CN1296101C - 用于医用植入体和假牙的生物活性表面层 - Google Patents

用于医用植入体和假牙的生物活性表面层 Download PDF

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CN1296101C
CN1296101C CNB018231101A CN01823110A CN1296101C CN 1296101 C CN1296101 C CN 1296101C CN B018231101 A CNB018231101 A CN B018231101A CN 01823110 A CN01823110 A CN 01823110A CN 1296101 C CN1296101 C CN 1296101C
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surface layer
metal
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calcium
oxide
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CN1505532A (zh
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V·M·弗劳奇杰
F·施洛特提格
M·泰克斯托
B·加塞
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AO Technology AG
Synthes GmbH
Dr HC Robert Mathys Stiftung
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Dr HC Robert Mathys Stiftung
Synthes AG Chur
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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Abstract

本发明的生物活性表面层特别适合用于医用植入体和假牙。份额可变的0.1-50.0μm厚的、多孔的表面层由磷酸钙相构成。其含有无定形的或纳米晶形的磷酸钙，表面层在表面处的孔密度为104-108孔/mm2。在整个表面层上Ca/P比例为0.5-2.0。表面层具有高的溶解度，以致于其可起到作为磷酸钙供体用于骨生成的作用。

Description

用于医用植入体和假牙的生物活性表面层
本发明涉及用于医用植入体和假牙的生物活性表面层以及一种用于制备含磷酸钙的、生物活性的、多孔的表面层的方法。
由US-A-5 478 237获知，ISHIZAWA是一种由钛制成的牙齿植入体，采用基材的阳极氧化使其具有表面层，表面层含有钙-和磷酸根-离子，并且是以羟基磷灰石-晶体的形式。这种镀层的缺点在于，羟基磷灰石-晶体是基本上不可溶的，以致于钙-和磷酸根-离子不能进入骨骼。这种已知的、结晶的镀层的另一个缺点在于其易碎性，这造成镀层剥落的危险。最后对于该公开的制备方法涉及到一种二步工艺过程，这也被视为是有缺陷的。
在此本发明提供辅助方案。本发明的任务在于开发一种生物活性的、多孔的含磷酸钙(CaP)的表面层，磷酸钙具有高的溶解度，以致于其可起到作为磷酸钙供体用于骨生成的作用。
本发明使用具有下述特征的表面层解决所提出的任务。
本发明提供一种用于医用植入体和假牙的生物活性表面层，其中
A)至少部分由磷酸钙相构成的表面层，
B)层的厚度为0.1-50.0μm，且
C)表面层是多孔状的，
其特征在于，
D)所述磷酸钙相是无定形的或纳米晶形的；
E)基于原子百分比份额，在整个表面层中Ca/P比为0.5-2.0；
F)表面层含有25-95原子百分比份额的金属氧化物，其中所述金属氧化物中的金属选自阀金属Ti，Zr，Ta，Nb，Al，V，Mg；
G)其中所述金属氧化物至少部分以纳米晶形或微晶形的形式存在；
H)在表面层中镀入的Ca2+离子和PO4 3-离子分布于整个金属氧化物层中；
I)表面层表面的孔密度为104-108孔/mm2，优选为105-107孔/mm2；且
J)所述无定形的或纳米晶形的磷酸钙相为整个表面层的1-40体积％。
本发明的其它优越特性如下说明。
通过本发明所达到的优点主要在于，由于根据本发明的具有在多孔结构中溶解性镀入的磷酸钙相的表面层，骨骼能更快地在多孔的载体结构中生长。在此，不仅涉及到用钙-和磷酸根离子的表面浸渍，而且还涉及到通过根据本发明的方法，依赖于工艺参数的选择可得到的，在已有的表面结构上叠加具有植入无定形的或纳米晶体的微结构，从而使溶解性磷酸钙相进入火花放电下的阳极氧化所形成的金属氧化物-层中。
根据本发明的方法的优点是一个工艺过程，该过程快速进行并且也适合于复杂的几何形状。
在一个本发明优选的实施方案中，表面层含有添加的羟基磷灰石。
优选在整个表面层中Ca/P比例为1.0-1.8，即类似于TCP、HA和Ca-缺失的HA。已经表明，近乎天然的、无机骨材料的羟基磷灰石的Ca/P比例(1.67)，基于进入溶液中的镀层份额是最佳的Ca/P比例。
在本发明的另一个优选的实施方案中，无定形的或纳米晶体的磷酸钙和/或羟基磷灰石为总的表面层的1-40体积％。因为磷酸钙-相与基材上生成的层合为一体，所以提供了更好的附着性。
在本发明的另一个优选的实施方案中，表面层含有份额为25-95原子百分比的金属氧化物，优选为30-80原子百分比。已经表明，在这样的金属氧化物份额下镀层基材(Schichtmatrix)的机械和化学耐久性是最佳的。
在本发明的另一个优选的实施方案中，金属氧化物以晶体的形式存在，优选以10-150纳米晶粒粒度的晶体形式，这对于Ca-和P-离子的溶解度是有利的。
在本发明的另一个优选的实施方案中，金属氧化物是二氧化钛，优选以锐钛矿或金红石的形式，其具有特殊的晶体结构。
在本发明的另一个优选的实施方案中，在表面层中镀入的Ca2+-离子和PO4 3--离子分布于整个金属氧化物层中。相对于纯粹的表面浸渍，一个这样的均质的表面组分具有优点，即其使得单位面积释放足够量的钙和磷酸根用于骨的形成。
在本发明的另一个优选的实施方案中，表面层的厚度为0.5-10.0μm。一个这样的较薄的层对于附着，特别在要求剪应力的情形下是有利的。它进一步保证了对腐蚀和特别对机械磨损的最佳保护，不会出现易碎的危险和/或在机械负荷下(特别在剪应力下)或热负荷下出现的(如其在太厚的层的情况下常常出现的)张力的危险。
在本发明的另一个优选的实施方案中，多孔表面层的细孔含有起药理学作用的物质，优选为肽、生长因子、骨形态生成蛋白质(BoneMorphogenetic Protein)、抗生素或消炎剂。这些添加物质的优点在于它们的感应作用。这些作用物质使得骨组织在治疗过程中生物性或生物化学性支持成为可能。在此可通过选择孔的大小(直径)和孔的容积(孔径、孔密度)而控制释放动力学(单位时间内活性物质的释放量或单位面积的活性物质释放量)。
根据本发明的表面层优选涂镀到一种基材上，其含有一种或多种Ti、Zr、Ta、Nb、Al、V、Mg元素或它们的合金。元素Ti、Zr、Ta、Nb、Al、V、Mg也被称为阀金属(Ventilmetalle)(参见M.M.Lohrengel《在铝和其他的阀金属上的阳极氧化层》，材料科学和工程，R11，No.6，December 15，1993)(M.M.Lohrengel“Thinanodic oxide layers on aluminium and other valve metals”，Materials Science and Engineering，R11，No.6，December15，1993)。将根据本发明的表面层镀到这种基材上已经证明是特别有利的。
在这些基材上所镀上的、根据本发明的表面层优选地至少部分地由金属基材的纳米晶体的或微米晶体的氧化物或混合氧化物构成。其导致产生一种至少是骨传导的、结构化的、多孔的层，从而直接与骨的接触。
表面层的主要成份优选由金属基材的纳米-或微米晶体氧化物或混合氧化物构成，典型的份额为60-99体积％。
在一个优选的实施方案中，基材由塑料构成，优选由聚甲醛(POM)、聚醚醚酮(PEEK)、聚丙烯醚酮(PAEK)、聚醚酰亚胺(PEI)或液晶聚合物(LCP)、聚甲基戊烯(PMP)、聚砜(PSU)、聚醚砜(PESU或PES)、聚对苯二甲酸亚乙基酯(PETP)、聚甲基丙烯酸甲酯(PMMA)或超高分子聚乙烯(UHMW-PE)构成，在此，基材具有由阀金属构成的金属层。从而可以应用于弹性植入体和假牙。
根据本发明的用于制备在阀金属或它们的合金或在基材上的阀金属镀层上的含磷酸钙的、生物活性的、多孔的表面层的方法，即在基材上阀金属电镀的方法，其中将所要电镀的基材作为阳极放入水性的电解液中，电解液中含有钙-和磷酸根-离子，其应沉积到所生成的镀层中，且在电解液中，采用直流电压或直流电压脉冲或时间性改变电压的火花放电而进行阳极-等离子化学表面改性，其特征在于，
A)具有钙-和磷酸根加入物的水性电解液的pH-值调节到大于或等于9，并且电解液含有至少下列组分；
B1)一种或多种浓度为0.01-6.00mol/l的有机螯合物形成剂或无机络合物形成剂；
B2)一种或多种浓度为0.01-6.00mol/l的磷酸盐化合物，优选为0.01-0.05mol/l的磷酸盐化合物；
B3)一种或多种浓度为0.01-6.00mol/l的用于调节所期望的钙/磷酸根-比例的水溶性钙化合物；和
B4)一种或多种浓度为0.01-6.00mol/l的用于调节所期望的pH-值的碱性添加剂。
下列物质适合作为螯合物形成剂：
a)羧酸，特别是二-或多齿配位基或它们的羧酸盐，特别是：柠檬酸、酒石酸、氨三乙酸(NTA)、乙二胺四乙酸(EDTA)、1，2-环己二胺四乙酸(CDTA)、二亚乙基三胺五乙酸(DTPA)、2-羟乙基乙二胺三乙酸、三亚乙基四胺六乙酸(TTHA)；
b)酮，特别是二-或多酮，尤其是β-二酮(CH3-CO-CH2-CO-CH3)；
c)有机磷酸或有机磷酸盐(具有≥2个磷酸根)；
d)有机膦酸或有机膦酸盐(具有≥2个膦酸根)；
e)有机亚磷酸或有机亚磷酸盐(具有≥2个亚磷酸根)；
以及所有上述物质的合适的盐。
作为无机络合物形成剂特别合适的是CaX6 4-，特别是X＝氟化物。
络合物形成剂的浓度优选为0.06-0.24mol/l。双(磷酸二氢)钙优选用作为磷酸盐化合物，典型的浓度为0.01-0.05mol/l。水溶的钙化合物(优选为乙酸钙)优选以0.03-0.15mol/l的浓度应用。
作为碱性添加剂合适的是氢氧化物，优选为氢氧化钠或氢氧化钾，典型的浓度为0.5-1.5mol/l。
在一个优选的镀层方法的实施方案中，阳极化工艺过程的参数(电压、电流、频率、电镀时间、浴槽几何尺寸等)这样选择，以致于通过基材和电解液之间的反应形成镀层，其中已经形成的层通过火花放电部分重结晶。在电镀进行期间电解液适宜的温度为10-90℃，优选为20-75℃。
优选基材由元素Ti、Zr、Ta、Nb、Al、V、Mg或它们的合金构成，或者将形成阻挡层的金属镀层全方位或部分地电镀到任意的形式和表面特性的任意基材上。优选地通过对起始表面的化学性和/或机械性预处理而对表面形状或表面形态产生影响，在此，化学性预处理可以是一种浸蚀性方法和机械性预处理可以是一种射线辐照过程。
下面用一个实施例更清楚地解释本发明和本发明的进一步构成。
实施例：
一纯钛圆柱形片(高1mm，直径7mm)在25℃下于下述的电解液中80mA的电流强度下电镀90秒。
10.5g  磷酸二氢钙
22g    二乙酸钙
74g    乙二胺四乙酸二钠
13g    氢氧化钠
用纯水定容到1升。所得到的、淡灰色的镀层具有下列的浓度比(以原子百分比计)：Ca/Ti：1.05 P/Ti：0.83和Ca/P：1.27。

Claims (36)

1.一种用于医用植入体的生物活性表面层，其中
A)至少部分由磷酸钙相构成的表面层，
B)层的厚度为0.1-50.0μm，且
C)表面层是多孔状的，
其特征在于，
D)所述磷酸钙相是无定形的或纳米晶形的；
E)基于原子百分比份额，在整个表面层中Ca/P比为0.5-2.0；
F)表面层含有25-95原子百分比份额的金属氧化物，其中所述金属氧化物中的金属选自阀金属Ti，Zr，Ta，Nb，Al，V，Mg；
G)其中所述金属氧化物至少部分以纳米晶形或微晶形的形式存在；
H)在表面层中镀入的Ca2+离子和PO4 3-离子分布于整个金属氧化物层中；
I)表面层表面的孔密度为104-108孔/mm2；且
J)所述无定形的或纳米晶形的磷酸钙相为整个表面层的1-40体积％。
2.根据权利要求1的表面层，其特征在于，所述磷酸钙相包含羟基磷灰石。
3.根据权利要求1或2的表面层，其特征在于，孔密度为105-107孔/mm2。
4.根据权利要求1或2的表面层，其特征在于，基于原子百分比份额，在整个表面层上的Ca/P比为1.0-1.8。
5.根据权利要求1或2的表面层，其特征在于，其含有30-80原子百分比的份额的金属氧化物。
6.根据权利要求5的表面层，其特征在于，金属氧化物以晶体的形式存在。
7.根据权利要求6的表面层，其特征在于，金属氧化物是二氧化钛。
8.根据权利要求7的表面层，其特征在于，二氧化钛以锐钛矿或金红石的形式存在。
9.根据权利要求1或2的表面层，其特征在于，层厚为0.5-10.0μm。
10.根据权利要求1或2的表面层，其特征在于，多孔表面层的孔含有起药理学作用的物质。
11.具有根据权利要求1或2的表面层的基材，其特征在于，基材含有一种或多种元素Ti、Zr、Ta、Nb、Al、V、Mg或它们的合金。
12.根据权利要求11的基材，其特征在于，表面层的金属氧化物由金属基材的纳米-或微米晶体的氧化物或混合氧化物构成。
13.具有根据权利要求1或2的表面层的基材，其特征在于，基材由塑料构成，在此，基材具有由阀金属构成的金属层。
14.用于在含有阀金属或它们的合金的基材上以及具有阀金属镀层的基材上制备根据权利要求1或2的含磷酸钙的、生物活性的、多孔的表面层的方法，其中将所要电镀的基材作为阳极放入水性的电解液中，电解液中含有钙-和磷酸根-离子，其应沉积到所生成的镀层中，且在电解液中，采用直流电压或直流电压脉冲或时间性改变电压的火花放电而进行阳极-等离子化学表面改性，其特征在于，
A)具有钙-和磷酸根加入物的水性电解液的pH-值调节到大于或等于9，并且电解液含有至少下列组分；
B1)一种或多种浓度为0.01-6.00mol/l的有机螯合物形成剂或无机络合物形成剂；
B2)一种或多种浓度为0.01-6.00mol/l的磷酸盐化合物；
B3)一种或多种浓度为0.01-6.00mol/l的用于调节所期望的钙/磷酸根-比例的水溶性钙化合物；和
B4)一种或多种浓度为0.01-6.00mol/l的用于调节所期望的pH-值的碱性添加剂。
15.根据权利要求14的方法，其特征在于，所述螯合物形成剂选自下列物质组：柠檬酸、酒石酸、氨三乙酸、乙二胺四乙酸、1，2-环己二胺四乙酸、二亚乙基三胺五乙酸、2-羟乙基乙二胺三乙酸、三亚乙基四胺六乙酸。
16.根据权利要求14的方法，其特征在于，螯合物形成剂是酮。
17.根据权利要求16的方法，其特征在于，所述酮为二酮。
18.根据权利要求17的方法，其特征在于，所述二酮为β-二酮。
19.根据权利要求14的方法，其特征在于，螯合物形成剂是有机磷酸或有机磷酸盐。
20.根据权利要求14的方法，其特征在于，螯合物形成剂是有机膦酸或有机膦酸盐。
21.根据权利要求14的方法，其特征在于，螯合物形成剂是有机亚磷酸或有机亚磷酸盐。
22.根据权利要求14的方法，其特征在于，螯合物形成剂作为盐类存在。
23.根据权利要求14的方法，其特征在于，无机络合物形成剂为CaX6 4-。
24.根据权利要求14的方法，其特征在于，无机络合物形成剂具有0.06-0.24mol/l的浓度。
25.根据权利要求14的方法，其特征在于，磷酸盐化合物是双(磷酸二氢)钙。
26.根据权利要求14的方法，其特征在于，磷酸盐化合物具有0.01-0.05mol/l的浓度。
27.根据权利要求14的方法，其特征在于，水溶性的钙化合物是乙酸钙。
28.根据权利要求14的方法，其特征在于，水溶性钙化合物具有0.03-0.15mol/l的浓度。
29.根据权利要求14的方法，其特征在于碱性添加剂是氢氧化物。
30.根据权利要求14的方法，其特征在于，碱性添加剂具有0.5-1.5mol/l的浓度。
31.根据权利要求14的方法，其特征在于，阳极化工艺过程的参数这样选择，以致于通过基材和电解液之间的反应形成镀层，其中已经形成的镀层通过火花放电部分重结晶。
32.根据权利要求14的方法，其特征在于，在电镀过程中电解液的温度为10-90℃。
33.根据权利要求14的方法，其特征在于，基材由元素Ti、Zr、Ta、Nb、Al、V、Mg或它们的合金构成，或者将形成阻挡层的金属镀层全方位或部分地镀到任意的形式和表面特性的任意基材上。
34.根据权利要求14的方法，其特征在于，通过对起始表面的化学性和/或机械性预处理而对表面形状或表面形态产生影响。
35.根据权利要求34的方法，其特征在于，化学性预处理是一种浸蚀法。
36.根据权利要求34的方法，其特征在于，机械性预处理是一种射线辐照过程。
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