光敏氨基丙烯酸酯树脂的合成及其油墨应用

Synthesis of UV curable amino-acrylate resin and its application in ink

采用两步法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),考察了反应物配比、反应时间、催化剂等对合成反应的影响。采用红外光谱表征了产物的结构;通过DSC分析了羟甲化反应产物六羟甲基三聚氰胺的熔点;采用高压液相色谱仪(HPLC)测定了醚化产物的醚化度。获得的优化反应条件为:羟甲基化反应中三聚氰胺/甲醛物质的量比为1∶8,反应温度为70℃,反应时间为3.5 h,催化剂选用三乙胺;醚化反应温度105℃,反应时间5 h,催化剂为对甲苯磺酸。合成的HEA-MF贮存性能良好,游离甲醛含量低。将合成的HEA-MF作为活性稀释剂与酚醛环氧丙烯酸树脂复配成光固油墨,采用热失重分析仪(TGA)分析了HEA-MF含量和醚化度对涂膜的耐热性等性能的影响。结果表明,当HEA-MF质量分数为30%时,热稳定性能得到明显改进,起始分解温度达到290℃。HEA-MF醚化度为3.46时,其漆膜的综合性能最佳。涂膜的光泽、硬度、附着力均有明显提高,且气味小。

The UV curable amino- acrylate resin（β- Hydroxyethyl acrylate modified melamine formaldehyde rosin, HEA- MF）was synthesized by two-step method. The effect of reactant ratio, reaction time and catalyst on the synthesis reaction was investigated. 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 determinated by HPLC. The optimum hydroxymethyl reaction conditions were as follows： n （melamine） ： n （formaldehyde） = 1 ： 8 , reaction temperature 70℃; reaction time 3.5 h and triethylamine as catalyst. The optimum etherization reaction temperature was 105℃ and reaction time was 5 h with p - toluene sulphonic acid as catalyst. HEA- MF had good storage stability and low content of free formaldehyde. The UV curable ink was prepared by novolac epoxy acrylate rosins with HEA- MF as reactive diluent. The effect of HEA - MF content and etherization degree on the heat resistance of the cured film was investigated by TGA. The result showed that when HEA - MF mass fraction was 30 %, the thermal stability was improved obviously. The initial thermal decomposition temperature reached 290℃. When the etherization degree of HEA- MF was 3.46, the cured paint film showed the best comprehensive properties. The gloss, hardness and adhesion of paint film were all improved significantly and it had less odour.