CN100434357C - 用金属离子部分取代或表面担载金属离子的磷酸钙多孔质多层球形粒子 - Google Patents

用金属离子部分取代或表面担载金属离子的磷酸钙多孔质多层球形粒子 Download PDF

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CN100434357C
CN100434357C CNB2004800241021A CN200480024102A CN100434357C CN 100434357 C CN100434357 C CN 100434357C CN B2004800241021 A CNB2004800241021 A CN B2004800241021A CN 200480024102 A CN200480024102 A CN 200480024102A CN 100434357 C CN100434357 C CN 100434357C
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calcium phosphate
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田中顺三
生驹俊之
田口哲志
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Abstract

本发明提供用金属离子取代或表面担载金属离子的粒径为0.1-100μm的磷酸钙多孔质球形粒子，作为可以微量分离正确量的化学物质的色谱用材料等有用的、新的功能性粒子。

Description

用金属离子部分取代或表面担载金属离子的磷酸钙多孔质多层球形粒子
技术领域
本申请的发明涉及对于细胞增殖用基础材料、色谱材料等有用的磷酸钙多孔质球形粒子和多孔质多层球形粒子。
背景技术
到目前为止，已知用喷雾干燥器喷雾磷酸钙制造磷酸钙球形粒子的方法(例如，专利文献1-3)。另外，也已知磷酸三钙的一部分用锌取代后的烧结体和多孔质体、其接合剂材料等。
再有，实际上，磷酸钙的球形粒子被利用于牙科用接合剂、色谱用材料等。还有，磷酸钙的粒子作为生物体适合材料，或DDS载体等生物体相关材料而为人所熟知，期待其可得到更广泛的利用。特别期待的是和生物体相关的物质的多层化及通过它们的担载而提高功能性或复合化。
专利文献1：特开昭62-230607号公报
专利文献2：特开平1-152580号公报
专利文献3：特开平4-175213号公报
发明内容
但是，以前的实际情况是，对于为提高功能性和复合化磷酸钙粒子所应具备的特性及为实现多层化、付着担载的要素的讨论几乎没有进展。实际上，例如，关于制造与磷酸钙球形粒子的高分子等的复合体的方法也仅停留在在磷酸钙球形粒子上只被覆多糖类和胶原等高分子材料上，为在纳米级制造被覆及被覆体的结构、它们的状态等的方法还不知道。
因此，本申请的发明的课题是，消除以上所述现有技术的局限和问题，提供通过对粒子的多层化就连微量的化学物质也可以准确分离的作为色谱材料等有用的、其结构和性质可控制的磷酸钙的新粒子和其焙烧体及其复合体。
作为解决上述课题的发明，本申请的发明第1提供磷酸钙多孔质多层球形粒子，其特征为，磷酸钙多孔质球形粒子上被覆有无机多孔质材料，其中，金属离子在0.0001-10wt％的范围内取代或表面担载在磷酸钙上，该磷酸钙多孔质球形粒子的粒径为0.1-100μm的范围。第2，提供上述磷酸钙多孔质多层球形粒子，其特征为根据BET法的比表面积·细孔分布测定得出的气孔率为大于或等于20％，比表面积为大于或等于20m2/g。第3，提供上述磷酸钙多孔质多层球形粒子，其特征为多孔质粒子是从磷酸钙的微晶通过喷雾干燥而形成的。第4，提供上述第1项或第2项的磷酸钙多孔质多层球形粒子，其特征为取代或表面担载的金属离子为锌、镁、铁及铜的各离子的1种或2种或更多种。第5，提供上述第1项的磷酸钙多孔质多层球形粒子，其特征为该粒子是在100℃-800℃的温度范围内焙烧的粒子。第6，提供上述第1项的磷酸钙多孔质多层球形粒子，该磷酸钙多孔质球形粒子被作为生物体高分子或聚乙二醇的生物体适合性高分子被覆或担载。第7，提供上述第1项的磷酸钙多孔质多层球形粒子，其中，无机多孔质材料为磷酸钙材料或碳酸钙材料。还有，第8，提供上述第1项的磷酸钙多孔质多层球形粒子，生物体高分子或聚乙二醇的生物体适合性高分子担载。第9，提供上述第6项或第8项的磷酸钙多孔质多层球形粒子，其特征为生物体高分子为葡萄糖胺聚糖。
附图的简单说明
图1为用本发明的方法制造的多孔质球形粒子的电子显微镜照片。
图2为示例实施例3的透过型电子显微镜图像的图。
图3为在180℃下焙烧时用BET法测定的细孔分布图。
具体实施方式
本申请的发明是具有如上所述特征的发明，以下就其实施方式进行说明。
首先，众所周知金属离子对于多数的高分子具有高结合性，本申请的发明利用这样的性质，通过使磷酸钙类微晶结构的一部分与金属离子置换或使表面担载金属离子，使其成为多孔质球形粒子，在保持磷酸钙的生物体适合性的情况下，使其和各种高分子，特别是生物体高分子的结合性得到提高。进一步，本申请的发明，通过用无机多孔质材料被覆来自用金属离子部分取代或表面担载的磷酸钙类微晶的多孔质球形粒子的表面，还提高其吸附性。
这样，通过提高磷酸钙表面的结合性及吸附性，可提供作为具有无机材料和有机材料的复合材料的性质的细胞增殖的基础用材料、空气洁净过滤器、色谱用等有用的功能性材料。
本申请的发明的磷酸钙多孔质粒子的基本特征为：
A)用金属离子部分取代或表面担载
B)粒径在0.1-100μm的范围内
C)是多孔质球形粒子。
关于该场合的金属离子，其种类根据多孔质球形粒子的用途、目的可选择各种金属离子，一般作为其代表例可举出锌(Zn)、镁(Mg)、铁(Fe)、铜(Cu)。其他可考虑钛(Ti)、锆(Zr)、铝(Al)、锡(Sn)、银(Ag)等等。
另外，关于磷酸钙，可以是以众所周知的磷灰石为首的各种。通过金属离子对磷酸钙部分取代或表面担载，可以是作为其构成原子的钙的取代或者也可以是通过离子结合和离子性的吸附使金属离子在表面上担载。
这样的通过金属离子使一部分被取代或担载的粒径在0.1-100μm范围的磷酸钙多孔质球形粒子至今为止还是不为人所知的。
在粒径不足0.1μm或超过100μm的场合，作为多孔质球形粒子的制造变得困难。
另外，作为形状，虽然规定为球形，但变形形状和椭圆形等也包括在该球形的规定中。
还有，本申请的发明的磷酸钙多孔质球形粒子为了作为载体或载体材料使用，优选其根据BET法(比表面积测定法)的比表面积·细孔分布测定得出的气孔率为大于或等于20％，比表面积为大于或等于20m2/g。再有，关于该场合的气孔率是根据下式算出的。
气孔率＝BET总容积/(BET总容积+磷灰石的容积)
磷灰石的密度＝3.16g/cm3
                →磷灰石的容积＝1/3.16
另外，关于该申请的发明的上述磷酸钙多孔质球形粒子，显示通过喷雾干燥法等由磷酸钙微晶形成的球形粒子为优选粒子。在该场合，例如，可以使用通过在金属盐等的金属化合物的共存下磷酸水溶液和氢氧化钙混悬液的混合生成的微晶混悬液，通过喷雾干燥形成球形粒子。
用金属离子部分取代或表面担载的磷酸钙微晶可以用这样的湿式法和/或干式法合成，接着通过喷雾干燥法喷雾形成球形微粒。也可接着再将得到的粒子在100℃-800℃下焙烧。
磷酸钙微晶的大小虽然没有限定，但优选粒径为1nm-100nm左右，如果考虑物性和操作性等优选5nm-50nm左右的范围。
用金属离子取代，担载金属离子的磷酸钙多孔质球形粒子，可在其内部或表面被覆或担载高分子，例如生物体高分子和聚乙二醇等生物体适合性高分子。生物体高分子，可考虑作为构成生物体组织的1种或2种或更多种的生物体高分子，例如可举例透明质酸和硫酸软骨素等的葡萄糖胺聚糖。另外，多孔质粒子中，其细孔的内部和表面上担载或被覆无机多孔质材料，或进一步，也可在该被覆体的内部或表面上担载和上述同样的高分子，例如生物体高分子。
高分子和无机多孔质材料的担载、被覆可通过各种方法实现，例如可通过将磷酸钙多孔质粒子在这些高分子和无机多孔质材料水溶液或混悬液中浸渍或对磷酸钙多孔质粒子的喷雾或反应堆积等手段实现。
当然，以上的担载和被覆量(比例)不用说就可根据得到的多孔质粒子和多孔质多层粒子的使用目的、用途适当确定。
作为被覆的无机多孔质材料优选磷酸钙类的材料和碳酸钙类的材料等。
这里，列举出以下的实施例对该申请的发明进行进一步详细说明。当然本发明并不受以下的例子的限定。
实施例
<实施例1>
将1.36g或13.6g的氯化锌溶解在1升磷酸水溶液(0.6mol/l)中制备成2种试样。将该2种试样分别以20ml/min的滴入速度一边搅拌一边加入到2升的氢氧化钙混悬液(0.5mol/l)中。通过使用保持在180℃的双流体喷嘴的喷雾干燥器喷雾这样得到的担载锌(Zn)离子的磷灰石混悬液，制成球形粒子。球形粒子的粒径在1-10μm的范围内。附加的图1为示例扫描电子显微镜(SEM)图像的图。
进一步，将分散于10ml精制水中的30mg硫酸软骨素(ChS)添加到500mg上述球形粒子中，一边用精制水洗涤一边吸引过滤后，冷冻干燥。
另外，为了比较，将除了不溶解氯化锌外用完全相同的条件制造的磷灰石球形粒子在同样的条件下处理后，冷冻干燥。
用红外光谱(IR)、热分析(TG-DTGA)、扫描电子显微镜观察(SEM)、能量分散型X射线(EDX)对这样制成的3种球形粒子进行分析。通过IR测定，含有锌离子的磷灰石，观察到了ChS的官能团SO3。但是，不含锌的磷灰石，没有观察到SO3。热分析的结果，含有锌的磷灰石在300℃附近观察到了ChS特有的放热。不含锌的磷灰石没有观察到放热。EDX分析结果，含有锌的磷灰石显示出硫特有的光谱，而不含锌的磷灰石没有观察到。再有，对应于锌的含量，硫酸软骨素(ChS)的含量从约2wt％增加到约4wt％。
<实施例2>
使用实施例1中制造的球形粒子，代替硫酸软骨素(ChS)，在10ml精制水中分散30ml透明质酸(HyA)，一边用精制水进行洗涤，一边吸引过滤后，进行冷冻干燥。热分析的结果，在使用含锌磷灰石的场合，在300℃附近观察到了透明质酸(HyA)特异的放热。透明质酸(HyA)的含量和使用硫酸软骨素(ChS)的场合几乎相同。
<实施例3>
对实施例1(13.6g：氯化锌)中制造的磷灰石球形粒子进行薄片化，用透过型电子显微镜观察其内部结构。图2是示例其观察图像的图。确认得到的球形粒子其内部为空洞样的多孔质体。
<实施例4>
将实施例1(13.6g：氯化锌)中制造的磷灰石粒子浸渍在1mol/l的氯化钙溶液中，离心分离后，再浸渍在1mol/l的NaHCO3溶液中。得到的复合体的X射线衍射测定的结果，检测出了碳酸钙。通过进一步的热分析，在研究其重量变化的时候，发现相对于磷灰石含有12wt％的碳酸钙。另外，SEM观察的结果，由于在磷灰石的表面没有观察到碳酸钙的晶体，确认碳酸钙存在于磷灰石球形粒子的内部。
<实施例5>
将实施例1(13.6g：氯化锌)中制造的磷灰石球形粒子在各温度焙烧，通过BET法(比表面积测定法)进行使用氮气的比表面积·细孔分布测定。根据焙烧温度的不同，比表面积·BET总容量变小，例如，在180℃的焙烧中，比表面积为88m2/g，BET总容量为0.44ml/g，气孔率为58％；在600℃，比表面积为56m2/g，BET总容量为0.24ml/g，气孔率为43％；在800℃，比表面积为45m2/g，BET总容量为0.13ml/g，气孔率为29％，在1200℃焙烧的试样中几乎没有检测出细孔。再有，细孔分布在180℃焙烧的场合，根据BET法在60nm显示出最大分布。显示该关系的图为图3。
再有，不管在上述焙烧温度的哪一种焙烧中，都确认实际上没有发生粒子的凝聚。
工业实用性
如以上详细说明的那样，根据本申请的发明，可提供一方面有效地利用作为生物体适合材料的磷酸钙的特征，又作为通过利用生物体高分子或无机多孔材料使粒子多层化和担载生物体高分子或无机多孔材料，尽管是微量的化学物质也可以准确分离的色谱用材料等有用的，其结构和性质可控制的磷酸钙的新的功能性粒子和其焙烧体，还有它们的复合体。

Claims (9)

1.磷酸钙多孔质多层球形粒子，其特征为，磷酸钙多孔质球形粒子上被覆有无机多孔质材料，其中，金属离子在0.0001-10wt％的范围内取代或表面担载在磷酸钙上，该磷酸钙多孔质球形粒子的粒径为0.1-100μm的范围。
2.权利要求1所述的磷酸钙多孔质多层球形粒子，其特征为，根据BET法的比表面积·细孔分布测定得出的气孔率为大于或等于20％，比表面积为大于或等于20m2/g。
3.权利要求1或2所述的磷酸钙多孔质多层球形粒子，其特征为，磷酸钙多孔质球形粒子是从磷酸钙的微晶通过喷雾干燥而形成的。
4.权利要求1或2所述的磷酸钙多孔质多层球形粒子，其特征为，取代或表面担载的金属离子为锌、镁、铁及铜的各离子的1种或2种或更多种。
5.权利要求1所述的磷酸钙多孔质多层球形粒子，其特征为，磷酸钙多孔质球形粒子是在100℃-800℃的温度范围内焙烧而成的粒子。
6.权利要求1所述的磷酸钙多孔质多层球形粒子，其特征为，该磷酸钙多孔质球形粒子被作为生物体高分子或聚乙二醇的生物体适合性高分子被覆或担载。
7.权利要求1所述的磷酸钙多孔质多层球形粒子，其特征为，无机多孔质材料为磷酸钙材料或碳酸钙材料。
8.权利要求1所述的磷酸钙多孔质多层球形粒子，其特征为，被生物体高分子或为聚乙二醇的生物体适合性高分子担载。
9.权利要求6或8所述的磷酸钙多孔质多层球形粒子，其特征为，生物体高分子为葡萄糖胺聚糖。
CNB2004800241021A 2003-08-22 2004-03-25 用金属离子部分取代或表面担载金属离子的磷酸钙多孔质多层球形粒子 Expired - Fee Related CN100434357C (zh)

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