JP5658561B2 - ナノ表面 - Google Patents
ナノ表面 Download PDFInfo
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- JP5658561B2 JP5658561B2 JP2010515496A JP2010515496A JP5658561B2 JP 5658561 B2 JP5658561 B2 JP 5658561B2 JP 2010515496 A JP2010515496 A JP 2010515496A JP 2010515496 A JP2010515496 A JP 2010515496A JP 5658561 B2 JP5658561 B2 JP 5658561B2
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- Prior art keywords
- implant
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- titanium
- biocompatible
- nanostructure
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C23C—COATING 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
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Description
a)少なくとも部分的に金属酸化物で被覆された生体適合性部材を備えること;及び
b)該部材の部分が該金属酸化物で被覆された、その部材の少なくとも一部を、シュウ酸を含む水性組成物で処理すること;
を含み、そのことによって改質された金属酸化物が得られる、方法に関する。
c)i)イオン化されたフッ素及びイオン化された塩素を含むグループから選ばれる少なくとも1つの物質;及び
ii)少なくとも1つの酸;
を含む第二の水性組成物で、前記改質された酸化物の少なくとも部分を処理する工程を更に含む。
a)プラトー及び/又はリッジによって分離された微細ピットを含む微細構造;及び
b)該微細構造の上に重なっている一次ナノ構造、ここで該一次ナノ構造は波状の形に配置された窪みを含む;
を含む表面を有する基体を含む生体適合性部材に関する。
T ら、「Ultrastructural analysis of the interface zone of titanium and gold implants」、Advances in Biomaterials 4, 167-177, 1982; Albrektsson, Tら,「Interface analysis of titanium and zirconium bone implants」、Biomaterials 6, 97-101, 1985; Albrektsson T, Hansson, H-A,「An ultrastructural characterization of the interface between bone and sputtered titanium or stainless steel surfaces」、Biomaterials 7, 201-205, 1986; Hansson, H-A ら、「Structural aspects of the interface between tissue and titanium implants」、Journal of Prosthetic Dentistry 50, 108-113, 1983; Johansson, C ら、「Ultrastructural differences of the interface zone between bone and Ti6A14V or commercially pure titanium」、Journal of Biomedical Engineering 11, 3-8, 1989; Johansson, C. ら、「Qualitative, interfacial study between bone and tantalum, niobium or commercially pure titanium」、Biomaterials 11, 277-280, 1990; Sennerby, L ら、「Structure of the bone-titanium interface in retrieved clinical oral implants」、Clinical Oral Implants Research 2, 103-111, 1991; Sennerby, L ら、「Ultrastructure of the bone-titanium interface in rabits」、Journal of Materials Science: Material in Medicine 3, 262-271, 1992; Sennerby,
L ら、「Early tissue response to titanium implants inserted in rabit cortical bone, Part II: Ultrastructural observations」、Journal of Materials Science: Material in Medicine 4, 494-502, 1993)。微細構造及び一次ナノ構造を含む階層的表面トポグラフィーによって、部材と引続いて形成される骨組織との間の改善された機械的相互作用が与えられ、その結果、強度が低下したより薄い組織層が形成されると考えられる。二次ナノ構造によって、埋め込み後の生体適合性部材と周囲の骨組織間の機械的相互作用が更に改善される。従って、本発明の生体適合性部材によって、改善されたせん断強さ及び引張り強さを有する骨組織−インプラント界面が供される。
i)上記記載の生体適合性部材を備えること;及び
ii)該生体適合性部材をヒト又は動物の体にインプラントすること;
を含むインプラント方法に関する。
実施例 1−表面改質
(i)サンプル調製
コインの形状を有するチタンサンプル(各々機械加工されたものとブラスチングされたもの)、固定具(ブラスチングされたもの)及び橋脚歯(機械加工されたもの)を従来の化学的処理によって洗浄した。これらのサンプルを1Mのシュウ酸水溶液中に浸漬し、そして80℃で30分間、激しい撹拌下に置いた。30分後シュウ酸水溶液から、サンプルを取出して水中でゆすぎ、続いて超音波浴中の水中で2分間、ゆすいだ。ゆすぎの約10分後、サンプルを0.1Mのフッ化水素酸(HF)水溶液中に室温で浸漬し、活発な溶解が始まるまで撹拌し、引続いて追加の活性化処理を40秒間行った。次に、HF溶液からサンプルを取出して水中でゆすぎ、引き続いて超音波浴中の水中で5分間、ゆすいだ。これらのサンプルを、滅菌前に室温で空気中において約60分間、乾燥した。
ESEM XL30(FEI)を用いて、工程bに続いてゆすいだ後のサンプル及び工程cに続いて乾燥した後のサンプルについて走査型電子顕微鏡(SEM)観察を実施した。500×及び15000×の間の倍率を用いて、立体画像を撮影し、そしてMeX 5.0 programme(Alicona)によって評価した。フィルターは使用しなかった。微細構造のピット及び一次ナノ構造の窪みの深さ及び直径、並びに及び微細構造の隣接ピットの間の距離を求めた。結果を一次微細構造に対して図13a−c(機械加工されたサンプル)、及び図14a−c(ブラスチングされたサンプル)、そして一次ナノ構造に対して図15a−b(機械加工されたサンプル)、及び図16a−b(ブラスチングされたサンプル)に提示する。滅菌後に撮られたSEM画像を図8、9及び11に提示する。
(コインの形状をした)ブラスチング処理されたチタンサンプルを、0.1Mのフッ化水素酸及び1Mのシュウ酸を含む水溶液中に室温で浸漬し、そして各々、5、15、30及び42分間、撹拌した。溶液から、サンプルを取出して水中でゆすぎ、続いて超音波浴中の水中で2分間、ゆすいだ。サンプルを乾燥後、走査型電子顕微鏡(ESEM XL30、FEI)によって表面トポグラフィーを調べた。
チタンサンプルを0.1MのHF水溶液中に室温で浸漬し、そして活発な溶解が始まるまで撹拌し、続いて40秒の追加の処理時間をかけた。次いでHF溶液から、サンプルを取出して水中でゆすぎ、続いて超音波浴中の水中で5分間、ゆすいだ。ゆすぎの約10分後、サンプルを1Mのシュウ酸水溶液中に浸漬し、80℃で30分間、激しく撹拌した。30分後、シュウ酸溶液からサンプルを取出して水中でゆすぎ、引き続いて超音波浴中の水中で2分間、ゆすいだ。これらのサンプルを、室温で1時間、乾燥させた。
細胞増殖、及びアルカリホスファターゼ(ALP)及びプロスタグラジンE2(PGE2)各々の産生を、本発明に従ってチタン表面上でインビトロで成長させたヒト骨芽細胞に対して調べ、市販のインプラント表面(OsseoSpeed(商標);Asta Tech AB、スウェーデン)上で成長させた細胞と比較した。
MG−63は、骨芽細胞のインビトロの研究のために従来から使用されているヒト細胞株である。この研究においては、MG-63cells(MG-63、ATCC No CRL-1427、米国)を、300mLのFalcon細胞培養フラスコ(BD、WWR、スウェーデン)内の、5%のウシ胎児血清(FCS;Gibco、英国)及び1%のペニシリン−ストレプトマイシン(PEST;Gibco、英国)を含むダルベッコ最少必須培地(Dulbecco's Minimun Essential Medium(D-MEM))(Gibco、英国)中で、冷凍細胞の膨大部からの2回目の継代から、成長させた。 接着した細胞が密集度まで成長したら、0.05%トリプシン−EDTA(Gibco、英国)を用いて、それらを3継代の継代をさせた。光学顕微鏡を用いてカウントした細胞生存率は高かった(>98%)。
三つのコイン形状をした、β−滅菌されたチタン試験体;その中の1つは本発明の工程bにかけられたもの;その中の1つは本発明の工程b及び工程cにかけられたもの;そしてその中の1つは市販の表面(OsseoSpeed(商標);Asta Tech AB、スウェーデン)を有したもの;を各々別のFalcon24ウェルプレート(BD、WWR、スウェーデン)中に置いた。各々のウエルに、5%のFCS(Gibco、英国)及び1%のPEST(Gibco、英国)を含有し、20,000細胞/mLの細胞濃度を有する1mlのD−MEM(Gibco、英国)を添加した。これらのプレートを37℃、5%のCO2及び湿度100%で36時間、インキュベートした。従来のSEMサンプル調製手順に従って、サンプルを4℃でグルタルアルデヒドを用いて、続いて四酸化オスミウムによって固定し、脱水及び金スパッタリングした。細胞形態をSEM(ESEM XL30、FEI)によって調べた。細胞のSEM画像を図20a(従来の表面上で成長させた細胞)、図20b(本発明の工程bに従って処理された部材上で成長させた細胞)、図20c(本発明の工程b及び工程cに従って処理された部材上で成長させた細胞)に示す。
三セット(n=6)のコイン形状をした、β−滅菌されたチタン試験体;一組は本発明の工程bにかけられたもの(「本発明の表面1」);一組は本発明の工程b及び工程cにかけられたもの(「本発明の表面2」);そして一組は市販の表面(OsseoSpeed(商標);Asta Tech AB、スウェーデン)を有するもの;を各々別のFalcon24ウェルプレート(BD、WWR、スウェーデン)中に置いた。各々のウエルに5%のFCS(Gibco、英国)及び1%のPEST(Gibco、英国)を含有し、そして20,000細胞/mLの細胞濃度を有する1mlのD−MEM(Gibco、英国)を添加した。これらのプレートを37℃、5%のCO2及び湿度100%で14日間インキュベートした。
本発明に記載のインプラントの完全性をウサギモデルにおいて試験した。その目的は、市販の参照インプラントに対する応答と比較して、本発明に記載の二つのインプラント表面改質に対するインビボの骨組織応答を定性的に及び定量的に調べることであった。
シュウ酸中に、そして引き続きHF中に浸漬することによって、実施例1において述べられた通りに(つまり工程b及びcを含んで)、調製したチタントルク固定具(四角形の頭をした除去トルク設計、3.5×8.2ミリメーター)を使用した(試験インプラント2と称する)。また、シュウ酸中に浸漬することによって、実施例1において述べられた通りに(つまり工程cが省略されて)、調製したトルク固定具(3.5×8.2ミリメーター)(試験インプラント1と称する)も使用した。更に、市販のOsseoSpeed(商標)口腔インプラントを代表するトルク固定具(3.5×8.2ミリメーター)を参照固定具として使用した。
上記実施例1において述べられた通りに調製した口腔インプラント(3.5×8ミリメーター)のヒト設計の固定具を使用した(試験インプラント2)。また、HF処理(つまり工程c)を省略した以外は、実施例1において述べられた通りに調製した固定具(3.5×8ミリメーター)も使用した(試験インプラント1)。更に、市販のOsseoSpeed(商標)口腔インプラントを代表する固定具(3.5×8ミリメーター)を参照固定具として使用した。
12把の成体の雄のニュージーランド白ウサギを手術用として予定した。一把のウサギは初期の麻酔で死んだ(#8)。手術は平穏に進んだ。連続食塩冷却を用いて、低速穴開け(穴開けのために1500rpg、そしてインプラント挿入のために20rpm)を行った。
6週間後に、試験を終了し、そしてウサギを犠牲にした。インプラント及び周囲の組織を調べた。脛骨インプラントは容易に位置が分かり、それらの全てで、骨膜骨組織成長の兆候が見られた。除去トルク試験(RTQ)を用いて、インプラント−骨界面の生体力学的試験を実施した。RTQ装置(Detektor AB、Goteborg、スウェーデン)は、骨層におけるインプラントの安定性(Ncmを単位とするピークゆるみトルク)を試験するために使用される歪ゲージトランスジューサーを含む電子機器であり、従って、骨組織及びインプラントの間の界面せん断力を大まかに反映する三次元試験と見なすことができる(Johansson C. B.,Albrektsson T.,Clin Oral implants Res 1991;2:24-9)。直線的に増大するトルクがインプラントの同じ軸上に、一体化が破壊されるまでかけられ、そしてピーク値が記録された。大腿骨中に挿入されたインプラントは、よりしばしば骨組織によるインプラント頭部の「完全な被覆」を示した。大腿骨インプラントを固定液中に浸漬し、そして組織学及び組織学形態計測研究のために更に処理した。
6週間後に、試験を終了し、そしてウサギを犠牲にした。ウサギ#1及び#5からの骨組織及びインプラントを含む大腿骨インプラント部位の選択サンプルを、骨−インプラント接触(BIC)及び内側のネジ山(thread)内の骨領域(内部領域、ia)及び大腿骨から回収されたインプラント周辺の種々の領域における対応する鏡像(mi)に関して組織学形態計測的に評価した。
(a)ミクロ−ネジ山;
(b)マクロ−ネジ山;
(c)骨髄空洞における先端側(ネジ山がない)に沿った領域;及び
(d)インプラントの先端底部中(この領域は、骨インプラント接触についてのみ報告される)
図23aはウサギ#1、試験インプラント2を示す;
図23bはウサギ#1、参照インプラントを示す;
図24aはウサギ#5、試験インプラント1を示す;及び
図24bはウサギ#5、参照インプラントを示す;
骨形成を調べるための1つの従来からのインビトロのモデルは、疑似体液(SBFs)中への生体材料の浸漬である。SBFsはヒトの血漿のそれにほぼ等しいイオン濃度を有する溶液である(Kokubo T.,Kushitani H.,Sakka S.,Kitsugi T.,Yamamuro T.,J Biomed Mater Res 1990;24:721-734;Oyane A.,Kim H. K.,Furuya T.,Kokubo T.,Miyazaki T., Nakamura T.,J Biomed Mater Res 2003;65A、188-195)。生体材料の核形成能力に依存して、骨状のリン酸カルシウムがその表面上に沈殿することになる。インビボの骨生理活性を有するSBF中でのアパタイト形成の定量的相関が報告されている(Kokubo T.,Takadama H.,Biomaterials 2006;27:2907-2915)。今日では、SBFのインビトロモデルはしばしば使用され、そして国際標準、ISO 23317:2007Eによって記載されている。
ヒトの血漿の電解質濃度に類似した電解質濃度を有する修正SBF(Oyane A.ら、J Biomed Mater Res 2003;65A、188-195)が選択された(Vander A.J., Sherman J.H., Luciano D.S.,「Human physiology The mechanisms of body function)」、5th ed. McGraw-Hill Publishing Company、ニューヨーク、1990:349-400)。SBFは10.806gのNaCl、1.480gのNaHCO3、4.092gのNa2CO3、0.450gのKCl、0.460gのK2HPO4・3H2O、0.622gのMgCl2・6H2O、23.856gの2−(4−(2−ヒドロキシエチル)−1−ピペラジニル)エタンスルホン酸(HEPES)、0.776gのCaCl2及び0.144gのNa2SO4を、2000ミリリッターの脱イオン水中に溶解させることによって調製した。HEPESは溶液に添加する前に、200ミリリッターの脱イオン水中に溶解させた。最終的なpHは1.0MのNaOHを用いて37℃で7.40に調節された。全ての試薬は、NaCl及びNa2SO4 (これらはFluka(スウェーデン)から得られた)を除いて、Merck(スウェーデン)から得られた。
可能なアパタイトの形成の解析を、環境走査型電子顕微鏡(ESEM、XL 30、FEI)を用いて実施した。SBF浸漬前の表面構造のSEM画像を、図25a(参照)、26a(本発明の表面1)、及び27a(本発明の表面2)に提示する。SBF浸漬後の表面構造を調べたとき、サンプルの全ての組上でリン酸カルシウムの薄い層が形成されたと結論付けられた;参照(図25b)、本発明の表面1(図26b)、及び本発明の表面2(図27b)。
アパタイト形成前後のサンプルの化学的解析のためにエネルギー分散分光法(EDS,Apollo 40,EDAX)を使用した。チタンシグナルを解析することによって、リン酸カルシウムによるサンプルの被覆度が間接的に評価できた。本発明表面2は、SBF浸漬後のチタンシグナルにおいて最大の低下を示し(図28)、調査した資料の組の中で最も広範囲なアパタイト形成を示した。
Claims (51)
- 生体適合性部材の改質方法であって、以下の工程:
a)少なくとも部分的に金属酸化物で被覆された生体適合性部材を備えること;及び
b)該部材の部分が該金属酸化物で被覆された、その部材の少なくとも一部を、シュウ酸を含む水性組成物で処理すること;そして、さらに、
c)i)イオン化されたフッ素及びイオン化された塩素を含むグループから選ばれる少なくとも1つの材料;及び
ii)少なくとも1つの酸;
を含む第二の水性組成物で、改質された金属酸化物の少なくとも部分を処理すること、ここで、改質された金属酸化物上に不動態化酸化物が形成される前に、工程cが実行されること;
を含み、そのことによって、改質された金属酸化物の部分が溶解し、そして引き続いて沈殿して金属酸化物を含む二次ナノ構造を形成する、方法。 - 工程bの組成物が、0.001から5Mの範囲内のシュウ酸濃度を有し;工程bの処理が、10から60分の範囲内の処理時間で実行される、請求項1記載の方法。
- 処理時間が20から30分の範囲内である、請求項2記載の方法。
- 工程bの組成物が、20℃から100℃の範囲内の温度を有する、請求項1〜3の何れか1項に記載の方法。
- 工程bの完了後、0℃又はそれより高い温度で、そして酸素含有大気における通常の大気圧で、部材が保持される時間としてカウントされた、180時間又はそれより短い時間以内で、工程cが実行される、請求項1〜4の何れか1項に記載の方法。
- 工程bの完了後、72時間又はそれより短い時間以内で、工程cが実行される、請求項1〜5の何れか1項に記載の方法。
- 工程bの完了後、24時間又はそれより短い時間以内で、工程cが実行される、請求項1〜5の何れか1項に記載の方法。
- 工程bの完了後、1時間又はそれより短い時間以内で、工程cが実行される、請求項1〜5の何れか1項に記載の方法。
- 工程bの完了後、10分又はそれより短い時間以内で、工程cが実行される、請求項1〜5の何れか1項に記載の方法。
- 第二の水性組成物がフッ化水素酸を含む、請求項1〜9の何れか1項に記載の方法。
- 第二の水性組成物が、0.5から5の範囲内のpH;0.05から0.3Mの範囲内の、イオン化されたフッ素及びイオン化された塩素を含むグループから選ばれる少なくとも1つの材料の濃度を有し;そして10秒から3分の範囲内の活性化処理時間で工程cの処理が実行される、請求項1〜10の何れか1項に記載の方法。
- 第二の水性組成物が15℃から25℃の範囲内の温度を有する、請求項1〜11の何れか1項に記載の方法。
- 工程bの水性組成物が骨成長増強物質を含む、請求項1〜12の何れか1項に記載の方法。
- 第二の水性組成物が骨成長増強物質を含む、請求項1〜13の何れか1項に記載の方法。
- 骨成長増強物質が金属イオン又はそれらの塩を含む、請求項13又は14に記載の方法。
- 金属イオンが、チタンイオン、マグネシウムイオン、カルシウムイオン、リチウムイオン、ストロンチウムイオン、又はそれらの如何なる組合せから成るグループから選ばれるイオンを含む、請求項15に記載の方法。
- 金属イオンがリチウムイオンを含む、請求項15に記載の方法。
- 金属イオンがストロンチウムイオンを含む、請求項15に記載の方法。
- 部材が少なくとも部分的にチタン又はチタン合金から成る、請求項1〜18の何れか1項に記載の方法。
- 金属酸化物が酸化チタンを含む、請求項1〜19の何れか1項に記載の方法。
- 金属酸化物が本質的に酸化チタン又は酸化チタンの組合せから成る、請求項1〜20の何れか1項に記載の方法。
- 金属酸化物が不動態化酸化チタンを含む、請求項1〜21の何れか1項に記載の方法。
- 工程bの前の部材が機械的表面処理にかけられる、請求項1〜22の何れか1項に記載の方法。
- 機械的表面処理がブラスチングを含む、請求項23に記載の方法。
- 工程bの前の部材が化学的表面処理にかけられる、請求項1〜24の何れか1項に記載の方法。
- 化学的表面処理が脱脂又は洗浄処理を含む、請求項25記載の方法。
- 生体適合性部材が、インプラント、固定具、橋脚歯、ワンピースインプラント又はそれらの組合せから成るグループから選ばれる歯科用部材である、請求項1〜26の何れか1項に記載の方法。
- 生体適合性部材が整形外科用部材である、請求項1〜26の何れか1項に記載の方法。
- 請求項1〜28の何れか1項に記載の方法によって得られ得る部材。
- 少なくとも部分的に金属酸化物で被覆された生体適合性部材であって:
a)プラトー及び/又はリッジによって分離されたピットを含む微細構造;
b)該微細構造の上に重なっている一次ナノ構造、ここで該一次ナノ構造は波状の形に配置された窪みを含む;及び
c)前記一次ナノ構造の上に重なっている二次ナノ構造
を含む金属酸化物の表面を有する基体を含む生体適合性部材。 - 微細構造が、0.5から15μmの範囲内のピット直径;0.1から2.5μmの範囲内の深さ;及び0から10μmの範囲内の互いに隣接するピット間の距離を有する、請求項30に記載の生体適合性部材。
- 一次ナノ構造の窪みが10nmから1μmの範囲内の直径;及び10nmから300nmの範囲内の深さを有する、請求項30又は31に記載の生体適合性部材。
- 一次ナノ構造の個々の窪みの直径が、該個々の窪みの深さを超える、請求項30〜32の何れか1項に記載の生体適合性部材。
- 一次ナノ構造の窪みの直径が、該窪みが重なる微細構造のピットの直径より小さく、そして該一次ナノ構造の窪みの深さが、該窪みが重なる上記微細構造のピットの深さより小さい、請求項30〜33の何れか1項に記載の生体適合性部材。
- 一次ナノ構造の窪みの境界の少なくとも部分が、該一次ナノ構造の他の窪みの境界の少なくとも部分を構成する、請求項30〜34の何れか1項に記載の生体適合性部材。
- 部材が機械的表面処理にかけられている、請求項30〜35の何れか1項に記載の生体適合性部材。
- 機械的表面処理がブラスチングを含む、請求項36記載の生体適合性部材。
- 基体が少なくとも部分的にチタン又はチタン合金から成る、請求項30〜37の何れか1項に記載の生体適合性部材。
- 基体がチタンから成る、請求項30〜37の何れか1項に記載の生体適合性部材。
- 二次ナノ構造が一様に分布したパターンで一次ナノ構造の上に重なっていて、丸みのあるピークの形状を有する分離した突起を含む、請求項30〜39の何れか1項に記載の生体適合性部材。
- 二次ナノ構造が、20から550nmの範囲内のピーク直径;5から200nmの範囲内の平均ピーク高さ;そして10から450nmの範囲内のピーク間距離を有する、請求項40に記載の生体適合性部材。
- 二次ナノ構造が、15から150ピーク/平方μmの範囲内のピーク密度を含む、請求項40又は41に記載の生体適合性部材。
- ナノ要素が金属酸化物を含む、請求項30〜42の何れか1項に記載の生体適合性部材。
- ナノ要素が酸化チタンを含む、請求項43に記載の生体適合性部材。
- 表面が骨成長増強物質を含む、請求項30〜44の何れか1項に記載の生体適合性部材。
- 二次ナノ構造の少なくとも一部が骨成長増強物質を含む、請求項30〜45の何れか1項に記載の生体適合性部材。
- 骨成長増強物質が、チタンイオン、マグネシウムイオン、カルシウムイオン、リチウムイオン、ストロンチウムイオン、又はそれらの任意の組合せから成るグループから選ばれる金属イオン又はその塩を含む、請求項45又は46に記載の生体適合性部材。
- 骨成長増強物質がリチウムイオンを含む、請求項45又は46に記載の生体適合性部材。
- 骨成長増強物質がストロンチウムイオンを含む、請求項45、46及び48の何れか1項に記載の生体適合性部材。
- 部材が、インプラント、固定具、橋脚歯、ワンピースインプラント又はそれらの組合せから成るグループから選ばれる歯科用部材である、請求項30〜49の何れか1項に記載の生体適合性部材。
- 部材が整形外科用部材である、請求項30〜49の何れか1項に記載の生体適合性部材。
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PCT/EP2008/058860 WO2009007373A1 (en) | 2007-07-09 | 2008-07-08 | Nanosurface |
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AU (1) | AU2008274303A1 (ja) |
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EP2022447A1 (en) * | 2007-07-09 | 2009-02-11 | Astra Tech AB | Nanosurface |
US20090035723A1 (en) * | 2007-08-03 | 2009-02-05 | Claus Daniel | Material with a repetitive pattern of micro-features for application in a living organism and method of fabrication |
ES2315194B1 (es) * | 2007-09-10 | 2010-02-26 | Francisco J. GARCIA SABAN | Procedimiento para obtener una nueva superficie de un implante metalico a base de titanio destinado a ser insertado en tejido oseo. |
WO2009061887A2 (en) * | 2007-11-06 | 2009-05-14 | University Of Connecticut | Ceramic/structural protein composites and method of preparation thereof |
EP3159018B1 (en) * | 2008-02-29 | 2022-04-20 | Smith & Nephew, Inc | Gradient coating for biomedical applications |
CA2722661A1 (en) * | 2008-04-28 | 2009-11-05 | Kuraray Medical Inc. | Dental composition and composite resin |
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Also Published As
Publication number | Publication date |
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AU2008274303A1 (en) | 2009-01-15 |
US20130013081A1 (en) | 2013-01-10 |
US8632836B2 (en) | 2014-01-21 |
CN101686862A (zh) | 2010-03-31 |
CN102961193A (zh) | 2013-03-13 |
BRPI0814563A2 (pt) | 2015-01-06 |
EP2319461B1 (en) | 2012-09-19 |
CN101686862B (zh) | 2014-08-06 |
EP2537485B1 (en) | 2015-05-13 |
BRPI0814563B8 (pt) | 2021-06-22 |
ES2358776T3 (es) | 2011-05-13 |
DE602008004546D1 (en) | 2011-02-24 |
EP2022447A1 (en) | 2009-02-11 |
BRPI0814563B1 (pt) | 2018-12-26 |
EP2537485A1 (en) | 2012-12-26 |
ES2397633T3 (es) | 2013-03-08 |
EP2178466B1 (en) | 2011-01-12 |
EP2178466A1 (en) | 2010-04-28 |
ES2542243T3 (es) | 2015-08-03 |
CA2693478A1 (en) | 2009-01-15 |
ATE494861T1 (de) | 2011-01-15 |
CN102961193B (zh) | 2016-05-18 |
JP2011509098A (ja) | 2011-03-24 |
EP2319461A1 (en) | 2011-05-11 |
US20100173264A1 (en) | 2010-07-08 |
US9642708B2 (en) | 2017-05-09 |
WO2009007373A1 (en) | 2009-01-15 |
KR20100055403A (ko) | 2010-05-26 |
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