齿科用可见光固化胶粘剂的制备及性能研究
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摘要
近年来,可见光固化胶粘剂在牙科修复中应用广泛。由于此类胶粘剂能起到抵抗微渗漏,封闭基牙和修复体之间的间隙,并且通过机械的、化学的结合方式将基牙和修复用复合树脂粘接在一起的作用,因此其对于固定修复用复合树脂,防止继发龋显得尤为重要。但由于牙齿组织结构和口腔环境的特殊性,以至一直未能完全解决粘接强度和耐久性的问题。为此,本课题的主要目的在于研究开发出一种具有良好粘接强度和耐水性的可见光固化胶粘剂。
本论文的研究工作分为两部分,第一部分为可见光固化胶粘剂基质树脂的制备及表征;第二部分为粘接体系的制备及其性能测试。
首先,制备出四种基质树脂。采用直接酯化法,以顺丁烯二酸酐、环氧树脂、甲基丙烯酸为原料合成出顺丁烯二酸酐改性的环氧甲基丙烯酸酯;以甲苯2,4-二异氰酸酯、甲基丙烯酸羟乙酯、聚乙二醇-400为原料合成出聚氨酯甲基丙烯酸酯,然后与顺丁烯二酸酐改性的环氧甲基丙烯酸酯共混;分别以六亚甲基二异氰酸酯、环氧甲基丙烯酸酯和二苯基甲烷二异氰酸酯、环氧甲基丙烯酸酯为原料合成出两种异氰酸酯改性的环氧甲基丙烯酸酯。其次,将四种基质树脂配合稀释剂、光引发剂、偶联剂、填料等制备出可见光固化胶粘剂及复合树脂,考察了不同基质树脂及各个组分对胶粘剂及复合树脂性能的影响。最后,通过正交试验得到胶粘剂的最佳配比。
试验结果表明,四种基质树脂中,以二苯基甲烷二异氰酸酯作基质树脂制备的粘接体系效果最好。并且当基质树脂与稀释剂质量比为3:2、光引发剂含量为0.4%、偶联剂含量为0.5%时,胶粘剂对玻璃和牙齿的粘接剪切强度分别达到8.64MPa和12.18MPa。当基质树脂与稀释剂质量比为3:2、光引发剂含量为0.3%、填料含量为30%时,复合树脂的压缩强度和固化深度分别达到240MPa和4.14mm。
In recent years, visible light cured adhesive is being widely employed in restorative dentistry. Because of this kind of adhesive can be used to act as a barrier against microleakage, sealing the interface between the teeth and the filling and holding them together through some forms of surface attachment that may be mechanical, chemical or a combination of both methods. So the clinical success of fixed restorative composite resin and against secondary caries is heavily dependent on the visible light adhesive with good performance. But the durable problem and strength problem of adhesive have not been altogether resolved because of peculiarities of the oral circumstances and teeth texture. The goal of this subject is to develop a kind of visible light cured adhesive which has excellent adhesive strength and water-resistant property.
In this thesis, the experiments included two parts: firstly, the matrix resin of visible light cured adhesive and composite resin were synthesized and characterized; secondly, adhesive system was prepared and tested.
Firstly, four matrix resins were synthesized. The maleic anhydride modified epoxy methylacrylate was synthesized from the reaction of the maleic anhydride, the epoxy resin and the methacrylic acid by direct esterification. The polyurethane methylacrylate was synthesized from tolylene 2,4-diisocyanate, hydroxyethyl methacrylate and polyethylene glycol-400, and then altogether mixed with the maleic anhydride modified epoxy methacrylate. One isocyanate modified epoxy methylacrylate was prepared with hexamethylene diisocyanate and epoxy methylacrylate. The other one was synthesized from diphenylmethane diisocyanate and epoxy methylacrylate. Secondly, visible light cured adhesive and composite resin were made through adding active diluent, photoinitiator, coupling agent and filling material etc. into the matrix resin. The effects of the different matrix resins and each component on properties of adhesive system were investigated also. Finally, the best formulation of adhesive was obtained through orthogonal experiment.
The experimental results about the four matrix resins indicated that the adhesive system would obtain the best performance when the diphenylmethane diisocyanate modified epoxy methylacrylate was used to act as the matrix resin in the four matrix resins. When the mass ratio of the matrix resin and the active diluent was 3:2 and the content of photoinitiator and coupling agent was 0.4% and 0.5% respectively, the shearing strength of adhesive achieved 8.64MPa and 12.18MPa for the glass and the tooth respectively. When the mass ratio of the matrix resin and active diluent was 3:2, the content of photoinitiator was 0.3%, the content of filling material was 30%, the compressive strength and cured depth of composite resin achieved 240MPa and 4.14mm respectively.
本论文的研究工作分为两部分,第一部分为可见光固化胶粘剂基质树脂的制备及表征;第二部分为粘接体系的制备及其性能测试。
首先,制备出四种基质树脂。采用直接酯化法,以顺丁烯二酸酐、环氧树脂、甲基丙烯酸为原料合成出顺丁烯二酸酐改性的环氧甲基丙烯酸酯;以甲苯2,4-二异氰酸酯、甲基丙烯酸羟乙酯、聚乙二醇-400为原料合成出聚氨酯甲基丙烯酸酯,然后与顺丁烯二酸酐改性的环氧甲基丙烯酸酯共混;分别以六亚甲基二异氰酸酯、环氧甲基丙烯酸酯和二苯基甲烷二异氰酸酯、环氧甲基丙烯酸酯为原料合成出两种异氰酸酯改性的环氧甲基丙烯酸酯。其次,将四种基质树脂配合稀释剂、光引发剂、偶联剂、填料等制备出可见光固化胶粘剂及复合树脂,考察了不同基质树脂及各个组分对胶粘剂及复合树脂性能的影响。最后,通过正交试验得到胶粘剂的最佳配比。
试验结果表明,四种基质树脂中,以二苯基甲烷二异氰酸酯作基质树脂制备的粘接体系效果最好。并且当基质树脂与稀释剂质量比为3:2、光引发剂含量为0.4%、偶联剂含量为0.5%时,胶粘剂对玻璃和牙齿的粘接剪切强度分别达到8.64MPa和12.18MPa。当基质树脂与稀释剂质量比为3:2、光引发剂含量为0.3%、填料含量为30%时,复合树脂的压缩强度和固化深度分别达到240MPa和4.14mm。
In recent years, visible light cured adhesive is being widely employed in restorative dentistry. Because of this kind of adhesive can be used to act as a barrier against microleakage, sealing the interface between the teeth and the filling and holding them together through some forms of surface attachment that may be mechanical, chemical or a combination of both methods. So the clinical success of fixed restorative composite resin and against secondary caries is heavily dependent on the visible light adhesive with good performance. But the durable problem and strength problem of adhesive have not been altogether resolved because of peculiarities of the oral circumstances and teeth texture. The goal of this subject is to develop a kind of visible light cured adhesive which has excellent adhesive strength and water-resistant property.
In this thesis, the experiments included two parts: firstly, the matrix resin of visible light cured adhesive and composite resin were synthesized and characterized; secondly, adhesive system was prepared and tested.
Firstly, four matrix resins were synthesized. The maleic anhydride modified epoxy methylacrylate was synthesized from the reaction of the maleic anhydride, the epoxy resin and the methacrylic acid by direct esterification. The polyurethane methylacrylate was synthesized from tolylene 2,4-diisocyanate, hydroxyethyl methacrylate and polyethylene glycol-400, and then altogether mixed with the maleic anhydride modified epoxy methacrylate. One isocyanate modified epoxy methylacrylate was prepared with hexamethylene diisocyanate and epoxy methylacrylate. The other one was synthesized from diphenylmethane diisocyanate and epoxy methylacrylate. Secondly, visible light cured adhesive and composite resin were made through adding active diluent, photoinitiator, coupling agent and filling material etc. into the matrix resin. The effects of the different matrix resins and each component on properties of adhesive system were investigated also. Finally, the best formulation of adhesive was obtained through orthogonal experiment.
The experimental results about the four matrix resins indicated that the adhesive system would obtain the best performance when the diphenylmethane diisocyanate modified epoxy methylacrylate was used to act as the matrix resin in the four matrix resins. When the mass ratio of the matrix resin and the active diluent was 3:2 and the content of photoinitiator and coupling agent was 0.4% and 0.5% respectively, the shearing strength of adhesive achieved 8.64MPa and 12.18MPa for the glass and the tooth respectively. When the mass ratio of the matrix resin and active diluent was 3:2, the content of photoinitiator was 0.3%, the content of filling material was 30%, the compressive strength and cured depth of composite resin achieved 240MPa and 4.14mm respectively.
引文
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[3] 王同. 口腔粘接材料[J]. 粘接(增刊), 1999, 3: 59~62
[4] John W. Nicholson. Adhesive dental materials–A review[J]. Adhesion& Adhesives, 1998, (18) : 229~236
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[6] Luis C.Mendesa, Andrea D.Tedescob, Mauro S.Mirandab. Determination of degree of conversion as function of depth of a photo-initiated dental restoration composite[J]. POLYMER TESTING, 2005, 24:418~422
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