【作者】 应明友；

【导师】 刘晓亚；

【作者基本信息】 江南大学 ， 材料学， 2008， 硕士

【摘要】 紫外光固化技术具有适用性广、节能、高效、经济和环保的特点。本文创新性地合成了可光固化的氨基丙烯酸树脂和有机硅改性聚氨酯丙烯酸树脂,并将他们作为预聚物分别应用于光成像阻焊油墨和UV塑料油墨。本文第一部分由三聚氰胺、甲醛、β-丙烯酸羟乙酯合成了光敏性氨基丙烯酸树脂(β-丙烯酸羟乙酯改性三聚氰胺甲醛树脂,HEA-MF),考察了投料比、反应温度、反应时间、催化剂用量等因素对HEA-MF合成的影响,优化了合成条件。用红外光谱分析了产物的主要基团,表征了产物的结构;用DSC分析了羟甲化反应产物六羟甲基三聚氰胺的熔点;用高压液相色谱仪(HPLC)分析了醚化产物的醚化度。获得优化反应条件为:羟甲基化反应投料比为1:8,反应温度为70℃,反应时间为3.5h;醚化反应投料比为1:10,反应温度为105℃,反应时间为5小时。合成的HEA-MF贮存性能良好,游离甲醛含量低。本文第二部分HEA-MF作为活性稀释剂和硬化剂应用于光成像阻焊油墨。将其与酚醛环氧丙烯酸树脂复配,用傅立叶实时红(FT-RTIR )对其光聚合性能进行了研究,用热失重分析仪(TGA)分析涂膜的耐热性能,考察了光引剂浓度、HEA-MF含量、HEA-MF醚化度对漆膜性能的影响;将HEA-MF应用于光成像阻焊油墨,用视频变焦显微镜分析了显影图形,考查了HEA-MF含量、HEA-MF醚化度和不同硬化剂等因素对漆膜性能的影响,结果表明,具有良好的光聚合性能和显影性能,光级值达到12,改善了油墨的硬度、耐热稳定性和综合性能,且气味小。本文第三部分用丙酮法以异佛尔酮二异氰酸酯(IPDI)、聚乙二醇(PEG-400)、三羟甲基丙烷(TMP)、甲基丙烯酸羟乙酯(HEMA)和γ-氨丙基三乙氧基硅烷(SCA-1113)为原料,二月桂酸二丁基锡(DBTDL)为催化剂,分三步合成了可光固化的有机硅改性聚氨酯丙烯酸酯(Si-M-PUA)。优化得到的反应条件:第一步反应温度30~40℃,第二步反应温度40~45℃,第三步温度控制60-65℃。用傅立叶红外光谱法对产物结构进行表征,证明得到了目标产物。将合成的PUA作为基体树脂,配以活性稀释剂、光引发剂、助剂等制成塑料油墨,将其应用于不同基材的塑料上,考察了不同PUA的比例、光引发剂复配和用量,活性稀释剂复配体系和用量对光固化塑料油墨性能的影响,实验结果表明,Si-M-PUA有助于提高油墨的附着力,且得到了综合性能较好的塑料油墨。更多还原

【Abstract】 UV curing technology has been developing rapidly for its enabling, energy saving, efficient, economical and environmental friendly etc. In this paper, two novel UV curable prepolymers were synthesized and they were respectively UV curable amino acrylate resin for photoimagineable solder resist inks and organic silicone modified polyurethane acrylate for UV curable plastic inks.In part 1, amino-acrylate resin (β-Hydroxyethyl acrylate modified melamine formaldehyde resin, HEA-MF) was synthesized by the raw materials of melamine, formaldehyde andβ-Hydroxyethyl acrylate, the optimum reaction conditions were investigated in terms of the influence of reaction temperature, reaction time and catalyst. The structure of the products was characterized by FT-IR, the melting point of hexamethylol melamine (HMM) was analyzed by DSC, the etherization degree of the HEA-MF was analyzed by HPLC. The optimum formula ratio was n (melamine) :n (formaldehyde) = 1:8 , and the optimum reaction conditions on hydroxymethyl reaction were follow: the reaction temperature was 70℃; the reaction time was 3.5 h; the optimum reaction conditions on etherization reaction were that the ratio of materials was n (HMM) :n (HEA) = 1:10 , reaction temperature was 105℃and reaction time was 5 h, HEA-MF has good storage stability and low content of free formaldehyde.In part 2, The UV curable HEA-MF as reactive diluent and hardness agent was applied in photoimagineable solder resist inks. The photopolymerization characteristics of this monomer was investigated by Fourier Transform Real Time Infrared spectroscopy ( FT-RTIR) in terms of the influence of the content of photoinitiator; the thermal resistance of the cured film was observed by TGA in terms of the influence of the content and the etherization degree of HEA-MF. the result indicated that HEA-MF has good photopolymerizeable ability and alkaline developable ability, and the cured film showed high hardness, good thermal resistance and excellent film performance, especially it had low volatile smell.In part 3, The UV curable organic silicone modified polyurethane acrylate (Si-M-PUA) was synthesized in acetone by three steps and by the raw materials of isophorone diisocyanate(IPDI), Polyethylene glycol(PEG-400), Trimethylol Propane(TMP),γ -aminopropyl triethoxysilane (SCA-1113), hydroxyl methylacrylate (HEMA) and the catalyst of dibutyltin dilaurate (DBTDL). The optimum reaction conditions were investigated, the optimum reaction conditions were follow: the first reaction temperature was 30-40℃, and the second reaction temperature was 40-45℃, and the third reaction temperature was 60-65℃. The structure of the products was characterized by FT-IR. The UV curable plastic ink was composited of PUA as the basic resin, reactive diluent, photoinitiator and addictives, and was applied onto the different plastic substrate. the optimum formulation were investigated, in terms of the influence of different PUA, reactive diluent and photoiniator. The result was indicated that the adhesion properties of UV curable plastic ink can be improved by the Si-M-PUA resin, and the film has good performance.更多还原