| 研究生: |
葉舒 Ye, Shu |
|---|---|
| 論文名稱: |
矽烷成分對10-MDP基底的通用型黏著劑黏著性能探討 Effects of silane content to the bonding performance of MDP-base universal adhesives |
| 指導教授: |
莊淑芬
Chuang, Shu-Fen |
| 共同指導: |
林睿哲
Lin, Jui-Che |
| 學位類別: |
碩士 Master |
| 系所名稱: |
醫學院 - 口腔醫學研究所 Institute of Oral Medicine |
| 論文出版年: | 2021 |
| 畢業學年度: | 109 |
| 語文別: | 英文 |
| 論文頁數: | 69 |
| 中文關鍵詞: | 氧化鋯 、通用型黏著劑 、矽烷 、飛行式二次離子質譜儀 、固態核磁共振 |
| 外文關鍵詞: | zirconia, universal adhesive, silane, ToF-SIMS, SSNMR |
| 相關次數: | 點閱:145 下載:0 |
| 分享至: |
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氧化鋯是一種美觀且高强度的陶瓷材料,在牙科領域中被應用於製作各式復形物。然而,其高化學穩定性卻不利於與這種材料與樹脂黏結劑的結合。爲了提高氧化鋯的黏著性能,一種名爲10-甲基丙烯酰氧基癸基二氫磷酸酯(10-MDP)的酸性單體被發展出來。其特有的磷酸基團能吸附在氧化鋯表面,而另一端的有機基團則能與樹脂發生共聚反應。這種獨特的雙官能團能和氧化鋯材料形成化學鍵結,並為其與樹脂黏著劑提供良好的鍵結。
至今爲止,許多公司都發展出了以10-MDP為基底的牙科通用型黏著劑,並在其中加入矽烷(Silane)成分,聲稱不僅可以提高氧化鋯的黏著性能,還能同時黏著玻璃陶瓷、金屬、金屬氧化物等多種材料。然而,10-MDP和矽烷之共存可能會抑制10-MDP和氧化鋯的黏結。10-MDP的酸性會促進矽烷的聚合反應,使其失效;反之,矽烷的存在也可能阻礙氧化鋯對10-MDP的吸附。本研究的目的是探討矽烷成分在以10-MDP為基底的通用型黏著劑中的作用。本研究分爲兩個部分,第一部分是檢測商業用通用型黏著劑,第二部分是檢測10-MDP黏著劑加入矽烷後,與氧化鋯的化學鍵結與黏著性能。
第一部分:本研究首先藉由飛行式二次離子質譜儀(ToF-SIMS)檢測兩種含矽烷之商業用通用黏著劑Scotchbond Universal (簡稱SBU)和Clearfil Universal Bond (簡稱CUB)與兩種不含矽烷通用型黏著劑Clearfil SE Bond (簡稱SE) 與All-Bond Universal (簡稱ABU),研究塗佈於氧化鋯上,矽烷與MDP在黏著層的分佈狀況,以及P-O-Zr鍵結相關離子之比例與分布;接著透過座滴法測量蒸餾水或樹脂黏著劑與氧化鋯之間的靜態接觸角;最後搭配使用兩種牙科黏著劑 (RelyX Ultimate, 3M-ESPE、Variolink II, Ivoclar/Vivadent),對黏著的樣本進行剪切强度測試,探究其黏著效果。
第二部分:在含有10-MDP為基底的SE BOND Primer中加入不同濃度的矽烷(5wt%,10wt%),製備實驗用黏著劑(SE-5,SE-10),並如上所述,對其進行ToF-SIMS分析、接觸角測量和剪切强度測試。此外,用固態核磁共振儀 (Solid state NMR)確認實驗用黏著劑中MDP成分與氧化鋯間的鍵結方式,以及矽烷成分對該鍵結的影響。
第一部份的ToF-SIMS的結果顯示,在商業通用型黏著劑中,不含矽烷通用型黏著劑SE與氧化鋯的界面上擁有最高的PO3-/ PO2-比值,其次是ABU。這一比值顯示可能存在磷酸鋯化合物。同時,經過兩者處理的氧化鋯,其表面與水或樹脂的親和性皆高於SBU和CUB。在剪切强度測試中,使用RelyX Ultimate黏著,SBU、CUB、ABU顯示出較高的强度;對於Variolink II,SBU和SE顯示出較高的數值。
於第二部分研究中,ToF-SIMS在單純SE primer與氧化鋯的界面上檢測到最多的P-O-Zr相關鍵結,該鍵結的數量在SE-5,SE-10中減少。另外,隨著矽烷濃度的增加,在氧化鋯表面檢測到更多的ZrO2(OH)-離子。接觸角測試和剪切黏著强度的結果分別顯示,在氧化鋯表面塗抹含矽烷的SE-5和SE-10後,其對樹脂的親和性、以及與樹脂的黏著强度均低於單純的SE。固態核磁共振儀顯示,單純的SE有較多的P-O-Zr離子鍵以及吸附的MDP二聚體;而在SE-5和SE-10中,P-OH-Zr 氫鍵增加。
從結論上看,通用型黏著劑中的10-MDP成分可與氧化鋯表面形成P-O-Zr離子鍵和P-OH-Zr氫鍵,增加氧化鋯的黏著性能。然而,矽烷的存在會增加氧化鋯表面(OH)基,減少10-MDP的吸附,不利於P-O-Zr 鍵結形成。
Zirconia has been widely used in dentistry due to its excellent strength and attractive aesthetics. Unfortunately, the intrinsic chemical stability makes it difficult in bonding with resin cement. To compensate this weakness, an acidic resin monomer 10-methacryloyloxy-decyl dihydrogen phosphate (10-MDP) has been developed. The phosphate group of 10-MDP can be absorbed to zirconia, and the organic group of which can copolymerized with resin. This bifunctional group of MDP improves the chemical affinity of zirconia.
Hitherto, 10-MDP based universal adhesives have been developed by various manufactures. Some of them contain silane monomer in order to facilitate the bonding performance between resin cement and various materials including zirconia, glass ceramics, metals, and metal oxides. However, the bonding between 10-MDP and zirconia can be compromised by the co-existence of 10-MDP and silane. The acidity caused by MDP may accelerate the polymerization process of silane, and the presence of silane may inhibit the adsorption of MDP to zirconia as well. Hereby, the purposes of this study were to investigate the presence of silane in affecting the bonding and chemical actions of MDP based universal adhesives. This study was divided into two parts: the first was the examination of commercial 10-MDP based universal adhesives, and the second was to examine the experimental silane-containing MDP primers in regards to chemical bonding and bond strengths.
Part I: Four commercial universal adhesives/primer were examined: two silane-containing agents Scotchbond Universal (SBU) and CLEARFIL Universal Bond (CUB); and two silane-free CLEARFIL SE Bond (SE) and All-Bond Universal (ABU). These agents were applied on zirconia disks, and was investigated by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis to reveal the distribution of MDP and silane ions in the adhesive layers and the presence and distributions of P-O-Zr bond-related ions. The contact angles of water/resin adhesive on treated zirconia were measured using a sessile drop method. The bonding performance of these universal adhesives were tested in combination with two resin cements (RelyX Ultimate; 3M-ESPE, and Variolink II; Ivoclar, Vivadent).
Part II: Experimental adhesives were formulated by adding 5wt% and 10wt% silane to MDP-based SE BOND Primer (SE-5, SE-10), which were evaluated using ToF-SIMS analysis, contact angle measurement and shear bond strength test. Additionally, the chemical states of zirconia-phosphate bonding as silane present were confirmed by a solid-state nuclear magnetic resonance (SSNMR) instrument.
The Part I results of ToF SIMS analysis showed the highest PO3-/ PO2- ion ratio at the zirconia interface, which has been considered as an indicator of zirconia phosphate compound formation, in group SE, followed by ABU. SE and ABU also showed lower water/adhesive contact angles, implying a higher affinity to both liquids. Regarding to the shear bond strength, higher values were presented by SBU, CUB and ABU when combined with RelyX Ultimate. While with Variolink II, SBU and SE showed significantly higher strengths.
The Part II results revealed that the treated zirconia in SE group showed the greatest amount of P-O-Zr related ions, which reduced in SE-5 and SE-10. More ZrO2(OH)- related ions were examined with more silane ions added. In regards of the contact angle measurement and shear bond strength test, SE-5 and SE-10 treated zirconia presented lower water/adhesive affinity and shear bond strength value compared to SE. In the result of SSNMR, SE showed more P-O-Zr ionic bonds and physisorbed MDP dimer, SE-5 and SE-10 showed more P-OH-Zr hydrogen bonds.
In conclusion, the study demonstrated 10-MDP can be adsorbed onto zirconia particles by either monomer and dimer forms, via ionic bond (P-O-Zr) or hydrogen bond (P-OH-Zr), and thus the bond strength can be improved. Unfortunately, the presence of silane may increase the hydroxylation of zirconia, reduce the adsorption of MDP, and adversely affected the formation of P-O-Zr bond.
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