本文選題：義齒基托 + 雜化涂料　； 參考：《吉林大學(xué)》2013年博士論文

【摘要】：聚甲基丙烯酸甲酯(PMMA)樹脂材料具有成本低、容易加工和生物相容性好等特點(diǎn)，因而廣泛應(yīng)用于牙科醫(yī)學(xué)上。義齒基托是人工義齒的重要組成部分，主要由PMMA樹脂制成。研究表明，佩戴義齒會(huì)改變口腔內(nèi)的微生態(tài)平衡，一些微生物，例如白色念珠菌和變形鏈球菌，會(huì)粘附在樹脂材料表面并大量增殖，導(dǎo)致義齒性口炎和繼發(fā)齲等口腔疾病。傳統(tǒng)的義齒清潔方法存在著抗菌時(shí)間短、操作繁瑣、容易破壞義齒表面形貌等缺點(diǎn)，不能完全滿足臨床上的應(yīng)用。因此賦予基托樹脂抗菌性成為口腔醫(yī)學(xué)的重要研究課題。 眾所周知，銀具有很高的抗菌活性和廣譜的抗菌性，因此被廣泛應(yīng)用在各種抗菌材料中。與傳統(tǒng)的有機(jī)物抗菌劑相比，載銀無機(jī)抗菌劑具有更高的安全性、持久性和耐熱性。介孔二氧化硅材料由于其良好的生物相容性，形貌多樣性以及易修飾性，在作為銀載體方面具有很大的應(yīng)用潛力。通常情況下，載銀抗菌劑被直接摻雜到樹脂材料中，但是只有靠近樹脂表面的抗菌劑才能起到抗菌作用，而樹脂內(nèi)部的抗菌劑完全起不到抗菌作用，造成了一定的浪費(fèi)，而且過多的抗菌劑還可能影響樹脂的機(jī)械性能。因此，使用含銀的抗菌涂層是一個(gè)更經(jīng)濟(jì)有效的辦法。 本論文的主旨是設(shè)計(jì)和制備可應(yīng)用于義齒基托表面的抗菌涂層。我們在載銀抗菌劑的制備和雜化涂層的設(shè)計(jì)上進(jìn)行了一些有意義的探索。我們制備了幾種不同的載銀介孔二氧化硅微球作為抗菌劑，分別摻雜到我們設(shè)計(jì)的一種有機(jī)無機(jī)雜化涂料中，制備成了抗菌涂層。 在本論文第一章，我們簡要介紹了義齒基托及其使用中的問題，簡單回顧了一下抗菌劑和抗菌涂層的發(fā)展情況，簡單的介紹了介孔材料及其在載銀方面的應(yīng)用，并提出了本論文的設(shè)計(jì)思想及主要內(nèi)容。 在本論文第二章，我們設(shè)計(jì)合成了一種由聚合物涂料和雜化硅溶膠混合制成的雜化涂料。聚合物涂料由甲基丙烯酸縮水甘油酯(GMA)、丙烯酸(AA)和甲基丙烯酸甲酯(MMA)三種單體共聚而成；雜化硅溶膠由縮水甘油醚基丙基三甲氧基硅烷(KH560)和正硅酸乙酯(TEOS)共水解縮合制得。聚合物作為有機(jī)組分可以為提高涂層與基底的附著力，硅溶膠作為無機(jī)組分可以高涂層的硬度。同時(shí)聚合物鏈和硅溶膠網(wǎng)絡(luò)上都含有環(huán)氧基團(tuán)，利用環(huán)氧基團(tuán)的交聯(lián)反應(yīng)，形成有機(jī)無機(jī)互穿網(wǎng)絡(luò)結(jié)構(gòu)，可以進(jìn)一步提高涂層的硬度。我們制備了一系列具有不同有機(jī)無機(jī)組分質(zhì)量比值的雜化涂層，并表征了涂層的刮傷硬度、附著力和抗破裂性等性能。我們發(fā)現(xiàn)，當(dāng)增加硅溶膠中TEOS的使用量以及增加雜化涂層中的硅溶膠含量時(shí)，涂層的硬度有所上升，但相應(yīng)的附著力和抗破裂性有所下降。綜合考慮，我們選擇了KH560/TEOS摩爾比為2/5，有機(jī)無機(jī)組分質(zhì)量比為9/1的雜化涂層。該涂層的硬度達(dá)到了4H，附著力和抗破裂性等級(jí)最高。同時(shí)，為了提高樹脂材料的固位力，我們還嘗試對(duì)涂層表面進(jìn)行親水化處理。利用六亞甲基二異氰酸酯與羥基的反應(yīng)，在涂層表面接枝了不同分子量的PEG。通過紅外光譜和接觸角測試，證明我們成功在涂層表面接枝了PEG分子。PEG接枝前涂層親水角為64°，，PEG-1000和PEG-2000接枝后的涂層的親水角分別為46°和35°。 在本論文的第三章，我們先制備了具有介孔結(jié)構(gòu)的純二氧化硅微球，并探索了硅源加入方式、催化劑種類、催化劑用量以及水醇質(zhì)量比等因素對(duì)微球粒徑和形貌的影響。我們發(fā)現(xiàn)采用分批加入硅源和采用氨水做催化劑，有助于避免微球的團(tuán)聚；增大催化劑的用量和降低水醇比能夠使微球粒徑變大，但是容易導(dǎo)致團(tuán)聚發(fā)生。最終我們制備了粒徑為400nm、分散性好的介孔二氧化硅微球，然后將氯化銀負(fù)載到微球上，并將載銀微球作為抗菌劑添加到有機(jī)無機(jī)雜化涂層中，制備了抗菌涂層。結(jié)果表明制得的無機(jī)涂層具有良好的抗菌性，當(dāng)抗菌劑在涂層中固含量達(dá)到2%時(shí)，涂層抑菌率達(dá)到了99%以上。同時(shí)抗菌涂層的硬度達(dá)到4H，附著力等級(jí)在測試中達(dá)到最高等級(jí)。 在本論文的第四章，我們制備了氨基、巰基和磺酸基修飾的介孔二氧化硅微球作為銀的載體，探索了有機(jī)基團(tuán)種類以及基團(tuán)負(fù)載量對(duì)微球結(jié)構(gòu)以及載銀量的影響。巰基修飾的介孔微球具有更規(guī)則的孔道結(jié)構(gòu)和更高的載銀量，但是銀離子的釋放率較低。磺酸根修飾的介孔微球具有較高的載銀量，同時(shí)也具備很高的銀離子釋放率。通過測試針對(duì)白色念珠菌的最小殺菌濃度，將具有最高的殺菌活性的載銀硅球作為抗菌劑以不同的濃度摻雜到第二章制備的雜化涂層中。由此制備的抗菌涂層具有很高的抗菌活性、較高的硬度、良好的附著力。當(dāng)抗菌劑在涂層中固含量達(dá)到2%時(shí)，抑菌率達(dá)到100%，涂層硬度為4H，附著力在測試中為最高等級(jí)。 在本論文的第五章，我們采用具有空心介孔結(jié)構(gòu)的硅鋁氧化物微球作為氯化銀的載體。空心微球上的載銀量達(dá)到29.7wt%。我們將氯化銀負(fù)載的空心球以不同的濃度摻雜到雜化涂層中，得到的涂層具有良好的抗菌效果，當(dāng)載銀空心球在涂層中固含量達(dá)到2%時(shí)，抑菌率達(dá)到100%。同時(shí)涂層還具有最高級(jí)別的附著力和較高的硬度4H。 綜上，我們制備的雜化抗菌涂層具有較高的抗菌活性、較高的硬度，對(duì)PMMA基底具有良好的附著力，因此在義齒基托上具有很大的應(yīng)用潛力。
[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.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2013
【分類號(hào)】：R783.1

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本文編號(hào)：1901170