JPH06285149A - Artificial raw material for organism excellent in organism affinity and manufacture thereof - Google Patents
Artificial raw material for organism excellent in organism affinity and manufacture thereofInfo
- Publication number
- JPH06285149A JPH06285149A JP5073423A JP7342393A JPH06285149A JP H06285149 A JPH06285149 A JP H06285149A JP 5073423 A JP5073423 A JP 5073423A JP 7342393 A JP7342393 A JP 7342393A JP H06285149 A JPH06285149 A JP H06285149A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- ion
- calcium phosphate
- artificial
- evaporation source
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002994 raw material Substances 0.000 title claims description 4
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 15
- 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 claims abstract description 15
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000012620 biological material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 239000012237 artificial material Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 18
- 210000000988 bone and bone Anatomy 0.000 abstract description 17
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 9
- 239000001506 calcium phosphate Substances 0.000 abstract description 9
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract description 7
- 238000005468 ion implantation Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001771 vacuum deposition Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 5
- 238000007750 plasma spraying Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 210000004746 tooth root Anatomy 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医療分野で利用される
人工骨や人工歯根等の生体用人工素材及びその製造法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial material for living body such as artificial bone and artificial tooth root used in the medical field and a method for producing the same.
【０００２】[0002]
【従来の技術】チタンやチタン系合金などは生体用金属
材料として優れた生体適合性を有しており人工骨や人工
歯根として従来から用いられているが、近年、生体親和
性（骨組織親和性）をさらに向上させる目的で生体用金
属材料の表面をカルシウムイオンの注入やリン酸カルシ
ウム塩のコーティングなどで処理することが行われるよ
うになってきた（例えば「表面技術」、Vol.43, pp739-
743,(1992)参照）。金属基材にリン酸カルシウム塩をコ
ーティングする方法としては、一般に電解質水溶液中で
の陽極酸化処理、プラズマ溶射法、イオンプレーティン
グ法などが挙げられる。以下１例としてプラズマ溶射法
によるコーティング法について説明する。2. Description of the Related Art Titanium and titanium-based alloys have excellent biocompatibility as biomaterials and have been used as artificial bones and dental roots. The surface of biomedical materials has been treated with calcium ion injection or calcium phosphate salt coating for the purpose of further improving the property (for example, “Surface Technology”, Vol.43, pp739-
743, (1992)). As a method of coating the metal phosphate with a calcium phosphate salt, anodizing treatment in an electrolyte aqueous solution, a plasma spraying method, an ion plating method and the like are generally mentioned. As one example, a coating method by the plasma spraying method will be described below.
【０００３】添付図面の図２は公知のプラズマ溶射法の
模式図であり、中心電極Ａを陰極とし、ノズルＢを陽極
として、プラズマガス導入口ＣからＡr 、Ｎ2 、Ｈ2 等
のガスを導入し、陰極Ａと陽極Ｂの間にアーク放電を発
生させてプラズマ化し、これを陽極Ｂから噴出させ、超
高温、高速流のプラズマジェットＤを形成する。こうし
て形成されたプラズマジェットＤに溶射原料供給部Ｅか
らリン酸カルシウム塩粉末を点線で示すように導入し、
溶融させて飛ばし、陽極に対向して位置された金属基材
から成る基板Ｆに膜Ｇをコーティングする。このような
コーティング法により金属基材の表面を骨と類似の物質
であるリン酸カルシウム塩で被覆した人工骨は、生体内
に埋め込まれた後、コーティング膜が骨組織と結合し、
次第に接合が密になっていく。FIG. 2 of the accompanying drawings is a schematic diagram of a known plasma spraying method. The center electrode A serves as a cathode, the nozzle B serves as an anode, and gases such as Ar, N 2 and H 2 are supplied from a plasma gas inlet C. Then, an arc discharge is generated between the cathode A and the anode B to generate plasma, which is ejected from the anode B to form a plasma jet D having an ultrahigh temperature and a high speed flow. Into the plasma jet D thus formed, calcium phosphate salt powder is introduced from the spraying raw material supply section E as shown by a dotted line,
The film G is coated on the substrate F which is made of a metal base material and is positioned to face the anode. The artificial bone in which the surface of the metal base material is coated with calcium phosphate, which is a substance similar to bone, by such a coating method is embedded in the living body, and then the coating film binds to the bone tissue,
The joint gradually becomes denser.
【０００４】また、チタン及びチタン合金製の人工骨の
表面にカルシウムイオンを注入することも公知であり、
これによりチタン及びチタン合金製の人工骨の表面にチ
タンイオンだけではなくカルシウムイオンが存在するた
めリン酸イオンの吸着が早まり、リン酸カルシウムの生
成が加速されると考えられている。このカルシウムイオ
ンの注入による生体内でのリン酸カルシウムの生成の促
進について表面分析した例が雑誌“IONICS”1992年11月
号、pp. 31〜34に開示されており、30日間擬似体液中に
浸漬した後で純チタン試料とカルシウム注入したチタン
試料とを比較した結果、カルシウムを注入した場合の方
が表面でのリン酸カルシウムの生成量は増加することが
報告されている。It is also known to implant calcium ions into the surface of artificial bones made of titanium and titanium alloys,
It is considered that, as a result, not only titanium ions but also calcium ions are present on the surface of the artificial bone made of titanium and titanium alloy, so that phosphate ions are adsorbed earlier and calcium phosphate production is accelerated. A surface analysis example of the promotion of the production of calcium phosphate in vivo by the injection of calcium ions is disclosed in the magazine "IONICS" November 1992, pp. 31-34, and immersed in simulated body fluid for 30 days. As a result of later comparing a pure titanium sample and a titanium sample injected with calcium, it has been reported that the amount of calcium phosphate produced on the surface is increased when calcium is injected.
【０００５】[0005]
【発明が解決しようとする課題】リン酸カルシウム塩を
コーティングした人工骨は生体親和性に優れているが、
しかしながら、基材であるチタンなどの金属とリン酸カ
ルシウム塩であるコーティング膜との濡れ性（化学結合
性）が乏しいため、現在行われている電解質水溶液中で
の陽極酸化処理、プラズマ溶射法、イオンプレーティン
グ法などのコーティング法では、基材とコーティング膜
との密着性が不十分であり、そのため上記のような従来
のコーティング法を利用して用意した人工骨が生体内に
埋め込まれた場合、コーティング膜と人工骨基材との界
面の密着性が劣化していき、著しい場合にはコーティン
グ膜が剥離するという問題が指摘されている。[Problems to be Solved by the Invention] Although artificial bone coated with calcium phosphate has excellent biocompatibility,
However, since the wettability (chemical bondability) between the base metal such as titanium and the coating film of calcium phosphate is poor, the anodizing treatment in the aqueous electrolyte solution, the plasma spraying method, the ion spray method that is currently being performed. In coating methods such as the coating method, the adhesion between the base material and the coating film is insufficient, so if the artificial bone prepared using the conventional coating method as described above is implanted in the living body, the coating It has been pointed out that the adhesiveness at the interface between the membrane and the artificial bone substrate deteriorates, and in a significant case, the coating membrane peels off.
【０００６】そこで本発明は、人工骨や人工歯根として
用いられる生体用人工素材におけるコーティング膜と骨
組織との親和性を損なわずに、コーティング膜と生体用
人工素材との密着性を改善した生体用人工素材及びその
製造法を提供することを目的としている。Therefore, the present invention provides a living body in which the adhesiveness between the coating film and the artificial artificial material is improved without impairing the affinity between the coating film and the bone tissue in the artificial biological material used as an artificial bone or an artificial tooth root. The purpose of the present invention is to provide an artificial material for use and a manufacturing method thereof.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めに本発明の第１の発明による生体親和性に優れた生体
用人工素材は、チタンやチタン系合金などの金属または
セラミック材料から成る基材の表面に、イオンミキシン
グ法によりリン酸カルシウム塩をコーディングしたこと
を特徴としている。好ましくは、本発明による生体親和
性に優れた生体用人工素材は、チタンやチタン系合金な
どの金属またはセラミック材料から成る基材の表面にコ
ーティングされたリン酸カルシウム塩には、カルシウム
元素が注入され得る。また、本発明の第２の発明による
生体親和性に優れた生体用人工素材の製造法は、真空容
器内にチタンやチタン系合金などの金属またはセラミッ
ク材料から成る基材を配置し、蒸発原料としてリン酸カ
ルシウム塩を用い、蒸着法により基材表面に蒸着しなが
ら、密着性または親和性促進用イオンを同時にイオン注
入することを特徴としている。各発明において基材の表
面にコーティングされるリン酸カルシウム塩は、例えば
結晶質または非結晶質のハイドロキシアパタイトから成
ることができる。In order to achieve the above object, the artificial biomaterial having excellent biocompatibility according to the first aspect of the present invention is made of metal such as titanium or titanium-based alloy or ceramic material. It is characterized in that a calcium phosphate salt is coded on the surface of the base material by an ion mixing method. Preferably, the artificial biomaterial having excellent biocompatibility according to the present invention is such that calcium phosphate can be injected into the calcium phosphate salt coated on the surface of a substrate made of a metal such as titanium or titanium-based alloy or a ceramic material. . The method for producing an artificial biomaterial having excellent biocompatibility according to the second aspect of the present invention is characterized in that a base material made of a metal such as titanium or titanium-based alloy or a ceramic material is placed in a vacuum container, and an evaporation raw material is used. It is characterized in that calcium phosphate is used as the material, and ions for promoting adhesion or affinity are simultaneously implanted while being vapor-deposited on the surface of the substrate by the vapor deposition method. The calcium phosphate salt coated on the surface of the substrate in each invention can be composed of, for example, crystalline or amorphous hydroxyapatite.
【０００８】[0008]
【作用】本発明の製造法によれば、リン酸カルシウム塩
の蒸着と同時にカルシウムイオンの注入を行なうイオン
ビームダイナミックミキシング技術を採用したことによ
り、高エネルギーのイオンビームによるミキシング効果
が得られ、基材とコーティング層の界面に、基材とコー
ティング層の混ざりあった中間層が生成されることにな
り、密着性が改善される。また、注入イオン種としてカ
ルシウムイオンを用いた場合には、生体用人工素材の基
材表面にカルシウム富化層が形成されることになり、こ
の基材表面に存在するカルシウムの働きにで親和性の改
善が期待できることになる。According to the manufacturing method of the present invention, by adopting the ion beam dynamic mixing technique of injecting calcium ions at the same time as the deposition of calcium phosphate salt, the mixing effect by the high energy ion beam can be obtained, An intermediate layer in which the base material and the coating layer are mixed is formed at the interface of the coating layer, and the adhesion is improved. Also, when calcium ions are used as the implanted ion species, a calcium-enriched layer is formed on the surface of the base material of the bioartificial material, and the calcium existing on the surface of the base material has an affinity for the action. Can be expected to improve.
【０００９】[0009]
【実施例】以下、添付図面の図１を参照して本発明の実
施例について説明する。図１には本発明による生体用人
工素材の製造に用いられるイオンビームダイナミックミ
キシング法を利用した装置の一例を概略的に示してい
る。図１において１は真空容器で、この真空容器１内に
は、コーティング処理すべき基板２を保持する基板ホル
ダー３及び蒸発源ハース４が図示したように配設され、
蒸発源ハース４には、蒸発させるハイドロキシアパタイ
ト焼結体５が入れられている。また蒸発源ハース４の上
部に臨んでガス導入ノズル６が設けられている。また、
真空容器１にはイオン源及びイオン加速器７が連接され
ており、このイオン源及びイオン加速器７自体は公知の
ものであるので、その具体的構成は省略されている。真
空容器１内に示された矢印８はイオン源及びイオン加速
器７から基板ホルダー３上の基板２へ向かって打ち込ま
れるイオンビームを表し、また矢印９は、図示してない
E/B ガンによって加熱蒸発された蒸発源ハース４内のハ
イドロキシアパタイト焼結体の蒸発粒子を表している。Embodiments of the present invention will be described below with reference to FIG. 1 of the accompanying drawings. FIG. 1 schematically shows an example of an apparatus using the ion beam dynamic mixing method used for manufacturing an artificial biomaterial according to the present invention. In FIG. 1, reference numeral 1 denotes a vacuum container. Inside the vacuum container 1, a substrate holder 3 for holding a substrate 2 to be coated and an evaporation source hearth 4 are arranged as shown in the drawing.
The evaporation source hearth 4 contains a hydroxyapatite sintered body 5 to be evaporated. Further, a gas introduction nozzle 6 is provided facing the upper part of the evaporation source hearth 4. Also,
An ion source and an ion accelerator 7 are connected to the vacuum container 1, and since the ion source and the ion accelerator 7 themselves are publicly known, their specific configurations are omitted. The arrow 8 shown in the vacuum container 1 represents an ion beam that is bombarded from the ion source and the ion accelerator 7 toward the substrate 2 on the substrate holder 3, and the arrow 9 is not shown.
It shows the vaporized particles of the hydroxyapatite sintered body in the vaporization source hearth 4 which is heated and vaporized by the E / B gun.
【００１０】本発明の一実施例では、図１に示す装置を
用いてチタン基板にイオンビームダイナミックミキシン
グ法によりハイドロキシアパタイトをコーティングし
た。蒸発源材料は、ハイドロキシアパタイト（Ca10（PO
4 ）6 (OH)2 、以下HAp ）であり、コーティング手法と
しては図１に示す装置において、Ｈ2 Ｏ雰囲気下で蒸発
源ハース４内のHAp をE/B ガンを用いて加熱蒸発させ、
蒸発粒子をチタン基板に蒸着させると同時に、イオン源
及びイオン加速器７からカルシウムイオンを加速電圧50
Kvでチタン基板に注入した。なおコーティング膜厚は約
１μｍである。すなわち、まず、真空容器１内を高真空
（６×10-4Pa）に排気した状態でイオン源及びイオン加
速器７から引き出されたカルシウムイオンをチタン基板
２に注入した。この場合、イオンビームのエネルギーは
50Kev 、電流密度は6.7 μA/cm2 、イオン注入量は５×
10-16 個／cm2 とした。次に、ガス導入ノズル６からＨ
2 Ｏガスを導入して、真空容器１内のの圧力を1.2×10
-2Paに保ち、この状態で、上述と同一の条件でイオンビ
ームをチタン基板２に注入しながら、電子ビーム加熱に
より蒸発源ハース４内のハイドロキシアパタイト焼結体
５を蒸発させて、チタン基板２上に蒸着した。この場
合、蒸着速度は１〜３A/S に調節した。この操作をチタ
ン基板２へのカルシウムイオンの注入量が１×10-17 個
／cm2 になるまで続けた。尚、蒸着の際にＨ2 Ｏガスを
導入することにより、コーティング膜中のＯＨ基の形成
が促進されることになる。その後、イオン注入条件は同
一にしてハイドロキシアパタイトの蒸着速度を約10オン
グストローム／秒にしてチタン基板２に形成されるコー
ティング膜の厚さが約１μｍになるまで続けた。このよ
うにしてハイドロキシアパタイト膜をコーティングした
試料について密着性や表面状態の変化を調べるため、試
料を簡便な体液の模擬として一般に使用される１％NaCl
溶液中に約１カ月浸漬した後観察した結果、試料表面の
変化はほとんど見られず、密着性も良好であることが認
められた。In one embodiment of the present invention, a titanium substrate was coated with hydroxyapatite by an ion beam dynamic mixing method using the apparatus shown in FIG. The evaporation source material is hydroxyapatite (Ca 10 (PO
4 ) 6 (OH) 2 , hereinafter referred to as HAp). As a coating method, in the apparatus shown in FIG. 1, HAp in the evaporation source hearth 4 is heated and evaporated using an E / B gun in an H 2 O atmosphere.
At the same time as vaporized particles are deposited on the titanium substrate, calcium ions are accelerated from the ion source and the ion accelerator 7 at an accelerating voltage of 50.
The titanium substrate was injected with Kv. The coating film thickness is about 1 μm. That is, first, calcium ions extracted from the ion source and the ion accelerator 7 were injected into the titanium substrate 2 in a state where the inside of the vacuum container 1 was evacuated to a high vacuum (6 × 10 −4 Pa). In this case, the energy of the ion beam is
50Kev, current density 6.7 μA / cm 2 , ion implantation dose 5 ×
It was set to 10 -16 pieces / cm 2 . Next, from the gas introduction nozzle 6 to H
Introduce 2 O gas to adjust the pressure in the vacuum vessel 1 to 1.2 x 10
-2 Pa, in this state, while injecting an ion beam into the titanium substrate 2 under the same conditions as described above, the hydroxyapatite sintered body 5 in the evaporation source hearth 4 is evaporated by electron beam heating, and the titanium substrate is It was vapor-deposited on 2. In this case, the vapor deposition rate was adjusted to 1 to 3 A / S. This operation was continued until the injection amount of calcium ions into the titanium substrate 2 became 1 × 10 −17 / cm 2 . The introduction of H 2 O gas during vapor deposition promotes the formation of OH groups in the coating film. Thereafter, the ion implantation conditions were the same, and the deposition rate of hydroxyapatite was set to about 10 angstroms / second until the thickness of the coating film formed on the titanium substrate 2 became about 1 μm. In order to investigate the change in adhesion and surface condition of the sample coated with the hydroxyapatite film in this way, the sample is used as a simple body fluid simulation of 1% NaCl.
As a result of observation after immersing in the solution for about 1 month, almost no change was observed on the sample surface, and it was confirmed that the adhesiveness was also good.
【００１１】ところで、上記実施例では、蒸発源原料と
してハイドロキシアパタイトを用いているが、代わりに
例えばＴＣＰCa3 （PO4 ）2 などのようなその他の多く
のリン酸カルシウム塩を用いてもよい。また、密着性、
親和性促進用イオン種として上記実施例ではカルシウム
イオン（Ca+ ）を用いているが、代わりに、Ti+ 、
Ｐ+ 、Ｏ2 + 、Ar+ などを用いることもできる。さらに
蒸発源としてE/B 加熱法を用いているが、代わりにレー
ザーによる加熱法（レーザーアブレーション法）を利用
してもよい。さらにまた基板としてチタン以外にTi−6A
1 −4V、Ti−Ni形状記憶合金などのチタン合金やステン
レス鋼、或いはAl2 Ｏ3 などのセラミックス材料を使用
することも可能である。By the way, in the above embodiment, hydroxyapatite is used as the evaporation source material, but many other calcium phosphate salts such as TCPCa 3 (PO 4 ) 2 may be used instead. Also, the adhesion,
Although calcium ions (Ca + ) are used as the affinity-promoting ionic species in the above examples, Ti + ,
It is also possible to use P + , O 2 + , Ar + or the like. Further, although the E / B heating method is used as the evaporation source, a heating method using a laser (laser ablation method) may be used instead. Furthermore, as a substrate, in addition to titanium, Ti-6A
It is also possible to use titanium alloys such as 1-4V and Ti-Ni shape memory alloys, stainless steel, or ceramic materials such as Al 2 O 3 .
【００１２】[0012]
【発明の効果】以上説明してきたように、本発明の方法
によれば、イオンビームダイナミックミキシング法を利
用して、蒸着と同時にイオン注入を行なうように構成し
ているので、高エネルギーのイオンビームによるミキシ
ング効果が得られ、それにより基材とコーティング層と
の界面に、基材とコーティング層との混ざりあった中間
層が生成されるため、基材とコーティング層との密着性
を大幅に改善することができるようになる。また、本発
明による生体用人工素材は、リン酸カルシウム塩コーテ
ィング膜と基材との密着性が長期に渡って良好に維持で
きるので、例えば人工骨として生体内に埋め込まれた場
合に、基材とコーティング膜との剥離が生じにくくな
り、骨と人工骨の接合性を改善することができるように
なる。さらに、基材表面に形成されるコーティング層に
カルシウムイオン等のイオンを注入した場合にはコーテ
ィング膜の密着性の改善だけではなく、骨組織に対する
親和性をより一層改善することができるようになる。As described above, according to the method of the present invention, the ion beam dynamic mixing method is used to perform the ion implantation simultaneously with the vapor deposition. The mixing effect is obtained by this, and since an intermediate layer in which the base material and the coating layer are mixed is generated at the interface between the base material and the coating layer, the adhesion between the base material and the coating layer is greatly improved. You will be able to. Further, since the bioartificial material according to the present invention can maintain good adhesion between the calcium phosphate salt coating film and the base material over a long period of time, for example, when it is embedded in a living body as artificial bone, the base material and the coating Peeling from the membrane is less likely to occur, and the bondability between the bone and the artificial bone can be improved. Furthermore, when ions such as calcium ions are injected into the coating layer formed on the surface of the base material, not only the adhesion of the coating film can be improved but also the affinity for bone tissue can be further improved. .
【図１】 本発明の実施例に使用される装置の構成を示
す図。FIG. 1 is a diagram showing a configuration of an apparatus used in an embodiment of the present invention.
【図２】 従来のコーティング法の１例であるプラズマ
溶射法の構成図。FIG. 2 is a configuration diagram of a plasma spraying method which is an example of a conventional coating method.
１‥‥真空容器 ２‥‥コーティングを施す基板 ３‥‥基板を保持する基板ホルダー ４‥‥蒸発源ハース ５‥‥蒸発させるハイドロキシアパタイト焼結体 ６‥‥ガス導入ノズル ７‥‥イオン源及びイオン加速器 ８‥‥イオンビーム ９‥‥蒸発粒子 1 ... Vacuum container 2 ... Substrate to be coated 3 ... Substrate holder for holding substrate 4 ... Evaporation source hearth 5 ... Evaporating hydroxyapatite sintered body 6 ... Gas introduction nozzle 7 ... Ion source and ion Accelerator 8 ・ ・ ・ Ion beam 9 ・ ・ ・ Evaporated particles
───────────────────────────────────────────────────── フロントページの続き (72)発明者 住井 俊夫 千葉県千葉市花見川区作新台７−８−16 (72)発明者 吉成 正雄 千葉県千葉市美浜区真砂１−７−３ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Sumii 7-8-16 Sakushindai, Hanamigawa-ku, Chiba-shi, Chiba (72) Inventor Masao Yoshinari 1-7-3 Masago, Mihama-ku, Chiba-shi
Claims (5)
ラミック材料から成る基材の表面にイオンビームダイナ
ミックミキシング法によりリン酸カルシウム塩をコーデ
ィングしたことを特徴とする生体親和性に優れた生体用
人工素材。1. An artificial biomaterial having excellent biocompatibility, characterized in that a calcium phosphate salt is coded on the surface of a base material made of a metal such as titanium or a titanium-based alloy or a ceramic material by an ion beam dynamic mixing method.
質のハイドロキシアパタイトからなる請求項１に記載の
生体親和性に優れた生体用人工素材。2. The artificial material for living body having excellent biocompatibility according to claim 1, wherein the calcium phosphate salt is crystalline or amorphous hydroxyapatite.
ラミック材料から成る基材の表面にカルシウム元素が注
入されているリン酸カルシウム塩をコーティングしたこ
とを特徴とする生体親和性に優れた生体用人工素材。3. An artificial biomaterial having excellent biocompatibility, characterized in that the surface of a base material made of a metal such as titanium or a titanium-based alloy or a ceramic material is coated with a calcium phosphate salt in which calcium element is injected. .
質のハイドロキシアパタイトからなる請求項３に記載の
生体親和性に優れた生体用人工素材。4. An artificial biomaterial having excellent biocompatibility according to claim 3, wherein the calcium phosphate salt is crystalline or amorphous hydroxyapatite.
金属またはセラミック材料から成る基材を配置し、蒸発
原料としてリン酸カルシウム塩を用い、蒸着法により基
板表面に蒸着しながら、密着性、親和性促進用イオンを
同時にイオン注入することを特徴とする生体親和性に優
れた生体用人工素材の製造法。5. A base material made of a metal such as titanium or a titanium-based alloy or a ceramic material is placed in a vacuum container, and calcium phosphate salt is used as an evaporation raw material, while vapor deposition is performed on the surface of the substrate by vapor deposition, and adhesion and affinity are improved. A method for producing an artificial biomaterial having excellent biocompatibility, which comprises simultaneously injecting sex promoting ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5073423A JPH06285149A (en) | 1993-03-31 | 1993-03-31 | Artificial raw material for organism excellent in organism affinity and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5073423A JPH06285149A (en) | 1993-03-31 | 1993-03-31 | Artificial raw material for organism excellent in organism affinity and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06285149A true JPH06285149A (en) | 1994-10-11 |
Family
ID=13517809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5073423A Pending JPH06285149A (en) | 1993-03-31 | 1993-03-31 | Artificial raw material for organism excellent in organism affinity and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06285149A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1066721A (en) * | 1996-08-28 | 1998-03-10 | Showa Gomme Kk | Surface treatment method for medical articles by gas cluster ion beam |
| KR20010073801A (en) * | 2000-01-20 | 2001-08-03 | 김현이 | Manufacturing method of composite implant material |
| KR100855017B1 (en) * | 2006-12-06 | 2008-08-28 | 연세대학교 산학협력단 | Biological graft material coated with bioglass thin film and method for manufacturing same |
| JP2011078745A (en) * | 2009-09-09 | 2011-04-21 | Kinki Univ | Bone prosthetic material |
| JP2011078749A (en) * | 2009-09-10 | 2011-04-21 | Tokyo Metropolitan Industrial Technology Research Institute | Artificial bone member |
-
1993
- 1993-03-31 JP JP5073423A patent/JPH06285149A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1066721A (en) * | 1996-08-28 | 1998-03-10 | Showa Gomme Kk | Surface treatment method for medical articles by gas cluster ion beam |
| KR20010073801A (en) * | 2000-01-20 | 2001-08-03 | 김현이 | Manufacturing method of composite implant material |
| KR100855017B1 (en) * | 2006-12-06 | 2008-08-28 | 연세대학교 산학협력단 | Biological graft material coated with bioglass thin film and method for manufacturing same |
| JP2011078745A (en) * | 2009-09-09 | 2011-04-21 | Kinki Univ | Bone prosthetic material |
| JP2011078749A (en) * | 2009-09-10 | 2011-04-21 | Tokyo Metropolitan Industrial Technology Research Institute | Artificial bone member |
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