低收縮可見光聚合多官能基壓克力系牙用複合材料之性質探討

A Study of Low Shrinkage Multifunctional Methacrylate Dental Restorative Materials for Visible-light Curing

黃致豪(Chih-Hao Huang)

指導教授 ： 林俊彬

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2008年)

https://doi.org/10.6342/NTU.2008.01102

摘要

本實驗藉由聚丙醇 (polypropylene glycol, PPG)中含有三個莫爾當量的氫氧基的添加，來改質環氧丙烯酸酯 (epoxy acrylate, EA) ，期望藉由聚丙醇 (polypropylene glycol, PPG)，可以增加改質後壓克力系樹脂單體的官能度，合成多官能基壓克力樹脂單體。同時，也藉由官能度的增加及分子量的增大，在聚合過程中可高度交聯，以減低因聚合反應所產生的聚合收縮(polymerization shrinkage)效應。

實驗中利用異氰酸鹽(diisocyanate)與甲基丙烯酸-2-羫基乙酯 (2-hydroxyethyl methacrylate, HEMA)以莫爾比1：1反應，合成改質側鏈，再以此改質側鏈，添加入聚丙醇 (polypropylene glycol, PPG)，以2：1之莫爾比進行反應，而後再添加入異氰酸鹽(diisocyanate)與聚丙醇 (polypropylene glycol, PPG)之氫氧基(-OH)進行反應，完成改質側鏈之全部反應。而後加入環氧丙烯酸酯 (epoxy acrylate, EA)，以莫爾比1：2.07反應，藉以反應掉環氧丙烯酸酯 (epoxy acrylate, EA)上之氫氧基(-OH)以完成樹脂之製備。而本實驗所選用之異氰酸鹽(diisocyanate)為2,4-二異氰酸甲苯 (toluene 2,4-diisocyanate, TDI)。而此反應改質過後之環氧丙烯酸酯 (epoxy acrylate, EA)，分子量增大，且產物間產生較強之分子間氫鍵，較未改質前具有較多之官能度，在進行聚合反應時，能產生高分子交聯網狀結構，有效減低聚合反應過程中所產生之體積收縮量。

改質過後之環氧丙烯酸酯 (epoxy acrylate, EA)，由於其分子基團變大，流動性不佳，因此本實驗選用三丙烯乙二醇雙丙烯酸酯 (tripropylene glycol diacrylate, TPGDA)為稀釋單體，進行不同比例之添加。而牙用復形複合材料中，主要用以支撐機械固持力之無機填料粒子部分，則是選用市售奈米級燻矽與二氧化矽溶膠懸浮液，藉由不同比例之添加，搭配D,L-樟腦醌 (D,L-camphoroquinone, CQ)、對二甲胺基苯甲酸乙酯 (ethyl 4-dimethylaminobenzoate, EDMAB)完成牙用復形複合樹脂材料之製作。以波長為410-500 nm之可見光照射，可聚合硬化。藉由傅立葉轉換紅外線光譜儀 (Fourier Transform Infrared Spectrometer, FT-IR) 、凝膠滲透色層分析儀 (Gel Permeation Chromatography, GPC) 、聚合收縮量測試(polymerization shrinkage test)與微硬度測試，並與以Bisphenol A glycerolate dimethacrylate (Bis-GMA)為樹脂主體和市售產品為對照組，相比較後可發現，以奈米級燻矽添加量可達80wt%，二氧化矽懸浮液添加至80wt%，硬度測試有顯著提升，最大硬度為53.9(Hv)。此外在聚合收縮量測試，添加無機填料粒子量增大，有助於減少聚合收縮量的產生，且其聚合收縮量比市售材料小約1/6，且與以Bisphenol A glycerolate dimethacrylate (Bis-GMA)相比其聚合收縮量小約1/5~1/6。

關鍵字

多官能基 ； 牙用復形複合材料 ； 可見光聚合 ； 壓克力樹脂 ； 聚合收縮 ； 微硬度

並列摘要

By adding of polypropylene glycol (PPG) which contains three molar equivalent of hydroxyl groups, the more funtionalities will provide in the modified epoxy acrylate (EA). At the same time, by increasing the funtionalities and molecular weight of modified composite resin which crosslinking in polymerization and decreasing polymerization shrinkage.

The multifuntional methacrylate resin were prepared by modified reaction of epoxy acrylate (EA). The hydroxyl groups of epoxy acrylate (EA) were reacted with modified side chain, which pre-reacted by isocyanate groups of toluene 2,4-diisocyanate (TDI), 2-hydroxyethyl methacrylate (HEMA) and polypropylene glycol (PPG) with proper molar ratio. The dental monomers were obtained. The methacrylate resin synthesis of following procedures with more functionalities than un-modified epoxy acrylate (EA). As the reaction proceeded, the reaction underwent the nucleophilic reaction and the stronger hydrogen bonding, resulted in the decrease of flowing property. By adding different ratio of tripropylene glycol diacrylate (TPGDA) in resin matrix adjust the flowing property.

The dental restorative materials were composed of modified multifuntional methacrylate resin, tripropylene glycol diacrylate (TPGDA), D,L-camphoroquinone (CQ), ethyl 4-dimethylaminobenzoate (EDMAB) and inorganic particles, which chosen nano fumed silica and dispersed silica solution with different ratio. After visible light curing (410-500 nm), the composite dental material were formed and analyzed by Fourier Transform Infrared Spectrometer (FT-IR), Gel Permeation Chromatography (GPC), polymerization shrinkage test and micro-hardness test. And those data were compared with bisphenol A glycerolate dimethacrylate (Bis-GMA) as resin matrix and commercial materials. In this study, the loading of fumed silica was 80wt% and the dispersed silica solution was 80%. The later obtained higher hardness, and the maximum hardness was 53.9(Hv). Besides, the polymerization shrinkage test was lower by increasing inorganic particles adding. And also compared with bisphenol A glycerolate dimethacrylate (Bis-GMA)(lower 1/5~1/6 ) as resin matrix and commercial materials(lower 1/6), the polymerization shrinkage was much lower.

並列關鍵字

multifunctional ； dental restorative materials ； visible light curing ； acrylate resin ； polymerization shrinkage ； micro-hardness.

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