Development of Scratch- and Abrasion-Resistant Coating Materials Based on Nanoparticles,Cured by Radiation

The aim of this study was to compare the effect of monomers, prepolymers, and nanosilica on the scratch and abrasion resistance of nanocomposite coatings. Ultraviolet (UV) and electron beam (EB) curing were used to cure the nanocomposite coatings. The effect of monomers, prepolymers and nanosilica particles on the viscosity, pendulum hardness, gel content, scratch and abrasion resistance were studied. It was found that the optimum formulation for scratch and abrasion resistance contained 15% Ebecryl 600 epoxy acrylate resin with 30% monomer PETIA and 30% of Aerosil OX-50 nanosilica.     

全球辐射固化产业概况(二)

本文简述了辐射固化发展史,辐射固化的技术优势,以及该技术的工业应用进展。介绍了UV/EB固化产业的基本结构和产业价值链。列出了美国、欧洲、日本和中国辐射固化的产业概况,生产原材料、涂料、油墨和胶粘剂的主要企业,以及制造UV固化装置和电子加速器(EB装置)的主要厂家。以及随着经济全球一体化趋势,辐射固化产业内公司的重组与并购。     

全球辐射固化产业概况(一)

本文简述了辐射固化发展史,辐射固化的技术优势,以及该技术的工业应用进展。介绍了UV/EB固化产业的基本结构和产业价值链。列出了美国、欧洲、日本和中国辐射固化的产业概况,生产原材料、涂料、油墨和胶粘剂的主要企业,以及制造UV固化装置和电子加速器(EB装置)的主要厂家。以及隨着经济全球一体化趋势,辐射固化产业内公司的重组与并购。     

电子束固化木器清漆的制备及性能研究

电子束（ EB）固化技术作为一种重要的辐射固化技术，其固化的清漆涂层性能在许多方面优于紫外（ UV）光固化清漆涂层。本研究通过选取不同类型的商品化丙烯酸树脂及活性稀释剂配制木器涂料配方，分别利用电子束（ EB）和紫外光（ UV）对其进行固化，然后对固化后的涂层进行基本性能、热性能和机械性能的表征。研究结果表明： EB固化速度快，固化膜具有较高的铅笔硬度和附着力，而且树脂种类和单体结构的不同会对电子束固化涂层的热性能及机械性能产生影响。     

辐射固化的全球产业化与市场动态（一）

介绍辐射固化的产业基本结构和产业价值链。对全球高速发展的辐射固化企业进行了概述,包括美国、欧洲和日本的原材料生产企业,涂料、油墨和胶粘剂生产企业,以及UV和EB的设备制造企业。并对企业的整合以及辐射固化的市场现状与发展趋势进行了详细的综述与分析。     

紫外光固化涂料中活性单体的选择

紫外光(UV)固化涂料是以采用辐射固化技术为特征的环保节能型涂料。固化材料的各组分中,预聚物是光固化树脂的主体,它的性能基本决定了固化后材料的主要性能。重点讨论各类不同丙烯酸酯官能度化合物在紫外光固化涂料中的选用及配合,讨论了它们对涂料表面附着力、硬度、耐磨、耐腐等性能的影响。     

新型光学薄涂层材料的研制(英文)

本文以特殊异氰酸酯合成的六官能度脂肪族聚氨酯丙烯酸酯,己内基改性二(聚)季戊四醇六丙烯酸酯(DPHA)为主要成膜物质,采用UV固化的方法制备了一种具有超高耐磨性的新型光学薄涂层材料。讨论了光固化树脂、功能单体、光引发剂、助剂及辐照强度对固化涂层性能的影响,通过实验得出最优配方设计,并进行了简单的理论分析。结果表明:实验制备的涂层经0000#钢丝绒测试(1000g,130cycles),硬度4H、透过率99%以上,彩虹纹及表面晶点极少,并具有出色的柔韧性和良好的抗化学性;因此,它是IMD视窗、液晶荧幕、触控面板等产品理想的原材料。     

多重交联UV固化水性聚氨酯木器涂料的研制

通过UV固化和有机硅交联改性及多官能度扩链剂的引入,研制了多重交联UV固化水性聚氨酯木器涂料。形成的涂膜在UV固化前即具有较好的涂膜强度和机械性能,耐沾污;经UV固化后,涂膜具有更加优异的耐水性、耐醇性、耐磨性和耐干热性,以及良好的硬度和装饰效果。     

紫外/电子束辐射固化材料的市场发展趋势

分析了1998年以来紫外/电子束(UV/EB)辐射固化材料的全球市场需求量和销售量,重点介绍了近几年欧洲、北美、日本和中国等四个区域和国家的UV/EB辐射固化材料市场的发展情况。同时,对21世纪初世界该类辐射固化材料市场的发展趋势也进行了预测。     

辐射固化材料的市场及发展

近几年来,紫外/电子束(UV/EB)辐射固化技术在国内外都处于高速发展时期。在许多应用领域,辐射固化技术显示了它的优越性。一些UV/EB固化新技术、新材料的发展,将促进辐射固化技术和产品在新的应用领域的进展。通过“RadTechAisa2001”会议报道的一些数据,介绍了辐射固化市场的状况及趋势和新领域的技术进展。     

辐射固化涂料

介绍了辐射固化的原理,ＵＶ／ＥＢ固化涂料的配方构成、光源选择及原材料选择,并列举了各种用途的配方实例     

A macroscopically nondestructive method for characterizing surface mechanical properties of polymeric coatings under accelerated weathering

The surface of coatings and plastics is the first target in any degradation process initiated by ultraviolet (UV) radiation or mechanical stress (via scratch and abrasion). Surface damage can lead to changes in optical, morphological, and mechanical properties and can result in pathways for ingress of moisture and corrosive agents. Current test methods for monitoring performance of protective coatings focus on chemical properties and optical properties, such as color and gloss measurements, or invasive tests such as abrasion and cross-cut adhesion. In this study, a macroscopically nondestructive performance protocol using nanoindentation metrology via a well-controlled scratch test was applied to evaluate the scratch resistance and monitor the surface mechanical property changes in a protective coating under accelerated weathering. Polyurethane (PU) coatings with different polyol compositions were chosen for this study. Coating specimens were exposed to high-intensity UV radiation at 55°C and 75% RH conditions. Exposed specimens were removed at specified UV exposure times for surface modulus/hardness and scratch resistance characterization via nanoindentation and scratch test. The effect of polyol type and UV radiation dose on the scratch damage (scratch morphology) was investigated and correlated with the surface hardness and modulus of the materials.     

UV Curable Acrylate Nanocomposites: Properties and Applications

Transparent nanocomposites were prepared from nano-sized silica and radiation curable acrylates. To improve the embedding of silica nanoparticles within the acrylate matrix the filler surface was modified by trialkoxysilanes. Instead of an expected monomeric silane grafting polysiloxane structures were anchored on the nanoparticle surface due to acid catalyzed pre-hydrolysis/condensation of trialkoxysilanes. The polysiloxanes structures covering the silica surface were characterized by temperature-programmed oxidation, infrared and multinuclear MAS NMR spectroscopy. MALDI-TOF mass spectroscopy revealed the formation of polysiloxane oligomers with more than 20 monomeric silane units. Ladder-like polysiloxane chains have been proposed and atomic force microscopy were used to visualize the structure of surface-anchored organosilanes. These ladder-like structures are assumed to build up a short range interpenetrating network with polyacrylate chains during UV or EB curing.Due to the organophilic modification of silica nanoparticles reinforced acrylate formulations can contain up to 50 wt.-% nanofiller maintaining satisfactory rheological properties. These formulations can be used as coatings on substrates such as polymer films, paper, metal, wood, engineered wood, etc. After UV/EB curing nanoparticle reinforced polyacrylate coatings are obtained which show markedly improved properties as compared to neat polymers, e.g., increased microhardness and modulus, improved scratch and abrasion resistance, higher gas barriers and temperature resistance. Due to the nano-sized silica filler the cured coatings remain transparent, hazeless and glossy.On a pilot scale unit acrylate nanocomposite coatings are manufactured for roll coating, curtain coating and spray applications. Basic properties of acrylate nanocomposite coatings are described.     

紫外固化涂料固化工艺参数的研究

本文研究了UV固化工艺参数与涂层性能的关系,实验显示涂层厚度影响着涂层的硬度、附着力、柔韧性和耐磨擦性能,UV固化光源和制造环境对涂层材料性能同样有较大的影响.设计合理的涂层厚度,选择合适的固化工艺和环境条件,可以获得目标性能的涂层.     

紫外光固化涂料耐磨性研究

研究了紫外光固化漆膜的耐磨性，探讨了光固化树脂、活性单体以及耐磨粉料和光引发剂等各因素对耐磨性的影响。     

低能电子束辐射固化涂料的研究

以低能电子束处理多种配方的涂料,研究了辐射剂量、加速电压和氧气浓度对涂料固化性能的影响。结果表明：氧气浓度高于一定程度时将会导致涂层固化困难,辐射剂量对涂膜性能有着直接的影响,较高的加速电压有利于较厚涂层的固化。并对EB固化与UV固化后的涂膜性能进行了对比测试,表明EB固化涂料在性能上存在明显的优势。     

How to speed up the UV curing of water-based acrylic coatings

Water-based polyurethane-acrylate (PUA) coatings have been cured, after drying, by a short exposure to UV radiation in the presence of a radical-type photoinitiator. The light induced polymerization has been followed quantitatively by means of real-time infrared spectroscopy, by monitoring continuously the disappearance of the acrylate double bonds. The UV curing of the dry film was markedly accelerated by adding to the PUA formulation a reactive plasticizer (diacrylate monomer), by operating in a humid atmosphere or by raising the temperature. The neutralizer of the carboxylic groups, needed to get a stable dispersion, plays a key role in both the polymerization kinetics and in the hydrophilic character of the UV-cured polymer, the best performance being achieved by using a volatile tertiary amine. Water-based UV-cured PUA coatings combine hardness and flexibility and are, therefore, quite resistant to abrasion and scratching. Presented at the Spring 2003 Meeting of the American Chemical Society, March 23–27, New Orleans LA.     

Preparation and evaluation of epoxy methacrylate UV‐curable coatings containing phthalazinone

Epoxy methacrylate resin (EMA) UV‐curable coatings exhibit high reactivity, low viscosity and excellent chemical resistance in environmentally friendly coatings. A novel EMA containing phthalazinone moieties for high temperature resistant UV‐curable coatings was synthesized. The formulations were cured with hexanediol diacrylate (HDDA) and trimethylol propane triacrylate (TMPTA) as reactive diluents promoted by a photoinitiator, and then interpenetrating polymer networks were generated. The mechanical, chemical and thermal properties of the clear coatings were characterized using Chinese National Standard methods (GB). EMA was used with UV radiation curing in combination with 6.7 wt% of HDDA and 13.4 wt% of TMPTA, and the properties of the cured films were as follows: pencil hardness of 5 H, 30% NaOH resistance for 30 days, 15% HCl resistance for 10 days, 3% NaCl resistance for 30 days and 5% weight loss temperature of 300.5 °C. EMA UV‐curable coatings containing phthalazinone exhibit excellent chemical and thermal stability, and could be potential candidates for UV‐curable zero volatile organic compound coatings applied in the fields of salt spray corrosion, strong radiation and high‐temperature resistance. Copyright © 2009 Society of Chemical Industry     

全球辐射固化材料近期市场分析（一）

辐射固化技术于20世纪60～70年代,在欧美市场上初步确立了自身的产业地位,成为全球经济体系中的一个组成部分.各种专业分工不同的企业（原材料生产供应商、化学配方产品生产供应商、装置设备制造供应商和下游客户）,共同构建了UV/EB固化产业的价值链.近年来,世界三大主要地区（北美、欧洲和亚洲）辐射固化市场以近两位数的速度在增长,尽管全球经济形势持续低迷.2012年,全球辐射固化市场配方产品的消耗量据统计大约为457000t.亚洲市场消耗量已超过欧美市场而居全球首位.辐射固化配方产品在世界三大主要地区市场中应用的重点领域虽然各不相同,然而工业涂料在全球的市场份额中仍然比例最大.本文还列出了辐射固化原材料在不同市场中的消费量与价格.     

Effect of pigment colour on the printing performance of synthetic leather using a ultraviolet‐curable water‐borne polyurethane acrylate binder

The effect of pigment colours, cyan (C), magenta (M) and yellow (Y), and a blend of these (CMY blend) on the printing performance of synthetic leather using a ultraviolet (UV)‐curable water‐borne polyurethane acrylate binder and two types of photoinitiators was investigated. The curing process was carried out at different radiation doses using gallium and mercury UV lamps in combination. The performance of the prints was evaluated with abrasion resistance, crock fastness, gloss and hardness values and K/S. Chemical changes in the cured film structures due to UV curing were analysed by Fourier Transform–infrared spectroscopy measurements. The highest hardness values for clear and pigmented cured films were obtained with a gallium and mercury lamp combination at the highest energy density (1529 mJ/cm²). The highest K/S was obtained for the sample printed with the formulation including the C pigment and cured under a gallium and mercury lamp combination at low energy density (398 mJ/cm²). The M‐pigmented film displayed the highest hardness and abrasion resistance, whereas lower values were obtained with films pigmented with Y and C, and CMY blend, successively. The highest dry and wet crock values were obtained with the formulation including the M pigment. CMY‐pigmented film showed the highest gloss values at all energy densities. The pigment colour affected the curing degree of printed films due to the different absorption/transmission intervals of each colour in the UV spectrum.