JPH0557010A - Compound implant - Google Patents

Compound implant

Info

Publication number
JPH0557010A
JPH0557010A JP3250209A JP25020991A JPH0557010A JP H0557010 A JPH0557010 A JP H0557010A JP 3250209 A JP3250209 A JP 3250209A JP 25020991 A JP25020991 A JP 25020991A JP H0557010 A JPH0557010 A JP H0557010A
Authority
JP
Japan
Prior art keywords
layer
core material
calcium phosphate
alpha
intermediate layer
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
Application number
JP3250209A
Other languages
Japanese (ja)
Other versions
JP3076636B2 (en
Inventor
Hideki Aoki
秀希 青木
Masaru Akao
勝 赤尾
Miharu Hata
美治 奏
Yasushi Hayashi
靖 林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Advance Co Ltd
Original Assignee
Advance Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Advance Co Ltd filed Critical Advance Co Ltd
Priority to JP03250209A priority Critical patent/JP3076636B2/en
Publication of JPH0557010A publication Critical patent/JPH0557010A/en
Application granted granted Critical
Publication of JP3076636B2 publication Critical patent/JP3076636B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61CDENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61CDENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A61C8/0013Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating

Landscapes

  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Dental Prosthetics (AREA)

Abstract

PURPOSE:To increase the chemical stability and strength of an implant by forming a titanium phosphide layer around the external surface of a core material, and covering the layer with a calcium phosphate layer. CONSTITUTION:A phosphoric triester solution diluted double with propanol is uniformly applied to a core material 11 of titanium, dried at a temperature of approximately 120 deg.C and baked at a temperature of approximately 600 deg.C, thereby forming a titanium phosphide layer 12 on the surface of the core material 11. Then, plasma flame spraying is applied, using alpha-TCP (alpha-tricalcium phosphate) as a flame spraying material, thereby forming an alpha-TCP layer 13 on the outermost surface of the core material 11. In addition, the material 11 so coated is subjected to hydrothermal treatment in a water solution of a calcium phosphate for converting the alpha-TCP layer 13 to a hydroxyapatite layer 13.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は複合インプラントに関す
る。
FIELD OF THE INVENTION This invention relates to composite implants.

【0002】[0002]

【従来の技術】金属あるいはセラミックス等の基材界面
に中間層を設け、最表層にアパタイト等のリン酸カルシ
ウム系セラミックスをコーティングする複合インプラン
トに関しては次の様な従来技術文献を提示し得る。特開
昭58−50737号公報:中間層として、金属:M
o,Ta,Ni,Ni−Cr−Al,Al、セラミック
ス:Al2O3,TiO2,ZrO2,SiO2,SnO2,
P2O5,CaO,B2O5を使用し、コーティング方法と
して、プラズマ溶射を用いている。該文献の目的は、コ
ーティング層と芯材との密着強度を向上させることにあ
る。特開平2−6537号公報:中間層として、酸化チ
タン、酸化スズを使用し、コーティング方法として熱分
解法を用いている。該文献の目的は、コーティング層と
芯材との密着強度を向上させることにある。特開昭60
−48751号公報:中間層として、樹脂(PMMA,
シリコンゴム,ポリウレタン,高密度ポリエチレン,テ
フロン)を使用し、コーティング方法として、アパタイ
ト系セラミックス粉末の塗布乾燥方法を用いている。該
文献の目的は、芯材の折り曲げの際にコーティング層が
剥離しないことにある。すなわち芯材とコーティング層
との密着強度を向上させることにある。特開昭63−1
60665号公報:該文献の概要としては、4層の積層
構成を示すものであり、傾斜機能材料を開示している。
他、類似するものとして、特開昭63−160666号
公報が示される。特開平2−5088号公報:中間層と
して、リン酸カルシウム系ガラス、長石系ガラスを使
し、コーティング方法としては、上記中間層に水酸アパ
タイトを融着させる方法を採用している。該文献の目的
は、インプラントとしての強度を向上させる点にある。
類似する文献として特開昭63−105766号公報が
示される。特開昭63−46166号公報:中間層とし
て、Al2O3を使用し、コーティング方法として、プラ
ズマCVD、蒸着法を用いている。該文献の目的は、基
材とコーティング層との密着強度を向上させることにあ
る。これら従来技術文献に於いて、中間層を設ける目的
としては総じて基材との密着強度を高めるところにあ
り、物理的接着以外に化学的接着を考慮している。
2. Description of the Related Art Regarding a composite implant in which an intermediate layer is provided on the interface of a base material such as metal or ceramics and calcium phosphate ceramics such as apatite is coated on the outermost layer, the following prior art documents can be presented. JP-A-58-50737: As an intermediate layer, metal: M
o, Ta, Ni, Ni-Cr-Al, Al, ceramics: Al2O3, TiO2, ZrO2, SiO2, SnO2,
P2O5, CaO and B2O5 are used, and plasma spraying is used as a coating method. The purpose of this document is to improve the adhesion strength between the coating layer and the core material. Japanese Patent Laid-Open No. 2-6537: Titanium oxide and tin oxide are used as an intermediate layer, and a thermal decomposition method is used as a coating method. The purpose of this document is to improve the adhesion strength between the coating layer and the core material. JP-A-60
-48751 gazette: As an intermediate | middle layer, resin (PMMA,
Silicon rubber, polyurethane, high-density polyethylene, and Teflon) are used, and the coating and drying method of apatite-based ceramic powder is used. The purpose of this document is that the coating layer does not peel off when the core material is bent. That is, it is to improve the adhesion strength between the core material and the coating layer. JP 63-1
Japanese Laid-Open Patent Publication No. 60665: As an outline of the document, a laminated structure of four layers is shown, and a functionally graded material is disclosed.
Other similar ones are disclosed in Japanese Patent Laid-Open No. 63-160666. Japanese Patent Laid-Open No. 2-5088: Calcium phosphate-based glass and feldspar-based glass are used as the intermediate layer, and the coating method is a method in which hydroxyapatite is fused to the intermediate layer. The purpose of this document is to improve the strength as an implant.
As a similar document, Japanese Patent Laid-Open No. 63-105766 is disclosed. JP-A-63-46166: Al2O3 is used as the intermediate layer, and plasma CVD or vapor deposition is used as the coating method. The purpose of this document is to improve the adhesion strength between the substrate and the coating layer. In these prior art documents, the purpose of providing the intermediate layer is generally to increase the adhesion strength with the base material, and chemical adhesion is considered in addition to physical adhesion.

【0003】[0003]

【発明が解決しようとする課題】複合コーティングイン
プラント材の基本的な考え方として、次の4項目が上げ
られる。 1:中間層の目的は基材と最外層リン酸カルシウム被膜
との密着強度を高める為にあること、またその効果とし
ては物理的な密着だけによらず、化学的に相互拡散をと
もなったものであること。 2:最外層リン酸カルシウム層からのCa,PO4イオ
ン以外の溶出が極力少ないこと。 3:コーティング層の破壊により、マクロファージの原
因となるような粒状、粉状の脱落がないこと。 4:長期インプラントを考えた場合、リン酸カルシウム
層そのものが比較的安定であり溶解性が低いこと、さら
に埋入後長期経過の後、リン酸カルシウム層が溶解し、
中間層が露出した場合でも2:、3:を満たしているこ
と。
The following four items are listed as the basic idea of the composite coating implant material. 1: The purpose of the intermediate layer is to increase the adhesion strength between the base material and the calcium phosphate coating of the outermost layer, and the effect is not only physical adhesion but also chemical interdiffusion. thing. 2: Elution except Ca and PO4 ions from the outermost calcium phosphate layer is as small as possible. 3: There is no granular or powdery dropout that causes macrophages due to the destruction of the coating layer. 4: When considering a long-term implant, the calcium phosphate layer itself is relatively stable and has low solubility, and further, the calcium phosphate layer dissolves after a long time after implantation,
Even if the intermediate layer is exposed, it should satisfy 2: 3 :.

【0004】以上のことを考えたとき、現状況の課題と
しては、 *中間層として樹脂あるいは金属の場合は4:を満たさ
なくなり、長期埋入には不適当である。特に樹脂の場合
は生体内での劣化が考えられる。 *中間層としてAl2O3の場合、基材と中間層の密着強
度は高まるが、中間層とリン酸カルシウムとの間での密
着力は期待できないこと。(他のセラミックスの場合も
同じ様なことが言える。) *中間層として、TiO2の場合、動物実験において結
果が思わしくなかった。 原因として生体内組織へのT
iイオン、粒状TiO2の拡散が考えられた。 *中間層がガラス層の場合、中間層としての強度そのも
のに原因がある。さらに長期埋入の後には4:を満たさ
なくなる。総じて中間層そのものが非常に薄い場合は、
層そのものの強度はある程度無視できるようになるが、
長期埋入を考慮した場合、化学的密着を実現しかつ、C
a、PO4以外の金属、陰イオンの溶出を行なわないよ
うな安定な中間層としては、未だ適当なものがない。
Considering the above, as the problem of the present situation, * 4 is not satisfied in the case of resin or metal as the intermediate layer, which is not suitable for long-term embedding. In particular, in the case of resin, deterioration in vivo is considered. * When Al2O3 is used as the intermediate layer, the adhesive strength between the base material and the intermediate layer is increased, but the adhesive strength between the intermediate layer and calcium phosphate cannot be expected. (The same can be said for other ceramics.) * When TiO2 was used as the intermediate layer, the results were not good in animal experiments. T to the in vivo tissue as a cause
The diffusion of i ions and granular TiO2 was considered. * If the intermediate layer is a glass layer, the strength of the intermediate layer itself is the cause. Furthermore, after long-term implantation, 4: is no longer satisfied. In general, if the middle layer itself is very thin,
Although the strength of the layer itself can be ignored to some extent,
When long-term implantation is considered, chemical adhesion is achieved and C
a, a stable intermediate layer that does not elute metals other than PO4 and anions is not yet suitable.

【0005】[0005]

【課題を解決する為の手段】上記に鑑み本考案は、T
i、Ti系合金等よりなる芯材の外周に中間層としてリ
ン化チタン層を設け、更にその外周に最表層としてアパ
タイト、あるいはリン酸三カルシウム等のリン酸カルシ
ウム層を形成させることにより、基材とリン酸カルシウ
ム層をカルシウムイオンあるいはリンイオンの相互拡散
により化学的に密着させ、長期埋入の後も他のイオンの
溶出が行なわれない化学的長期安定で強度の高いインプ
ラントを得ることを実現した。
In view of the above, the present invention provides a T
i, a titanium phosphide layer is provided as an intermediate layer on the outer periphery of a core material made of a Ti-based alloy and the like, and an apatite or calcium phosphate layer such as tricalcium phosphate is formed as the outermost layer on the outer periphery thereof to form a base material. The calcium phosphate layer was chemically adhered by mutual diffusion of calcium ions or phosphorus ions, and it was possible to obtain a chemically long-term stable and high-strength implant in which other ions were not eluted even after long-term implantation.

【0006】インプラントの説明 本発明でインプラントとは、人工歯根、人工骨、骨プレ
ート等生体硬組織に対する代替、補綴、補強物を示す。
芯材とは、上記インプラントによって形状が異なるが別
名で基材と称することもある。材質としてはTi、Ti
系合金等を示す。リン化チタンとはTiP2,Ti4P
3,TiP2O7,Ti1.7P等を示す。又、それらの複合
材としてCaTi4(PO4)6等も挙げられる。
Description of Implant The term “implant” as used in the present invention refers to an artificial tooth root, an artificial bone, a substitute for a biological hard tissue such as a bone plate, a prosthesis, or a reinforcement.
The core material has a different shape depending on the implant, but may be referred to as a base material by another name. Ti, Ti as material
Indicates a system alloy or the like. Titanium phosphide is TiP2, Ti4P
3, TiP2O7, Ti1.7P, etc. are shown. Moreover, CaTi4 (PO4) 6 etc. are also mentioned as those composite materials.

【0007】リン化チタン層の形成方法としては、次に
示す方法が例示される。 有機リン化合物を芯材に塗布し焼成する焼付き方法 有機リン化合物を原料とするCVD法 以上の方法によりリン化チタン中間層を形成後、水酸ア
パタイト、リン酸三カルシウム等のリン酸カルシウム層
を形成させる。その方法としては中間層とのカルシウム
イオンあるいはリンイオンの相互拡散を行なわせるた
め、 熱分解法(焼成行程により上記拡散反応が起こる。) スパッタリング法により形成後、焼成行程を経る。 スパッタリング、CVD法により中間層を形成後ドライ
エッチングにより中間層を還元状態とし、その上にコー
ティングする方法。 (この方法では中間層とリン酸カルシウム界面で強い結
合が得られる。) プラズマ溶射法、(高温のプラズマ炎により中間層が急
加熱されるところにリン酸カルシウム粉末を積層する
為。)以上のようにして形成されたリン酸カルシウム層
はできるだけ化学的に安定な物が望ましく、水熱処理等
により安定化を促進させた物を用いる。尚、リン化チタ
ン層の形成方法並びにリン酸カルシウム層の形成方法
は、上述に限るものではなく、他の方法を使用してもよ
い。尚、リン化チタン層は、芯材とリン酸カルシウム層
の間に少なくとも介在していればよく、更に他のセラミ
ックス層が中間層として付加されていても良い。
As a method for forming the titanium phosphide layer, the following method is exemplified. A baking method in which an organic phosphorus compound is applied to a core material and baked A CVD method using an organic phosphorus compound as a raw material After the titanium phosphide intermediate layer is formed by the above method, a calcium phosphate layer such as hydroxyapatite and tricalcium phosphate is formed. Let As the method, in order to cause mutual diffusion of calcium ions or phosphorus ions with the intermediate layer, a pyrolysis method (the above diffusion reaction occurs according to the firing process) is performed by a sputtering method and then a firing process. A method in which the intermediate layer is reduced by dry etching after forming the intermediate layer by sputtering or the CVD method, and the intermediate layer is coated thereon. (By this method, a strong bond is obtained at the interface between the intermediate layer and the calcium phosphate.) Plasma spraying method (since the calcium phosphate powder is laminated on the place where the intermediate layer is rapidly heated by the high-temperature plasma flame). The calcium phosphate layer thus obtained is preferably as chemically stable as possible, and the one whose stabilization is promoted by hydrothermal treatment or the like is used. The method for forming the titanium phosphide layer and the method for forming the calcium phosphate layer are not limited to the above, and other methods may be used. The titanium phosphide layer may be at least interposed between the core material and the calcium phosphate layer, and another ceramic layer may be added as an intermediate layer.

【0008】実施例1 図1に本発明の一実施例を示す。図1は人工歯根の一例
である。Ti製の芯材(11)にプロパノールにより2倍に
希釈したリン酸トリエステル溶液を均一に塗り、120℃
で乾燥後600℃大気下で10分間焼成を行なう。これによ
り芯材(11)の表面にリン化チタン層(12)が形成され、そ
の後α−TCPを溶射原料としてプラズマ溶射を行な
い、最表層としてα−TCP層(13)を40μm形成させ
る。最後にリン酸カルシウム水溶液中にて120℃、15H
rの水熱処理を行ない、α−TCP層(13)を水酸アパタ
イト層(13)に変換する。
Embodiment 1 FIG. 1 shows an embodiment of the present invention. FIG. 1 is an example of an artificial tooth root. The Ti core material (11) is evenly coated with a phosphoric acid triester solution that has been twice diluted with propanol, and the temperature is 120 ° C.
After drying at 600 ° C, calcination is performed in the atmosphere for 10 minutes. As a result, a titanium phosphide layer (12) is formed on the surface of the core material (11), and then plasma spraying is performed using α-TCP as a spraying raw material to form an α-TCP layer (13) of 40 μm as the outermost layer. Finally, in calcium phosphate aqueous solution, 120 ℃, 15H
Hydrothermal treatment of r is performed to convert the α-TCP layer (13) into a hydroxyapatite layer (13).

【0009】[0009]

【発明の効果】以上詳細の如く本発明は、リン化チタン
を中間層として設けることにより化学的にも密着力が高
く、生体中に長期埋入後、リン酸カルシウム層が溶解し
た後も、生体に害の無いインプラントが得られ、量産的
にも製造方法が簡単なことから重要な効果を奏出する。
INDUSTRIAL APPLICABILITY As described above in detail, the present invention provides titanium phosphide as an intermediate layer so that it has high chemical adhesion, and even after the calcium phosphate layer is dissolved in the living body after long-term implantation in the living body, An important implant is obtained because a harmless implant can be obtained and the production method is simple in mass production.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の一実施例を示す図である。FIG. 1 is a diagram showing an embodiment of the present invention.

【符号の説明】[Explanation of symbols]

11 芯材 12 リン化チタン層 13 水酸アパタイト層 11 core material 12 titanium phosphide layer 13 hydroxyapatite layer

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】芯材、前記芯材外周に被覆形成したリン化
チタン層、前記リン化チタン層の外周に被覆形成したリ
ン酸カルシウム層よりなることを特徴とする複合インプ
ラント。
1. A composite implant comprising a core material, a titanium phosphide layer formed on the outer periphery of the core material, and a calcium phosphate layer formed on the outer periphery of the titanium phosphide layer.
JP03250209A 1991-09-04 1991-09-04 Composite implant Expired - Fee Related JP3076636B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP03250209A JP3076636B2 (en) 1991-09-04 1991-09-04 Composite implant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP03250209A JP3076636B2 (en) 1991-09-04 1991-09-04 Composite implant

Publications (2)

Publication Number Publication Date
JPH0557010A true JPH0557010A (en) 1993-03-09
JP3076636B2 JP3076636B2 (en) 2000-08-14

Family

ID=17204448

Family Applications (1)

Application Number Title Priority Date Filing Date
JP03250209A Expired - Fee Related JP3076636B2 (en) 1991-09-04 1991-09-04 Composite implant

Country Status (1)

Country Link
JP (1) JP3076636B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013100A1 (en) * 1993-11-09 1995-05-18 The Foundation For The Promotion Of Ion Engineering Bone substitute material and process for producing the same
CN111655301A (en) * 2018-02-09 2020-09-11 普罗米米克公司 Zirconium and titanium phosphate coatings for implants and other substrates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013100A1 (en) * 1993-11-09 1995-05-18 The Foundation For The Promotion Of Ion Engineering Bone substitute material and process for producing the same
CN1101705C (en) * 1993-11-09 2003-02-19 离子工学振兴财团 Bone substitute material and process for producing the same
CN111655301A (en) * 2018-02-09 2020-09-11 普罗米米克公司 Zirconium and titanium phosphate coatings for implants and other substrates
JP2021513451A (en) * 2018-02-09 2021-05-27 プロミミック アーベー Zirconium and Titanium Phosphate Coatings for Implants and Other Substrate

Also Published As

Publication number Publication date
JP3076636B2 (en) 2000-08-14

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