a thickness of 1 mm. Thereafter, it was air-dried and fired under the same method and conditions as in Example 1.
焼成後の皮膜は実施例１と同様に光沢があり、干渉縞
があった。The fired film was glossy and had interference fringes as in Example 1.
皮膜の厚さを膜厚計にて測定した結果、その厚さは約
0.3μｍであった。As a result of measuring the thickness of the film with a film thickness meter, the thickness was approximately
0.3 μm.
得られた基体を実施例１と同様に生理食塩水に１週間
浸漬したが、皮膜は何ら変化せず強固であった。The obtained substrate was immersed in physiological saline for one week in the same manner as in Example 1, but the film was strong without any change.
実施例３ 実施例１と同様のヒドロゾル並びにアルミナ緻密焼結
体を用い、実施例１と同様に該焼結体の凹部内にヒドロ
ゾルを注入し風乾した。Example 3 The same hydrosol and alumina dense sintered body as in Example 1 were used, and the hydrosol was injected into the recesses of the sintered body and air-dried as in Example 1.
引続き該焼結体を５％グルタルアルデヒド溶液に20時
間浸漬して不溶化処理した。Subsequently, the sintered body was immersed in a 5% glutaraldehyde solution for 20 hours for insolubilization.
該焼結体を実施例１と同様に生理食塩水に１週間浸漬
したが、皮膜は何ら変化せず強固であった。The sintered body was immersed in physiological saline for one week in the same manner as in Example 1, but the film was strong without any change.
実施例４ 基体として表面粗さRa＝0.2μｍのチタン板（JIS 2
種、縦10mm、横10mm、厚さ1mm）をアセトンで洗浄した
ものを準備した。Example 4 A titanium plate having a surface roughness Ra = 0.2 μm (JIS 2
A seed, 10 mm long, 10 mm wide, and 1 mm thick) washed with acetone was prepared.
該チタン板の表面に実施例１で用いたヒドロゾルを滴
下して厚さ1mmの液膜を形成した。その後実施例１と同
様の方法、条件で風乾し焼成した。The hydrosol used in Example 1 was dropped on the surface of the titanium plate to form a liquid film having a thickness of 1 mm. Thereafter, it was air-dried and fired under the same method and conditions as in Example 1.
焼成後の皮膜は実施例１と同様に光沢があり、干渉縞
があった。The fired film was glossy and had interference fringes as in Example 1.
皮膜の厚さを膜厚計にて測定した結果、その厚さは約
0.3μｍであった。As a result of measuring the thickness of the film with a film thickness meter, the thickness was approximately
0.3 μm.
得られたチタン板を実施例１と同様に生理食塩水に１
週間浸漬したが、皮膜は何ら変化せず強固であった。The obtained titanium plate was placed in physiological saline in the same manner as in Example 1.
After soaking for a week, the film was strong without any change.
比較例１ 第二リン酸アンモニウム水溶液と硝酸カルシウム水溶
液を混合し調製したヒドロキシアパタイト（未焼成品）
0.50gを0.1％ゼラチン水溶液1000gに添加し攪拌したと
ころ、１日後に全て沈澱した。これを再び攪拌し懸濁物
を実施例１と同様のアルミナ緻密焼結体の凹部内に充填
し、風乾した結果、白色の皮膜が形成した。引き続き実
施例１と同様の焼成条件にて焼成したが、得られた皮膜
は触れると容易に剥離した。Comparative Example 1 Hydroxyapatite prepared by mixing an aqueous solution of dibasic ammonium phosphate and an aqueous solution of calcium nitrate (unfired product)
When 0.50 g was added to 1000 g of a 0.1% aqueous gelatin solution and stirred, all precipitated after one day. This was stirred again, and the suspension was filled in the recess of the same dense alumina sintered body as in Example 1, and air-dried. As a result, a white film was formed. Subsequently, the film was fired under the same firing conditions as in Example 1, but the resulting film was easily peeled off when touched.
比較例２ ゼラチン存在下でない以外は実施例１と同じ濃度およ
び量の水酸化カルシウム水溶液、リン酸水溶液を混合し
たところpHの変化は同様であったが、混合直後に沈澱が
生成しヒドロゾルの形成はなかった。Comparative Example 2 A calcium hydroxide aqueous solution and a phosphoric acid aqueous solution of the same concentration and amount as in Example 1 were mixed except that gelatin was not present, but the change in pH was the same, but immediately after mixing, a precipitate was formed to form a hydrosol. There was no.
得られた沈澱を濾取し風乾後に粉末Ｘ線回折を行った
が、第１図と全く同様のパターンを示し、低結晶性のヒ
ドロキシアパタイトであることが判った。The resulting precipitate was collected by filtration and air-dried, and then subjected to powder X-ray diffraction. The pattern was exactly the same as that shown in FIG. 1 and was found to be low crystalline hydroxyapatite.
基体として実施例１で使用したアルミナ緻密焼結体を
用い、該焼結体の凹部内に上記沈澱物を充填した後、実
施例１と同様の方法、条件で風乾し、焼成した。The dense alumina sintered body used in Example 1 was used as a substrate, and the above-mentioned precipitate was filled in the recessed portions of the sintered body. The resultant was air-dried and fired under the same method and conditions as in Example 1.
得られた皮膜は触れると容易に剥離した。 The resulting coating was easily peeled off when touched.
比較例３ 0.060％リン酸水溶液434gを使用した以外は実施例１
と同じものを使用し、同様の方法にてCa/P＝1.40のヒド
ロゾルを調整した。このヒドロゾルの一部を取り凝集剤
である硫酸ナトリウムを添加して凝集させ濾取した。得
られたスラリーを風乾後に実施例１と同様に粉末Ｘ線回
折を行った結果、低結晶性のヒドロキシアパタイトの第
二リン酸カルシウムの混合物であった。Comparative Example 3 Example 1 except that 434 g of a 0.060% phosphoric acid aqueous solution was used.
A hydrosol having Ca / P = 1.40 was prepared in the same manner as described above. A part of the hydrosol was taken out, sodium sulfate as a flocculant was added thereto, flocculated and collected by filtration. The resulting slurry was air-dried and subjected to powder X-ray diffraction in the same manner as in Example 1. As a result, the slurry was a mixture of low-crystalline hydroxyapatite and dicalcium phosphate.
比較例４ 0.060％リン酸水溶液243gを使用した以外は実施例１
と同じものを使用し、同様の方法にてCa/P＝2.50のヒド
ロゾルを調製した。このヒドロゾルの一部を取り凝集剤
である硫酸ナトリウムを添加して凝集させ濾取した。得
られたスラリーを風乾後に実施例１と同様に粉末Ｘ線回
折を行った結果、低結晶性のヒドロキシアパタイトと低
結晶性の水酸化カルシウムの混合物であった。Comparative Example 4 Example 1 except that 243 g of a 0.060% phosphoric acid aqueous solution was used.
A hydrosol having a Ca / P of 2.50 was prepared in the same manner as described above. A part of the hydrosol was taken out, sodium sulfate as a flocculant was added thereto, flocculated and collected by filtration. After the resulting slurry was air-dried and subjected to powder X-ray diffraction in the same manner as in Example 1, it was a mixture of low-crystalline hydroxyapatite and low-crystalline calcium hydroxide.
第１図は本発明によって得られたヒドロゾルを凝集させ
て濾取し、風乾した後の粉末Ｘ線回折図を示す。FIG. 1 shows a powder X-ray diffraction pattern after the hydrosol obtained by the present invention was aggregated, collected by filtration, and air-dried.
Claims (1)
水溶液とリン酸水溶液をCa/P＝1.50〜2.0（原子比）の
割合で混合した後に母液中に保持して複分解反応を終結
させることにより調整したヒドロゾルを基体に被覆した
後、乾燥し不溶化処理することを特徴とするヒドロキシ
アパタイト皮膜の形成方法。(1) An aqueous solution of calcium hydroxide and an aqueous solution of phosphoric acid are mixed at a ratio of Ca / P = 1.50 to 2.0 (atomic ratio) in the presence of a protective colloid, and then retained in a mother liquor to terminate the metathesis reaction. A method for forming a hydroxyapatite film, comprising coating a substrate with the prepared hydrosol, followed by drying and insolubilization.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327727A JP2629761B2 (en) | 1987-12-23 | 1987-12-23 | Method for forming hydroxyapatite film |
| DE8888312265T DE3865421D1 (en) | 1987-12-23 | 1988-12-22 | COATING LIQUID CONTAINING HYDROXYAPATITE AND METHOD FOR PRODUCING A HYDROXYAPATITE COVER USING THE SAME. |
| EP88312265A EP0322250B1 (en) | 1987-12-23 | 1988-12-22 | Coating liquor containing hydroxyapatite and method for forming hydroxyapatite coating film using the same |
| US07/576,166 US5030474A (en) | 1987-12-23 | 1990-08-31 | Method for forming hydroxyapatite coating film using coating liquor containing hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327727A JP2629761B2 (en) | 1987-12-23 | 1987-12-23 | Method for forming hydroxyapatite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01168872A JPH01168872A (en) | 1989-07-04 |
| JP2629761B2 true JP2629761B2 (en) | 1997-07-16 |
Family
ID=18202311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62327727A Expired - Fee Related JP2629761B2 (en) | 1987-12-23 | 1987-12-23 | Method for forming hydroxyapatite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2629761B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4586170B2 (en) * | 2003-12-09 | 2010-11-24 | 富士通株式会社 | Apatite-containing film having photocatalytic activity and method for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62221359A (en) * | 1986-03-24 | 1987-09-29 | ペルメレツク電極株式会社 | Titanium composite material coated with calcium phosphate and its production |
| JPS62252307A (en) * | 1986-04-25 | 1987-11-04 | Sekisui Plastics Co Ltd | Wet synthesis of hydroxy apatite |
-
1987
- 1987-12-23 JP JP62327727A patent/JP2629761B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01168872A (en) | 1989-07-04 |
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