硅氧烷类聚合物耐磨透明涂层的制备及其性能研究

发布时间：2019-05-29 05:59

【摘要】：有机硅高分子化合物因其特殊的化学结构而拥有优越的性能,应用已遍及于各个领域,尤其是涂料行业。有机硅耐磨加硬涂层是其众多应用中应用最广泛的一种,作为光学塑料表面的保护涂层在改善光学塑料表面易被擦伤方面取得了突出效果,具有良好的经济效益和社会效益。本论文主要围绕硅氧烷类耐磨涂层的制备及其性能开展研究。(1)通过E 03型双酚A环氧树脂与丙烯酸反应合成了双酚A环氧丙烯酸树脂,探究了不同摩尔比对反应产率的影响；用硅烷偶联剂MPS(Y-甲基丙烯酰氧丙基三甲氧基硅烷)对双酚A环氧丙烯酸树脂进行改性,将所得产物均匀涂覆在PMMA(聚甲基丙烯酸甲酯)基材表面进行固化,制备了硅烷偶联剂MPS质量分数分别为10%、15%、20%、30%、40%和60%的耐磨加硬透明涂层,并对其物理性能、光学性能和耐磨性能等进行测试,着重分析了硅烷偶联剂MPS的含量对涂层各种性能的影响。观察发现硅烷偶联剂MPS含量为10%、15%、20%时,涂层表面平整、光滑,通过对该三组涂层进行性能测试发现：固化后的涂层透光率达到92%左右;铅笔硬度最高达6H,附着力为1级,而且提高了基材的抗刮性能和耐磨性能,表现为在相同擦拭次数下,涂覆涂层的PMMA基材的失重率明显低于未涂覆涂层的PMMA基材的失重率；基于接触角数据可以发现,随着硅烷偶联剂MPS含量的增加,材料表面张力减小,表现为蒸馏水和乙二醇在耐磨涂层上的接触角随着硅烷偶联剂MPS含量的增加而变大,赋予耐磨涂层表面比较低的表面自由能。(2)以正硅酸乙酯(TEOS)和Y-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)为反应原料,利用溶胶-凝胶法制得了摩尔比分别为1.33、1.50、1.86、2.00、2.33、2.50、3.00和4.00的八组有机硅溶胶复合耐磨涂层,着重研究分析了不同的摩尔比组成对耐磨涂层物理性能、光学性能和耐磨性能等的影响。观察发现摩尔比为2.33和4.00的两组溶胶涂层表观呈现起皱、破裂现象,而其余的六组样品涂层表面平整、光滑且具有良好的储存稳定性。通过性能测试发现：涂层的铅笔硬度和附着力等级随着溶胶体系中TEOS含量的增加呈现先增大后减小的趋势,最大铅笔硬度可达5H,附着力等级为1级。同时发现溶胶的陈化时间对涂层的硬度和附着力也有影响,随着陈化时间的延长,溶胶涂层的铅笔硬度和附着力随之提高。制备的耐磨涂层具有很好的透光率,而且可以有效提高PMMA基材的抗刮性能和耐磨性能,表现为在相同擦拭次数下,涂覆涂层的PMMA基材的失重率明显小于未涂覆涂层的PMMA基材的失重率,而且能够使涂层表面产生明显划痕的最小砝码质量相比涂覆前有所增加。基于接触角数据可以发现,随着溶胶体系中TEOS含量的增加,材料表面张力减小,表现为蒸馏水和乙二醇在涂层上的接触角随着TEOS含量的增加而变大,赋予涂层表面比较低的表面自由能。(3)选择了三种不同的光引发剂Irgacute 184、Irgacure MBF和Irgacure 907在紫外光下用硅烷偶联剂MPS对双酚A环氧丙烯酸树脂进行改性,同时添加分散剂、消泡剂和流平剂等助剂,制得了九组耐磨加硬涂层,探讨了光引发剂的差别对耐磨涂层的物理性能、光学性能、耐磨性能及抗刮性能的影响。通过测定三种光引发剂的紫外吸收曲线发现,在紫外光区内三种光引发剂具有截然不同的紫外吸收峰。Irgacure184的吸收波长在205 nm和248 nm,Irgacure 907的吸收波长在204 nm、238 nm和305 am,而Irgacure MBF的吸收波长在204 nm和256 nm。通过观察不同光引发剂制备的九组耐磨涂层样品发现涂料本身均一、透明且具有良好的稳定性,涂层表面平整、光滑。通过对涂层进行性能测试发现：所有涂层都具有良好的铅笔硬度、附着力和透光率。同时发现Irgacure 907光引发剂制备的耐磨涂层相较于其他两种光引发剂制备的耐磨涂层有着更好的铅笔硬度、光学性能、耐磨性能和抗刮性能。
[Abstract]:The organosilicon polymer compound has excellent performance due to its special chemical structure and has been applied in various fields, especially in the coating industry. The organic silicon wear-resistant hardcoat is one of the most widely used in many applications, and the protective coating which is used as the surface of the optical plastic has the outstanding effect in improving the surface of the optical plastic, and has good economic and social benefits. This paper mainly studies the preparation and properties of the silicone-based wear-resistant coating. (1) The bisphenol A epoxy acrylic resin was synthesized by the reaction of the E 03 bisphenol A epoxy resin and the acrylic acid, and the effect of different molar ratios on the reaction yield was investigated. the bisphenol A epoxy acrylic resin is modified by using a silane coupling agent MPS (Y-methylpropylidene trimethoxy silane), the obtained product is uniformly coated on the surface of the PMMA (polymethyl methacrylate) substrate for curing, and the mass fraction of the silane coupling agent MPS is 10 percent, 15%,20%,30%,40% and 60% wear-resistant and hard transparent coatings, and the physical properties, optical properties and wear resistance of the coatings were tested, and the effects of the content of the silane coupling agent MPS on the various properties of the coatings were analyzed. when the content of the silane coupling agent is 10%,15% and 20%, the surface of the coating is flat and smooth, and the performance test of the three groups of coatings shows that the light transmittance of the cured coating reaches about 92%; the pencil hardness is up to 6 h and the adhesion force is grade 1, and the scratch resistance and the wear resistance of the base material are improved, the weight loss rate of the PMMA base material coated with the coating is obviously lower than the weight loss rate of the PMMA base material of the uncoated coating under the same wiping frequency, and based on the contact angle data, the content of the silane coupling agent MPS is increased, The surface tension of the material is reduced, the contact angle of the distilled water and the ethylene glycol on the wear-resistant coating is increased as the content of the silane coupling agent MPS is increased, and the surface free energy of the surface of the wear-resistant coating is relatively low. (2) an eight-group organic silica sol composite wear-resistant coating with the molar ratio of 1.33, 1.50, 1.86, 2.00, 2.33, 2.50, 3.00 and 4.00, respectively, is obtained by using the orthosilicate (TEOS) and the Y-glycidyl ether oxypropyltrimethoxysilane (GPTMS) as the reaction raw material, The effects of different molar ratios on the physical properties, optical properties and wear resistance of wear-resistant coatings were studied. The apparent wrinkling and cracking of two groups of sol coatings with a molar ratio of 2.33 and 4.00 were observed, while the remaining six groups of sample coatings were flat, smooth and have good storage stability. The performance test shows that the pencil hardness and the adhesion grade of the coating exhibit a tendency to decrease with the increase of the TEOS content in the sol system, and the maximum pencil hardness can be up to 5 H and the adhesion level is grade 1. At the same time, it is found that the aging time of the sol has an effect on the hardness and the adhesion of the coating, and the pencil hardness and the adhesion of the sol coating are improved as the aging time is prolonged. the prepared wear-resistant coating has good light transmittance and can effectively improve the scratch resistance and the wear resistance of the PMMA base material, But also an increase in the quality of the minimum weight of the coating surface that has a significant scratch. Based on the contact angle data, it can be found that with the increase of the content of TEOS in the sol system, the surface tension of the material is reduced, and the contact angle of the distilled water and the glycol on the coating increases with the increase of the TEOS content, giving a relatively low surface free energy to the coating surface. (3) Three different photo-initiators, Irgacute 184, Irgacure MBF and Irgacure 907, were selected to modify the bisphenol A epoxy acrylic resin with the silane coupling agent MPS under the ultraviolet light, and the addition of the additives such as the dispersing agent, the defoaming agent and the leveling agent were added. The effects of the difference of photoinitiator on the physical properties, optical properties, wear resistance and anti-scratch properties of the wear-resistant coatings were discussed. The UV-absorption curve of three kinds of photo-initiators showed that the three kinds of photo-initiators in the ultraviolet region had different ultraviolet absorption peaks. The absorption wavelength of Irgacure 184 was at 205 nm and 248 nm, and the absorption wavelength of Irgacure 907 was at 204 nm,238 nm and 305 am, while the absorption wavelength of Irgacure MBF was at 204 nm and 256 nm. The nine-group wear-resistant coating samples prepared by observing the different photo-initiators find that the coating itself is uniform, transparent and has good stability, and the surface of the coating is smooth and smooth. The performance test of the coating found that all the coatings had good pencil hardness, adhesion and light transmittance. At the same time, it is found that the wear-resistant coating prepared by the Irgacure 907 photoinitiator has better pencil hardness, optical performance, wear resistance and scratch resistance compared with the wear-resistant coating prepared by the other two photoinitiators.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB306

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