应用于义齿基托的杂化抗菌涂层的制备与研究

发布时间：2018-05-17 11:21

本文选题：义齿基托 + 杂化涂料　；参考：《吉林大学》2013年博士论文

【摘要】：聚甲基丙烯酸甲酯(PMMA)树脂材料具有成本低、容易加工和生物相容性好等特点，因而广泛应用于牙科医学上。义齿基托是人工义齿的重要组成部分，主要由PMMA树脂制成。研究表明，佩戴义齿会改变口腔内的微生态平衡，一些微生物，例如白色念珠菌和变形链球菌，会粘附在树脂材料表面并大量增殖，导致义齿性口炎和继发龋等口腔疾病。传统的义齿清洁方法存在着抗菌时间短、操作繁琐、容易破坏义齿表面形貌等缺点，不能完全满足临床上的应用。因此赋予基托树脂抗菌性成为口腔医学的重要研究课题。众所周知，银具有很高的抗菌活性和广谱的抗菌性，因此被广泛应用在各种抗菌材料中。与传统的有机物抗菌剂相比，载银无机抗菌剂具有更高的安全性、持久性和耐热性。介孔二氧化硅材料由于其良好的生物相容性，形貌多样性以及易修饰性，在作为银载体方面具有很大的应用潜力。通常情况下，载银抗菌剂被直接掺杂到树脂材料中，但是只有靠近树脂表面的抗菌剂才能起到抗菌作用，而树脂内部的抗菌剂完全起不到抗菌作用，造成了一定的浪费，而且过多的抗菌剂还可能影响树脂的机械性能。因此，使用含银的抗菌涂层是一个更经济有效的办法。本论文的主旨是设计和制备可应用于义齿基托表面的抗菌涂层。我们在载银抗菌剂的制备和杂化涂层的设计上进行了一些有意义的探索。我们制备了几种不同的载银介孔二氧化硅微球作为抗菌剂，分别掺杂到我们设计的一种有机无机杂化涂料中，制备成了抗菌涂层。在本论文第一章，我们简要介绍了义齿基托及其使用中的问题，简单回顾了一下抗菌剂和抗菌涂层的发展情况，简单的介绍了介孔材料及其在载银方面的应用，并提出了本论文的设计思想及主要内容。在本论文第二章，我们设计合成了一种由聚合物涂料和杂化硅溶胶混合制成的杂化涂料。聚合物涂料由甲基丙烯酸缩水甘油酯(GMA)、丙烯酸(AA)和甲基丙烯酸甲酯(MMA)三种单体共聚而成；杂化硅溶胶由缩水甘油醚基丙基三甲氧基硅烷(KH560)和正硅酸乙酯(TEOS)共水解缩合制得。聚合物作为有机组分可以为提高涂层与基底的附着力，硅溶胶作为无机组分可以高涂层的硬度。同时聚合物链和硅溶胶网络上都含有环氧基团，利用环氧基团的交联反应，形成有机无机互穿网络结构，可以进一步提高涂层的硬度。我们制备了一系列具有不同有机无机组分质量比值的杂化涂层，并表征了涂层的刮伤硬度、附着力和抗破裂性等性能。我们发现，当增加硅溶胶中TEOS的使用量以及增加杂化涂层中的硅溶胶含量时，涂层的硬度有所上升，但相应的附着力和抗破裂性有所下降。综合考虑，我们选择了KH560/TEOS摩尔比为2/5，有机无机组分质量比为9/1的杂化涂层。该涂层的硬度达到了4H，附着力和抗破裂性等级最高。同时，为了提高树脂材料的固位力，我们还尝试对涂层表面进行亲水化处理。利用六亚甲基二异氰酸酯与羟基的反应，在涂层表面接枝了不同分子量的PEG。通过红外光谱和接触角测试，证明我们成功在涂层表面接枝了PEG分子。PEG接枝前涂层亲水角为64°，，PEG-1000和PEG-2000接枝后的涂层的亲水角分别为46°和35°。在本论文的第三章，我们先制备了具有介孔结构的纯二氧化硅微球，并探索了硅源加入方式、催化剂种类、催化剂用量以及水醇质量比等因素对微球粒径和形貌的影响。我们发现采用分批加入硅源和采用氨水做催化剂，有助于避免微球的团聚；增大催化剂的用量和降低水醇比能够使微球粒径变大，但是容易导致团聚发生。最终我们制备了粒径为400nm、分散性好的介孔二氧化硅微球，然后将氯化银负载到微球上，并将载银微球作为抗菌剂添加到有机无机杂化涂层中，制备了抗菌涂层。结果表明制得的无机涂层具有良好的抗菌性，当抗菌剂在涂层中固含量达到2%时，涂层抑菌率达到了99%以上。同时抗菌涂层的硬度达到4H，附着力等级在测试中达到最高等级。在本论文的第四章，我们制备了氨基、巯基和磺酸基修饰的介孔二氧化硅微球作为银的载体，探索了有机基团种类以及基团负载量对微球结构以及载银量的影响。巯基修饰的介孔微球具有更规则的孔道结构和更高的载银量，但是银离子的释放率较低。磺酸根修饰的介孔微球具有较高的载银量，同时也具备很高的银离子释放率。通过测试针对白色念珠菌的最小杀菌浓度，将具有最高的杀菌活性的载银硅球作为抗菌剂以不同的浓度掺杂到第二章制备的杂化涂层中。由此制备的抗菌涂层具有很高的抗菌活性、较高的硬度、良好的附着力。当抗菌剂在涂层中固含量达到2%时，抑菌率达到100%，涂层硬度为4H，附着力在测试中为最高等级。在本论文的第五章，我们采用具有空心介孔结构的硅铝氧化物微球作为氯化银的载体。空心微球上的载银量达到29.7wt%。我们将氯化银负载的空心球以不同的浓度掺杂到杂化涂层中，得到的涂层具有良好的抗菌效果，当载银空心球在涂层中固含量达到2%时，抑菌率达到100%。同时涂层还具有最高级别的附着力和较高的硬度4H。综上，我们制备的杂化抗菌涂层具有较高的抗菌活性、较高的硬度，对PMMA基底具有良好的附着力，因此在义齿基托上具有很大的应用潜力。
[Abstract]:Polymethyl methacrylate (PMMA) resin material has the characteristics of low cost, easy processing and good biocompatibility, so it is widely used in dental medicine. Denture base is an important part of artificial denture, mainly made of PMMA resin. Research shows that the denture will change the microecological balance in the mouth, some microbes, such as Candida albicans and Streptococcus mutans will adhere to the surface of resin materials and proliferate in large quantities, leading to oral diseases such as denture stomatitis and secondary caries. Traditional denture cleaning methods have shortcomings of short antibacterial time, tedious operation, easy destruction of denture surface morphology and so on. Bacteria have become an important research topic in stomatology.
As we all know, silver has very high antibacterial activity and broad-spectrum antibacterial properties, so it is widely used in various antibacterial materials. Compared with the traditional organic antibacterial agents, silver carrying inorganic antibacterial agents have higher safety, durability and heat resistance. Mesoporous silica materials have good biocompatibility, diversity of morphology and easy to use. Modified, it has great potential to be used as a silver carrier. In general, the silver carrying antibacterial agent is directly doped into the resin material, but only the antibacterial agent near the surface of the resin can act as an antibacterial agent, and the antibacterial agent inside the resin can not be used as an antibacterial agent completely, resulting in a certain waste and too many antiseptic agents. It may also affect the mechanical properties of the resin. Therefore, the use of silver containing antibacterial coating is a more economical and effective way.
The main purpose of this paper is to design and prepare antibacterial coatings that can be applied to the denture base surface. We have made some meaningful explorations on the preparation of the silver carrying antibacterial agents and the design of the hybrid coatings. We have prepared several different kinds of silvery mesoporous silica microspheres as antibacterial agents, and were doped into a kind of organic matter designed by us, respectively. In the hybrid coating, an antibacterial coating was prepared.
In the first chapter of this paper, we briefly introduce the problems in denture base and its use, briefly review the development of antiseptic and antibacterial coatings, briefly introduce the mesoporous materials and their application in the field of silver carrying, and put forward the design ideas and main contents of this paper.
In the second chapter of this paper, we designed and synthesized a hybrid coating made of a polymer coating and a hybrid silica sol. The polymer coatings are composed of GMA, AA and methyl methacrylate (MMA), and the mixed silica sol is composed of glycidyl ether based propyl trimethoxy silane (KH). 560) the co hydrolysis and condensation of ethyl orthosilicate (TEOS) can be obtained. As an organic unit, the polymer can improve the adhesion of the coating to the substrate. The silica sol can be used as an inorganic component for the high coating hardness. At the same time, the polymer chain and the silica sol network contain epoxy groups, and the organic and inorganic interpenetrating networks are formed by the crosslinking reaction of the epoxy group. The structure can further improve the hardness of the coating. We have prepared a series of hybrid coatings with different organic and inorganic component mass ratios, and characterized the scratch hardness, adhesion and rupture resistance of the coating. We found that when increasing the use of TEOS in the silica sol and increasing the silica sol content in the hybrid coating, the coating is coated. The hardness has risen, but the adhesion and resistance to rupture have declined. Considering the overall consideration, we have selected the KH560/TEOS mole ratio of 2/5 and the organic and inorganic component mass ratio of 9/1. The coating has the highest hardness of 4H, adhesion and rupture resistance. At the same time, we also try to improve the retention of the resin material. The surface of the coating was hydrophilic. With the reaction of six methylene diisocyanate with the hydroxyl group, the PEG. was grafted on the coating surface through infrared spectrum and contact angle test. It was proved that we successfully grafted the coating surface of the coating on the coating surface after the graft of the hydrophilic angle of 64 degrees, PEG-1000 and PEG-2000 after.PEG grafting. The hydrophilic angles are 46 and 35 degrees, respectively.
In the third chapter of this paper, we first prepared the pure silica microspheres with mesoporous structure, and explored the influence of the addition mode of the silicon source, the type of catalyst, the amount of catalyst and the mass ratio of water and alcohol on the particle size and morphology. We found that the microspheres were helped to avoid the microspheres by adding the silicon source and using the ammonia as the catalyst. The size of the microspheres could be increased by increasing the amount of catalyst and reducing the ratio of water to alcohol, but it was easy to lead to agglomeration. Finally, we prepared the mesoporous silica microspheres with a good particle size of 400nm and good dispersion. Then, the silver chloride was loaded onto the microspheres and the silver loaded microspheres were added to the organic and inorganic hybrid coatings. The antibacterial coating has been prepared. The results show that the inorganic coating has good antibacterial properties. When the solid content of the coating is 2%, the antibacterial rate of the coating is above 99%, and the hardness of the antibacterial coating reaches 4H and the adhesion grade reaches the highest grade in the test.
In the fourth chapter of this paper, we prepared mesoporous silica microspheres modified by amino, sulfhydryl and sulfonic acid based mesoporous silica microspheres as the carrier of silver. The effects of the types of organic groups and the amount of group load on the structure of microspheres and the amount of silver were explored. The mesoporous microspheres modified by sulfhydryl groups have a more regular pore structure and higher silver load, but silver ions The rate of release is low. The mesoporous microspheres modified by sulfonic acid have high silver load and high silver ion release rate. By testing the minimum bactericidal concentration of Candida albicans, the silver silicon ball with the highest bactericidal activity is doped into the hybrid coating prepared in the second chapter at different concentrations. The antibacterial coating prepared has high antibacterial activity, high hardness and good adhesion. When the solid content of the coating is 2%, the bacteriostasis rate is 100%, the coating hardness is 4H, and the adhesion is the highest in the test.
In the fifth chapter of this paper, we use the silicon aluminum oxide microspheres with hollow mesoporous structure as the carrier of silver chloride. The silver load on the hollow microspheres reaches 29.7wt%.. We doped the hollow spheres loaded with silver chloride in the hybrid coating at different concentrations. The coating has good antibacterial effect, when the silver hollow ball is applied to the coating. When the solid content reaches 2%, the bacteriostatic rate reaches 100%., and the coating has the highest level of adhesion and high hardness 4H..
In conclusion, the hybrid antibacterial coating prepared by us has high antibacterial activity, high hardness and good adhesion to the PMMA substrate, so it has great potential in the denture base.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：R783.1

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