CN1893822A - 抗微生物复合材料 - Google Patents
抗微生物复合材料 Download PDFInfo
- Publication number
- CN1893822A CN1893822A CNA2004800376048A CN200480037604A CN1893822A CN 1893822 A CN1893822 A CN 1893822A CN A2004800376048 A CNA2004800376048 A CN A2004800376048A CN 200480037604 A CN200480037604 A CN 200480037604A CN 1893822 A CN1893822 A CN 1893822A
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- CN
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- Prior art keywords
- biocide
- coating material
- transmission control
- layer
- control layer
- 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.)
- Granted
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Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- A—HUMAN NECESSITIES
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A—HUMAN NECESSITIES
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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Abstract
本发明涉及一种抗微生物的并且优选非细胞毒性的复合材料,并涉及所述复合材料的用途。
Description
技术领域
本发明涉及一种抗微生物的并且优选非细胞毒性的涂层材料,并涉及所述涂层材料的用途。
背景技术
很多领域中,一直需要控制微生物的定居、繁殖和生存,尤其是原核生物(prokaryontae)和真菌。具体而言,常常希望限制特定区域上微生物的浓度,或者使所述区域完全没有微生物,或者某些情况下使所述区域完全没有特定类型或种类的微生物。力求从最广的意义上在医疗、医疗技术和卫生技术领域实现该目的。为此,例如在医疗和卫生产品领域通常使用抗微生物的材料和涂层,如外科使用的涂银线(参见S.Silver,FEMS Microbiology Reviews(2003):pp.341-353)或者含铜的防污漆。在这一点上,广谱杀生物剂尤其是无机杀生物剂例如银及其离子被证实是特别有效的。随着时间推移,用该杀生物剂处理的材料释放出其内所含的杀生物剂,并减少或者完全防止微生物在该材料本身上或者甚至在其周围定居或者繁殖。
常常出现的问题是,传统的抗微生物材料在初始时释放高浓度的杀生物剂,结果所释放的杀生物剂的浓度不仅对所对抗的微生物有毒性作用,而且无意识地还对高等细胞有毒性作用。这对于医用产品,尤其是例如创伤覆盖物、导管、接触透镜和植入物来说是破坏性的,因为这样处理的医用产品会延迟愈合,并导致组织过敏和刺激。当杀生物剂由卫生产品例如卫生巾、棉塞和尿布释放时以及在生产和加工食品的过程中也出现相应的缺点,尤其是在释放杀生物剂的包装以及释放杀生物剂的部件用于生产或加工食品的情况下。此外,由于从含有杀生物剂的材料中浸析,导致抗微生物作用迅速耗尽。传统涂层的另一缺点在于,如果由于磨损而受到破坏,则它们常常会释放大量的杀生物剂,至少是局部地释放,例如,这种破坏可以发生在即使当涂覆的目标以预定方式使用时。
为了消除这些缺点,WO 03/024494提出一种抗微生物的粘附涂层材料,其含有金属银颗粒并且银、钠和钾离子浓度小于5ppm,该粘附涂层材料是合成制得的有机材料,通常在加工后进行硬化。银颗粒均匀分布在该粘附涂层材料中。具体而言,该粘附涂层材料应该是漆或者粘合剂,尤其是热固性或热塑性的漆或粘合剂。不过,后者的一个缺点在于,难以控制或者调节金属离子的释放速率。
从US 2002/0006887 A1中已知一种含有抗微生物剂的表面擦拭物。为了延缓抗微生物剂的释放,该擦拭物具有聚(乙烯醋酸乙烯酯)层,其中,抗微生物剂次氯酸钙完全或者部分包封在该涂层中。不过,所释放的试剂量太多,以至于不能排除细胞毒性作用。例如所述文件中描述的涂层只对擦拭物有用,而通常不能用于医用产品,尤其是不能用于可植入性产品。
从WO 00/60297中已知一种含有抗微生物剂的管。不过,所述管不包括不含有抗微生物剂颗粒的传输控制层。这意味着该试剂始终与该管的表面直接接触,因此也会以细胞毒性的浓度得到释放。
发明内容
因此,本发明的目的是定义一种可简便并低成本制得的涂层材料,其具有抗微生物性能,但不是细胞毒性的。涂层材料如果抑制表皮葡萄球菌(Staphylococcusepidermidis)的繁殖至少十小时,则认为其是抗微生物的,如DE 197 58 598 A1所述进行测定。例如,该测量方法确定,与不含杀生物剂的对比试样相比,上述种类的细菌是否可以在18小时内在该涂层材料表面上产生少于0.1%的子细胞。如DIN-ISO10993-5标准所述,当涂层材料有细胞毒性作用时,也认为其是细胞毒性的。此外,该涂层材料应该具有最大可能持久性的抗微生物和非细胞毒性作用。例如,其应该可以尽可能普遍地用在绒头织物材料、膜、塑料、金属和复合材料上,并且还可以制备薄涂层,尤其是厚度为40-200nm的薄涂层。该涂层材料还应该含有最少量的杀生物剂。应该可以尽可能宽范围地调节该涂层材料的表面性质。该涂层材料还应该非常好地粘附在所涂覆的基底上,其应该是尽可能透明、食物级并且耐水解的,并且具有可调节的阻隔性质。
因此,本发明提供一种抗微生物和非细胞毒性的涂层材料,其包含:
a)含有杀生物剂的杀生物剂层,和
b)覆盖该杀生物剂层的传输控制层,具有所选择的厚度和孔隙度,使得抗微生物和非细胞毒性量的活性杀生物剂从该杀生物剂层中并通过该传输控制层释放。
与传统的抗微生物材料相比,本发明的涂层材料可以在该涂层材料本身中提供通常是细胞毒性的高杀生物剂浓度,其中杀生物剂的总量可有利地保持少量。该杀生物剂层形成该杀生物剂的贮存处,也就是说,从而可以延缓性释放该杀生物剂。通过提供传输控制层,可以将从杀生物剂层中通过传输控制层释放的杀生物剂浓度限制到一定的程度,使得该试剂不再是细胞毒性的,不过仍然有抗微生物作用。因此,该传输控制层有控制和调节功能。此外,该传输控制层可以防止环境与该杀生物剂层之间的任何直接接触。从而提高了该涂层材料的耐久性,这是因为可以有效阻止或者限制例如体液或者食物(尤其是汁)的腐蚀性侵蚀。该传输控制层可以位于该杀生物剂层的两侧上或者只在一侧上。只要本发明的涂层材料在固体上形成涂层,该传输控制层只位于该杀生物剂层的一侧上都是特别优选的。这种情况下,涂覆有本发明涂层材料的固体可以覆盖没有被该传输控制层覆盖的杀生物剂层那侧。
本发明意义范围内的杀生物剂是可以在上述意义上发挥抗微生物作用(狭义的杀生物剂)的任何物质。杀生物剂范畴也包括这样的物质,其在将使用涂层材料的特定环境中通过转化而产生狭义上的杀生物剂。例如,如果狭义上的杀生物剂是金属离子,尤其是银、铜和/或锌阳离子,则金属银、铜和/或锌、以及合金、络合物和其他这样的物质都是杀生物剂,上述阳离子可以从中释放到合适的环境中,例如创伤区。根据本发明,优选金属杀生物剂。
本领域技术人员理解,根据本发明的涂层材料也可以对其他微生物产生抗微生物作用,而非或者不仅抗表皮葡萄球菌。根据DE 197 58 598 A1,用相应的微生物代替表皮葡萄球菌,测量本发明涂层材料对其他微生物的抗微生物作用。特别优选对包括芽胞杆菌(Bacillus)、梭菌(Clostridium)、肠杆菌(Enterobacter)、埃希氏菌(Escherichia)、假单胞菌(Pseudomonas)、沙门氏菌(Salmonella)、葡萄球菌(Staphylococcus)、耶尔森氏菌(Yersinia)、假丝酵母(Candida)和李斯特氏菌(Listeria)的集合中的一种或者多种微生物有抗微生物作用但没有细胞毒性的本发明涂层材料。根据本发明的涂层材料还可以具有抗病毒作用。
本发明涂层材料的传输控制层优选被设计成具有100到1000(立方厘米·巴)/(天·平方米),优选为600到700(立方厘米·巴)/(天·平方米)的氧气(O2)透气性。可以以特别合适的方式通过真空蒸发或者等离子体聚合而产生这样的传输控制层。基于上述的渗透性标准,本领域技术人员可以进行一般性常规试验,并确定用于制备相应传输控制层的合适的起始材料和参数。本说明书其余部分和实施例中定义了特别优选的传输控制层。
通过上述的真空辅助薄层法,尤其是溅射和等离子体聚合,可以以有利的简单方式调节本发明涂层材料的粘附性能、耐水解性和表面能。而且,以此方式制得的传输控制层是透明的,并且可以涂覆于几乎任何基底上。对任何实际相关的处理温度没有限制。
在真空辅助薄层法中,尤其是溅射和等离子体聚合中,涂层材料的亲水性优选通过选择为制备涂层所选气氛的高氧气含量而加以影响。当O2含量为至多95%、工作气氛压力为0.07毫巴(其余工作气氛:HMDSO)、等离子体功率为2500W和反应器体积为400升时,得到有利的强疏水性涂层材料(参见实施例)。可优选用40-95%的O2含量(其余工作气氛:HMDSO)获得本发明的亲水性涂层材料;通常,所选的工作气氛的O2含量越高,则涂层材料疏水性越高。因此,也可以以有利的简单方式影响银离子从传输控制层扩散的速率;通常,涂层材料的亲水性越强,则扩散速率越高。
作为替代方案或者额外地,可以用真空辅助薄层法制备根据本发明的亲水性涂层材料,其中,制得传输控制层后,在纯氧气气氛中处理该涂层材料,工作气氛压力为0.02到0.04毫巴,优选0.06毫巴,等离子体功率为500到2000W,优选1000W,在400升反应器中进行。
根据本发明,可以使用真空辅助薄层法在含有氢和六氟乙烷(C2F6)的工作气氛下制备疏水性涂层材料,如果需要,进行后活化步骤。氢与六氟乙烷之比为2∶1到4∶1,优选为3∶1,等离子体功率为400W,并且反应器体积为400升。
如果需要,本领域技术人员可容易地使上述值适用于其他等离子体额定功率和其他反应器体积。
通过上述制备方法,也可以影响本发明涂层材料的表面能;尤其是可以在10-105mN/m范围内自由选择表面能。表面能越高,粘附表皮葡萄球菌和其他微生物的倾向越小。通过以根据本发明的方式调节表面能,可以以有利的简单方式控制本发明涂层材料的抗微生物作用。还可以以可控方式调节革兰氏阳性和/或革兰氏阴性微生物的粘附。此外,可以获得具有高水平生物相容性的类硅酸盐结构。
特别优选其中杀生物剂是无机杀生物剂的本发明涂层材料。这样的杀生物剂通常是廉价、易于得到的并且易于处理的。该杀生物剂可以用多种方法提供;具体地,其可以被涂覆到将用本发明涂层材料涂覆的表面上。真空蒸发、溅射和化学气相沉积是涂覆无机杀生物剂特别合适的方法。
在本发明涂层材料一种特别优选的实施方案中,杀生物剂选自包含银、铜和锌、其离子及其金属络合物、或者所述元素的混合物或者合金的集合。这些杀生物剂对许多不同的微生物有效,以多种方式进攻它们的代谢。当使用这些杀生物剂时,与使用具有特定作用机理的有机杀生物剂尤其是抗生素相比,细菌更少地产生耐受性。
已经发现,特别有利的本发明涂层材料是这样的涂层材料,其中杀生物剂是银、银阳离子或者释放银或银阳离子的络合物或者合金。具体地,金属银可以容易地进行处理,并且可以以相对低的价格高质量地得到,因此可以相对低成本地制得本发明的涂层材料。
该杀生物剂以粒状存在于本发明涂层材料中是合适的,初级颗粒的平均粒径优选为5-100nm。这种细粉末状的杀生物剂可以容易地制得,尤其是对于无机杀生物剂而言并且特别是对于银,但也对于铜和锌以及所述三种金属的混合物、络合物和合金。由于平均粒径如此小,所以该杀生物剂具有高的比表面,因此它可以通过扩散从杀生物剂层良好地释放。另一有利方面在于,如有时在伤口周围所需要,由于其高的比表面,所述粒状试剂的化学激活作用通常只影响部分表面,因此甚至在不利条件下也能够从该杀生物剂层释放出该杀生物剂。已经发现特别有利的是,本发明涂层材料中杀生物剂的平均粒径为5-50nm,优选为5-20nm。当杀生物剂是银或者银合金时,这些粒径分布也被称为纳米级的银或纳米级的银合金。
按照特定的应用,杀生物剂层可具有至少为1nm的厚度,优选不大于1mm。当使用粒状杀生物剂时,杀生物剂层至少如粒状试剂那么厚。杀生物剂层的厚度优选为5nm-100nm,特别优选的层厚度为10nm-50nm,尤其是当该杀生物剂是银、铜和/或锌或其离子、金属络合物或混合物,或者所述元素的合金时。现已发现,在本发明的涂层材料中,即使这样的薄层杀生物剂(尤其是含纳米级银的杀生物剂)也足以达到持久的抗微生物且非细胞毒性的作用。
杀生物剂层优选不涂覆在涂有涂层材料的基底的整个表面上,而是只覆盖部分基底。在局部有限面积上,传输控制层直接接触基底,因此特别良好地粘附在基底上。该传输控制层提高的粘附性也改善了粒状杀生物剂的粘附性,例如银颗粒,尤其是纳米级银。
真空辅助方法非常适合于制备本发明的涂层材料,尤其是当需要制备很薄的层时。在此情况下,特别优选用溅射或者蒸发沉积方法制备该杀生物剂层,因为这样可以使金属杀生物剂直接沉积在基底上,而不会发生任何化学过程。相反,当采用浸渍或者溶胶凝胶方法时,使用金属盐,其在基底中或基底上还原为金属。确切地说,该还原过程经常不能进行完全,因此,使得制备难以再现。此外,制备常规的涂层还会产生残留物,尤其是采用溶胶凝胶方法,随后必须以一定成本洗掉并处理该残留物。这样的残留物可以通过使用由真空辅助薄层法制得的本发明涂层材料而避免。
还优选杀生物剂层还包含以下物质的根据本发明的涂层材料:金、铂、钯、铱、锡、锑、它们的离子、它们的金属络合物、或者具有一种或多种所述元素的杀生物物质的混合物或合金。向该杀生物剂中添加上述元素提高和/或延长了其抗微生物效果。上述元素优选以阳离子形式结合在离子交换剂中,形成络合物或盐的形式,优选聚合物羧酸的形式。
还优选根据本发明的涂层材料,其中,传输控制层具有选自包含以下物质的集合的基底材料:
a)有机基底材料,尤其是等离子体聚合物、溶胶凝胶、清漆或涂料、以及硅化基底材料,或者
b)无机基底材料,尤其是SiO2和SiC、金属氧化物尤其是TiO2和Al2O3、以及非杀生物性的金属尤其是钛或者医用不锈钢。
应当理解,该基底材料具有一定的厚度和孔隙度,使得将要通过传输控制层释放的杀生物剂达到一定的浓度,在该浓度下释放的杀生物剂可以非细胞毒性地起到抗微生物的作用。特别优选该基底材料是微孔性的。尤其是当制备薄层时,优选利用等离子体聚合法或者溅射法制备传输控制层。以此方式可以制得非常薄的传输控制层,通过该层,诸如原子或阳离子银的杀生物剂可以扩散,并将其抗微生物、非细胞毒性的活性赋予涂层材料。
优选以一定的方式制备该传输控制层,使得其层厚度、密度、吸湿能力、对水蒸气的扩散密闭性、其化学组成及其交联结构能够使得杀生物剂通过传输控制层而释放,这样,所释放的杀生物剂可以具有抗微生物和非细胞毒性的作用。例如,如果溅射的或者等离子体聚合物层用作传输控制层,则该层优选具有强交联性和对水蒸气和其他气体或蒸气的高扩散密闭性以及低吸湿能力。这种传输控制层只需要很小的层厚度,以确保杀生物剂仍具有足够的抗微生物效率,而没有细胞毒性作用。
优选选择使得细菌粘附性最小化的传输控制层。例如,这可以通过根据所研究细菌的类型而调节表面能来实现。通过改变如实施例7所述的层沉积参数而调节表面能。用DE 19751581 C2中所述的方法来定量测量细菌粘附性,采用该方法可以最优化与生物相容性(尤其是非细胞毒性)有关的层特性,同时使杀生物剂浓度最小。
因此,根据本发明的传输控制层可以使得能够以可控方式加强或抑制细胞毒性和表面层特性例如细菌粘附性以及生物分子和预选的组织类型的细胞的粘附性。
特别优选这样的本发明涂层材料,即其中传输控制层的硅含量为20-60%,优选为20-33%,碳含量至多为50%,尤其是10-30%,氧含量为25-66%,尤其是30-50%。在此应理解,各浓度必须是相互匹配的,使得总体上不超过100%。通过X射线光电子能谱(XPS)测量这些浓度;当测定硅、碳和氧含量时,用XPS分析不能测量的元素例如氢被忽略。因此,除了硅、碳和氧外,还会有其他元素(即,用XPS不能检测的元素)存在于传输控制层中,当测定硅、碳和氧含量时,不考虑这些额外的元素。硅、碳和氧含量被表示为通过XPS分析检测到的总元素含量的原子或摩尔百分数。
本发明涂层材料的传输控制层的平均厚度优选为5nm-500nm。不过,当使用等离子体聚合物传输控制层时,优选该传输控制层的厚度为5-200nm,特别是不超过100nm的厚度,优选为10-100nm的厚度。具有该量级的层厚度时,尤其是具有由等离子体聚合制得的传输控制层时,可以制得优异的抗微生物性而没有细胞毒性的涂层材料。这些传输控制层也是非常薄的,所以它们在视觉上是不引人注意的,甚至可以是透明的。
特别优选为本发明的涂层材料提供可通过溅射或者等离子体聚合制得的传输控制层。当以此方式制备时,可以获得非常好的涂层,甚至是具有复杂形状的物体的涂层;细孔(fine-cell)体尤其是绒头织物材料可以可靠地用传输控制层涂覆,使得它们可以保持其柔性、渗透性和透气性。如果接受相当的缺陷,溅射和等离子体聚合还使得能够涂覆只能以厚膜法进行涂覆的基底;这样的基底包括骨钉和其他的骨植入物。当以常规涂覆方式涂覆所述基底时,在对基底进行进一步处理时会发生涂层脱离,尤其是在骨中植入的过程中,结果在局部形成凸起;这种情况下,在整个基底组件上杀生物剂的释放速率不再是均匀和可控制的。具体而言,该杀生物剂可以以细胞毒性的浓度被释放,从而延迟或防止愈合。通过等离子体聚合,使用本发明涂层材料还可以制得用于传输控制的梯度层,其表面性质(亲水性、疏水性、抗粘附性和透明性——以下进行详细描述)可以预选择地从一个位置到下一位置进行变化。在溅射或者等离子体聚合过程中,例如可以在沉积期间椭圆对称性地形成层,以确保层结构的再现性。在使用溅射或者蒸发沉积法沉积杀生物剂的过程中,也可以进行同类控制。
根据本发明的薄层涂层材料(优选厚度至多100nm,参见上文)也是优选的。这些涂层材料具有有利的密封性能,从而使得它们可用作包装食物和医用产品的涂层。
杀生物剂层和传输控制层都有相同的基底材料是特别有利的。在这种情况下,具体而言可以首先提供优选纳米级形式的杀生物剂(尤其是银、铜和/或锌),然后,在单独的另一步骤中,通过涂覆传输控制层的基底材料来制备本发明的涂层材料,从而由此将该杀生物剂包埋在所述涂层材料中。
还可以选择传输控制层的基底材料,使得该传输控制层除了能够使杀生物剂通过传输控制层而释放外,还可以具有别的有利的性质。具体而言,通过选择合适的基底材料或者通过其他措施,可以使该传输控制层是透明、亲水性、疏水性、疏油性和/或非粘附性的(也对细菌而言)。亲水性传输控制层对于以下详细描述的医用产品例如创伤覆盖物来说是特别优选的。涂有本发明涂层材料的医用产品特别适合用于湿法处理伤口以及用于改善骨生长,具体是因为它们防止感染、局部组织不会被抗微生物剂的过度释放而损害或者停止或延缓局部组织的愈合速度。另一方面,只要是在对表面而言易于擦拭或清洁很重要的情况下以及特别是在加工食品时,具有更强疏水性传输控制层的本发明涂层材料都是特别优选的实施方案。
本发明的杀生物剂层和涂层材料总体上可以以任何形式存在。具体而言,本发明的杀生物剂层和涂层材料可以在固体上形成涂层,例如在纤维上或者在金属、塑料和/或玻璃表面上。不过,本发明的杀生物剂层和涂层材料也可以在颗粒上形成涂层。
当使用银(尤其是纳米级银)作为杀生物剂时,本发明涂层材料的银含量优选为1-100ppm。已经令人惊讶地发现,即使在所述量的情况下,根据本发明的涂层材料中的固体银可以发挥出充分的抗微生物作用。
根据本发明,以上描述的涂层材料(包括其实施方案)可以用于在固体上制备抗微生物和非细胞毒性的涂层。具体而言,可以用于在下列物质上制备抗微生物和非细胞毒性的涂层:医用产品,尤其是导管、创伤覆盖物、接触透镜、植入物、医用钉和/或螺状物、骨固定钉、医疗器械;或者卫生产品,尤其是卫生巾、棉塞或尿布;或者医用或卫生产品的包装;或者生产或加工食物的部件;或者需要特殊卫生防护措施的一些其他产品。如开始所述,医用和卫生产品领域中尤其需要抗微生物而非细胞毒性的产品。通过提供具有根据本发明的涂层材料的传统产品,例如用所述涂层材料涂覆它们,可以以非常简单的方式满足该需要。具有可调节表面能的抗微生物、非细胞毒性涂层也适合并且特别适合涂覆牙植入物,其中,可以以有利的简单方式通过改变表面能来改善和调节植入物的骨整合(osteointegration)。
附图说明
现在参考优选的实施方案更详细地描述本发明。附图为:
图1:抗微生物和非细胞毒性涂层材料的截面图,
图2:多种聚氨酯表面上的细菌生长图。
具体实施方式
实施例1:制备本发明的涂层材料
在第一涂覆步骤中,用多孔纳米级银涂覆将用本发明的抗微生物和非细胞毒性涂层材料涂覆的固体基底。这通过在惰性气体气氛例如氩气中、在约10毫巴的工作压力下使金属银气化而实现。在该基底上产生银涂层(杀生物剂层),所述涂层含有单一的银颗粒或者银颗粒链。该银颗粒的平均粒径为10-20nm。该银涂层(杀生物剂层)的厚度为约20nm。
在第二涂覆步骤中,涂覆含有作为前体的六甲基二硅醚(HMDSO)的等离子体聚合物层。在0.07毫巴的工作压力下用由95%O2和5%HMDSO组成的工作气体进行等离子体聚合。在所述条件下进行45秒等离子体聚合后,该银层被涂覆45nm厚的亲水性等离子体聚合物(传输控制层)。该涂层的表面能为105mN/m。
具体而言,以此方式可以用根据本发明的涂层材料涂覆医用产品,例如创伤覆盖物和导管。
实施例2:使用增粘层制备根据本发明的涂层材料
在第一步骤中,通过等离子体聚合用二氧化钛膜涂覆将用本发明涂层材料涂覆的基底。所用的前体是与氧混合的四异丙基氧化钛。聚合时间是5分钟。形成25nm厚并具有良好粘附性的TiO2膜。
在第二涂覆步骤中,在超高真空中,将薄金属银层沉积在TiO2膜上。在沉积过程中,工艺压力为10-4毫巴。进行蒸发,使得10-20nm厚的银层(杀生物剂层)沉积在该TiO2膜上。
在第三涂覆步骤中,将等离子体聚合物膜(传输控制层)涂覆在该银层上。如实施例1所述进行等离子体聚合。形成45nm厚的高度亲水性等离子体聚合物层。
使用根据本发明的涂层材料可以特别好地涂覆以下材料:金属,尤其是钛和(医用的)不锈钢;塑料,尤其是聚氨酯;以及纤维素,尤其是创伤覆盖物和纤维素绒头织物。
实施例3:将传输控制层涂覆到杀生物性固体上
使用实施例1中描述的等离子体聚合方法,将等离子体聚合物膜作为传输控制层沉积在铜固体层上。与实施例1相比,进行等离子体涂覆工艺450秒。这样制得的传输控制层的厚度为100nm。得到根据本发明的涂层材料,杀生物剂层是固体铜的初始层。
实施例4:分析由实施例1中的方法制得的根据本发明的涂层材料
根据XPS分析,该传输控制层的表面的硅含量为36.6%,碳含量为24%,氧含量为39.4%。通过XPS分析不能测定出氢含量。该涂层材料的红外光谱还显示出少量的甲基。因此,尽管该传输控制层主要是无机的,但仍有低浓度的有机基团。
根据能量色散X射线分析,本发明涂层材料中硅与银浓度之比为约10∶1。相对于形成本发明涂层材料的所有化学元素(除了氢)而言,银含量小于3重量%。
本发明涂层材料中银的分布不是均匀的。图1示意性表明,在涂层材料面向基底而远离基底的外部40-50nm中,只有很小的银含量。该外部40-50nm层(传输控制层)下,有约20nm厚的纳米级含银层(杀生物剂层),除了银外,该层还含有传输控制层的基底材料的其他元素。因此,纳米级银作为杀生物剂层包埋在该传输控制层的基底材料中。
图2表明,与未处理的聚氨酯表面相比,涂覆有根据实施例1的本发明涂层材料的聚氨酯表面具有抗微生物作用。以DE 19758598A1中描述的方式测试对表皮葡萄球菌的抗微生物作用。图2表示24小时内光密度以及细菌计数的变化。左侧分图表示未处理的聚氨酯表面上的细菌生长曲线。中间和右侧分图分别表示涂有不同的本发明涂层材料的聚氨酯表面上细菌生长的曲线。
可以看到,在很短时间内在未处理的聚氨酯表面上发生细菌生长,而在本发明涂层材料上在所示时间内没有发生细菌细胞计数的增长(右侧分图),或者出现明显延缓的细菌生长(中间分图)。因此,本发明涂层材料是抗微生物的。而且根据DIN-ISO10993-5也是非细胞毒性的(没有图)。
实施例5:制备另一种本发明涂层材料的方法
在第一涂覆步骤中,以多孔纳米级银层涂覆将用本发明的抗微生物和非细胞毒性的涂层材料涂覆的固体基底。这通过在惰性气体气氛例如氩气中、在约10毫巴的工作压力下通过气化金属银而实现。在该基底上产生银涂层(杀生物剂层),所述涂层含有单一银颗粒或者银颗粒链。该银颗粒的平均粒径为10-20nm。该银涂层(杀生物剂层)的厚度为约20nm。
在第二涂覆步骤中,涂覆具有作为前体的六甲基二硅醚(HMDSO)的传输控制等离子体聚合物层。在体积400升的反应器中进行等离子体聚合,工作压力为0.07毫巴,等离子体功率为2500W,工作气体由95%O2和5%HMDSO组成。在所述条件下进行45秒等离子体聚合后,该银层被涂有45nm厚的等离子体聚合物层。根据DE 19758598A1,抗微生物作用导致测量信号的35小时漂移,所以该涂层材料实际上是自无菌化的;但是,与未涂覆的聚氨酯基底相比,细菌粘附性没有下降。
在该方法的第三步骤中,在功率为1500W、氧流量为100sccm(标准状态毫升/分)并且工作压力为0.04毫巴的条件下,进行两分钟的氧活化。氧活化后,表面能升高到105nN/m,并且细菌粘附性下降到初始值的约10%。
实施例6:制备另一种本发明涂层材料的方法
通过制备含铜的氟碳层,结合起抗细菌作用并且血相溶性的传输控制层。在DC磁控溅射法中使用铜靶涂覆杀生物剂层。在离子化气体氩气的分压为5*10-2毫巴的条件下,在该基底上形成多孔的铜层。在该方法的第二步骤中,通过等离子体聚合方法,用六氟乙烷(C2F6)作为前体,将传输控制层涂覆到杀生物剂层上。为了提高沉积速率,以3∶1的比例将氢加入到C2F6中。在0.1毫巴的工作压力下处理3分钟后,形成膜厚为55nm并且表面能为19mN/m的氟碳层。在最后的步骤中,在50℃下的回火步骤中,在氧气氛中将杀生物剂层的铜氧化为铜(I)氧化物。该传输控制层中的氟含量为54.8%,碳含量为42.5%,并且氧含量为2.7%。氟本身一半是作为CF2基团而存在,三分之一作为CF3并且六分之一作为CF基团。
实施例7:制备另一种本发明涂层材料的方法
在实施例1中,使用含有六甲基二硅醚(HMDSO)作为前体的等离子体聚合物膜作为传输控制层。然后可以在第三步骤中修饰该层的表面。通过沉积具有HMDSO前体的很薄的类硅氧烷膜,可以将表面能调节在105mN/m-22mN/m的范围内,而不明显影响其抗细菌性能。用以此方式修饰的表面,不仅可以控制细菌的生长行为,而且可以控制其他细胞的生长行为。
实施例8:制备另一种本发明涂层材料的方法
如果在非反应性DC溅射中使用钒靶,则可以制得适当孔隙度的钒膜作为杀生物剂层。该层的厚度在50nm范围内。为了形成传输控制层,利用等离子体聚合沉积基于丙烯酸的等离子体聚合物膜。在丙烯酸流量为40sccm并且氩气流量为200sccm的条件下沉积半小时后,产生50nm厚的膜,其红外光谱与聚丙烯酰胺凝胶的红外光谱一致。以此方式制得的层具有约55mN/m的高表面能,而且也是长时间稳定的。
实施例9:
不一定必须通过等离子体聚合方法制备传输控制层;反应性中频(MF)溅射法也会产生疏散开的层。在离子化气体氩气的分压为8*10-4毫巴并且氧气的分压为2*10-4毫巴的条件下溅射Si靶。这些层不含碳,并且具有Si∶O=1∶2的原子组成。除了传输控制层的表面修饰外,还可以通过浸渍法例如将钙离子浸入该层中。这通过将该抗细菌层浸在0.01摩尔的氢氧化钙溶液中24小时而完成。在该方法的另一步骤中,进行″Ship-in-a-bottle″反应,浸渍的氢氧化钙例如可被转化为氯化钙、硫酸钙或者碳酸钙。除了钙离子外,也可以在随后的浸渍过程中将BMPs(骨形态发生蛋白质)结合到该涂层的表面。以此方式修饰的层可以改善骨细胞的生长。
Claims (14)
1.抗微生物和非细胞毒性的涂层材料,包含:
a)含有杀生物剂的杀生物剂层,和
b)覆盖该杀生物剂层的传输控制层,其具有所选择的厚度和孔隙度,使得抗微生物和非细胞毒性量的活性杀生物剂从该杀生物剂层中并通过该传输控制层释放。
2.根据权利要求1的涂层材料,其特征在于,所述传输控制层具有100-1000(立方厘米·巴)/(天·平方米)、优选500-700(立方厘米·巴)/(天·平方米)范围内的氧气(O2)透气性。
3.根据权利要求1或2中任一项的涂层材料,其中,杀生物剂是无机杀生物剂。
4.根据权利要求3的涂层材料,其中,杀生物剂选自包含银、铜和锌、它们的离子和它们的金属络合物、或者包含两种或者多种所述元素的混合物或合金的集合。
5.根据权利要求3或4中任一项的涂层材料,其中,杀生物剂的平均粒径为5-100nm。
6.根据前述权利要求中任一项的涂层材料,其中,杀生物剂层还包含:金、铂、钯、铱、锡、锑、它们的离子、它们的金属络合物、或者该杀生物剂与一种或多种所述元素的合金。
7.根据前述权利要求中任一项的涂层材料,其中,传输控制层具有选自包含以下物质的集合的基底材料:
a)有机基底材料,尤其是等离子体聚合物、溶胶凝胶、清漆或涂料、以及硅化基底材料,或者
b)无机基底材料,尤其是SiO2和SiC、金属氧化物尤其是TiO2和Al2O3、以及非杀生物性的金属尤其是钛或者医用不锈钢。
8.根据权利要求7的涂层材料,其中,所述传输控制层具有20-60%的硅含量、10-30%的碳含量和30-50%的氧含量。
9.根据前述权利要求中任一项的涂层材料,其中,杀生物剂层具有5-100nm的平均厚度。
10.根据前述权利要求中任一项的涂层材料,其中,传输控制层具有5-500nm的平均厚度。
11.根据权利要求1-10中任一项的涂层材料的用途,用于在固体上制备抗微生物和非细胞毒性的涂层。
12.根据权利要求1到10中任一项的涂层材料的用途,用于在下列物质上制备抗微生物和非细胞毒性的涂层:医用产品,尤其是导管、创伤覆盖物、接触透镜、植入物、医用钉和/或螺状物、骨固定钉、牙植入物、医疗器械;或者卫生产品,尤其是卫生巾或尿布;或者医用或卫生产品的包装;或者用于生产或加工食品的部件;或者需要特殊卫生防护措施的一些其他产品。
13.传输控制层的用途,用于制备根据权利要求1到10中任一项的涂层材料,所述传输控制层具有100-1000(立方厘米·巴)/(天·平方米)、优选500-700(立方厘米·巴)/(天·平方米)范围内的氧气(O2)透气性。
14.传输控制层的用途,用于覆盖和/或包封杀生物剂以使得抗微生物和非细胞毒性量的所述物质能够通过该传输控制层而被释放,所述传输控制层具有100-1000(立方厘米·巴)/(天·平方米)、优选500-700(立方厘米·巴)/(天·平方米)范围内的氧气(O2)透气性。
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2004
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CN103889232A (zh) * | 2011-09-08 | 2014-06-25 | 康宁股份有限公司 | 抗微生物复合材料 |
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ATE358417T1 (de) | 2007-04-15 |
DE10353756A1 (de) | 2005-06-30 |
EP1790224B1 (de) | 2011-01-12 |
DE502004012116D1 (de) | 2011-02-24 |
CA2546230C (en) | 2013-05-28 |
EP1691606B1 (de) | 2007-04-04 |
WO2005049699A2 (de) | 2005-06-02 |
KR20060132834A (ko) | 2006-12-22 |
CN100563440C (zh) | 2009-12-02 |
WO2005048708A1 (de) | 2005-06-02 |
EP1790224A1 (de) | 2007-05-30 |
CA2546230A1 (en) | 2005-06-02 |
JP2007517772A (ja) | 2007-07-05 |
US9622471B2 (en) | 2017-04-18 |
WO2005049699A3 (de) | 2005-07-21 |
ATE494779T1 (de) | 2011-01-15 |
ES2282919T3 (es) | 2007-10-16 |
EP1686855A2 (de) | 2006-08-09 |
NO20062826L (no) | 2006-08-09 |
US20090035341A1 (en) | 2009-02-05 |
EP1691606A1 (de) | 2006-08-23 |
KR101177104B1 (ko) | 2012-09-28 |
AU2004290901A1 (en) | 2005-06-02 |
US10299472B2 (en) | 2019-05-28 |
DE502004003433D1 (de) | 2007-05-16 |
ES2355298T3 (es) | 2011-03-24 |
US20170181428A1 (en) | 2017-06-29 |
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