JPH021286A - Living body material - Google Patents
Living body materialInfo
- Publication number
- JPH021286A JPH021286A JP1048524A JP4852489A JPH021286A JP H021286 A JPH021286 A JP H021286A JP 1048524 A JP1048524 A JP 1048524A JP 4852489 A JP4852489 A JP 4852489A JP H021286 A JPH021286 A JP H021286A
- Authority
- JP
- Japan
- Prior art keywords
- film
- hydroxyapatite
- substrate
- amorphous
- axis oriented
- 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
- 239000000463 material Substances 0.000 title abstract description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 60
- 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 60
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000012620 biological material Substances 0.000 claims description 25
- 239000010408 film Substances 0.000 abstract description 59
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000004544 sputter deposition Methods 0.000 abstract description 21
- 239000010409 thin film Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 210000000988 bone and bone Anatomy 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000860832 Yoda Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037074 physically active Effects 0.000 description 1
- 238000007586 pull-out test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 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 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は人工骨として使用される生体材料、詳しくは非
晶質、Ｃ軸配向結晶及びそれらの混在するハイドロキシ
アパタイトを基質にある膜厚でコーティングさせた生体
材料に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention is directed to biomaterials used as artificial bones, specifically amorphous, C-axis oriented crystals, and hydroxyapatite containing a mixture of these, in a film thickness of a substrate. It concerns coated biomaterials.
骨欠損部に使用するため種々の人工骨が開発されている
が、それらには生体親和性と適当な機械的強度が要求さ
れる。ハイドロキシアパタイトは骨の主構成要素で、骨
と直接結合して生体組織に同化するので、生体材料とし
て優れている。然しなから合成したハイドロキシアパタ
イトそのま＼では、水に対する溶解度が高く、機械的強
度も弱いので、焼成することによりこれらの性質を矯正
し、生体材料として使用することが試みられている。し
かし十分な機械的強度をえるため高温で焼成すると生体
親和性が減少する。そこでハイドロキシアパタイトを生
体材料として使用するために種々の加工法が検討されて
おり、チタン、アルミナ、ステンレス、セラミック、そ
の他（以下基質と記す）にハイドロキシアパタイトをコ
ーティングさせる方法がある。基質にハイドロキシアパ
タイトをコーティングする方法として基質にハイドロキ
シアパタイトをコーティングして焼成する、或は基質に
焼成ハイドロキシアパタイトをコーティングするなどの
加工法は、比較的筒車な操作で、比較的機械強度の高い
生体材料かえられるが、ノ１イドロキシアパタイトを基
質に均一にコーティングしにくく、コーティング層が厚
くなり、基質との結合が弱いため、ハイドロキシアパタ
イトのコーティング層が剥がれ易く、精密な加工がむつ
かしい。又焼成されているため、ハイドロキシアパタイ
トの生体親和性も完全とは云えない。東方らは、プラズ
マ溶射法によりステンレスにハイドロキシアパタイトを
コーティングさせた生体材料を、用田はステンレスに骨
粉をスパッタリングでコーティングさせた生体材料を報
じている。しかしながら、−ａにハイドロキシアパタイ
トのコーティングにはプラズマ溶射法が多く用いられて
いる。Various artificial bones have been developed for use in bone defects, but they are required to have biocompatibility and appropriate mechanical strength. Hydroxyapatite is the main component of bone, and it is an excellent biomaterial because it directly binds to bone and assimilates into living tissue. However, synthesized hydroxyapatite as it is has high solubility in water and low mechanical strength, so attempts have been made to correct these properties by firing and use it as a biomaterial. However, if it is fired at a high temperature to obtain sufficient mechanical strength, its biocompatibility decreases. Therefore, various processing methods are being considered in order to use hydroxyapatite as a biomaterial, including methods of coating titanium, alumina, stainless steel, ceramics, and others (hereinafter referred to as substrates) with hydroxyapatite. Processing methods such as coating a substrate with hydroxyapatite and firing it, or coating a substrate with fired hydroxyapatite require relatively simple operations and have relatively high mechanical strength. Although it can be used as a biomaterial, it is difficult to uniformly coat the substrate with hydroxyapatite, the coating layer becomes thick, and the bond with the substrate is weak, so the hydroxyapatite coating layer easily peels off and precise processing is difficult. Furthermore, since it is fired, the biocompatibility of hydroxyapatite cannot be said to be perfect. Azuma et al. reported a biomaterial made by coating stainless steel with hydroxyapatite using plasma spraying, and Yoda reported a biomaterial made by coating stainless steel with bone powder by sputtering. However, plasma spraying is often used for coating -a with hydroxyapatite.
プラズマ溶射法による生体材料は、コーティング層のハ
イドロキシアパタイトの組成と結晶性が溶射条件により
大きく変動し、ハイドロキシアパタイトの結晶化と同時
に燐酸カルシウム、酸化カルシウム及びガラス相への分
解が促進され、均質なハイドロキシアパタイトのコーテ
ィング層かえられにくい。又非晶質と結晶質のハイドロ
キシアパタイトが混在していることは認められていたが
、非晶質だけの膜を成形することは勿論、結晶の均一に
配向した膜をえることはできなかった。その理由はプラ
ズマ溶射がセラミック粉末を熔融させ噴射することによ
り基質上に被膜を形成させるだけのものであるため、結
晶が配向することがなく、膜成形速度が速く、大きな粒
子が膜を形成するためであり、最小膜厚でも２０μｍ程
度となり非晶質膜をえることは困難で、成形された膜は
ポーラス状で、緻密な膜とはならない。又骨粉コーティ
ング生体材料は、その生体親和性について考慮されてお
らず、骨粉の入手に問題がある。In biomaterials produced by plasma spraying, the composition and crystallinity of the hydroxyapatite in the coating layer vary greatly depending on the spraying conditions, and at the same time as the crystallization of hydroxyapatite, the decomposition into calcium phosphate, calcium oxide, and glass phases is promoted, resulting in a homogeneous structure. The hydroxyapatite coating layer is difficult to change. Although it was recognized that amorphous and crystalline hydroxyapatite coexist, it was not possible to form a film made of only amorphous material, and it was not possible to obtain a film with uniformly oriented crystals. . The reason for this is that plasma spraying simply forms a film on the substrate by melting and spraying ceramic powder, so the crystals do not become oriented, the film formation speed is fast, and large particles form the film. This is because even the minimum film thickness is about 20 μm, making it difficult to obtain an amorphous film, and the formed film is porous and not dense. Furthermore, the biocompatibility of bone powder-coated biomaterials has not been considered, and there is a problem in obtaining bone powder.
ハイドロキシアパタイトを基質にコーティングさせた従
来の生体材料は、基質とハイドロキシアパタイトの結合
が弱かったり、コーティング層の組成が均質でなかった
りするため、生体との親和性に問題を含んでいる。本発
明の目的は、基質と強固に結合しているので、ハイドロ
キシアパタイトが基質から剥離することがなく、コーテ
ィング質のハイドロキシアパタイトが均質な非晶質、定
の配向を有する結晶及びそれらの混合物であり、生体親
和性が極めて良好な生体材料を提供することにある。Conventional biomaterials in which a substrate is coated with hydroxyapatite have problems with their compatibility with living organisms because the bond between the substrate and hydroxyapatite is weak or the composition of the coating layer is not homogeneous. The object of the present invention is that the hydroxyapatite is firmly bonded to the substrate, so that the hydroxyapatite does not peel off from the substrate, and that the hydroxyapatite in the coating is a homogeneous amorphous, crystalline with a fixed orientation, or a mixture thereof. The objective is to provide a biomaterial with extremely good biocompatibility.
化合物が非晶質化すると結晶質とは異った性質を示す、
即ち非晶質物質は、結晶質物質に比し、物理的に活性で
、結晶質ではえられないような高強度、超耐蝕性などを
示す。又骨のハイドロキシアパタイトが非晶質物質であ
ることも知られているので、生体材料として非晶質ハイ
ドロキシアパタイトを使用すると摩耗しない、生体親和
性のよいものができると考えられる。従って非晶質ハイ
ドロキシアパタイトを基質にコーティングさせた生体材
料は、従来のものに比し機械的強度及び生体親和性のよ
りすくれたものになるであろう。かかる考えにもとすき
、非晶質性ハイドロキシアパタイトをコーティングさせ
た生体材料をえるため、種々検討を加えた。そして非晶
質物質をえる方法は種々存在しているが、本発明の目的
には、真空蒸着、スパッタリング、イオンブレーティン
グ、その他の蒸着法、特にスパッタリング、イオンブレ
ーティング法の条件を選択することにより容易に達成で
きることを知った。スパッタリングコーティングはコー
ティング材料を原子、分子の形で放出させ、基質に被膜
を形成させるため、膜形成速度が遅く、薄い被膜が形成
されるうえ、基質の温度及び操作時間を制御することに
より、まず始めに非晶質膜が形成され、該膜が緻密で硬
く、基質と強力に密着していること、その後Ｃ軸（ＣＯ
Ｏ２）面（６角形状〕）方向に配向した結晶の結晶膜か
現われ、初めに出来た非晶質膜とＣ軸配向の結晶が混在
するようになり、更にその後はＣ軸配向の結晶だけの膜
となる。このようにしてえられたＣ軸配向膜は、綺麗に
結晶が並んだ状態であり、結晶同志が緻密に接着してい
るので、緻密で硬い膜である。即ち本発明は非晶質、及
びＣ軸配向結晶のハイドロキシアパタイトをコーティン
グさせた生体材料を提供するものである。ハイドロキシ
アパタイトは、１００°Ｃ以下の水溶液中カルシウムと
リン酸とを中性ないしアルカリ性で反応させることによ
り容易に合成できる。合成ハイドロキシアパタイトを空
気中で加熱すると、６００℃付近から結晶化が起こり、
１０００℃前後で焼結現象をみ、１６００〜１７００℃
で融解分解反応を生じる。従ってハイドロキシアパタイ
トを蒸着により基質にコーティングさせる場合、ハイド
ロキシアパタイトが熱により分解され、その分解物がハ
イドロキシアパタイトと共に基質に蒸着され、プラズマ
溶射法によるコーティング生体材料のように、コーティ
ング層の組成が蒸着条件により変動する可能性がある。When a compound becomes amorphous, it exhibits properties different from those of a crystalline state.
That is, amorphous materials are more physically active than crystalline materials, and exhibit high strength, ultra-corrosion resistance, etc. that cannot be obtained from crystalline materials. It is also known that bone hydroxyapatite is an amorphous substance, so it is thought that if amorphous hydroxyapatite is used as a biomaterial, it will not wear out and has good biocompatibility. Therefore, a biomaterial whose substrate is coated with amorphous hydroxyapatite will have better mechanical strength and biocompatibility than conventional materials. Based on this idea, we conducted various studies in order to obtain a biomaterial coated with amorphous hydroxyapatite. There are various methods of obtaining an amorphous material, but for the purpose of the present invention, it is important to select the conditions for vacuum evaporation, sputtering, ion blating, and other vapor deposition methods, especially sputtering and ion blating methods. I learned that it can be easily achieved. Sputtering coating releases the coating material in the form of atoms and molecules to form a film on the substrate, so the film formation rate is slow and a thin film is formed. First, an amorphous film is formed, which is dense, hard, and strongly adheres to the substrate, and then the C axis (CO
A crystalline film of crystals oriented in the O2) plane (hexagonal shape) appears, and the initially formed amorphous film and C-axis oriented crystals come to coexist, and then only C-axis oriented crystals appear. It becomes a film of The C-axis oriented film thus obtained has crystals arranged neatly, and the crystals are tightly adhered to each other, so that it is a dense and hard film. That is, the present invention provides a biomaterial coated with amorphous and C-axis oriented crystal hydroxyapatite. Hydroxyapatite can be easily synthesized by reacting calcium and phosphoric acid in an aqueous solution at 100° C. or lower in neutral or alkaline conditions. When synthetic hydroxyapatite is heated in air, crystallization occurs around 600℃,
Sintering phenomenon was observed at around 1000℃, 1600-1700℃
A melting and decomposition reaction occurs. Therefore, when coating a substrate with hydroxyapatite by vapor deposition, the hydroxyapatite is decomposed by heat, and the decomposed product is vapor-deposited on the substrate together with hydroxyapatite. This may vary depending on the situation.
然しなから、スパッタリング、イオンブレーティング法
などの蒸着法を使用し、基質温度を出来るだけ低温に、
コーテイング膜形成速度を出来るだけ低いように操作条
件を選択することにより、ハイドロキシアパタイトの熱
分解物のコーティング層への混入が極めて僅かであり、
真質的に熱分解物を含まないハイドロキシアパタイトの
非晶質及びＣ軸配向結晶性コーティング層を有する生体
材料かえられることを知った。即ち８００〜１３００℃
で、好ましくは１０００〜１３００℃で、１時間以上焼
成したハイドロキシアパタイトをターゲットとし、スパ
ッタリング電圧を出来るだけさげ、Ａｒのような不活性
ガス又はそ鋏れらと酸素との混合ガスの存在下、作動圧
１０４〜１０−’トール、基質温度６００℃以下、好ま
しくは３００℃以下、膜形成速度２μ／時、好ましくは
１μ／時以下で操作する。必要に応じ操作時間を調整す
ることにより膜厚を任意に調製する。例えば非晶質膜を
えたい場合はコーティング膜厚が５μｍ前後になるよう
操作時間を調整する。非晶質とＣ軸配向結晶の混在膜、
及びＣ軸配向の結晶膜をえたい場合は、更に長時間操作
するか、スパッタリングの出力、成膜温度などの操業条
件をコントロールすることで可能である。ノ＼イドロキ
シアパタイトの非晶質膜、及びＣ軸配向結晶はＸ線回折
、電子顕微鏡観察により確認できる。However, by using vapor deposition methods such as sputtering and ion blating, the substrate temperature can be kept as low as possible.
By selecting operating conditions to keep the coating film formation rate as low as possible, the amount of pyrolyzed hydroxyapatite mixed into the coating layer is extremely small.
It has now been discovered that biomaterials having amorphous and C-axis oriented crystalline coating layers of hydroxyapatite that are essentially pyrolyzate-free can be obtained. i.e. 800-1300℃
Using hydroxyapatite as a target, preferably fired at 1000 to 1300°C for at least 1 hour, the sputtering voltage is lowered as much as possible, and in the presence of an inert gas such as Ar or a mixed gas of sputtering and oxygen. It is operated at an operating pressure of 104 to 10-' Torr, a substrate temperature of 600 DEG C. or less, preferably 300 DEG C. or less, and a film formation rate of 2 .mu./hour, preferably 1 .mu./hour or less. The film thickness can be arbitrarily adjusted by adjusting the operation time as necessary. For example, when it is desired to obtain an amorphous film, the operation time is adjusted so that the coating film thickness is approximately 5 μm. Mixed film of amorphous and C-axis oriented crystals,
If it is desired to obtain a crystal film with C-axis orientation, this can be achieved by operating for a longer time or by controlling operating conditions such as sputtering output and film-forming temperature. The amorphous film and C-axis oriented crystals of nohydroxyapatite can be confirmed by X-ray diffraction and electron microscopy.
このようにしてえられた生体材料は、コーティング層が
非晶質及びＣ軸配向性結晶のハイドロキシアパタイトで
あり、基質とコーティング層の結合が強固でハイドロキ
シアバタイト力＜ ｆｆ１ｌＪ離することがなく、骨と
の親和性も極めて良好である。In the biomaterial thus obtained, the coating layer is amorphous and C-axis oriented crystal hydroxyapatite, and the bond between the substrate and the coating layer is strong and the hydroxyapatite force < ff1lJ does not separate. It also has extremely good affinity with bones.
非晶質及びＣ軸配向結晶ハイドロキシアパタイトを基質
にコーティングさせた生体材料は、耐磨耗び機械的強度
が強く、ハイドロキシアパタイトと基質との結合が強い
のでハイドロキシアパタイトが剥離することがなく、生
体親和性もすぐれている。加えて均質に加工でき、膜厚
の調整も容易で、基質温度の選択によりコーティング層
を緻密にできる。Biomaterials whose substrates are coated with amorphous or C-axis oriented crystalline hydroxyapatite have strong abrasion resistance and mechanical strength, and because the bond between the hydroxyapatite and the substrate is strong, the hydroxyapatite does not peel off, and the biomaterials It also has excellent compatibility. In addition, it can be processed homogeneously, the film thickness can be easily adjusted, and the coating layer can be made dense by selecting the substrate temperature.
以下に実施例をあげて本発明を具体的に説明する。The present invention will be specifically explained below with reference to Examples.
例１゜
ハイドロキシアパタイトは、湿式合成後、乾燥、粉砕、
圧縮成形し、１，０００℃で５時間焼成した円盤を、基
質はφ１０１０Ｘ４の円板状に加工したチタニウムを研
磨後、アセトン、酸及び水で洗浄、乾燥したものを使用
した。Example 1゜Hydroxyapatite is produced by drying, pulverizing, and
A disk was compression molded and fired at 1,000° C. for 5 hours, and the substrate was a titanium disk of φ1010×4, which was polished, washed with acetone, acid, and water, and dried.
ＲＦ−ダイオードスパッタ装置、スパッタガスＡｒｓス
パッタガス１×１０−３トール、基質温度３００℃、ス
パッタ電力３００〜４００ Ｖ （１３，５６ＭＨ２）
で３時間操作し、厚さ２．５μのハイドロキシアパタイ
トをコーティングさせたチタニウムをえた。RF-diode sputtering equipment, sputtering gas Ars sputtering gas 1 x 10-3 Torr, substrate temperature 300°C, sputtering power 300-400 V (13,56MH2)
After 3 hours of operation, titanium coated with hydroxyapatite with a thickness of 2.5 μm was obtained.
Ｘ線回折で皮膜は分解物を含まず非晶質であることをみ
とめた。X-ray diffraction revealed that the film contained no decomposition products and was amorphous.
例２゜
例１と同じハイドロキシアパタイト焼成円盤、チタニウ
ム円板を使用し、ＲＦ−プレナマグネトロン装置で試験
した。スパッタリングガスＡｒ、スパッタガス圧４Ｘ１
０−”トール、基質温度１００〜５００℃、スパッタ電
圧４００■、３時間操作し２μの厚さのコーテイング膜
を有するチタニウムをえた。Example 2 The same calcined hydroxyapatite disks and titanium disks as in Example 1 were used and tested in an RF-planar magnetron device. Sputtering gas Ar, sputtering gas pressure 4X1
After operating for 3 hours at 0-" Torr, substrate temperature of 100-500 DEG C., and sputtering voltage of 400 .ANG., a titanium coating having a thickness of 2.mu.m was obtained.
例３゜
基質をチタニウム及び５ＵＳ３０４を使用し操作時間を
１．５時間とした以外は例１と同様に処理。Example 3° Processed as in Example 1 except that titanium and 5US304 were used as substrates and the operating time was 1.5 hours.
してハイドロキシアバタイトコーティングチタニラム及
び５ＵＳ３０４をえ、この物質の膜厚及び基質との接着
力及び膜表面の状態を観察した。膜と基質との接着力は
ピン代引張試験により測定し表−１にその結果を示した
。接着剤自体の接着力は３ｋｇ／龍２程度であり、コー
ティングビンが完全のまま接着剤より破断されたので膜
と基質との接着力は８ｋｇ／＊＊”以上であることを示
している。Titanium and 5US304 coated with hydroxy abatite were prepared, and the film thickness, adhesion to the substrate, and surface condition of the film were observed. The adhesive strength between the membrane and the substrate was measured by a pin-to-metal tensile test, and the results are shown in Table 1. The adhesive force of the adhesive itself was approximately 3 kg/2, and since the coating bottle was broken intact by the adhesive, this indicates that the adhesive force between the membrane and the substrate was 8 kg/**'' or more.
第１図及び第２図に５ＵＳ３０４、Ｔｉ基質の膜表面図
を示した。膜はそれぞれの基質表面形状に沿って形成さ
れており、Ｍｉ織のようなものは見られない。又、マイ
クロクラックのような膜の欠陥も観察されなかった。そ
れらの膜厚は約１．２μで表１．ビン代引張試験法によ
る膜の接着力ｋｇ／龍２
例４゜
例１でえたチタニウム試料を雑種成人の４肢長管骨々幹
部にあけた穿孔に挿入し、挿入後２週、４週、８週経過
後試料を含む骨を取出し引き抜き試験により挿入試料の
引き抜き強さを測定し、２週間で平均３０ｋｇ／ｃｕｔ
、４週間で平均４９ ｋｇ ／ ｃＪ、８週間で平均４
５ｋｇ／ｃｎｌの強度をえた。対照として参考例でえら
れたチタニウム試料を同様に試験し、２週間で平均２０
ｋｇ ／ ｃｒＡ、４週間で平均３０ｋｇ ／ ｃｉ
、の強度をえた。これらの結果は非晶質性コーティング
層が新生骨発生の早いこと、即ち生体親和性がよいこと
を示している。Figures 1 and 2 show the membrane surface diagrams of 5US304 and Ti substrate. The film was formed along the surface shape of each substrate, and no Mi texture was observed. Furthermore, no film defects such as microcracks were observed. Their film thickness is approximately 1.2μ, as shown in Table 1. Adhesive strength of the membrane according to the bottle age tensile test method kg/dragon 2 Example 4゜The titanium sample obtained in Example 1 was inserted into a hole made in the 4-limb long bone trunk of an adult mongrel, and 2 weeks, 4 weeks after insertion, After 8 weeks, the bone containing the sample was taken out and the pullout strength of the inserted sample was measured by a pullout test, and the pullout strength was 30kg/cut on average in 2 weeks.
, averaged 49 kg/cJ in 4 weeks, averaged 4 in 8 weeks
A strength of 5 kg/cnl was obtained. As a control, the titanium sample obtained in the reference example was similarly tested, and an average of 20
kg/crA, average 30 kg/ci in 4 weeks
, gained strength. These results indicate that the amorphous coating layer generates new bone quickly, that is, has good biocompatibility.
参考例
基質温度を７００〜８００゛Ｃにした以外は例１と同じ
操作をなし、厚さ２．７μのコーティング層のチタニウ
ムをえた。Reference Example The same procedure as in Example 1 was carried out except that the substrate temperature was 700-800°C, and a titanium coating layer with a thickness of 2.7 μm was obtained.
例５゜
例１と同じハイドロキシアパタイト焼成円板を使用して
基質に５ＵＳ３１６およびチタンを用いて、例２と同様
のＲＦ−ブレマグネトロン装置で試験した。スパッタリ
ングガスＡｒ、スパッタ≠≠シガス圧４Ｘ１０−”）−
ル、基質温度５０〜３００℃、スパッタ電圧２００Ｖで
それぞれ２時間、６時間、１００時間操して３種類のハ
イドロキシアパタイトコーテイング膜圧を有する５ＵＳ
３１６およびチタンを得た。Example 5 The same hydroxyapatite calcined disks as in Example 1 were used and the substrates were 5US316 and titanium, and tested in the same RF-bre magnetron apparatus as in Example 2. Sputtering gas Ar, sputter≠≠gas pressure 4X10-”)-
5US with three types of hydroxyapatite coating film thickness by operating at a substrate temperature of 50-300℃ and a sputtering voltage of 200V for 2 hours, 6 hours, and 100 hours, respectively.
316 and titanium were obtained.
例６゜
例５と同様のハイドロキシアパタイト焼成円板、基質、
装置を用いてスパッタリングガスＡｒ、スパッタガス圧
ｔｘｉｏ−３トールで基質温度１００〜５００℃、スパ
ッタ電圧４００■で１００時間操し、ハイドロキシアパ
タイトコーテイング膜を有する５ＵＳ３１６およびチタ
ンを得た。Example 6゜ Hydroxyapatite calcined disk similar to Example 5, substrate,
The apparatus was operated for 100 hours at a sputtering gas of Ar, a sputtering gas pressure of txio-3 Torr, a substrate temperature of 100 to 500 DEG C., and a sputtering voltage of 400 .ANG. to obtain 5US316 and titanium having a hydroxyapatite coating film.
例７゜
例５、例６で得られた試料の膜厚、膜表面の状態の観察
、膜の硬度、基質との接着力を測定した。Example 7 The film thickness of the samples obtained in Examples 5 and 6, the state of the film surface, the hardness of the film, and the adhesive strength with the substrate were measured.
電子顕微鏡により膜厚の測定及び表面状態の観察を行な
った結果、例５で２時間源作した試料の膜厚は約１μｍ
、６時間操作した試料の膜厚は約３μｍで、これらの膜
の表面状態は非晶質であった。As a result of measuring the film thickness and observing the surface condition using an electron microscope, the film thickness of the sample prepared for 2 hours in Example 5 was approximately 1 μm.
The film thickness of the samples operated for 6 hours was about 3 μm, and the surface state of these films was amorphous.
又、１００時間操した試料の膜厚は約５μｍで膜の表面
状態は非晶質とＣ軸配向の結晶が混在するハイドロキシ
アパタイト膜であった。例６の試料の膜厚は約１５μｍ
でＣ軸配向のハイドロキシアパタイト膜であった。基質
にＳＵＳ ３１６及びチタンを用いた試料とも同様の結
果であった。Further, the film thickness of the sample operated for 100 hours was about 5 μm, and the surface state of the film was a hydroxyapatite film in which amorphous and C-axis oriented crystals were mixed. The film thickness of the sample of Example 6 is approximately 15 μm
It was a C-axis oriented hydroxyapatite film. Similar results were obtained for samples using SUS 316 and titanium as substrates.
１゜
２゜
膜の硬度（マイクロビッカース
膜の接着力（ビン式接着試験法
ｋｇ／ｉｎ２）
ｋｇ／ｉｎ”）
〔発明の効果〕
本発明によりえられたハイドロキシアパタイトコーティ
ング生体材料は、ハイドロキシアパタイトが非晶質及び
Ｃ軸配向結晶であるため、従来存在する結晶質ハイドロ
キシアパタイトコーティング生体材料に比し、基質とハ
イドロキシアパタイトの結合が強く、耐磨耗、耐磨擦性
にすぐれ、生体親和性がよい。加えてコーティング層の
厚さ、密度を任意に調整でき、精密な加工も容易である
。1゜2゜Membrane hardness (adhesive force of micro-Vickers membrane (bottle type adhesion test method kg/in2) kg/in") [Effects of the invention] The hydroxyapatite-coated biomaterial obtained by the present invention has Because it is amorphous and has C-axis oriented crystals, the bond between the substrate and hydroxyapatite is stronger than that of conventional crystalline hydroxyapatite-coated biomaterials, and it has excellent wear and abrasion resistance and biocompatibility. Good. In addition, the thickness and density of the coating layer can be adjusted arbitrarily, and precision processing is also easy.
第１図は５ＵＳ３０４基質及びそのコーテイング膜部分
の表面を示すグラフ図である。
第２図はチタニウムの基質及びそのコーティングＨり部
分の表面を示すグラフ図である。
接着剤の接着力が３ｋｇ／ｍｍ２であり、全てピンが接
着剤より破断した為、膜と基板の接着力は８ｋｇ／ｍ２
以上である。
＊：接着力が非常に弱く、測定不可能FIG. 1 is a graph showing the surface of the 5US304 substrate and its coating film portion. FIG. 2 is a graph showing the surface of a titanium substrate and its coated portion. The adhesive strength of the adhesive was 3 kg/mm2, and since all the pins were broken by the adhesive, the adhesive strength between the film and the substrate was 8 kg/m2.
That's all. *: Adhesive strength is very weak and cannot be measured.
Claims (3)
トを基質にコーティングさせ、該ハイドロキシアパタイ
トが非晶質であることを特徴とする生体材料。(1) A biomaterial characterized in that a substrate is coated with hydroxyapatite having a thickness of 5 μm or less, and the hydroxyapatite is amorphous.
トを基質にコーティングさせ、該ハイドロキシアパタイ
トの表面がＣ軸配向（〔００２〕）結晶であることを特
徴とする生体材料。(2) A biomaterial characterized in that a substrate is coated with hydroxyapatite having a thickness of 5 μm or more, and the surface of the hydroxyapatite is a C-axis oriented ([002]) crystal.
パタイトを基質にコーティングさせ、該ハイドロキシア
パタイトが非晶質中にＣ軸配向結晶が混在していること
を特徴とする生体材料。(3) A biomaterial characterized in that a substrate is coated with hydroxyapatite having a thickness of 3 μm to 10 μm, and the hydroxyapatite is amorphous with C-axis oriented crystals mixed therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1048524A JPH021286A (en) | 1988-03-04 | 1989-03-02 | Living body material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-49656 | 1988-03-04 | ||
| JP4965688 | 1988-03-04 | ||
| JP1048524A JPH021286A (en) | 1988-03-04 | 1989-03-02 | Living body material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH021286A true JPH021286A (en) | 1990-01-05 |
Family
ID=26388812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1048524A Pending JPH021286A (en) | 1988-03-04 | 1989-03-02 | Living body material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH021286A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369435A (en) * | 1989-10-27 | 1994-11-29 | Mitsubishi Denki Kabushiki Kaisha | Contrast detecting apparatus for controlling an automatic focusing operation of an imaging apparatus |
| JP2006501887A (en) * | 2002-09-13 | 2006-01-19 | ザ ユニバーシティ オブ ブリティッシュ コロンビア | Implantable medical device coated with calcium phosphate and method of manufacturing the same |
| JP2006131469A (en) * | 2004-11-08 | 2006-05-25 | National Institute Of Advanced Industrial & Technology | Apatite composite material coated with apatite having crystal orientation |
| JP2009213723A (en) * | 2008-03-11 | 2009-09-24 | National Institute Of Advanced Industrial & Technology | Apatite coated biological implant having biomolecule fixed on its surface, and cell culture carrier |
| JP2014148718A (en) * | 2013-02-01 | 2014-08-21 | Nippon Telegr & Teleph Corp <Ntt> | Method for producing hydroxyapatite thin film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109049A (en) * | 1981-12-23 | 1983-06-29 | 旭光学工業株式会社 | Appatite composite material and production thereof |
| JPS6346164A (en) * | 1986-08-13 | 1988-02-27 | 株式会社明電舎 | Production of implant material |
-
1989
- 1989-03-02 JP JP1048524A patent/JPH021286A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109049A (en) * | 1981-12-23 | 1983-06-29 | 旭光学工業株式会社 | Appatite composite material and production thereof |
| JPS6346164A (en) * | 1986-08-13 | 1988-02-27 | 株式会社明電舎 | Production of implant material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369435A (en) * | 1989-10-27 | 1994-11-29 | Mitsubishi Denki Kabushiki Kaisha | Contrast detecting apparatus for controlling an automatic focusing operation of an imaging apparatus |
| JP2006501887A (en) * | 2002-09-13 | 2006-01-19 | ザ ユニバーシティ オブ ブリティッシュ コロンビア | Implantable medical device coated with calcium phosphate and method of manufacturing the same |
| JP2006131469A (en) * | 2004-11-08 | 2006-05-25 | National Institute Of Advanced Industrial & Technology | Apatite composite material coated with apatite having crystal orientation |
| JP4595084B2 (en) * | 2004-11-08 | 2010-12-08 | 独立行政法人産業技術総合研究所 | Apatite composite coated with apatite with crystal orientation |
| JP2009213723A (en) * | 2008-03-11 | 2009-09-24 | National Institute Of Advanced Industrial & Technology | Apatite coated biological implant having biomolecule fixed on its surface, and cell culture carrier |
| JP2014148718A (en) * | 2013-02-01 | 2014-08-21 | Nippon Telegr & Teleph Corp <Ntt> | Method for producing hydroxyapatite thin film |
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