CN102208539A - 一种柔性光电子器件用基板及其制备方法 - Google Patents
一种柔性光电子器件用基板及其制备方法 Download PDFInfo
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- CN102208539A CN102208539A CN 201110096764 CN201110096764A CN102208539A CN 102208539 A CN102208539 A CN 102208539A CN 201110096764 CN201110096764 CN 201110096764 CN 201110096764 A CN201110096764 A CN 201110096764A CN 102208539 A CN102208539 A CN 102208539A
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Abstract
本发明公开了一种柔性光电子器件用基板,包括柔性衬底和导电层,所述柔性衬底和导电层由以下两种方式中的一种构成:①所述柔性衬底为紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有碳纳米管;②所述柔性衬底为掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有掺杂碳纳米管的紫外光固化的有机硅胶粘剂。该基板解决了银纳米线薄膜粗糙度大以及银纳米线薄膜与柔性衬底之间结合力差的问题,提高了银纳米线薄膜的电导率和表面的平整度,增加了银纳米线薄膜与柔性衬底之间结合力。
Description
技术领域
本发明涉及有机光电子技术领域,具体涉及一种柔性光电子器件用基板及其制备方法。
背景技术
光电子技术是继微电子技术之后迅速发展的科技含量很高的产业。随着光电子技术的快速发展,太阳能电池、光影像传感器、平面显示器、薄膜晶体管等光电子产品都逐渐发展成熟,它们大大改善了人们的生活。同时,光电子信息技术在社会生活各个领域的广泛应用,也创造了日益增长的巨大市场。发达国家都把光电信息产业作为重点发展的领域之一,光电子信息领域的竞争正在世界范围展开。
目前有机光电子器件大都是制备在刚性基板(如玻璃或硅片上),他们虽然具有优良的器件性能,但抗震动,抗冲击的能力较弱,重量相对较重,携带不甚方便,在某些场合的应用受到很大的限制。人们开始试图将有机光电子器件沉积在柔性基板上而不是刚性基板上。
用柔性基板代替刚性基板的好处是产品更轻、不易破碎、所占空间小且更便于携带。但是,尽管有这些优点,用柔性基板代替刚性基板还存在许多限制,柔性器件的制备仍然有许多基础问题需要解决。对于柔性衬底来说,由于柔性衬底的表面平整性远不及刚性衬底,而对柔性衬底进行表面平滑处理要特殊的设备且工艺难度较大,提高了基板的生产成本;柔性衬底的水、氧透过率远大于刚性衬底,导致光电子器件受从基板透过的水氧的影响,降低了器件的性能。
对于电极层来说,常规的电极层材料In2O3:SnO2(ITO)用作柔性基板的电极存在以下缺点:(1)ITO中的铟有剧毒,在制备和应用中对人体有害;(2)ITO中的In2O3价格昂贵,成本较高;(3)ITO薄膜易受到氢等离子体的还原作用,功效降低,这种现象在低温、低等离子体密度下也会发生;(4)在柔性衬底上的ITO薄膜会因为柔性衬底的弯曲而出现电导率下降的现象;(5)采用厚的ITO层会降低透光率,50-80%的光线在玻璃、ITO和有机层吸收掉,采用薄的ITO层工艺难度较大。近年来,由于银纳米线薄膜具有较高的电导率和可见光透过率已成为潜在的可代替ITO的电极材料,但银纳米线薄膜存在表面粗糙度大以及银纳米线薄膜与柔性衬底之间结合力差的缺点,降低了基于银纳米线薄膜电极的光电子器件的性能。
因此,如果能够解决上述这些问题,将会使光电子器件得到更为广泛的应用和更加快速的发展。
发明内容
本发明所要解决的问题是:如何提供一种柔性光电子器件用基板及其制备方法,该基板解决了银纳米线薄膜粗糙度大以及银纳米线薄膜与柔性衬底之间结合力差的问题,提高了银纳米线薄膜表面的平整度,增加了银纳米线薄膜与柔性衬底之间结合力。
本发明所提出的技术问题是这样解决的:提供一种柔性光电子器件用基板,包括柔性衬底和导电层,其特征在于,所述柔性衬底和导电层由以下两种方式中的一种构成:①所述柔性衬底为紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有碳纳米管;②所述柔性衬底为掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂原料包括以下质量百分比的组份:92~99.5%的光敏性的聚硅氧烷、0.1~5%的光引发剂和0.4~6%的稀释剂和助剂。
按照本发明所提供的柔性光电子器件用基板,其特征在于,在第②种方式中碳纳米管的掺杂质量比小于或等于40%。
按照本发明所提供的柔性光电子器件用基板,其特征在于,所述光敏性的聚硅氧烷包括硫醇-烯烃官能化聚硅氧烷、丙烯酸酯化聚硅氧烷、环氧官能化聚硅氧烷、苯乙烯基聚硅氧烷和乙烯基醚官能化聚硅氧烷。
按照本发明所提供的柔性光电子器件用基板,其特征在于,所述光引发剂包括安息香及其衍生物安息香甲醚、安息香乙醚和安息香异丙醚、苯乙酮类、二苯甲酮和2-羟基-2-甲基-1-苯基丙酮、烷基苯基酮类、α-羟烷基苯酮类、乙酰苯衍生物、二苯基碘鎓盐、二芳基碘鎓盐和三芳基碘鎓盐。
按照本发明所提供的柔性光电子器件用基板,其特征在于,所述稀释剂包括甲苯、二甲苯、活性环氧树脂稀释剂、环醚、环内酯和乙烯基醚单体;所述助剂包括填充剂、稳定剂和交联剂。
一种柔性光电子器件用基板的制备方法,其特征在于,包括以下步骤:
①对表面粗糙度小于1nm的刚性基板(如玻璃或硅片)进行清洗,清洗后用干燥氮气吹干;
②采取旋涂或喷涂或自组装或喷墨打印或丝网印刷的方式在洁净的基板上制备银纳米线薄膜;
③在银纳米线薄膜上旋涂或喷涂掺杂碳纳米管的紫外光固化的有机硅胶粘剂层,或先旋涂或滴涂或喷涂含碳纳米管的溶液,再旋涂或滴涂或喷涂紫外光固化的有机硅胶粘剂层,所述紫外光固化的有机硅胶粘剂原料包括以下质量百分比的组份:92~99.5%的光敏性的聚硅氧烷、0.1~5%的光引发剂和0.4~6%的稀释剂和助剂;
④对刚性基板表面进行紫外光固化处理30秒;
⑤将银纳米线薄膜和固化后的紫外光固化的有机硅胶粘剂层或掺杂碳纳米管的紫外光固化的有机硅胶粘剂层剥离刚性基板表面,形成柔性导电基板;
⑥测试柔性导电基板的透过率、电导率和表面形貌的各项参数。
本发明的有益效果:本发明的导电层在粗糙度小的刚性基板上制备,导电层空隙中填充有碳纳米管或掺杂碳纳米管的紫外光固化的有机硅胶粘剂,将导电层从刚性基板表面剥离,形成柔性基板的导电层,不仅提高了导电层表面的平整度,而且增加了导电层的电导率;本发明的柔性衬底中的紫外光固化的有机硅胶粘剂具有高的可见光透过率、粘结度以及快速固化的特点,提高了柔性基板的可见光透过率,增加了导电层与柔性衬底之间的结合力,减少了制备柔性基板所需的时间。
附图说明
图1是本发明实施例1-9的柔性光电子器件用基板的结构示意图;
图2是本发明实施例1中的基板的可见光透过率。
其中,1、柔性衬底,2、导电层。
具体实施方式
下面结合附图以及实施例对本发明作进一步描述:
本发明的技术方案是提供一种柔性光电子器件用基板,如图1所示,器件的结构包括柔性衬底1,导电层2。
本发明中柔性衬底1为导电层的依托,它有较好的弯折性能,有一定的防水汽和氧气渗透的能力,有良好的化学稳定性和热稳定性,导电层2要求有良好的导电能力,柔性衬底1和导电层2由以下两种方式构成:①所述柔性衬底为紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有碳纳米管;②所述柔性衬底为掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
本发明中紫外光固化的有机硅胶粘剂各成份说明如下:
紫外光固化有机硅胶粘剂由于不仅具有有机硅的耐温、耐候、电绝缘性能、低表面张力和低表面能的优良性能,还具有可以室温固化、固化速率快、无污染等紫外光固化材料的优异特性。其预聚物主要包括:硫醇-烯烃官能化聚硅氧烷、丙烯酸酯化聚硅氧烷、环氧官能化聚硅氧烷、苯乙烯基聚硅氧烷以及乙烯基醚官能化聚硅氧烷。
乙烯基化聚硅氧烷紫外光固化体系早期研究较多。该体系的光响应速度快,特别是在光引发剂促进下,基本上不受氧的阻聚干扰,可形成柔软而富有弹性的固化膜。产品可应用于纤维或其它基材,包括纸张、金属、玻璃以及聚乙烯、聚丙烯和聚酯薄膜等。但该体系存在暗反应,体系的粘度将逐渐增加,固化膜的拉伸强度下降。
丙烯酸酯基化聚硅氧烷紫外光固化体系对基材的粘附性好,固化速率高,固化层的化学、物理稳定性好,通过调整配方可获得理想的粘度;但在光固化过程中常伴有体积收缩,产生收缩应力。在许多场合下,收缩都是一个不利因素。丙烯酸酯基化聚硅氧烷涂布在金属、玻璃、塑料等基材上时,收缩会导致涂层附着力下降;涂布在软性基材(如纸品、塑料薄膜)上时,收缩会导致基材卷皱。但瑕不掩瑜,丙烯酸酯基化聚硅氧烷以其高反应活性和低成本的优势赢得了市场,成为紫外光固化有机硅预聚物研究领域的热点。
环氧基聚硅氧烷的环氧基在发生阳离子光固化时,具有环张力的环氧基被打开,形成无张力的醚键,体积收缩很小,甚至为零,成为阳离子光固化体系中的主要产品。含不饱和双键的环氧基化合物主要是含乙烯基或烯丙基的环氧基化合物,如烯丙基缩水甘油基醚、缩水甘油基丙烯酸酯、双环己基戊二烯和4-乙烯基环氧化环己烯,其中光固化活性最高的是环氧化环己烯。例如,将4-乙烯基环氧化环己烯与聚硅氧烷的端硅氢键进行硅氢加成反应,得到脂环族的环氧基化聚硅氧烷。环氧基化聚硅氧烷可与多种成分混合,填料、颜料、交联剂、催化剂、紫外光吸收剂等都可以应用到环氧基化聚硅氧烷体系中。现在,环氧基化聚硅氧烷紫外光固化体系的应用越来越广泛,成为阳离子光固化体系中的主流产品。
苯乙烯基化聚硅氧烷紫外光固化体系的最大优点是价廉,其中苯乙烯基由于具有较高的光聚合反应活性,可将苯乙烯基引入到硅氧主链中进行紫外光固化,其目的主要是提高有机硅材料的硬度和其它力学方面的性能。但该体系存在的缺点也较多,如挥发性高、易燃、气味大、反应速度较慢等,固化性能也不如其它紫外光固化体系。
乙烯基醚基化聚硅氧烷的单体是含有HZC=CH-O-基的单体。由于,氧原子的孤对电子与双键发生共轭,使双键的电子云密度增大导致乙烯基醚基的C=C是富电子基团,聚合反应活性高于一般的烯类单体,在紫外光辐照下,可进行自由基聚合、阳离子电荷转移复合物交替共聚等反应。因此,乙烯基醚类的紫外光固化预聚物可应用种光固化体系中,如自由基固化体系、阳离子固化体系以及混杂固化体系。乙烯基醚类预聚物具有毒性低、气味小、反应活性,固化产物具有收缩小、冲击强度高等性能,其潜在应用领域广泛。但由于乙烯基醚类单体的价格较高,使乙烯基醚类紫外光固化有机硅材料在国内外还未获得普遍应用。
光引发剂:紫外光固化胶粘剂中,往往需要加入光活性化合物,以引发或加速反应的进行。按其作用机理的不同可以分为光引发剂和光敏剂。区别在于光引发剂在反应开始时,吸收适当波长及强度的光能,发生光物理过程达到其某一激发态,若该激发态能量大于断裂键所需要的能量,则产生自由基引发聚合;而光敏剂吸收光能至其某一激发态后,只是将能量在分子内或分子间进行转移,由获得能量的另一个分子产生自由基引发聚合。与光引发剂相比,光敏剂本身并不消耗或改变结构,它可以看作是光化学反应的催化剂。它的作用机理大致有三种:一是能量转移机理,二是夺氢机理,三是经生成电荷转移的光敏机理。已开发的具有实用价值的光引发剂有安息香及其衍生物和乙酰苯衍生物,光敏剂有二苯甲酮、硫杂蒽醌和米蚩酮。各种引发剂的稳定性、耐黄变性、引发速率各不相同,在不同的树脂体系中,引发效率也不一样,应根据不同场合的需要合理选用。如三烯丙基异氰脲酸酯和C(CH2OCCH2CH2SH)体系,分别用安息香甲醚、安息香乙醚,安息香异丙醚引发,固化时间分别为18s、20s、和25s,而用二苯甲酮引发时,固化时间仅为15s,同时固化物的透光率也会由于波长不同而差别较大,这要根据实际情况合理选用。
光引发剂的作用是在其吸收紫外光能量后,经分解产生自由基,从而引发体系中的不饱和键聚合,交联固化成一个整体。常用的自由基型光引发剂有裂解和提氢型两大类。
裂解型光引发剂:裂解型光引发剂主要有苯偶姻醚类(安息香醚类)、苯偶酰缩酮和苯乙酮等。裂解型光引发剂在吸收紫外光后皲裂,产生两个自由基,自由基引发不饱和基团聚合。苯偶姻醚类(安息香醚类)包括:安息香(Benzoin)、安息香甲醚、安息香乙醚(Benzoin ethyl ether)、安息香丁醚(Benzoin butyl ether)、安息香亏(Benzoin oxime)、安息香异丙醚;酰基膦氧化物包括:2,4,6三甲基苯甲酰二苯基氧膦(TPO)和(2,4,6-三甲基苯甲酰)苯基氧化膦(BAPO phenyl bis(2,4,6-trimethyl benzoyl)phosphine oxide)、苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)、四甲基哌啶酮氧化物(TMPO)、磷酸三乙酯(TEPO),它们是比较理想的光引发剂,具有很高的光引发活性,对长波近紫外线有吸收,适用于白色涂料和膜较厚的情况,而且具有很好的稳定性,不会变色或褪色。
提氢型引发剂:提氢型引发剂主要有二苯甲酮类和硫杂蒽酮类等。其中硫杂蒽酮类光引发剂在近紫外光区的最大吸收波长在380-420nm,且吸收能力和夺氢能力强,具有较高的引发效率。提氢型引发剂必须要有供氢体作为协同成份,否则,引发效率太低,以至不能付诸应用。三线态羰基游离基从供氢体分子的三级碳上比二级碳上或甲基上更有可能提取氢,接在氧或氮等杂原子上的氢比碳原子上的氢更易提取。这类供氢体有胺、醇胺(三乙醇胺、甲基二乙醇胺、三异丙醇胺等)、硫醇、N,N-二乙基-对二甲氨基苯甲酰胺。
二苯酮光引发体系,二苯酮需要与醇、醚或胺并用才能使烯类单体进行光聚合。主要包括:二苯甲酮、硫杂蒽醌、米蚩酮、二甲氧基苯甲基苯基酮(DMPA)、α-羟基-2,2二甲基苯乙酮(1173)、α-羟基环己基苯基酮(184)、α-胺烷基苯酮、2-甲基-1(4-甲琉基苯基)-2-吗啉基丙酮(MMMP)、2’2-二苯甲酰氨基二苯基二硫化物(DBMD)、(4-二甲氨基苯基)-(1-哌啶基)-甲酮、异丙基硫杂蒽酮(ITX)、(4-二甲氨基苯基)-(4-吗啉基)-甲酮、2-羟基-2-甲基-1-苯基-1-苯基-1-丙酮、二苯氧基二苯酮、羟基-2-甲基苯基丙烷-1-酮。以及混合体系,如可消除胶膜中的氧气对自由基聚合反应的阻聚作用的二苯甲酮与叔氨的配合引发剂体系;米蚩酮和二苯甲酮配合使用,可得到较便宜和很有效的引发剂体系。
阳离子型光引发剂:芳香硫鎓盐和碘鎓盐类引发剂具有优异的高温稳定性,与环氧树脂配合后也具有稳定性,所以被广泛应用于阳离子固化体系。但它们的最长吸收波长在远紫外区,在近紫外区没有吸收,一般要添加光增感剂,如:自由基引发剂或光敏染料进行增感。
此类引发剂包括:二甲苯基碘六氟磷酸盐(P1810)、羟基苯基碘鎓盐(HTIB)、4,4-双十二烷基苯碘鎓六氟锑酸盐、二甲苯基碘鎓盐、二苯基六氟砷酸碘鎓盐、[4-(2-羟基-3-丁氧基-1-丙氧基)苯基]苯碘鎓-六氟锑酸盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、[4-(4-苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸盐、4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、4,4′-二甲基二苯基碘鎓盐六氟磷酸盐(IHT-PI 820)、4,4′-二乙酰胺基二苯基碘六氟磷酸盐、3,7一二硝基二苯并环状碘鎓盐及3,7一二硝基二苯并环状溴鎓盐、四氟硼酸二芳基碘鎓盐、3,3′-二硝基二苯基碘鎓盐、3,3′-二硝基二苯基碘鎓盐和几种2,2′-二取代(碘、溴、氯)-5,5′-二硝基苯基碘鎓盐、碘化2-[2-(3-中氮茚)乙烯基]-1-甲基喹啉鎓盐、碘化4-(2-苯并噁唑)-N-甲基吡啶鎓盐、3-硝基苯基二苯基硫六氟磷酸盐、三芳基膦二氢咪唑鎓盐、三芳基膦1,1′-联萘二氢咪唑环鎓盐、3,7-二硝基二苯并溴五环盐、对甲基苯磺酸三苯基硫鎓盐、溴化三苯基硫鎓盐、(4-苯硫基-苯基)二苯基硫鎓六氟磷酸盐、4-(苯硫基)三苯基硫鎓六氟磷酸盐、3,3′-二硝基二苯基碘六氟磷酸盐、3-硝基苯基二苯基硫六氟磷酸盐、三苯基硫鎓盐、4-氯苯基二苯基硫六氟磷酸盐、3-硝基苯基二苯基硫六氟磷酸盐、4-乙酰胺基苯基二苯基硫六氟磷酸盐、3-苯甲酰基苯基二苯基硫六氟磷酸盐、三苯基硫氟硼酸盐、三苯基硫六氟磷酸盐、三苯基硫六氟锑酸盐、4-甲苯基二苯基硫六氟磷酸盐、六氟化磷三芳基硫鎓盐、六氟化锑三芳基硫鎓盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、1-(4′-溴-2′-氟苄基)吡啶鎓盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、{4-[4-(对硝基苯甲酰基)苯硫基]苯}苯基碘鎓六氟磷酸盐、{4-[4-(对甲基苯甲酰基)苯硫基]苯}苯基碘鎓六氟磷酸盐、{4-[4-(对甲基苯甲酰基)苯氧基]苯}苯基碘鎓六氟磷酸盐、[4-(对苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸盐、4,4-双十二烷基苯碘鎓六氟锑酸盐。
茂铁盐类:茂铁盐类光引发体系是继二芳香碘鎓盐和三芳香硫鎓盐后发展的一种新阳离子光引发剂,在光照下茂铁盐离子首先形成芳香基配位体,同时产生与一个环氧化合物分子配位的不饱和铁的络合物,此络合物具路易斯酸的特点并接着形成与三个环氧化合物分子配位的络合物,其中一个环氧化合物可开环形成阳离子,它能引发阳离子开环聚合反应,形成聚合物。在常温下由于二茂铁盐-环氧基配合物、环氧化合物阳离子活性种的形成需要时间,故需在外界加热的条件下,以提高聚合速度。
此类盐类包括:环戊二烯基-铁-苯盐、环戊二烯基-铁-甲苯盐、环戊二烯基-铁-对二甲苯盐、环戊二烯基-铁-萘盐、环戊二烯基-铁-联苯盐、环戊二烯基-铁-2,4-二甲基苯乙酮盐、乙酰基-环戊二烯基-铁-对二甲苯盐、环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、环戊二烯基-铁-2,4-二乙氧基苯盐、二茂铁四氟硼酸盐、甲苯茂铁四氟硼酸盐、环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、环戊二烯基-铁-1,4-二乙氧基苯盐、环戊二烯基-铁-氯苯盐、环戊二烯基-铁-(1,4-二乙氧基苯)六氟磷酸盐、环戊二烯基-铁-二苯醚六氟磷酸盐、1,10-邻二氮杂菲高氯酸亚铁盐、1,10-邻二氮杂菲硫酸亚铁盐环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、[1,1′-双(二苯基膦)二茂铁]二氯化镍、乙烯基二茂铁、N,N′-双二茂铁亚甲基丁二胺季铵盐、二茂铁甲酰胺、二茂铁酰基丙酸、乙酰基二茂铁、乙基二茂铁,丁酰基二茂铁,丁基二茂铁,N,N-二甲基-胺甲基二茂铁、1,1′-二苯甲酰基二茂铁、(3-羧丙酰基)二茂铁、1,1′-二溴二茂铁、氨基二茂铁。
高分子负载的光引发剂:光固化体系中,光引发剂在光固化过程中往往不是完全耗尽,未光解的部分会迁移到涂层表面,使涂层泛黄和老化,影响产品的质量;另一方面,一些引发剂和体系不相容或相容性不好,使其应用受到限制。为解决这些问题,人们将光引发剂高分子化。高分子化的引发剂相对低分子的引发剂具有如下优点:A、在聚合物链中能量迁移和分子间反应变得更加容易,使高分子光引发剂具有更高的活性。B、通过与非活性基团共聚,调节并设计光敏基团的距离,或改变光活性基团与主链的距离,从而获得具有不同光活性的引发剂。C、可以在同一高分子链引入不同的光活性基团,利用它们的协同效应来提高光敏效应。D、引发剂的高分子化,限制了引发剂的迁移,防止涂层变黄和老化。E、由于大多数光解碎片仍连在高分子基体上,因此,可以降低体系的气味和毒性。
引发剂的高分子化可以将引发剂直接连在高分子或低聚物的链上,如将硫杂蒽酮或酸基氧化膦等引入高分子链上;也可以在引发剂中引入可以发生聚合的官能团,使其在光固化过程中实现高分子化,如将二苯甲酮结构引入四丙烯酸酯中。
各种光引发剂的配伍也是近年来的一个研究方向,经过配伍后再使用,既可以降低成本,又可以扩大吸收波长的区域,提高紫外光辐射能量的吸收,从而获得好的固化效果。光引发剂的配伍既可以是同一类型之间,如同是自由基型的,例如Ciba新推出的Irgacure-1700就是由25%的(2,4,6-三甲基苯甲酰)苯基氧化膦(BAPO)和75%的α-羟基-2,2二甲基苯乙酮(1173)组成,Irgacure-1800就是由25%的BAPO和75%的α-羟基环己基苯基酮(184)组成等;也可以是由不同类型的引发剂组成,如自由基型的和阳离子型的光引发剂配伍,例如,将三芳基硫蒽盐和二苯甲酮配合,可以使环氧化合物的固化速度得到提高。
活性稀释剂,主要用于调节体系的粘度,也可影响固化速率和材料性能,包括甲苯、二甲苯、正己烷、活性环氧树脂稀释剂、环醚、环内酯和乙烯基醚单体。
催化剂可以选用二(2-乙基己酸)二丁基锡、二乙酸二丁基锡或二月桂酸二丁基锡等。其中二乙酸二丁基锡催化活性大,固化速度快。二月桂酸二丁基锡的活性较小,固化速度慢。
助剂:一般来说,为适应不同环境的粘结要求,紫外光固化胶粘剂中还需要加入各种助剂,如增塑剂、触变剂、填充剂、防静电剂、阻燃剂、偶联剂等。它们在胶粘剂中所占的分量虽然不多,有时却对胶的加工性能或粘结性能产生至关重要的作用。如三烯丙基异氰脲酸酯和C(CH2OCCH2CH2SH)在二苯甲酮的引发下,若加入1%的硅偶联剂CH2=CHSi(OCH2CH2OCH3)3,经紫外光固化后,置于80~100%湿度的环境下,一年后未发现变化,而若不加偶联剂,相同条件下,2日后粘结部位便发生白蚀,一周后胶层完全剥离下来。
增塑剂包括:壬二酸二异辛酯(DIOZ)、壬二酸二辛酯(DOZ)、邻苯二甲酸二己酯(DHP)、暌二酸二辛酯(DOS)、己二酸二辛酯(DOA)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二丙酯(DAP)、三丁氧基乙烯基磷酸酯、聚乙烯醇缩丁醛、乙酰柠檬酸三丁酯、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、己二酸二(丁氧基乙氧基)乙酯、钛酸异丙酯、钛酸正丁酯、柠檬酸三乙酯、柠檬酸三丁酯、乙酰柠檬酸三丁酯、偏苯三酸三(2-乙基)己酯(TOTM)、邻苯二甲酸二(2-乙基)己酯、癸二酸二(2-乙基)己酯(DOS)、一缩二乙二醇二苯甲酸酯(DEDB)、邻苯二甲酸酐、二丙二醇二苯甲酸酯、暌二酸二苄酯(DBS)、硬脂酸正丁酯(BS)、氯磺化聚乙烯(增韧弹性体)、磷酸三苯酯(TPP)、磷酸三(二甲苯)酯(TXP)、聚己二酸亚丙基酯(PPA)、环氧大豆油(ESO)、环氧硬脂酸辛酯(OES2)、氯化石蜡-42(CP-42)、氯化石蜡-48(CP-48)、氯化石蜡-52(CP-52)、二硬脂酸二甘醇(DEDR)、磷酸三苯甲酯(TCP)、磷酸二苯辛酯(DPO)、聚己二酸亚丁基酯(PBA)、环氧硬脂酸丁酯(BES)、氯代联苯(CDP)、二甲苯缩甲醛树脂(增塑剂FH)、轻石蜡型基础油(PROCESS OIL637)、大豆油、环烷类加工油(310)、W150软化油(石油碳氢化合物,氢化合成油)、锆铝系偶合剂、WB215(脂肪酸18%;脂肪酸脂52%;碳酸钙20%)。
偶联剂是一类具有两性结构的物质,它们分子中的一部分基团可与无机物表面的化学基团反应,形成强固的化学键合;另一部分基团则有亲有机物的性质,可与有机分子反应或物理缠绕,从而把两种性质大小不同的材料牢固结合起来。目前工业上使用的偶联剂按化学结构分为硅烷类、酰酸酯类、锆类和有机铬络合物四大类。其中在胶粘剂中应用较多的是硅烷类,如甲基乙烯基二氯硅烷、甲基氢二氯硅烷、二甲基二氯硅烷、二甲基一氯硅烷、乙烯基三氯硅烷、γ-氨丙基三甲氧基硅烷、聚二甲基硅氧烷、聚氢甲基硅氧烷、聚甲基甲氧基硅氧烷、γ-甲基丙烯酸丙醋基三甲氧基硅烷(KH-570)、γ-氨丙基三乙氧基硅烷(KH-550)、γ-缩水甘油醚丙基三甲氧基硅烷、氨丙基倍半硅氧烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、长链烷基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、双-(γ-三乙氧基硅基丙基)、苯胺甲基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲基硅烷、γ-巯基丙基三甲氧基硅烷、γ-巯基丙基三乙氧基硅烷。
流平剂是用来改善树脂的流平性能,防止缩孔和针眼等涂层弊病的产生,使涂膜平整,并可以提高光泽度,包括混合溶剂、有机硅、聚丙烯酸酯、醋酸丁酸纤维、硝化纤维素和聚乙烯醇缩丁醛。其中有机硅类,包含二苯基聚硅氧烷、甲基苯基聚硅氧烷、有机基改性聚硅氧烷、聚醚有机硅。
消泡剂是用来防止和消除涂料在制造和使用过程中产生气泡,防止涂层产生针眼等弊病。磷酸酯、脂肪酸酯和有机硅等都可以作消泡剂。具体有磷酸三丁酯、磷酸二丁酯、磷酸酯抑泡剂(AD-14L)、消泡王(FAG470)、消泡剂(FAG470)、消泡剂(BYK-141)、消泡剂(BYK 037)、三(丁氧基乙基)磷酸酯、三乙基磷酸酯、三丁基磷酸酯、磷酸三乙酯、磷酸三氯异丙基酯、磷酸三丁氧基乙基酯、聚氧丙烯聚氧乙烯和二醇或三醇醚的混合体(浅黄色至无色透明粘稠液体)、聚二甲基硅氧烷、甘油聚氧丙烯醚(GP330)、月桂醇聚醚、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯、聚醚、聚乙二醇脂肪酸酯、硬脂酸金属皂、聚脲、高碳醇脂肪酸酯复合物;有机硅消泡剂有聚醚改性有机硅氧烷、有机聚硅氧烷混合物、乳化硅油。
阻聚剂是用来减少存放时发生聚合,提高树脂的存储稳定性。常用的阻聚剂一般分为分子型阻聚剂和稳定自由基型阻聚剂,前者主要有:对苯二酚、对苯醌、酚噻嗪、β-苯基萘胺、对叔丁基邻苯二酚、亚甲基蓝、三(N-亚硝基-N-苯基羟胺)铝盐、氯化亚铜、三氯化铁等无机物以及硫黄等也可作阻聚剂稳定自由基型阻聚剂主要有1,1-二苯基-2-苦肼(DPPH)、2,2,6,6-四甲基哌啶氮氧自由基(TMP)、对苯二酚、乙酸烯丙酯、对羟基苯甲醚(MEHQ)、氮氧自由基哌啶醇、亚磷酸(2,2,6,6-四甲基哌啶氮氧自由基)混合酯、4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基(TMHPHA)、8%三(N-亚硝基-N-苯基羟胺)铝盐:92%的2-酚基乙氧基丙烯酸酯、4%三(N-亚硝基-N-苯基羟胺)铝盐、96%乙氧基单油三丙烯酸酯、氢醌甲基醚、阻聚剂铜盐、邻甲基对苯二酚、2,6-二叔丁基甲苯酚、二甲基对苯二酚、对叔丁基邻苯二酚(TBC)、邻苯二酚、对甲氧基苯酚、2.6-二叔丁基对甲酚、2.5-二叔丁基对苯二酚、对苯醌、甲基氢醌、1.4-萘醌,吩噻嗪、叔丁基对苯二酚(TBHQ)、邻仲丁基-4,6二硝基苯酚(DNBP)、乙二醇单丙醚、烷基苯磺酸胺盐、对-特丁基邻苯二酚、甲基丙烯酸甲酯(MMA)、2,4,6-三硝基苯酚(TNP)、2,4-二甲基-6-叔丁基苯酚(TBX)、N,N-二乙基羟胺(DEHA)、对特丁基邻苯二酚、2,5-二特丁基对苯二酚、邻甲基对苯二邻甲基对苯醌、3-特丁基-4-羟基苯甲醚(BHA)、2,6-二硝基对甲酚(DNPC)、聚乙烯醇缩乙醛、氮氧自由基哌啶醇、4,6-二硝基邻仲丁基酚、丁二酰丁二酸二甲酯(DMSS)、丙炔醇。
触变剂加入树脂中,能使树脂胶液在静止时有较高的稠度,在外力作用下又变成低稠度流体的物质。有机膨润土丁腈橡胶(NBR)、蒙脱石(Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2})、膨润土[(Nax(H2O)4(Al2-xMg0.83)Si4O10)(OH)2]、硅藻土(无定形的SiO2组成,并含有少量Fe2O3、CaO、MgO、Al2O3及有机杂质)、石棉、硅灰石(CaSiO3)、白云母(KAl2(AlSi3O10)(OH)2)、金云母(KMg3(AlSi3O10)(FOH)2)、镁硅白云母[K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)]、蒙脱石[Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2}]、膨润土[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2]、氢化蓖麻油、气相法二氧化硅、金属皂(硬脂酸铅、钡、镉、钙、锌、镁、铝、稀土)。在水性体系中则用羟乙基纤维素等纤维素衍生物,聚乙烯醇、聚丙烯酸、聚环氧乙烷、聚甲基丙烯酸、脲醛树脂、三聚氰胺甲醛树脂、甲阶段酚醛树脂、酚醛树脂水溶性树脂为增稠剂。
填充剂的作用是部分代替粘结剂,减少粘结剂的耗用量,以达到填充、补强、减磨和降低成本的效果。填充剂要求粒子细而匀,能均匀地分散于浆液中,对粘结剂和其他组分结合性良好。填充剂的用量应适当,否则也会影响浆膜质量。包括无机矿物膨润土丁腈橡胶(NBR)、硅铝酸钾钠(霞石)、碳酸钙、含水的矽酸镁[Mg3[Si4O10](OH)2]、硅灰石(CaSiO3)、白云母[KAl2(AlSi3O10)(OH)2)]、金云母[KMg3(AlSi3O10)(F,OH)2]、镁硅白云母[K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)]、蒙脱石[Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2}]、膨润土[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2]、高岭土、赤泥(Al1-xOx)、硫酸钙、丙烯酸酯高聚物、聚丙烯酸丁酯、聚氨酯。
分散剂促使物料颗粒均匀分散于介质中,形成稳定悬浮体的试剂。分散剂一般分为无机分散剂和有机分散剂两大类。常用的无机分散剂有硅酸盐类(例如水玻璃)和碱金属膦酸盐类(氨基三甲叉膦酸四钠、氨基三甲叉膦酸五钠、氨基三甲叉膦酸钾、羟基乙叉二膦酸钠、羟基乙叉二膦酸二钠、羟基乙叉二膦酸四钠、羟基乙叉二膦酸钾、乙二胺四甲叉膦酸五钠、二乙烯三胺五甲叉膦酸五钠、二乙烯三胺五亚甲基膦酸七钠、二乙烯三胺五甲叉膦酸钠、2-膦酸丁烷-1,2,4-三羧酸四钠、己二胺四甲叉膦酸钾盐、双1,6亚己基三胺五甲叉膦酸钠、三聚膦酸钠、六偏磷酸钠和焦磷酸钠等)。有机分散剂包括三乙基己基膦酸、氨基三甲叉膦酸、羟基乙叉二膦酸(HEDP)、乙二胺四甲叉膦酸钠(EDTMPS)、乙二胺四甲叉膦酸(EDTMPA)、二乙烯三胺五甲叉膦酸(DTPMP)、2-膦酸丁烷-1,2,4-三羧酸(PBTCA)、多元醇磷酸酯(PAPE)、2-羟基膦酰基乙酸(HPAA)、己二胺四甲叉膦酸(HDTMPA)、多氨基多醚基甲叉膦酸(PAPEMP)、双1,6亚己基三胺五甲叉膦酸(BHMTPMPA)、十二烷基硫酸钠、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、水解聚马来酸酐(HPMA)、马来酸-丙烯酸共聚物(MA-AA)、丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物(AA/AMPS)、丙烯酸-丙烯酸羟丙酯共聚物、丙烯酸-丙烯酸酯-膦酸-磺酸盐四元共聚物、丙烯酸-丙烯酸酯-磺酸盐三元共聚物、膦酰基羧酸共聚物(POCA)、聚丙烯酸盐、羧酸盐-磺酸盐-非离子三元共聚物、聚环氧琥珀酸钠(PESA)、聚天冬氨酸钠(PASP)、基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯等。
抗氧剂以抑制聚合物树脂热氧化降解为主要功能的助剂,属于抗氧化试剂的范畴。抗氧剂是塑料稳定化助剂最主要的类型,几乎所有的聚合物树脂都涉及到抗氧剂的应用。按照作用机理,传统的抗氧剂体系一般包括主抗氧剂、辅助抗氧剂和重金属离子钝化剂等。主抗氧剂以捕获聚合物过氧自由基为主要功能,又有“过氧自由基捕获剂”和“链终止型抗氧剂”之称,涉及芳胺类化合物和受阻酚类化合物两大系列产品。芳香胺类抗氧剂有:二苯胺、对苯二胺、N,N-双-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]己二胺、二氢喹啉;受阻酚类抗氧剂有:2,5-二特丁基对苯二酚、2,6-二叔丁基-4-甲基苯酚、叔丁基对苯二酚、2,5-二特丁基对苯二酚(DBHQ)、2,6-三级丁基-4-甲基苯酚、双(3,5-三级丁基-4-羟基苯基)硫醚、四[β-(3,5-三级丁基-4-羟基苯基)丙酸]季戊四醇酯;亚磷酸三苯酯(TPPi)、亚磷酸酯三(2,4-二特丁基苯基)酯、季戊四醇双亚磷酸酯二(2,4-二特丁基苯基)酯、多烷基双酚A亚磷酸酯的双聚体和三聚体的复合物、3,5-二叔丁基-4-羟基苄基二乙基膦酸酯、亚磷酸三(2,4-二叔丁基苯基)酯、β-(4-羟基苯基-3,5-二叔丁基)丙酸正十八碳醇酯、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯甲基)苯。辅助抗氧剂具有分解聚合物过氧化合物的作用,也称“过氧化物分解剂”,包括硫代二羧酸酯类和亚磷酸酯化合物,通常和主抗氧剂配合使用。双十二碳醇酯、双十四碳醇酯、硫代二丙酸双十八酯(DSTP)、硫代二丙酸双酯、双十八碳醇酯、硫代二丙酸双月桂酯、三辛酯、三癸酯、三(十二碳醇)酯和三(十六碳醇)酯、3,6,9-三氧杂癸烷-1,11-二醇-双-正十二烷巯基丙酸酯、磷酸三苯酯TPP、亚磷酸三壬基苯酯、亚磷酸辛基二苯基酯。
重金属离子钝化剂,俗称“抗铜剂”,能够络合过渡金属离子,防止其催化聚合物树脂的氧化降解反应,典型的结构如酰肼类化合物等。最近几年,随着聚合物抗氧理论研究的深入,抗氧剂的分类也发生了一定的变化,最突出的特征是引入了“碳自由基捕获剂”的概念。这种自由基捕获剂有别于传统意义上的主抗氧剂,它们能够捕获聚合物烷基自由基,相当于在传统抗氧体系中增设了一道防线。此类稳定化助剂主要包括2-乙基苯并呋喃酮、2-甲基苯并呋喃酮、二氢苯并呋喃酮、苯并呋喃酮、二苯并呋喃酮、3-芳基-苯并呋喃-2-酮、3-芳基苯并呋喃酮、2-芳基二氢苯并呋喃酮、2-芳基苯并呋喃酮、5-氰基-1-(4-氟苯基)-1,3-二氢异苯并呋喃酮、5-取代1-(4-氟苯基)-1,3-二氢异苯并呋喃酮、2,3-二羟基-2,2-二甲基-7-苯并呋喃酚、3-(2-酰氧基乙氧基苯基)苯并呋喃-2-酮、异苯并呋喃酮、5-[(咪唑并[4,5-b]吡啶-3-基)甲基]苯并呋喃酮、1,2,3,4-四氢-苯并呋喃酮、2,3-二氢-2-甲基-2-烷基苯并呋喃酮、4-乙氧基双酚-A-二丙烯酸酯、(2-10)-乙氧化双酚-A-二甲基丙烯酸酯、2-[1-(2-羟基-3,5-二特戊基苯基)-乙基]-4,6-二特戊基苯基丙烯酸酯、双酚-A-丙三醇双甲基丙烯酸酯、双酚-A-二甲基丙烯酸酯、4-乙氧基双酚-A-二甲基丙烯酸酯、N,N-二苄基羟胺、N-乙基-N-羟基乙胺、N,N-二乙基羟胺、异佛尔酮二胺丙烯酰胺硫酸羟胺、异丙基羟胺、盐酸羟胺、氯化羟铵、氢氯羟胺、N-甲基-羟胺、醋羟胺酸、N-羟基乙酰胺。
加工改性剂旨在改善塑化性能、提高树脂熔体黏弹性和促进树脂熔融流动的改性助剂,此类助剂以丙烯酸酯类共聚物(ACR)为主。
抗冲击改性剂提高硬质聚合物制品抗冲击性能的助剂。主要包括氯化聚乙烯(CPE)、丙烯酸酯共聚物(ACR)、甲基丙烯酸酯-二烯-乙烯共聚物(MBS)、乙烯-烯基醋酸酯共聚物(EVA)和丙烯腈-二烯-乙烯共聚物(ABS)等。聚丙烯增韧改性中使用的三元乙丙橡胶(EPDM)亦属橡胶增韧的范围。
抗静电剂的功能在于降低聚合物制品的表面电阻,消除静电积累可能导致的静电危害,主要包括为阳离子表面活性剂和阴离子表面活性剂。阳离子表面活性剂有:烷基磷酸酯二乙醇胺盐、十八烷基二甲基苄基氯化铵、硬脂酰三甲基氯化铵、硬脂酰胺、硬脂酰二甲基戊基氯化铵、N,N-双(2-羟乙基)-N-(3’-十二烷氧基-2’-羟基丙基)甲铵硫酸甲酯盐、三羟乙基甲基季铵硫酸甲酯盐、硬脂酰胺丙基二甲基-β-羟乙基铵二氢磷酸盐、N,N-十六烷基乙基吗啉硫酸乙酯盐、(月桂酰胺丙基三甲基铵)硫酸甲酯盐二溴化N,N-二(十八烷基二甲基)-3-氧杂-1,5-戊二铵、苯乙烯聚合物型季铵盐、棕榈酸酯季铵盐、烷基酚聚氧乙烯基季铵盐、双烷基季铵盐、聚丙烯酰胺季铵盐、十八烷基二甲基羟乙基季铵硝酸盐、聚苯乙烯磺酸铵盐、丙基二甲基-β-羟乙基硝酸盐,(3-月桂酰胺丙基)三甲基铵硫酸甲酯盐、2,2′-次氮基双乙醇与α-三癸基-ω-羟基聚(氧-1,2-乙二基)磷酸酯的聚合物、聚乙二醇十三烷基醚磷酸酯、二乙醇胺盐、油酸二乙醇胺盐、油酸三乙醇胺盐、乙氧化胺、N,N-二羟乙基十八胺、N,N-二羟乙基对甲苯胺、烷基酚聚氧乙烯基季铵盐、羟乙基季铵盐、氧杂含氟季铵盐;阴离子表面活性剂有:脂肪醇醚磷酸酯、酚醚磷酸酯(TXP-4)、酚醚磷酸酯(TXP-10)、异十三醇磷酸酯、月桂基磷酸酯(MA24P)、脂肪醇醚磷酸酯钾(MOA-3PK)、酚醚磷酸酯钾盐(NP-4PK)、酚醚磷酸酯钾盐(NP-10PK)、异十三醇醚磷酸酯钾盐、月桂基磷酸酯钾盐(MA24PK)、脂肪醇磷酸酯钾盐、烯丙基磺酸钠;非离子表面活性剂:烷基胺与环氧乙烷的缩合物、烷醇酰胺、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、双(β-羟乙基)椰油胺、双(β-羟乙基)硬脂胺、双(β-羟乙基)牛油胺、六甲基磷酰三胺、全氟烷基乙醇聚氧乙烯醚。
阴阳两性型表面活性剂包括:十二烷基-二甲基季铵乙内盐、十二烷基二甲基季铵乙内盐、烷基二羟乙基铵乙内盐、N-烷基氨基酸盐、环氧三聚体磺酸内盐、羧基甜菜碱、十三烷基二甲基(2-亚硫酸)乙基铵乙内盐、N-十二烷基丙氨酸、3-氯丙胺盐酸盐、N-叔丁氧羰基-D-3-(2-萘基)-丙氨酸、N-叔丁氧基羰基-D-2-萘丙氨酸、叔丁氧羰基-D-2-萘丙氨酸、叔丁氧羰基-D-3-(2-萘基)-丙氨酸、N-叔丁氧羰基-L-2-三氟甲基苯丙氨酸、草甘膦异丙胺盐。
高分子型抗静电剂包括:聚环氧乙烷(PEO)、聚醚酯酰亚胺、聚乙烯乙二醇甲基丙烯酸共聚体、聚醚酯酰胺(PEEA)、聚醚酯乙酰胺(PEAI)、聚氧化乙烯、环氧丙烷共聚物(PEO-ECH)、聚乙二醇甲基丙烯酸酯(PEGMA)、甲基丙烯酸(MAA)、甲基丙烯酸十八烷基酯(SMA)+聚乙二醇甲基丙烯酸酯(PEGMA)组成的两亲性共聚物。
阻燃剂中无机阻燃剂包括三氧化二锑、钼酸锌、氧化锌、氧化铁、氧化锡、氢氧化铝、氢氧化镁、氧化锑、硼酸锌和赤磷;有机阻燃剂包括十溴二苯醚、三(2,3-二溴丙基)磷酸酯、六溴环十二烷、聚2,6-二溴苯醚、氯化石蜡、多磷酸酯、红磷、双(四溴邻苯二甲酰亚胺)乙烷、二溴苯乙烯均聚物、三聚氰胺、三聚氰酸盐、异癸基二苯基磷酸酯、乙基己基二苯基磷酸酯、磷酸三异丙苯酯、双(2氯乙基)乙烯基膦酸酯、乙撑双[三(2氰乙基)溴化磷盐]、N,N双(2羟乙基)氨甲基膦酸二乙酯、聚苯基膦酸二苯砜酯、聚苯基膦酸二苯偶氮酯、聚苯基膦酸双酚A酯。
防霉剂又称微生物抑制剂,是一类抑制霉菌等微生物生长,防止聚合物树脂被微生物侵蚀而降解的稳定化助剂。绝大多数聚合物材料对霉菌并不敏感,但由于其制品在加工中添加了增塑剂、润滑剂、脂肪酸皂类等可以滋生霉菌类的物质而具有霉菌感受性。塑料用防霉剂所包含的化学物质很多,比较常见的品种包括有机金属化合物(如有机汞、有机锡、有机铜、有机砷等)、含氮有机化合物、含硫有机化合物、含卤有机化合物和酚类衍生物等。其中包括苯酚、五氯酚、油酸苯基汞、8-羟基喹啉铜、氯化三乙或三丁基锡、硫酸铜、氯化汞、氟化钠。
增感剂为对二甲氨基苯甲酰胺;促进剂中氨丙基倍半硅氧烷与低分子聚酰胺质量比为3∶1。
稳定剂是用来减少存放时发生聚合,提高树脂的存储稳定性。常用的稳定剂有对苯二酚、对甲氧基苯酚、对苯醌、2,6-二叔丁基甲苯酚、酚噻嗪、蒽醌、叔胺等。
以下是本发明的具体实施例:
实施例1
如图1所示基板结构,柔性衬底1采用紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂包括96%的光敏性的聚硅氧烷、2%的光引发剂和2%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充碳纳米管。
制备方法如下:
①对表面粗糙度小于1nm的硅基板进行清洗,清洗后用干燥氮气吹干;
②将银纳米线均匀分散在溶剂中,采取旋涂方式在洁净的硅基板上制备银纳米线薄膜,旋涂时转速为4000转/秒,时长60秒,膜厚约为80纳米;
③在银纳米线薄膜上喷涂含碳纳米管的溶液,将硅基板在80℃的环境中放置30分钟,除去银纳米线薄膜中残存的溶剂,再在银纳米线薄膜上喷涂紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂包括96%的光敏性的聚硅氧烷、2%的光引发剂和2%的稀释剂和助剂;
④对硅基板表面进行紫外光固化处理30秒;
⑤将银纳米线薄膜和固化后的紫外光固化的有机硅胶粘剂层剥离硅基板表面,形成柔性导电基板;
⑥测试柔性导电基板的透过率、电导率和表面形貌的各项参数。
实施例2
如图1所示基板结构,柔性衬底1采用紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂包括92%的光敏性的聚硅氧烷、5%的光引发剂和3%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充碳纳米管。
制备方法与实施例1相似。
实施例3
如图1所示基板结构,柔性衬底1采用紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂包括92%的光敏性的聚硅氧烷、2%的光引发剂和6%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充碳纳米管。
制备方法与实施例1相似。
实施例4
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为5%,所述紫外光固化的有机硅胶粘剂包括99.5%的光敏性的聚硅氧烷、0.1%的光引发剂和0.4%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
实施例5
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为10%,所述紫外光固化的有机硅胶粘剂包括95%的光敏性的聚硅氧烷、2%的光引发剂和3%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
实施例6
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为15%,所述紫外光固化的有机硅胶粘剂包括97%的光敏性的聚硅氧烷、1%的光引发剂和2%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
实施例7
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为20%,所述紫外光固化的有机硅胶粘剂包括98%的光敏性的聚硅氧烷、1%的光引发剂和1%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
实施例8
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为30%,所述紫外光固化的有机硅胶粘剂包括98%的光敏性的聚硅氧烷、1.6%的光引发剂和0.4%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
实施例9
如图1所示基板结构,柔性衬底1采用掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述碳纳米管的掺杂质量比为40%,所述紫外光固化的有机硅胶粘剂包括99%的光敏性的聚硅氧烷、0.4%的光引发剂和0.6%的稀释剂和助剂,导电层2采用银纳米线薄膜,所述银纳米线薄膜的空隙中填充掺杂碳纳米管的紫外光固化的有机硅胶粘剂。
制备方法与实施例1相似。
Claims (6)
1.一种柔性光电子器件用基板,包括柔性衬底和导电层,其特征在于,所述柔性衬底和导电层由以下两种方式中的一种构成:①所述柔性衬底为紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有碳纳米管;②所述柔性衬底为掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述导电层为银纳米线薄膜,所述银纳米线薄膜的空隙中填充有掺杂碳纳米管的紫外光固化的有机硅胶粘剂,所述紫外光固化的有机硅胶粘剂原料包括以下质量百分比的组份:92~99.5%的光敏性的聚硅氧烷、0.1~5%的光引发剂和0.4~6%的稀释剂和助剂。
2.根据权利要求1所述的柔性光电子器件用基板,其特征在于,在第②种方式中碳纳米管的掺杂质量比小于或等于40%。
3.根据权利要求1所述的柔性光电子器件用基板,其特征在于,所述光敏性的聚硅氧烷包括硫醇-烯烃官能化聚硅氧烷、丙烯酸酯化聚硅氧烷、环氧官能化聚硅氧烷、苯乙烯基聚硅氧烷和乙烯基醚官能化聚硅氧烷。
4.根据权利要求1所述的柔性光电子器件用基板,其特征在于,所述光引发剂包括安息香及其衍生物安息香甲醚、安息香乙醚和安息香异丙醚、苯乙酮类、二苯甲酮和2-羟基-2-甲基-1-苯基丙酮、烷基苯基酮类、α-羟烷基苯酮类、乙酰苯衍生物、二苯基碘鎓盐、二芳基碘鎓盐和三芳基碘鎓盐。
5.根据权利要求1所述的柔性光电子器件用基板,其特征在于,所述稀释剂包括甲苯、二甲苯、活性环氧树脂稀释剂、环醚、环内酯和乙烯基醚单体;所述助剂包括填充剂、稳定剂和交联剂。
6.一种柔性光电子器件用基板的制备方法,其特征在于,包括以下步骤:
①对表面粗糙度小于1nm的刚性基板进行清洗,清洗后用干燥氮气吹干;
②采取旋涂或喷涂或自组装或喷墨打印或丝网印刷的方式在洁净的基板上制备银纳米线薄膜;
③在银纳米线薄膜上旋涂或喷涂掺杂碳纳米管的紫外光固化的有机硅胶粘剂层,或先旋涂或滴涂或喷涂含碳纳米管的溶液,再旋涂或滴涂或喷涂紫外光固化的有机硅胶粘剂层,所述紫外光固化的有机硅胶粘剂原料包括以下质量百分比的组份:92~99.5%的光敏性的聚硅氧烷、0.1~5%的光引发剂和0.4~6%的稀释剂和助剂。
④对刚性基板表面进行紫外光固化处理30秒;
⑤将银纳米线薄膜和固化后的紫外光固化的有机硅胶粘剂层或掺杂碳纳米管的紫外光固化的有机硅胶粘剂层剥离刚性基板表面,形成柔性导电基板;
⑥测试柔性导电基板的透过率、电导率和表面形貌的各项参数。
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