JPH01275767A - Production of implant material - Google Patents

Production of implant material

Info

Publication number
JPH01275767A
JPH01275767A JP63106060A JP10606088A JPH01275767A JP H01275767 A JPH01275767 A JP H01275767A JP 63106060 A JP63106060 A JP 63106060A JP 10606088 A JP10606088 A JP 10606088A JP H01275767 A JPH01275767 A JP H01275767A
Authority
JP
Japan
Prior art keywords
metal
sol
hydroxyl groups
chloride layer
bar
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
Application number
JP63106060A
Other languages
Japanese (ja)
Inventor
Motoyuki Toki
元幸 土岐
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.)
Seiko Epson Corp
Original Assignee
Seiko Epson Corp
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 Seiko Epson Corp filed Critical Seiko Epson Corp
Priority to JP63106060A priority Critical patent/JPH01275767A/en
Publication of JPH01275767A publication Critical patent/JPH01275767A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1254Sol or sol-gel processing
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229Composition of the substrate
    • C23C18/1241Metallic substrates

Abstract

PURPOSE:To produce an implant material having a great affinity for a living body and high strength by adding P and Ca compds. to a soln. prepd. by hydrolyzing alkyl silicate to obtain sol, introducing hydroxyl groups into a metal chloride layer formed on the surface of a metal, dipping this metal in the sol, drying and calcining a formed sol film. CONSTITUTION:Ethyl silicate is hydrolyzed by mixing with a soln. of ethanol in hydrochloric acid and the resulting soln. is mixed with calcium ethoxide and phosphoric acid to obtain sol. A metal bar such as a stainless steel bar is heated in gaseous HCl or Cl2 to form a metal chloride layer on the surface of the bar and this bar is put in water, heated, taken out and dried to introduce hydroxyl groups into the metal chloride layer. The bar is then dipped in the sol and a formed sol film is dried at about 60 deg.C and heated at about 350 deg.C. An implant material having a great affinity for a living body and high strength and useful as an artificial tooth or bone is produced.

Description

【発明の詳細な説明】 (産業上の利用分野〕 本発明は人工歯、人工骨として用いられつるインプラン
ト材の製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a temple implant material used as an artificial tooth or bone.

(従来の技術) 従来のインプラント材は、セラミックス20、(198
5)No12、P4O10に記載されているように、生
体許容性(ポリエチレン、ステンレス鋼)、生体不活性
(アルミナ、カーボン)、生体活性(アパタイト、 T
 CP 、Ca 40 (P04)2)の3種類の材料
が有った。
(Prior art) Conventional implant materials include ceramics 20, (198
5) As described in No. 12, P4O10, bioacceptability (polyethylene, stainless steel), bioinertness (alumina, carbon), bioactivity (apatite, T
There were three types of materials: CP and Ca 40 (P04)2).

(発明か解決しようとする課題) しかし、前述の従来技術にはそれぞれ次のような問題点
を有しているため、一般に広くは普及していない。
(Problem to be Solved by the Invention) However, each of the above-mentioned prior art techniques has the following problems, and therefore has not been widely used.

生体許容性及び生体不活性材料の場合は、骨と直接結合
することなく、機械的なはめこみによってのみ固定され
ているだけなので、長期間使用でゆるみや脱落の恐れが
ある。
In the case of bioacceptable and bioinert materials, they are not directly bonded to the bone and are only fixed by mechanical fitting, so there is a risk of loosening or falling off after long-term use.

一方、生体活性材料の場合は、特にアパタイトでは圧縮
強度は十分であるか、引張り、曲げ、ねじり強度か不十
分である。従って過大な引張り応力のかかる部位には使
用できない。
On the other hand, in the case of bioactive materials, especially apatite, the compressive strength is sufficient or the tensile, bending, and torsional strengths are insufficient. Therefore, it cannot be used in areas subject to excessive tensile stress.

このようなことから、生体親和性を損なわないで材料強
度を向上させる試みかなされている。この試みについて
は今だに実用レベルまで達っしたという報告は一件もな
く、開発中である。
For this reason, attempts have been made to improve material strength without impairing biocompatibility. There are no reports of this attempt reaching a practical level yet, and it is still under development.

この試みの一つの方法としては、ステンレスやチタン合
金の表面にバイオガラスをコーティングすることて、強
度と生体親和性を同時に満足する材料を作成するものが
有る。この問題点は、コーティング膜と金属との間の接
着強度が弱いことと、従来はコーティングをバイオガラ
スの溶融で行っていたのであるが、作業性が悪く、量産
性がないという問題点を有していた。
One way to try this is to coat the surface of stainless steel or titanium alloy with bioglass to create a material that has both strength and biocompatibility. The problem is that the adhesive strength between the coating film and the metal is weak, and conventionally coating was done by melting bioglass, but this has problems such as poor workability and not being suitable for mass production. Was.

そこで、本発明は、このような問題点を解決するものて
、その目的とするところは、金属の表面に容易に、接着
力の強いバイオガラスの膜を形成する方法を提供するこ
とにある。
SUMMARY OF THE INVENTION The present invention aims to solve these problems, and its purpose is to provide a method for easily forming a bioglass film with strong adhesive strength on a metal surface.

〔課題を解決するための手段〕[Means to solve the problem]

本発明のインプラント材の製造方法は、金属表面に以下
の工程で、バイオガラスをコーティングしたことを特徴
とする。
The method for manufacturing an implant material of the present invention is characterized in that a metal surface is coated with bioglass in the following steps.

a)アルキルシリケートの加水分解溶液に、リン化合物
、カルシウム化合物を添加しゾルとする工程、 b)金属表面に、HCIあるいはCl,を作用させ、金
属の塩化物の層を形成し、以下のいずれかの方法によっ
て、金属表面に水酸基を生成する工程、 i)塩化物の層に水を反応させ水酸基を生成する方法 ii)塩化物の層にアルコールを反応させアルコキシド
とし、酸あるいは水を作用させて水酸基を生成する方法 iii)塩化物の層にソディウムアルコキシドを作用さ
せ金属の表面に金属アルコキシドの層を形成し、酸ある
いは水を作用させて水酸基を生成する方法 C)水酸基の生成した金属を前記ゾルに浸し、ディッピ
ングによりゾル膜の形成の工程。
a) Adding a phosphorus compound and a calcium compound to a hydrolyzed solution of alkyl silicate to form a sol; b) Applying HCI or Cl to the metal surface to form a layer of metal chloride; A process of generating hydroxyl groups on the metal surface by the above method, i) A method of reacting a chloride layer with water to generate a hydroxyl group, ii) A process of reacting an alcohol with a chloride layer to form an alkoxide, and then reacting it with acid or water. iii) A method in which sodium alkoxide is applied to a chloride layer to form a metal alkoxide layer on the surface of the metal, and acid or water is applied to the metal to generate hydroxyl groups. A step of forming a sol film by dipping in the sol.

d)前記コーティング物を乾燥し、適当な温度で焼成す
る工程。
d) Drying the coating and baking it at an appropriate temperature.

(作 用) 本発明の上記の構成によれば、金属表面の塩化物層を形
成し、直接あるいはアルコキシドを経由して、水酸基を
金属表面層に多量に導入することかできる。
(Function) According to the above configuration of the present invention, a chloride layer is formed on the metal surface, and a large amount of hydroxyl groups can be introduced into the metal surface layer directly or via an alkoxide.

水酸基を多量に表面に有する金属をバイオガラス組成の
ゾルに浸すと、水酸基とゾルが結合し、付着の強いコー
ティング膜が得られることになる。
When a metal having a large amount of hydroxyl groups on its surface is immersed in a sol of bioglass composition, the hydroxyl groups and the sol bond, resulting in a coating film with strong adhesion.

(実 施 例) エチルシリケート1モルに、エチルアルコール100m
u、0.1規定の塩酸水溶液を32mM加え、よくかき
まぜた、加水分解終了後に、カルシウムエト上シト1モ
ル及び、リン酸0.6モルを加えよくかきまぜた。必要
に応じて、膜厚や、膜性のコントロールのため、水、ア
ルコール、増粘剤(エチレングリコール等)、シリカ微
粒子等を適当量添加した。これをゾルと呼ぶ。
(Example) To 1 mole of ethyl silicate, 100 m of ethyl alcohol
32 mM of 0.1N hydrochloric acid aqueous solution was added and stirred well. After completion of hydrolysis, 1 mol of calcium chloride and 0.6 mol of phosphoric acid were added and stirred well. If necessary, appropriate amounts of water, alcohol, thickener (ethylene glycol, etc.), silica particles, etc. were added to control the film thickness and film properties. This is called sol.

一方、ステンレスや、チタン、チタン−クロム合金等の
金属棒を、塩素あるいは塩素ガス中で加熱し、金属棒表
面を塩素化した。次に、次の3通りの方法で水酸基を導
入した。
On the other hand, a metal rod made of stainless steel, titanium, titanium-chromium alloy, or the like was heated in chlorine or chlorine gas to chlorinate the surface of the metal rod. Next, hydroxyl groups were introduced using the following three methods.

■塩素化した金属棒を水中に入れ、加熱し、取り出して
乾燥した。
■ A chlorinated metal rod was placed in water, heated, and then taken out and dried.

■塩素化した金属棒をエタノール中に入れ、アルコキシ
ドを形成し、取り出した後、水と反応させ乾燥した。
■ A chlorinated metal rod was placed in ethanol to form an alkoxide, taken out, reacted with water, and dried.

■塩素化した金属棒をソディウムエトキシドの溶液に浸
し、アルコキシドを形成し、取り出した後、水と反応さ
せ乾燥した。
■ A chlorinated metal rod was immersed in a solution of sodium ethoxide to form an alkoxide, which was taken out, reacted with water, and dried.

このようにして水酸基を表面に導入した金属棒を上記の
ゾルに浸し、ディッピングによりコーティングした。つ
づいて、60℃で乾燥した後、350℃に加熱してバイ
オガラスのコーティング膜にした。
The metal rod with hydroxyl groups introduced onto its surface in this way was immersed in the above sol and coated by dipping. Subsequently, it was dried at 60°C and then heated to 350°C to form a bioglass coating film.

得られたインプラント材は、生体親和性と強度を十分に
兼ね備えており、実用化可能なものであった。
The obtained implant material had sufficient biocompatibility and strength, and was suitable for practical use.

(発明の効果) 以上述べたように本発明によれば、ゾル−ゲル法のゾル
にハイドロキシアパタイトの組成になるような添加を行
ない、さらに金属表面に水酸基を導入してから後にゾル
のコーティングを行うことで、強固な薄膜形成を可能に
し、生体親和性の優れた強度の強いインプラント材にす
ることができる。
(Effects of the Invention) As described above, according to the present invention, the sol of the sol-gel process is added with a composition of hydroxyapatite, and furthermore, hydroxyl groups are introduced onto the metal surface, and then the sol is coated. By doing so, it is possible to form a strong thin film, resulting in a strong implant material with excellent biocompatibility.

Claims (1)

【特許請求の範囲】 金属表面に以下の工程で、バイオガラスをコーティング
したことを特徴とするインプラント材の製造方法。 a)アルキルシリケートの加水分解溶液に、リン化合物
、カルシウム化合物を添加しゾルとする工程、 b)金属表面に、HClあるいはCl_2を作用させ、
金属の塩化物の層を形成し、以下のいずれかの方法によ
って、金属表面に水酸基を生成する工程、 i)塩化物の層に水を反応させ水酸基を生成する方法 ii)塩化物の層にアルコールを反応させアルコキシド
とし、酸あるいは水を作用させて水酸基を生成する方法 iii)塩化物の層にソディウムアルコキシドを作用さ
せ金属の表面に金属アルコキシドの層を形成し、酸ある
いは水を作用させて水酸基を生成する方法 c)水酸基の生成した金属を前記ゾルに浸し、ディッピ
ングによりゾル膜の形成の工程、d)前記コーティング
物を乾燥し、適当な温度で焼成する工程。
[Claims] A method for producing an implant material, characterized in that a metal surface is coated with bioglass in the following steps. a) Adding a phosphorus compound and a calcium compound to a hydrolyzed solution of alkyl silicate to form a sol; b) Applying HCl or Cl_2 to the metal surface;
A step of forming a chloride layer of the metal and generating hydroxyl groups on the metal surface by one of the following methods: i) A method of reacting water with the chloride layer to generate hydroxyl groups ii) A method of forming a hydroxyl group on the chloride layer A method in which alcohol is reacted to form an alkoxide, and then acid or water is applied to produce a hydroxyl group. iii) A layer of metal alkoxide is formed on the surface of the metal by applying sodium alkoxide to a chloride layer, and then acid or water is applied. Method for producing hydroxyl groups c) A step of immersing the metal with hydroxyl groups in the sol and forming a sol film by dipping; d) Drying the coated material and baking it at an appropriate temperature.
JP63106060A 1988-04-28 1988-04-28 Production of implant material Pending JPH01275767A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63106060A JPH01275767A (en) 1988-04-28 1988-04-28 Production of implant material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63106060A JPH01275767A (en) 1988-04-28 1988-04-28 Production of implant material

Publications (1)

Publication Number Publication Date
JPH01275767A true JPH01275767A (en) 1989-11-06

Family

ID=14424070

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63106060A Pending JPH01275767A (en) 1988-04-28 1988-04-28 Production of implant material

Country Status (1)

Country Link
JP (1) JPH01275767A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6285041B1 (en) 1996-08-29 2001-09-04 Nec Corporation Thin-film transistor having a high resistance back channel region am) fabrication method thereof
GB2461743A (en) * 2008-07-11 2010-01-20 Smith & Nephew Medical device or composition comprising at least two inorganic components

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6285041B1 (en) 1996-08-29 2001-09-04 Nec Corporation Thin-film transistor having a high resistance back channel region am) fabrication method thereof
GB2461743A (en) * 2008-07-11 2010-01-20 Smith & Nephew Medical device or composition comprising at least two inorganic components

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