UV/EB固化发展现状

随着世界范围内对环境保护的日益重视和绿色科技的蓬勃发展,辐射固化技术因其能有效控制空气污染特别是挥发性有机物(VOC)的排放而越来越受到青睐.与使用挥发性有机物作为溶剂的传统固化体系相比,辐射固化采用紫外光(UV)或电子束(EB)辐照无溶剂液体化学物质而发生快速聚合反应,使之很快生成三维网状结构,形成固态薄膜,因而实现了"可持续发展中的零排放".另外,体系的高效性和产品的优良性也是该技术得以快速发展的重要原因.     

ε-己内酯改性聚氨酯丙烯酸酯的制备及电子束固化涂料性能研究

本文以甲基丙烯酸羟乙酯、ε-己内酯及异氟尔酮二异氰酸酯为原料制备了己内酯改性聚氨酯丙烯酸酯。使用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(~1HNMR)表征了产物结构。探究了ε-己内酯链段含量对改性聚氨酯丙烯酸酯树脂黏度的影响,并进一步对比研究了其电子束(EB)固化膜和紫外光(UV)固化膜的热机械性能、拉伸性能和涂层基本性能的差异。     

光量热仪表征紫外光固化胶黏剂的固化过程

利用光量热仪对紫外光固化胶(UV胶)固化行为进行表征。使用光量热仪对UV胶进行测试并制作DSC曲线,根据固化前后的DSC曲线之差求得样品紫外光固化曲线,从而求得样品固化时间。结果表明光量热仪可方便地表征不同紫外光照射强度下光固化胶的固化行为,为UV胶的配方设计、固化剂类型及用量的选择、工艺应用参数的确定等提供参考数据。     

POP-290阻燃剂对丙烯酸酯光固化涂料的影响

制备了双酚A环氧丙烯酸酯(EA)/阻燃剂(POP-290,聚合物聚醚多元醇)/活性单体阻燃UV涂料,主要考察了不同用量的阻燃剂对丙烯酸酯UV涂料的阻燃性能和光固化的影响.研究结果表明,阻燃剂的使用提高了UV涂料体系的固化速度、凝胶含量及玻璃化转变温度(T_g).当m(EA):m(活性单体)=4:1,POP-290含量为7%(质量分数)时,水平燃烧等级达到FH-1,LOI从原来的21提高到26.     

光/潮气双重固化聚氨酯涂层的制备及性能研究

以甲苯-2,4-二异氰酸酯(TDI)和二乙醇胺(DEOA)为原料一步法合成了超支化聚氨酯,对其改性制备了光固化超支化聚氨酯丙烯酸酯(HPUA)和一系列双重固化(UV/潮气)超支化聚氨酯丙烯酸酯(DHPUA),使用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)以及凝胶色谱(GPC)对其分子结构进行了表征.并以其为预聚物制备光固化涂层,通过对双重固化涂层的表面形貌、热性能和物理性能的研究,结果表明,超支化双重固化涂层经过潮气固化后,涂层表面的粗糙度随着树脂中硅氧烷端基的含量的增加先下降后上升;超支化双重固化涂层的物理性能和热稳定性都随着树脂中硅氧烷端基的含量的增加而提升.     

UV固化涂料在修复底漆中的应用

综述了UV固化技术和UV固化涂料等相关领域的发展状况,以BASF公司在2005年获得美国总统绿色化学奖的产品为实例,通过与传统产品的对比全面地介绍了绿色环保底漆的组成成分、固化机理和影响因素,最后对UV固化涂料在绿色环保车漆领域的应用展望做一总结。     

紫外线固化喷墨打印墨水的研究及应用进展

紫外线(Ultra Violet, UV)固化喷墨打印技术将打印技术与UV固化系统结合，集成了喷墨打印技术无接触、操作简单、低成本及UV固化后无溶剂残留、环保的特点，广泛应用于印制电路板中阻焊层的制备，陶瓷材料、盲文及电子器件的制备，纺织品制造，木材表面的修饰或保护等领域。UV固化喷墨打印墨水是该技术的关键原料，它主要由UV单体、UV预聚物、光引发剂、添加剂及助剂等组成，并根据不同应用要求添加功能材料，如金属、金属氧化物、碳纳米材料或量子点等。UV固化喷墨打印技术用于阻焊层制备时的关键在于墨水固化后形成的涂层与基材粘附力的调控，涂层与基材结合既要保证阻焊的效果，又要在阻焊后易于分离并去除。了解UV固化喷墨打印技术在应用中的各种关键因素及对策，对于其进一步推广应用具有重要意义。     

用于UV固化的水性超支化聚酯合成及膜性能

以三羟甲基丙烷、2,2-双(羟甲基)丙酸、甲基四氢邻苯二甲酸酐、甲基丙烯酸缩水甘油酯、三乙醇胺作为原料合成了三种可UV固化的超支化聚合物，分别命名为UVHBP33、UVHBP42、UVHBP51，并对80%～90%固含量的UVHBP的粘度及水溶性进行了表征，粘度范围为4592～9973 cps^-1，室温和加热下具有较为良好的水溶性，可以保证涂料施工性。后续以三种UVHBP作为成膜物质，在马口铁板上进行UV固化，并对固化膜进行了性能表征。结果表明随着交联密度的提升，UVHBP51经UV固化后具有最优的涂层使用性能，硬度H级、涂层附着力5B级。热重实验表明UVHBP51优于UVHBP33和UVHBP42。     

NEPE推进剂固化交联的流变学研究

采用动态流变学方法研究了硝酸酯增塑聚醚(NEPE)推进剂的固化历程. 结果表明, 推进剂固化初期(黏流态)的储能模量(G′)和损耗模量(G″)随时间增加缓慢增大, G′gel)缩短, 但推进剂在凝胶点和固化结束时的储能模量G′_gel(622~781 Pa)和G′_∞(831.1×10³~868.3×10³ Pa)的变化不大. 推进剂在固化初期(反应控制阶段)符合一级反应动力学关系, 推进剂的固化过程符合Hsich动力学模型, 由反应速率常数(k_c)、凝胶时间(t_gel)和特征松弛时间(τ)得到推进剂的表观反应活化能ΔE_c, ΔE_g和ΔE_τ分别为129.6, 122.1和120.6 kJ/mol.     

紫外光固化水性油墨及墨膜耐磨性能

传统紫外光固化(UV)油墨具有粘度低、固化速度快、应用范围广等优点。 但存在使用少量有机溶剂、交联程度低等缺陷。 本文通过自由基聚合制备的苯乙烯丙烯酸共聚物与甲基丙烯酸羟乙酯(HEMA)反应制备水性预聚物。 通过甲基丙烯酸缩水甘油酯(GMA)和乙二胺反应制备了含有四丙烯酸官能团的活性稀释剂。 最后,通过水性预聚物、活性稀释剂、光引发剂以及少量溶剂制备了UV光固化水性油墨。 探讨了光引发剂的种类和质量分数、预聚物的相对分子质量和质量分数、活性稀释剂的结构和质量分数对UV油墨的光固化速度以及耐磨度的影响。 当预聚物的数均相对分子质量为1.98×10⁵且质量分数为30%、光引发剂质量分数为4%、活性稀释剂的官能团数目为4且质量分数为40%的UV水性油墨的光固化速率为1 s,经50次磨损质量损失为9%。 该方法所制得的UV水性油墨可用于柔版印刷、凹印、数字印刷等。     

Characterization of a clear coating cured by UV/EB radiation

The quality and performance of the polymeric materials cured by ultraviolet (UV)/electron beam (EB) radiation depends on the components of coating formulation, as well as the type of radiation used in the curing process. The aim of this study was to establish the correlation between the cure degree of a clear coating irradiated with different radiation doses of UV or EB and the tensile properties of the polymeric films obtained. The cure degree was measured by DSC and FTIR.     

紫外光-热双固化聚苯胺防腐涂料

以酸性磷酸酯为掺杂剂对本征态聚苯胺(EB)进行掺杂,制备了可在聚氨酯和聚氨酯丙烯酸酯中进行纳米分散的导电聚苯胺(ES),其粒径分布在80~750 nm之间可控。 在此基础上,制备了不含重金属的紫外光-热双固化聚苯胺防腐涂料。 该防腐涂料先后经过3~5 s紫外光固化和80 ℃下1~3 min的热固化,即可完成紫外光-热双固化过程。 由于ES与聚氨酯或聚氨酯丙烯酸酯之间是不相容体系,因此随着ES质量分数的增大,会导致ES的团聚,分散粒径增大。 当ES质量分数从1.0%增大到5.0%时,ES的粒径从80~119 nm增加到500~750 nm。 ES的分散粒径增大会导致防腐涂层的致密性变差,降低防腐效果。 与普通紫外光固化聚苯胺防腐涂层相比,当ES为1.0%时,紫外光-热双固化防腐涂层在质量分数为3.5%的NaCl水溶液中浸泡2160 h后,其0.1 Hz下的绝对阻抗值(|Z|_{0.1 Hz})仍高于1.0×10⁸ Ω·cm²,优于普通紫外光固化聚苯胺防腐涂层的|Z|_{0.1 Hz}(1.0×10⁷ Ω·cm²),表明紫外光-热双固化涂层的防腐效果有了显著改善。 经过500 h划叉中性盐雾试验后,普通紫外光固化防腐涂层的板面出现了锈蚀宽度小于1 mm的锈蚀,而紫外光-热双固化防腐涂层经过500 h划叉中性盐雾试验,板面没有出现生锈、起泡的现象,表明紫外光-热双固化路线对提高涂层的防腐性能具有较大的价值。     

紫外光固化设备与光固化合物的研究

涂层紫外光固化技术由于在能源节省、产品质量以及环保方面的优势,正在不断的迅速发展.本文综述了近年来辐照设备的进步,以及紫外光固化体系所涉及的单体、齐聚体和光引发剂的研究发展情况.     

UV curing behaviors and hydrophilic characteristics of UV curable waterborne hyperbranched aliphatic polyesters

A series of waterborne hyperbranched polyesters (WBHPs) endcapped with methacrylic and salt-like groups in different ratios have been investigated as UV curable resins. The kinetic studies of the drying step and UV curing were carried out by FT-IR measurements. The drying of the film of 100 μm thickness was completed in less than 6 hr at 70°C or within 10 hr at 50°C in an oven. The influence of different photoinitiators and their concentrations, extent of unsaturation and acid content of WBHP on final unsaturation conversion was studied. The surface free energy is a critical character, which affects the surface properties of a cured film. So one method based on the measurement of contact angle of a pure liquid on a solid surface was applied to determine the polar and dispersive components of the surface energy of UV cured films. The investigations of surface energy of WBHPs illustrated that those with more acid content and thus higher polar component are more sensitive to water, while those containing less acid content and thus lower polar term are less water sensitive. Moreover, the UV cured films of WBHPs and their blends with commercial waterborne resins (trade name EB 210, EB 2002, EB 11 and IRR 160) have acceptable pendulum hardness varying from 55 to 180 sec. Copyright © 2003 John Wiley & Sons, Ltd.     

混杂光固化体系的原理及应用

混杂光固化或双重固化是指在同一体系中采用两种或两种以上不同类型的聚合反应来使体系固化的方法,它是原位改性高分子的一种新方法.混杂光固化体系包括自由基-阳离子混杂光固化体系、自由基-缩聚混杂体系和自由基-自由基混杂体系等.本文综述了混杂光固化体系的原理及其应用.     

Preparation of modified monomer and studies on EB radiation curing of polyurethane-acrylate in the air

Preparation of the monomer modified by phosphite is described. According to the results of IR, MS and ¹H-NMR, the possible synthesis path was deduced. The coating was made up of polyurethane acrylate, modified monomer, active diluent and so on. A non-tacky transparent film can be obtained after EB curing in the air. The experiment indicated that the modified monomer plays a great role in resisting oxygen inhibition. Furthermore, it reduces the radiation dose that the curing needs, and takes effect on radiation sensitization. The optimum radiation condition is 40 KGy. The gel content was used to express the curing extent and the relationship between dose and P-H bond conversion was studied.     

EB/UV treatment of protective coatings for porous materials

A method for improving surface properties of porous inorganic materials is presented. The method is particularly tailored to cement-based materials in order to obtain properties suitable for mechanical applications such as dies manufacturing, where hardness, abrasion resistance and low friction are requested. The coating system is based upon using two coatings of different characteristics. The underlying base coating layer is infiltrated in air on three different formulations of hardened cement composite. Two different bi-component resins, one relatively soft and the other relatively hard, were tested as underlying surface coating. The outer surface coating, based upon a bi-component resin characterized by high hardness, is added after hardening and curing of the first layer. Both coatings were chemically hardened and then cured with EB. UV curing is also suitable for the outer surface coating. An experimental campaign was carried out in order to evaluate the influence of radiation processing as curing treatment with reference to particular investigated materials. Hardness and resistance to peeling of coating systems have been measured and are presented.     

Oxygen Inhibition and Coating Thickness Effects on Uv Radiation Curing of Weatherfast Clearcoats Studied by Photo-DSC

Radiation curing is an environmentally-friendly technology. Furthermore, radiation curing is a faster, energy saving and more efficient industrial process than the heat-curable process. One of the most important requirements for the widespread application of UV curable coatings in the coating industry is that they are stable vs. atmospheric degradation. Today's state of the art in oxidative drying and thermosetting coatings is the use of light stabilizers to protect polymers vs. the damage of outdoor exposure. Oxygen has a detrimental effect on the cure response of free radical systems, especially in thin-film coatings. Differential photocalorimetry (photo-DSC) was used to investigate the oxygen effect and the use of light stabilizers on UV curing of photocurable formulations based on acrylate materials. Coating thickness influence was also considered. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electron beam curing — taking good ideas to the manufacturing floor

Acsion is exploiting several emerging electron beam EB applications ranging from composite curing and repair to viscose manufacturing. EB curing of composite structures offers several advantages: significantly reduced curing times; improvements in part quality and performance; reduced environmental and health concerns; improvements in material handling; and reduced overall manufacturing costs compared to thermal curing. The aerospace industry is developing EB technology in all of their market sectors, including military aviation and space products. Some specific products include cryogenic fuel tanks, improved canopy frames for jet aircraft, and the all-composite military aircraft. This paper discusses each of these opportunities.