CN104752627A - 生物可降解的柔性光电子器件用基板及其制备方法 - Google Patents
生物可降解的柔性光电子器件用基板及其制备方法 Download PDFInfo
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- CN104752627A CN104752627A CN201510194897.0A CN201510194897A CN104752627A CN 104752627 A CN104752627 A CN 104752627A CN 201510194897 A CN201510194897 A CN 201510194897A CN 104752627 A CN104752627 A CN 104752627A
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- heterojunction
- alloy
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Abstract
本发明公开了一种生物可降解的柔性光电子器件用基板及其制备方法,本发明包括柔性衬底和导电层,所述导电层位于柔性衬底的上方,所述柔性衬底为掺有紫外敏感胶的虫胶,所述紫外敏感胶的组分为:不饱和聚酯树脂或者丙烯酸系树脂、苯乙烯及其衍生物、光引发剂、光敏剂和助剂。本发明利用紫外敏感胶的交联作用,显著提高衬底的光透过能力,进而提高光电子器件的性能,同时增加了衬底的柔韧性,降低了水氧渗透率,改善了衬底表面平整度,增加了导电层在衬底上的附着力;该基板可生物降解,对环境无破坏,可在柔性光电子器件领域得到广泛应用。
Description
技术领域
本发明属于有机光电子技术领域,具体涉及一种生物可降解的柔性光电子器件用基板及其制备方法。
背景技术
柔性光电子器件的制备工艺中衬底的选择至关重要,它是柔性器件弯曲性能的关键所在,因此各国企业、研究机构都纷纷展开柔性衬底材料的研究工作。用于柔性光电子器件的衬底材料,通常具备以下特点:致密性好、平整性高、韧度强和光透过率高。目前用于研究的柔性衬底材料主要有聚合物塑料、柔性玻璃、金属薄片。而近年来,由于垃圾排放导致了不断恶化的生态环境,从而使保护生态环境的观念深入人心。因此,在光电子器件领域,也对使用的材料提出了新的要求——环保、可回收、可降解。
尽管聚合物塑料柔性较好、重量轻,但大多数塑料具有一定的毒性且不可降解,而且对水汽和氧气的渗透率过大,容易造成光电子器件寿命的大幅衰减;而柔性玻璃和金属薄片虽然具有一定的柔韧性,但是在更大机械作用力下还是会发生断裂、变形的现象,并且这两种衬底材料不可降解,对环境有一定的破坏作用。因此,采用生物可降解的柔性衬底材料是柔性光电子领域的发展方向。然而柔性器件的制备还存在许多限制,仍然有许多基础问题和工艺难题亟待解决。例如,首先,柔性衬底的表面能低,所以对要沉积的薄膜来说,附着力较差,此外,其表面平整度也远不及玻璃衬底。同时,前面提到柔性衬底的水氧阻隔能力至关重要,否则器件的电极材料和有机材料很容易被侵蚀,造成器件性能降低。此外,柔性衬底的光透过率也不如玻璃基板高,所以器件性能也不如基于玻璃衬底的器件。
发明内容
本发明为了解决上述问题,而提供一种生物可降解的柔性光电子器件用基板及其制备方法,提高柔性衬底的柔韧性,降低水氧渗透率,同时改善衬底表面的平整度,同时使导电层与柔性衬底结合更加牢固,并增加衬底的光透过能力;此外,这种基板具有生物可降解能力,能解决目前电子垃圾对大自然的污染问题,可广泛应用于今后柔性光电子器件的制备。
为解决上述技术问题,本发明所采用的技术方案是:
一种生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,所述导电层位于柔性衬底的上方,其特征在于,所述柔性衬底为掺有紫外敏感胶的虫胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂。
所述丙烯酸系树脂为聚酯-丙烯酸酯、环氧-丙烯酸酯或聚醚-丙烯酸酯中的一种或者多种。
所述增塑剂为三丁氧基乙烯基磷酸酯、钛酸异丙酯、钛酸正丁酯、柠檬酸酯、偏苯三酸(2-乙基)己酯、癸二酸二(2-乙基)己酯、一缩二乙二醇二苯甲酸酯、二丙二醇二苯甲酸酯或氯磺化聚乙烯中的一种或者多种。
所述紫外敏感胶在柔性衬底中所占的质量比为0.2-6%。
所述导电层的材料为石墨烯、碳纳米管、金属单质纳米线、金属合金纳米线、金属异质结纳米线、氧化锌、氧化钛、氧化铟锡或聚合物电极材料中的一种或多种。
所述金属单质纳米线为铁纳米线、铜纳米线、银纳米线、金纳米线、铝纳米线、镍纳米线、钴纳米线、锰纳米线、镉纳米线、铟纳米线、锡纳米线、钨纳米线或铂纳米线中的一种或者多种。
所述金属合金纳米线为铜铁合金纳米线、银铁合金纳米线、金铁合金纳米线、铝铁合金纳米线、镍铁合金纳米线、钴铁合金纳米线、锰铁合金纳米线、镉铁合金纳米线、铟铁合金纳米线、锡铁合金纳米线、钨铁合金纳米线、铂铁合金纳米线、银铜合金纳米线、金铜合金纳米线、铝铜合金纳米线、镍铜合金纳米线、钴铜合金纳米线、锰铜合金纳米线、镉铜合金纳米线、锡铜合金纳米线、钨铜合金纳米线、铂铜合金纳米线、金银合金纳米线、铝银合金纳米线、镍银合金纳米线、钴银合金纳米线、锰银合金纳米线、镉银合金纳米线、铟银合金纳米线、锡银合金纳米线、钨银合金纳米线、铂银合金纳米线、铝金合金纳米线、镍金合金纳米线、钴金合金纳米线、锰金合金纳米线、镉金合金纳米线、铟金合金纳米线、锡金合金纳米线、钨金合金纳米线、钴镍合金纳米线、锰镍合金纳米线、镉镍合金纳米线、铟镍合金纳米线、锡镍合金纳米线、钨镍合金纳米线、铂镍合金纳米线、镉锰合金纳米线、铟锰合金纳米线、锡锰合金纳米线、钨锰合金纳米线、铂锰合金纳米线、铟镉合金纳米线、锡镉合金纳米线、钨镉合金纳米线、铂镉合金纳米线、锡铟合金纳米线、钨铟合金纳米线、铂铟合金纳米线、钨锡合金纳米线、铂锡合金纳米线或铂钨合金纳米线中的一种或者多种。
所述金属异质结纳米线为铜铁异质结纳米线、银铁异质结纳米线、金铁异质结纳米线、铝铁异质结纳米线、镍铁异质结纳米线、钴铁异质结纳米线、锰铁异质结纳米线、镉铁异质结纳米线、铟铁异质结纳米线、锡铁异质结纳米线、钨铁异质结纳米线、铂铁异质结纳米线、银铜异质结纳米线、金铜异质结纳米线、铝铜异质结纳米线、镍铜异质结纳米线、钴铜异质结纳米线、锰铜异质结纳米线、镉铜异质结纳米线、锡铜异质结纳米线、钨铜异质结纳米线、铂铜异质结纳米线、金银异质结纳米线、铝银异质结纳米线、镍银异质结纳米线、钴银异质结纳米线、锰银异质结纳米线、镉银异质结纳米线、铟银异质结纳米线、锡银异质结纳米线、钨银异质结纳米线、铂银异质结纳米线、铝金异质结纳米线、镍金异质结纳米线、钴金异质结纳米线、锰金异质结纳米线、镉金异质结纳米线、铟金异质结纳米线、锡金异质结纳米线、钨金异质结纳米线、钴镍异质结纳米线、锰镍异质结纳米线、镉镍异质结纳米线、铟镍异质结纳米线、锡镍异质结纳米线、钨镍异质结纳米线、铂镍异质结纳米线、镉锰异质结纳米线、铟锰异质结纳米线、锡锰异质结纳米线、钨锰异质结纳米线、铂锰异质结纳米线、铟镉异质结纳米线、锡镉异质结纳米线、钨镉异质结纳米线、铂镉异质结纳米线、锡铟异质结纳米线、钨铟异质结纳米线、铂铟异质结纳米线、钨锡异质结纳米线、铂锡异质结纳米线或铂钨异质结纳米线中的一种或者多种。
所述聚合物电极材料为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)或3,4-聚乙烯二氧噻吩。
一种生物可降解的柔性光电子器件用基板的制备方法,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在刚性基板上采用辊涂、LB膜法、刮涂、旋涂、滴涂、喷涂、提拉法、流延法、浸涂、喷墨打印、自组装或丝网印刷制备柔性衬底,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;
③在柔性衬底表面采用辊涂、LB膜法、滴涂、喷涂、提拉法、喷墨打印或丝网印刷法制备导电层;
④对步骤③得到的柔性衬底进行紫外光处理;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板。
进一步,在基板制作完成后再对基板进行降解特性、方阻、表面形貌、水氧透过率和光透过率进行测试。
与现有技术相比,本发明具有以下有益效果:
(1)掺入紫外敏感胶的虫胶通过紫外处理后,虫胶中树脂分子结晶度降低,从而减小了光的散射,提高了光透过率,进而提高器件的性能。
(2)在虫胶中掺入适量的紫外敏感胶,通过紫外光处理后分子之间相互交联,分子排列更加致密,从而提高柔性衬底的机械强度,同时也增加了柔性基板的抗水氧能力。
(3)有效地增加了导电层在柔性衬底上的结合力。
附图说明
图1是本发明的生物可降解的柔性光电子器件用基板的结构示意图;
图中标记:1、导电层,2、柔性衬底。
具体实施方式
下面结合实施例对本发明作进一步的描述,所描述的实施例仅仅是本发明一部分实施例,并不是全部的实施例。基于本发明中的实施例,本领域的普通技术人员在没有做出创造性劳动前提下所获得的其他所用实施例,都属于本发明的保护范围。
结合附图,本发明提供的生物可降解的柔性光电子器件用基板,包括柔性衬底2和导电层1,导电层1位于柔性衬底2的上表面,柔性衬底2为导电层1的依托,柔性衬底2有一定的弯折性能,有一定的防水汽和氧气渗透的能力,有良好的平整性,有良好的透光性。
本发明中导电层1要求具有良好的成膜性能,良好的导电性,通常采用石墨烯、碳纳米管、金属单质纳米线、金属合金纳米线、金属异质结纳米线、氧化锌、氧化钛、氧化铟锡或聚合物电极材料中的一种或多种。
其中,虫胶是一种天然树脂,具有独特的优良特性,被广泛应用于食品、医药、塑料、军事、电气、橡胶、油墨、皮革、涂料、染料和粘合剂等行业。虫胶无毒,目前在医药工业中主要用于药丸药片的防潮糖衣、药品密封、上光、肠溶药包衣和近年发展起来的营养物与化妆品的胶囊等。紫胶涂料同样可用于食品工业的很多方面,可被人体吸收、可自然降解,例如糖果和糕点涂了紫胶涂料之后,可变得甚为美观、光亮,可以防潮、防结块、防变质和延长贮存时间等。水果用紫胶涂料涂膜后,能在一定时期内抑制水分蒸发,保持新鲜,减少腐烂,改善外观,产生提高经济效益的效果。虫胶产品具有较好的抗张强度、耐磨性、回弹性和硬度,具有理想的机械性能。电学性能方面,虫胶的介电强度高,介电常数低,且在受电弧支配后,无导电性,加上它有良好的粘着性和热塑性,在电器绝缘上有特殊的用途。另外,被水解的虫胶形成的薄膜比天然虫胶形成的薄膜更柔软,这与虫胶中软树脂的增加有关。但水解虫胶膜的水汽浸透性比用天然虫胶膜低一些,所以需要进行一些处理来保证虫胶的水氧阻隔能力。
不饱和聚酯树脂:不饱和聚酯是由不饱和的二元酸(或酸酐)混以部分饱和二元酸(或酸酐)与二元醇在引发剂的作用下起反应制成的线型聚酯。在其分子结构中有不饱和的乙烯基单体存在,如果用活泼的乙烯基单体与这类不饱和的乙烯基单体共聚,则交联固化而成为体型结构。一般来说,由这种树脂制得的胶粘剂由于固化过程中体积收缩较大,胶接接头的内应力很大。在胶层的内部容易出现微裂纹而导致胶接力变小;同时,由于高分子链中含有酯键,遇酸、碱容易水解,因而耐介质性和耐水性较差,在高温多湿的环境下容易变形;另外,其固化速度较慢,因此,表现出较差的综合性能,故大都作为非结构胶使用。通过降低不饱和化学键含量、采用聚合收缩率低的单体、加入无机填料和热塑性高分子等手段,可以改善其整体性能。
丙烯酸系树脂:该树脂体系固化速度快,目前研究得较多。
单体(苯乙烯及其衍生物等)通常和树脂配合使用,一方面作为稀释剂,使胶液具有便于施工的粘度;另一方面又具有反应性,固化后进入树脂网络,对固化物的最终性能具有一定的改善。早期使用的单体是苯乙烯及其衍生物,这类稀释剂交联速度慢、挥发性大且有毒、耐热性差。现在,多采用单官能团或多官能团(甲基)丙烯酸酯,如甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙二醇酯、丙烯酸正丁酯等,这些酯配制的胶粘剂普遍存在耐热性较差的问题,而且有些分子量较低的酯还存在挥发性大的缺陷。若分子结构中引入芳香环,则可以改善胶的强度和耐水性,延长胶的贮存期。对单体的要求主要是:低粘度、高稀释效果和高度的反应能力,同时还要兼顾挥发性、毒性和异味小,对树脂的相容性好等。为了调节各种性能参数,往往采用混合单体,混合单体如下:自由基活性稀释剂和阳离子活性稀释剂。
自由基活性稀释剂分为开发较早的第一代丙烯酸多官能单体、近期开发的第二代丙烯酸多官能单体和更优异的第三代丙烯酸单体。
单官能活性稀释剂有:苯乙烯、N-乙烯基吡咯烷酮、丙烯酸异辛酯、丙烯酸羟乙酯和丙烯酸异冰片酯、甲基丙烯酸酯磷酸酯及甲基丙烯酸异冰片酯,后两个为良好的增塑增韧单体。
双官能活性稀释剂有:三乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、乙二醇二丙烯酸酯、聚乙二醇(200)二丙烯酸醇酯、新戊二醇二丙烯酸酯和丙氧基新戊二醇二丙烯酸酯,丙烯酸酯官能单体主要有1,6-己二醇二丙烯酸酯(HDDA)、1,4-丁二醇二丙烯酸酯(BDDA)、丙二醇二丙烯酸酯(DPGDA)、丙三醇二丙烯酸酯(TPGDA)和三官能团的三经甲基丙烷三丙烯酸酯(TMPTA)、季戊四醇三丙烯酸酯(PETA)、三羟基甲基丙烷三醇三丙烯酸酯(TMPTMA)、三羟甲基丙烷三丙烯酸酯、丙氧基化三经甲基丙烷三丙烯酸酯、季戊四醇三丙烯醇酯和丙氧基化季戊四醇丙烯醇酯、N,N-二羟乙基-3胺基丙酸甲酯、二缩三乙二醇双甲基丙烯酸酯、长链脂肪烃缩水甘油醚丙烯酸、间苯二酚双缩水甘油醚、双季戊四醇五丙烯酸酯、二缩三丙二醇二丙烯酸酯。它们取代了活性小的第一代丙烯酸单官能单体。但随着UV固化技术的飞速发展,它们对皮肤的刺激性大的缺点显露出来。
克服了刺激性大的缺点,还应具有更高的活性和固化程度。第二代丙烯酸多官能单体主要是在分子中引入乙氧基或丙氧基,如乙氧基化三羟基甲基丙烷三醇三丙烯酸酯(TMP(EO)TMA)、丙氧基化三羟基甲基丙烷三醇三丙烯酸酯(TMP(PO)TMA)、丙氧基化丙三醇三丙烯酸酯(G(PO)TA)。第三代丙烯酸单体主要为含有甲氧基的丙烯酸酯,较好的解决了高固化速度与收缩率、低固化程度的矛盾。这类材料有1,6-己二醇甲氧基单丙烯酸酯(HDOMEMA)、乙氧基化新戊二醇甲氧基单丙烯酸酯(TMP(PO)MEDA)。分子中引入烷氧基后,可以降低单体的粘度,同时降低单体的刺激性。
烷氧基的引入对稀释剂单体的相容性也有较大提高,乙烯基三乙氧基硅烷(A15I)、γ-甲基丙烯酰氧丙基三甲氧基硅烷(A174)可作为单体。
各种活性环氧树脂稀释剂及各种环醚、环内酷、乙烯基醚单体等都可以作为阳离子光固化树脂的稀释剂。其中乙烯基醚类化合物和低聚物固化速度快、粘度适中、无味、无毒的优点,可以与环氧树脂配合使用。乙烯基醚单体有:1,2,3-丙三醇缩水甘油醚(EPON-812)、三乙二醇二乙烯基醚(DVE-3)、1,4-丁二醇乙烯基醚(HBVE)、环己基乙烯基醚(CHVE)、全氟甲基乙烯基醚(PMVE)、全氟正丙基乙烯基醚、异丁基乙烯基醚、羟丁基乙烯基醚、乙烯基乙醚、乙基乙烯基醚、乙基乙烯基醚丙烯、乙二醇单烯丙基醚、羟丁基乙烯基醚、丁基乙烯基醚、三氟氯乙烯(CTFE)、三甘醇二乙烯基醚、乙烯基甲醚、乙烯基正丁醚、十二烷基乙烯基醚(DDVE)、环己基乙烯基醚、三苄基苯酚聚氧乙烯基醚、四氟乙烯-全氟丙基乙烯基醚、四氟乙烯-全氟丙基乙烯基醚、叔丁基乙烯基醚:
环氧化合物单体有:3,4-环氧基环己基甲酸-3',4'-环氧基环己基甲酯(ERL-4221)、双酚A型环氧树脂(EP)、环氧丙烯酸酯、环氧乙烯基酯、丙烯酸环氧酯、甲基丙烯酸环氧酯、水溶性衣康酸环氧酯树脂:
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均裂,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 ethylether)、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 phenylbis(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此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(PI810)、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。
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l%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)、暌二酸二辛酯(DOS)、已二酸二辛酯(DOA)、三丁氧基乙烯基磷酸酯、已二酸二(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、偏苯三酸三(2-乙基)己酯(TOTM)、癸二酸二(2-乙基)己酯(DOS)、一缩二乙二醇二苯甲酸酯(DEDB)、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)、聚已二酸亚丙基酯(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)、聚已二酸亚丁基酯(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、醋酸丁酸纤维和硝化纤维素。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。
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、2,6一二叔丁基甲苯酚、酚噻嗪、蒽醌等。
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)(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]、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。
本发明的生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,所述导电层位于柔性衬底的上方,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂。
所述丙烯酸系树脂为聚酯-丙烯酸酯、环氧-丙烯酸酯或聚醚-丙烯酸酯中的一种或者多种。
所述增塑剂为三丁氧基乙烯基磷酸酯、钛酸异丙酯、钛酸正丁酯、柠檬酸酯、偏苯三酸(2-乙基)己酯、癸二酸二(2-乙基)己酯、一缩二乙二醇二苯甲酸酯、二丙二醇二苯甲酸酯或氯磺化聚乙烯中的一种或者多种。
所述紫外敏感胶在柔性衬底中所占的质量比为0.2-6%。
所述导电层的材料为石墨烯、碳纳米管、金属单质纳米线、金属合金纳米线、金属异质结纳米线、氧化锌、氧化钛、氧化铟锡或聚合物电极材料中的一种或多种。
所述金属单质纳米线为铁纳米线、铜纳米线、银纳米线、金纳米线、铝纳米线、镍纳米线、钴纳米线、锰纳米线、镉纳米线、铟纳米线、锡纳米线、钨纳米线或铂纳米线中的一种或者多种。
所述金属合金纳米线为铜铁合金纳米线、银铁合金纳米线、金铁合金纳米线、铝铁合金纳米线、镍铁合金纳米线、钴铁合金纳米线、锰铁合金纳米线、镉铁合金纳米线、铟铁合金纳米线、锡铁合金纳米线、钨铁合金纳米线、铂铁合金纳米线、银铜合金纳米线、金铜合金纳米线、铝铜合金纳米线、镍铜合金纳米线、钴铜合金纳米线、锰铜合金纳米线、镉铜合金纳米线、锡铜合金纳米线、钨铜合金纳米线、铂铜合金纳米线、金银合金纳米线、铝银合金纳米线、镍银合金纳米线、钴银合金纳米线、锰银合金纳米线、镉银合金纳米线、铟银合金纳米线、锡银合金纳米线、钨银合金纳米线、铂银合金纳米线、铝金合金纳米线、镍金合金纳米线、钴金合金纳米线、锰金合金纳米线、镉金合金纳米线、铟金合金纳米线、锡金合金纳米线、钨金合金纳米线、钴镍合金纳米线、锰镍合金纳米线、镉镍合金纳米线、铟镍合金纳米线、锡镍合金纳米线、钨镍合金纳米线、铂镍合金纳米线、镉锰合金纳米线、铟锰合金纳米线、锡锰合金纳米线、钨锰合金纳米线、铂锰合金纳米线、铟镉合金纳米线、锡镉合金纳米线、钨镉合金纳米线、铂镉合金纳米线、锡铟合金纳米线、钨铟合金纳米线、铂铟合金纳米线、钨锡合金纳米线、铂锡合金纳米线或铂钨合金纳米线中的一种或者多种。
所述金属异质结纳米线为铜铁异质结纳米线、银铁异质结纳米线、金铁异质结纳米线、铝铁异质结纳米线、镍铁异质结纳米线、钴铁异质结纳米线、锰铁异质结纳米线、镉铁异质结纳米线、铟铁异质结纳米线、锡铁异质结纳米线、钨铁异质结纳米线、铂铁异质结纳米线、银铜异质结纳米线、金铜异质结纳米线、铝铜异质结纳米线、镍铜异质结纳米线、钴铜异质结纳米线、锰铜异质结纳米线、镉铜异质结纳米线、锡铜异质结纳米线、钨铜异质结纳米线、铂铜异质结纳米线、金银异质结纳米线、铝银异质结纳米线、镍银异质结纳米线、钴银异质结纳米线、锰银异质结纳米线、镉银异质结纳米线、铟银异质结纳米线、锡银异质结纳米线、钨银异质结纳米线、铂银异质结纳米线、铝金异质结纳米线、镍金异质结纳米线、钴金异质结纳米线、锰金异质结纳米线、镉金异质结纳米线、铟金异质结纳米线、锡金异质结纳米线、钨金异质结纳米线、钴镍异质结纳米线、锰镍异质结纳米线、镉镍异质结纳米线、铟镍异质结纳米线、锡镍异质结纳米线、钨镍异质结纳米线、铂镍异质结纳米线、镉锰异质结纳米线、铟锰异质结纳米线、锡锰异质结纳米线、钨锰异质结纳米线、铂锰异质结纳米线、铟镉异质结纳米线、锡镉异质结纳米线、钨镉异质结纳米线、铂镉异质结纳米线、锡铟异质结纳米线、钨铟异质结纳米线、铂铟异质结纳米线、钨锡异质结纳米线、铂锡异质结纳米线或铂钨异质结纳米线中的一种或者多种。
所述聚合物电极材料为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)或3,4-聚乙烯二氧噻吩。
一种生物可降解的柔性光电子器件用基板的制备方法,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在刚性基板上采用辊涂、LB膜法、刮涂、旋涂、滴涂、喷涂、提拉法、流延法、浸涂、喷墨打印、自组装或丝网印刷制备柔性衬底,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;
③在柔性衬底表面采用辊涂、LB膜法、滴涂、喷涂、提拉法、喷墨打印或丝网印刷法制备导电层;
④对步骤③得到的柔性衬底进行紫外光处理;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板。
在基板制作完成后再对基板进行降解特性、方阻、表面形貌、水氧透过率和光透过率进行测试。
实施例1
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为石墨烯,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为0.2%),膜厚为20μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷涂法将石墨烯水分散液制备导电层,高度20cm,喷涂气压0.3MPa,喷涂速率0.3mL/min,导电层厚度为40nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为129Ω/□。
实施例2
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为碳纳米管,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为0.6%),膜厚为50μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷涂法将碳纳米管水分散液制备导电层,高度20cm,喷涂气压0.3MPa,喷涂速率0.3mL/min,导电层厚度为60nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为145Ω/□。
实施例3
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为银纳米线,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为1%),膜厚为100μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷涂法将银纳米线异丙醇分散液制备导电层,高度20cm,喷涂气压0.3MPa,喷涂速率0.3mL/min,导电层厚度为80nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为99Ω/□。
实施例4
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为金铜合金纳米线,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为2%),膜厚为200μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷涂法将金铜合金纳米线水分散液制备导电层,高度20cm,喷涂气压0.3MPa,喷涂速率0.3mL/min,导电层厚度为100nm;;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为79Ω/□。
实施例5
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为氧化铟锡,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为3%),膜厚为500μm,所述紫外敏感胶的原料包括以下成份:
③在②表面丝网印刷法制备氧化铟锡导电层,导电层厚度为120nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为32Ω/□。
实施例6
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS),导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为5%),膜厚为800μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷墨打印法制备PEDOT:PSS导电层,导电层厚度为150nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为48Ω/□。
实施例7
如图1所示的基板结构,柔性衬底2为掺有紫外敏感胶的虫胶,导电层1为金银异质结纳米线,导电层位于柔性衬底的上方。
制备方法如下:
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在刚性基板上采用旋涂制备虫胶与紫外敏感胶混合薄膜(紫外敏感胶所占质量比为6%),膜厚为1200μm,所述紫外敏感胶的原料包括以下成份:
③在②表面喷墨打印法制备金银异质结纳米线导电层,导电层厚度为100nm;
④对步骤③得到的柔性衬底进行紫外光处理,处理时间30s;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板;
⑥测试柔性光电子器件用基板的降解特性、方阻、表面形貌、水氧透过率和光透过率。
测试所得,所制备的柔性光电子器件用基板方块电阻为27Ω/□。
表1为实施例1-7柔性衬底的光透过率测试结果,一种是掺入了紫外敏感胶的虫胶,另一种是未掺入紫外敏感胶的虫胶。
实施例 | 掺入紫外敏感胶后的透光率 | 未掺入紫外敏感胶的透光率 |
1 | 82% | 66% |
2 | 76% | 65% |
3 | 80% | 63% |
4 | 76% | 67% |
5 | 79% | 72% |
6 | 84% | 63% |
7 | 76% | 63% |
实施例8
本实施例的生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,导电层位于柔性衬底的上方,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶在柔性衬低中所占的质量比为0.2%,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;所述导电层的材料为氧化铟锡。
实施例9
本实施例的生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,导电层位于柔性衬底的上方,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶在柔性衬低中所占的质量比为6%,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;所述导电层的材料为聚合物电极材料,聚合物电极材料为3,4-聚乙烯二氧噻吩。
实施例10
本实施例的生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,导电层位于柔性衬底的上方,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶在柔性衬低中所占的质量比为5.5%,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;所述导电层的材料为聚合物电极材料,聚合物电极材料为3,4-聚乙烯二氧噻吩。
Claims (10)
1.生物可降解的柔性光电子器件用基板,包括柔性衬底和导电层,所述导电层位于柔性衬底的上方,其特征在于,所述柔性衬底为掺有紫外敏感胶的虫胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂。
2.根据权利要求1所述的生物可降解的柔性光电子器件用基板,其特征在于,所述丙烯酸系树脂为聚酯-丙烯酸酯、环氧-丙烯酸酯或聚醚-丙烯酸酯中的一种或者多种。
3.根据权利要求1所述的生物可降解的柔性光电子器件用基板,其特征在于,所述增塑剂为三丁氧基乙烯基磷酸酯、钛酸异丙酯、钛酸正丁酯、柠檬酸酯、偏苯三酸(2-乙基)己酯、癸二酸二(2-乙基)己酯、一缩二乙二醇二苯甲酸酯、二丙二醇二苯甲酸酯或氯磺化聚乙烯中的一种或者多种。
4.根据权利要求1所述的生物可降解的柔性光电子器件用基板,其特征在于,所述紫外敏感胶在柔性衬底中所占的质量比为0.2-6%。
5.根据权利要求1所述的生物可降解的柔性光电子器件用基板,其特征在于,所述导电层的材料为石墨烯、碳纳米管、金属单质纳米线、金属合金纳米线、金属异质结纳米线、氧化锌、氧化钛、氧化铟锡或聚合物电极材料中的一种或多种。
6.根据权利要求5所述的生物可降解的柔性光电子器件用基板,其特征在于,所述金属单质纳米线为铁纳米线、铜纳米线、银纳米线、金纳米线、铝纳米线、镍纳米线、钴纳米线、锰纳米线、镉纳米线、铟纳米线、锡纳米线、钨纳米线或铂纳米线中的一种或者多种。
7.根据权利要求5所述的生物可降解的柔性光电子器件用基板,其特征在于,所述金属合金纳米线为铜铁合金纳米线、银铁合金纳米线、金铁合金纳米线、铝铁合金纳米线、镍铁合金纳米线、钴铁合金纳米线、锰铁合金纳米线、镉铁合金纳米线、铟铁合金纳米线、锡铁合金纳米线、钨铁合金纳米线、铂铁合金纳米线、银铜合金纳米线、金铜合金纳米线、铝铜合金纳米线、镍铜合金纳米线、钴铜合金纳米线、锰铜合金纳米线、镉铜合金纳米线、锡铜合金纳米线、钨铜合金纳米线、铂铜合金纳米线、金银合金纳米线、铝银合金纳米线、镍银合金纳米线、钴银合金纳米线、锰银合金纳米线、镉银合金纳米线、铟银合金纳米线、锡银合金纳米线、钨银合金纳米线、铂银合金纳米线、铝金合金纳米线、镍金合金纳米线、钴金合金纳米线、锰金合金纳米线、镉金合金纳米线、铟金合金纳米线、锡金合金纳米线、钨金合金纳米线、钴镍合金纳米线、锰镍合金纳米线、镉镍合金纳米线、铟镍合金纳米线、锡镍合金纳米线、钨镍合金纳米线、铂镍合金纳米线、镉锰合金纳米线、铟锰合金纳米线、锡锰合金纳米线、钨锰合金纳米线、铂锰合金纳米线、铟镉合金纳米线、锡镉合金纳米线、钨镉合金纳米线、铂镉合金纳米线、锡铟合金纳米线、钨铟合金纳米线、铂铟合金纳米线、钨锡合金纳米线、铂锡合金纳米线或铂钨合金纳米线中的一种或者多种。
8.根据权利要求1所述的生物可降解的柔性光电子器件用基板,其特征在于,所述金属异质结纳米线为铜铁异质结纳米线、银铁异质结纳米线、金铁异质结纳米线、铝铁异质结纳米线、镍铁异质结纳米线、钴铁异质结纳米线、锰铁异质结纳米线、镉铁异质结纳米线、铟铁异质结纳米线、锡铁异质结纳米线、钨铁异质结纳米线、铂铁异质结纳米线、银铜异质结纳米线、金铜异质结纳米线、铝铜异质结纳米线、镍铜异质结纳米线、钴铜异质结纳米线、锰铜异质结纳米线、镉铜异质结纳米线、锡铜异质结纳米线、钨铜异质结纳米线、铂铜异质结纳米线、金银异质结纳米线、铝银异质结纳米线、镍银异质结纳米线、钴银异质结纳米线、锰银异质结纳米线、镉银异质结纳米线、铟银异质结纳米线、锡银异质结纳米线、钨银异质结纳米线、铂银异质结纳米线、铝金异质结纳米线、镍金异质结纳米线、钴金异质结纳米线、锰金异质结纳米线、镉金异质结纳米线、铟金异质结纳米线、锡金异质结纳米线、钨金异质结纳米线、钴镍异质结纳米线、锰镍异质结纳米线、镉镍异质结纳米线、铟镍异质结纳米线、锡镍异质结纳米线、钨镍异质结纳米线、铂镍异质结纳米线、镉锰异质结纳米线、铟锰异质结纳米线、锡锰异质结纳米线、钨锰异质结纳米线、铂锰异质结纳米线、铟镉异质结纳米线、锡镉异质结纳米线、钨镉异质结纳米线、铂镉异质结纳米线、锡铟异质结纳米线、钨铟异质结纳米线、铂铟异质结纳米线、钨锡异质结纳米线、铂锡异质结纳米线或铂钨异质结纳米线中的一种或者多种。
9.根据权利要求5所述的生物可降解的柔性光电子器件用基板,其特征在于,所述聚合物电极材料为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)或3,4-聚乙烯二氧噻吩。
10.根据权利要求1—9任一所述的生物可降解的柔性光电子器件用基板的制备方法,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在刚性基板上采用辊涂、LB膜法、刮涂、旋涂、滴涂、喷涂、提拉法、流延法、浸涂、喷墨打印、自组装或丝网印刷制备柔性衬底,所述柔性衬底为虫胶,所述虫胶中掺有紫外敏感胶,所述紫外敏感胶的组分及质量比为:
所述光引发剂为安息香或者安息香衍生物,所述安息香衍生物为安息香甲醚、安息香乙醚或安息香异丙醚中的一种或者多种;所述光敏剂为二苯甲酮,所述助剂包括增塑剂、触变剂和填充剂;
③在柔性衬底表面采用辊涂、LB膜法、滴涂、喷涂、提拉法、喷墨打印或丝网印刷法制备导电层;
④对步骤③得到的柔性衬底进行紫外光处理;
⑤将步骤④中紫外光处理后的柔性衬底从刚性基板上剥离,形成柔性光电子器件用基板。
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