TWI519326B - 用於方便取出植入物的自分離層 - Google Patents
用於方便取出植入物的自分離層 Download PDFInfo
- Publication number
- TWI519326B TWI519326B TW100124399A TW100124399A TWI519326B TW I519326 B TWI519326 B TW I519326B TW 100124399 A TW100124399 A TW 100124399A TW 100124399 A TW100124399 A TW 100124399A TW I519326 B TWI519326 B TW I519326B
- Authority
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- Taiwan
- Prior art keywords
- layer
- bone implant
- thickness
- implant
- bone
- Prior art date
Links
- 239000007943 implant Substances 0.000 title claims description 96
- 239000000463 material Substances 0.000 claims description 56
- 210000000988 bone and bone Anatomy 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000000560 biocompatible material Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002195 soluble material Substances 0.000 claims description 9
- 210000001124 body fluid Anatomy 0.000 claims description 8
- 239000010839 body fluid Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 6
- 238000002513 implantation Methods 0.000 claims description 6
- 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 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 239000002198 insoluble material Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 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 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 210000001519 tissue Anatomy 0.000 description 11
- 239000000758 substrate Substances 0.000 description 7
- 230000035876 healing Effects 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
Classifications
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Description
本申請案通常有關用於從骨中取出骨植入物的裝置。
在包括外傷和顱-頜面領域在內的整形手術中,在達到期望的癒合程度之後,通常需要取出骨植入物部件。這可能是出於美容的原因及/或允許植入位址周圍完全恢復。因為很多先進植入物係由生物相容的合金(例如鈦-鋁-鈮「Ti-Al-Nb」)製成,所以外科醫生經常會面對植入物過好地融入周圍組織中,使得將其取出會造成更大的侵害和損傷。
本發明係與利用防止組織與骨植入物面向組織的表面直接接觸的可溶層或生物可降解層和生物相容層塗佈骨植入物的系統和方法有關。可以藉由多種技術實施本發明的示例性的塗層,包括浸塗或噴塗和物理氣相沉積或化學氣相沉積(PVD/CVD)。這導致在組織接觸表面上直接形成生物相容的「隔離層」,這有利於植入物周圍的癒合,但是在體內預定時間之後,所述「隔離層」更容易分離,使植入物從周圍組織釋放,並使得取出過程的侵害和損傷更小。隨後,在第一隔離層上形成的生物相容外層將在較長的時間段被再吸收,生物相容外層的總體積和材料性質被選擇為使得當植入物主體內時,能提供不顯著的任何副反應。
本發明與具有基底材料的植入物有關,所述基底材料包
含金屬或金屬合金,所述基底材料塗佈有厚度為D的第一層,所述第一層包含水溶性材料或可在體液中降解的材料,所述第一層上具有厚度為d<D的第二層,所述第二層包含生物相容性材料。
該植入物在金屬植入物基底上提供自分離塗佈,保護植入物免受骨的面上生長和向內生長,而不會妨礙癒合過程。這允許植入物在實現其體內的短期功能之後可被容易取出。
在所述植入物的示例性實施例中,所述第二層包含生物可吸收性材料或生物溶解性材料。
在所述植入物的另一個實施例中,所述第二層包含非可吸收性材料或非溶解性材料。
在所述植入物的另一個實施例中,所述第二層的厚度d最小為1nm,較佳10nm。當厚度為10nm時,所述第二層可作為細胞穿過性生長的有效屏障,從而降低或阻止相關的擴散機制。
在所述植入物的另一個實施例中,所述第二層的厚度d最大為100nm。
在所述植入物的另一個實施例中,所述第二層的吸收/溶解速率小於所述第一層的吸收/溶解速率。
在所述植入物的另一個實施例中,所述第二層吸收/溶解所需的時間為2週-3個月。
在所述植入物的另一個實施例中,所述第一層由可吸收
性材料製成。較佳的材料是聚交酯(PLA)和磷酸鈣(CaP)。該構造允許細胞穿過性生長,這可能導致弱化的「細胞-第二層-細胞」結構,該結構在取出主體植入物時容易破裂。在所述第一層溶解/被吸收之後,所述第二層將在較長的時間段被吸收。
在所述植入物的另一個實施例中,所述第一層的厚度D為至少10μm,較佳至少100μm。
在所述植入物的另一個實施例中,所述第一層的厚度D不超過1000μm,較佳不超過500μm。
在所述植入物的另一個實施例中,D/d比值為10,000:1-1,000:1。
在所述植入物的另一個實施例中,所述第一層包含聚乙烯醇(PVA)或聚交酯。
在所述植入物的另一個實施例中,所述第二層包含非可吸收的金屬,較佳鈦或鈦合金,並且厚度d最大為100nm。
在所述植入物的另一個實施例中,所述第二層包含羥磷灰石,且厚度d最大為10μm。
在所述植入物的另一個實施例中,將包含第一層材料和第二層材料的混合物的第三層插在所述第一層和第二層之間。
在所述植入物的另一個實施例中,在所述第二層上施加其它層,並且在該其它層上施加包含生物相容性材料的
另一層。所述其它層包含水溶性材料或可在體液中降解的材料。
在所述植入物的另一個實施例中,包含水溶性材料或可在體液中降解的材料和生物相容性材料的交替層的數量是2x,其中x為3或更大。
在所述植入物的另一個實施例中,所述第一層的材料不同於所述第二層的材料。
按照另一態樣,提供一種製備所述植入物的方法,包括以下步驟:將水溶性材料或可在體液中降解的材料施加到包含金屬或金屬合金的基底上,從而在所述基底上形成第一層,以及在所述第一層上施加生物相容性材料。
在所述方法的另一個實施例中,在進行步驟B之前,將步驟A和B中所用材料的混合物施加到所述第一層上。
在所述方法的另一個實施例中,藉由浸塗或噴塗施加所述層。
下面藉由舉例的方式並結合附圖描述本發明的數個實施例。
本發明與塗佈的骨植入物和製備該骨植入物的方法有關,所述骨植入物用於固定斷裂的或受損的或弱化的骨。本發明的實施例可用於矯形固定、顱-頜面固定或用於需要短期或長期植入骨植入物的活體中的任何其它骨的固定。本發明的示例性實施例的骨板以一層或多層材料塗佈,所選的材料能防止在短期或長期的體內植入過程中
,所述骨板與該骨植入物的周圍組織發生融合。示例性的骨板中材料層中的一層或多層可以由表現出所需特性(例如,吸收速率、生物相容性等)的可吸收性材料製成。應當注意到,儘管利用具體的層厚度和構造並結合特定骨的固定來描述本發明的實施例,但是任何其它厚度或構造都可以用於固定任意骨,而不脫離本發明的實質和範圍。此外,儘管在本發明的實施例描述中,層僅位於骨植入物的一個表面上,但是所述骨植入物的任何或所有表面都可以用示例性的層塗佈,而不脫離本發明的實質和範圍。
如第一圖所示,按照本發明第一實施例的植入物10包括含有基底材料1的植入物主體12(例如,骨板或髓內釘)。植入物主體12的第一表面14塗佈有第一層2,第二層3在第一層2上延伸,使得第二層3形成植入物10的外表面,當植入物10被植入時,所述外表面形成與周圍組織的接觸層。本領域技術人員應當理解,植入物10的基底材料1可以是任何合適的金屬、金屬合金或聚合物。通常,本領域技術人員應當理解,為了用作手術植入物應用,基底材料1是鈦(Ti)、諸如TiAl6Nb7(「TAN」)的Ti合金、鋼或PEEK。
第一層2的厚度為D,並且包含可吸收性材料,所述可吸收性材料包括聚乙烯醇(PVA)或聚交酯。第一層2的厚度D可以為約10μm-1000μm,並且在示例性的實施例中可以為約100μm-500μm。
第二層3的厚度為d,並且包含生物相容性材料,所述生
物相容性材料可以是生物可吸收性材料或生物溶解性材料以及非可吸收性材料或非溶解性材料中的一種。在示例性的實施例中,第二層3包含非可吸收性金屬,例如鈦或鈦合金和/或羥磷灰石。第二層3的厚度d小於第一層2的厚度D,厚度d可以為1nm-100nm,並且在較佳的實施例中,厚度d最大為10μm。此外,第二層3的吸收/溶解時間長於第一層2的吸收/溶解時間,第二層3的吸收/溶解時間為2週-3個月。
由於在植入物主體12的表面14上形成第一層2並且在第一層2上形成第二層3,因此防止組織和植入物主體12的表面14之間發生接觸。由第一層2和第二層3所形成的生物相容層體系有利於植入物10周圍的癒合,並且由於在體內預定時間之後,至少第一層2從植入物主體12分離,所述生物相容層體系能減少取出植入物10過程的侵害性和破壞性。
在第二圖中,顯示植入物的另一個實施例,其與第一圖之實施例的不同點僅在於在植入物10’的第一層2和第二層3之間形成中間層4。第三層4包含第一層2和第二層3的材料的混合物。與第一圖的實施例相似,由基底材料1組成並具有骨板或髓內釘形式的植入物主體12’塗佈有厚度為D的第一層2。中間層4置於第一層2上,並且具有例如厚度δI,所述厚度δI小於第一層2的厚度D並大於第二層3的厚度d,第二層3與周圍組織形成接觸層。
第三圖顯示植入物的另一個實施例,其與第一圖實施例的不同點僅在於在第二層3上形成第三層21。第三層21包
含水溶性材料或可在體液中降解的材料。在第三層21上形成的第四層31包含生物相容性材料。與第一圖的實施例相似,具有由基底材料1組成的植入物主體12’,並形成骨板或髓內釘的植入物10’,塗佈有厚度為D的第一層2,厚度為d的第二層3位於第一層2之上。第三層21置於第二層3之上,且厚度為δF,例如,厚度δF等於第一層2的厚度D,同時第四層和最外層31的厚度為δA,例如,厚度δA等於第二層3的厚度d。第四層31形成與周圍組織的接觸層。
按照在本發明的植入物上施加層的示例性方法,使用通常與骨螺釘聯合用於骨折固定的骨板。這類骨板在體內使用的通常的時間為數週至數月,隨後通常將它們取出。骨板通常由TAN合金或鋼製成,還可以由諸如PEEK的塑膠製成。然而,應當指出,視需要,本發明的示例性骨板也可以被無限期的植入,而不脫離本發明的實質和範圍。
按照第一示例性的步驟,首先將TAN骨板浸入體積百分比為50/50的乙醇和丙酮混合物中,隨後將其置於超音波浴中大約5分鐘來清潔TAN骨板。該步驟之後,在乾燥CO2氣流中清潔植入物。然後,藉由在PVA/水溶液中以預定的去除速度(例如,mm/s)進行浸塗而使所述植入物塗佈上聚乙烯醇(PVA)的水溶性第一層2,從而得到乾燥後具有特定尺寸的強度為(例如,微米)的PVA層,其中如本領域技術人員所理解的,去除速度與得到的PVA層強度直接相關。在第一示例性的實施例中,去除速度可以為1mm/s,
得到的PVA層大約為50微米。然後將該骨板插入施加的壓力小於1e-4mbar的真空系統中。然後在PVA層上施加10nm的氧化鈦薄膜,例如藉由在90%Ar和10%O2的混合物中,用5e-3mbar的工作壓力進行反應性磁控濺鍍。得到的第二層3是生物相容性的,並且延遲之前施加的PVA層的水溶解。然後將塗佈過的骨植入物10從真空室中取出,並在乾燥空氣或真空中進行包裝。大約1個月後,第一PVA層2在體內分離,因此在從骨植入物中取出骨螺釘之後,能使骨植入物自由取出。
本領域技術人員應當理解,在不脫離後附申請專利範圍之寬廣範圍的情況下,可以對本發明進行各種修改和更改。其中一些已在上文作出討論,並且其它的修改和更改是本領域技術人員顯而易見的。例如,還可以將本發明的示例性的層應用在克氏針或髓內釘上,而不脫離本發明的實質和範圍。在本發明的的示例性技術中,可以按照與上述基本相同的方式,使用浸塗法隨後進行熱蒸發過程來塗佈克氏針。如果使用髓內釘,可以用100μm厚的生物可降解層噴塗髓內釘。然後用羥磷灰石層塗佈生物可降解層。隨著生物可降解層的溶解(即在植入體內預定的時間段之後),髓內釘和羥磷灰石層之間會保持足夠的空間,從而允許取出髓內釘,而仍能阻止周圍的弱組織向內生長。
儘管已經詳述本發明及其優點,但應當理解,在不脫離後附申請專利範圍所限定的實質和範圍的情況下,可以對本發明進行各種改變、替換和更改。例如,可以用熔
解夾層替換本發明的任意生物可降解層,所述熔解夾層例如在體內達到預定的溫度(例如靜息時的體溫)後能溶進周圍組織中。在另一個實例中,可以為僅需短期植入的骨植入物提供潤滑,以防止或降低組織的面上生長。
此外,本申請案的範圍不被本說明書中所描述的過程、機器、製造物、物質組成物、手段、方法和步驟的具體的實施例所限制。本領域技術人員從本發明的揭露應當容易理解到,可以按照本發明利用現有的或未來將被開發出的與本文描述的相應的實施例執行基本相同的功能或實現基本相同的結果的過程、機器、製造物、物質組成物、手段、方法和步驟。
1‧‧‧基底材料
2‧‧‧第一層
3‧‧‧第二層
4‧‧‧中間層
10‧‧‧植入物
10’‧‧‧植入物
10’’‧‧‧植入物
12‧‧‧植入物主體
12’‧‧‧植入物主體
12’’‧‧‧植入物主體
14‧‧‧第一表面
21‧‧‧第三層
31‧‧‧第四層
D‧‧‧厚度
d‧‧‧厚度
δ1‧‧‧厚度
δA‧‧‧厚度
δF‧‧‧厚度
第一圖示例本發明植入物的第一示例性實施例的橫截面;第二圖示例本發明植入物的另一示例性實施例的橫截面;及第三圖示例本發明植入物的另一示例性實施例的橫截面。
1‧‧‧基底材料
2‧‧‧第一層
3‧‧‧第二層
10‧‧‧植入物
12‧‧‧植入物主體
14‧‧‧第一表面
D‧‧‧厚度
d‧‧‧厚度
Claims (19)
- 一種骨植入物,包括:提供在該骨植入物的第一外表面上的一第一層,並且該第一層包含一第一材料,該第一材料是水溶性材料及可在體液中降解的材料中的一種,該第一層具有一第一厚度,其中該第一層由聚乙烯醇(PVA)、聚交酯及磷酸鈣中的一種製成;及提供在該第一層的外表面上的一第二層,並且該第二層由生物相容性材料製成,該第二層的一第二厚度小於該第一厚度,其中該第二層由鈦、鈦合金及羥磷灰石中的一種製成。
- 如請求項1所述的骨植入物,其中該第二層包含生物可吸收性材料或生物溶解性材料。
- 如請求項1所述的骨植入物,其中該第二層包含非可吸收性材料或非溶解性材料。
- 如請求項3所述的骨植入物,其中該第二厚度係介於1nm與100nm之間。
- 如請求項2所述的骨植入物,其中該第二層的吸收/溶解速率小於該第一層的吸收/溶解速率。
- 如請求項5所述的骨植入物,其中在植入體內之後,該第二層的吸收/溶解速率為2週-3個月。
- 如請求項1所述的骨植入物,其中該第一層係由可吸收性材料製成。
- 如請求項1所述的骨植入物,其中該第一層的第一厚度為約10μm-1000μm,該第一厚度與該第二厚度的比值為10,000:1-1,000:1。
- 如請求項1所述的骨植入物,其中該第二層由非可吸收性金屬製成,第二厚度最大為100nm。
- 如請求項1所述的骨植入物,其中該第二厚度最大為10μm。
- 如請求項1所述的骨植入物,其中該第一層和第二層中的至少一層包含至少一種選自鎂、鐵及其合金的生物可降解的金屬或金屬合金。
- 如請求項1所述的骨植入物,更包括插在該第一層和該第二層之間的中間層,該中間層由該第一層和該第二層的材料的混合物製成。
- 如請求項1所述的骨植入物,更包括提供在該第二層的外表面上的一第三層,該第三層係由水溶性材料及可在體液中降解的材料中的一種製成。
- 如請求項13所述的骨植入物,更包括提供在該第三層的外表面上的一第四層,該第四層係由生物相容性材料製成。
- 如請求項14所述的骨植入物,其中包含水溶性材料或可在體液中降解的材料和生物相容性材料的交替層的數量是2x,其中x為3。
- 如請求項1所述的骨植入物,其中該第一層的材料不同於該第二層的材料。
- 一種製備骨植入物的方法,包括:在該骨植入物的一第一表面上施加一第一材料的一第一層,該第一材料是水溶性材料或可在體液中降解的材料中的一種或兩種,其中該第一層由聚乙烯醇(PVA)及聚交酯中的一種製成,在該第一層的外表面上施加一第二材料的一第二層,該第二材料是生物相容的,其中該第二層由鈦、鈦合金及羥磷灰石中的一種製成。
- 如請求項17所述的方法,更包括在施加該第二層之前,在該第一層上施加一中間層的步驟,該中間層係由該第一材料和該第二材料的混合物製成。
- 如請求項17所述的方法,其中藉由浸塗和噴塗中的一種施加該第一層和該第二層。
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CN103908328A (zh) * | 2013-01-06 | 2014-07-09 | 香港中文大学 | 骨植入物 |
CN104740692B (zh) * | 2013-12-31 | 2017-09-05 | 上海微创骨科医疗科技有限公司 | 一种骨内固定植入物及其制备方法 |
WO2016159493A1 (ko) * | 2015-03-31 | 2016-10-06 | (주)웹스 | 생분해성 임플란트 구조체 |
US20220361872A1 (en) | 2021-05-10 | 2022-11-17 | Cilag Gmbh International | Cartridge assemblies with absorbable metal staples and absorbable implantable adjuncts |
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EP0523926A3 (en) * | 1991-07-15 | 1993-12-01 | Smith & Nephew Richards Inc | Prosthetic implants with bioabsorbable coating |
US6214049B1 (en) * | 1999-01-14 | 2001-04-10 | Comfort Biomedical, Inc. | Method and apparatus for augmentating osteointegration of prosthetic implant devices |
US6277150B1 (en) * | 1999-06-11 | 2001-08-21 | Gore Enterprise Holdings, Inc. | Facial implant having one porous surface |
DE10206627A1 (de) * | 2002-02-15 | 2003-08-28 | Diocom B V | Körpergelenk ersetzendes Titanimplantat mit einem oder mehreren Grundkörpern |
US7767222B2 (en) * | 2002-07-31 | 2010-08-03 | Mast Biosurgery Ag | Apparatus and method for preventing adhesions between an implant and surrounding tissues |
CN100515364C (zh) * | 2002-07-31 | 2009-07-22 | 马斯特生物外科股份公司 | 用于防止植入物与周围组织之间的粘附的装置 |
EP1572258A1 (en) * | 2002-11-25 | 2005-09-14 | Yissum Research Development Company, of The Hebrew University of Jerusalem | Organic-inorganic nanocomposite coatings for implant materials and methods of preparation thereof |
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DE102005032604A1 (de) * | 2005-07-13 | 2007-01-18 | Gfe Medizintechnik Gmbh | Resorbierbares, in den Körper einsetzbares medizinisches Element, insbesondere resorbierbares Implantat |
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DE102006044415B4 (de) * | 2006-09-18 | 2013-03-21 | Aap Implantate Ag | Titanhaltiges Implantat zur temporären Implantation |
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KR101826590B1 (ko) | 2018-02-07 |
CN105749345B (zh) | 2019-10-25 |
KR20130139831A (ko) | 2013-12-23 |
EP2982343A1 (en) | 2016-02-10 |
US10166105B2 (en) | 2019-01-01 |
US20160354208A1 (en) | 2016-12-08 |
KR20180008937A (ko) | 2018-01-24 |
TW201206509A (en) | 2012-02-16 |
BR112012033415A2 (pt) | 2016-11-29 |
CA2803262C (en) | 2018-09-11 |
JP5873490B2 (ja) | 2016-03-01 |
CA2803262A1 (en) | 2012-01-12 |
KR101882667B1 (ko) | 2018-07-30 |
EP2590596A1 (en) | 2013-05-15 |
US20120172997A1 (en) | 2012-07-05 |
EP2982343B1 (en) | 2017-01-04 |
CN105749345A (zh) | 2016-07-13 |
JP2013535239A (ja) | 2013-09-12 |
JP2016105789A (ja) | 2016-06-16 |
CN102958470B (zh) | 2016-04-20 |
EP2590596B1 (en) | 2015-08-26 |
JP6199419B2 (ja) | 2017-09-20 |
CN102958470A (zh) | 2013-03-06 |
WO2012006334A1 (en) | 2012-01-12 |
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