CN102939346A - 用于透明导电膜的抗腐蚀剂 - Google Patents
用于透明导电膜的抗腐蚀剂 Download PDFInfo
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- CN102939346A CN102939346A CN2010800656025A CN201080065602A CN102939346A CN 102939346 A CN102939346 A CN 102939346A CN 2010800656025 A CN2010800656025 A CN 2010800656025A CN 201080065602 A CN201080065602 A CN 201080065602A CN 102939346 A CN102939346 A CN 102939346A
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Abstract
已发现1,2-二嗪化合物在掺入含有银纳米线的膜中时可提供抗腐蚀特性。所述1,2-二嗪化合物具有一般结构(I)或(II)。
Description
发明领域
本发明涉及用于透明导电膜的抗腐蚀剂,所述透明导电膜包含银纳米线无规网络和聚合物粘合剂,以及涉及制造和使用含有这些抗腐蚀剂的膜的方法。
发明背景
透明导电膜(TCF)在近些年已被广泛用于多种应用,诸如触摸面板显示器、液晶显示器、电致发光照明、有机发光二极管装置和光伏太阳能电池。由于高导电性、透明度和相对好的稳定性,基于氧化铟锡(ITO)的透明导电膜一直是选择应用最多的透明导体。然而,基于氧化铟锡的透明导电膜具有局限性,因为铟的成本高、需要复杂且昂贵的真空沉积设备和方法,以及氧化铟锡固有的脆性且易于断裂,特别是当其在柔性基底上沉积时。
用于测量透明导电膜的特性的最重要参数中的两个是总光透射比(%T)和膜表面导电性。较高的光透射比使得显示器应用中画面质量清晰,照明和太阳能转化应用中效率较高。对于其中功率消耗可最小化的大多数透明导电膜应用,最期望较低的电阻率。因此,透明导电膜的T/R比率越高,透明导电膜越好。
美国专利申请公布2006/0257638A1描述了包含碳纳米管(CNT)和氧乙烯树脂聚合物粘合剂的透明导电膜。
美国专利申请公布2007/0074316A1和2008/0286447A1描述了这样的透明导电膜,其中将银纳米线沉积在基底上形成裸露的纳米线网络,随后用聚合物基质材料在外涂布所述银纳米线网络以形成透明导电膜。这要求在仅含有表面活性剂和溶剂的溶液中涂布银纳米线的困难方法。提出诸如聚丙烯酸酯和羧基烷基纤维素聚合物之类的聚合材料为基质的适用材料。
美国专利申请公布2008/0292979描述了一种包含银纳米线或银纳米线与碳纳米管的混合物的透明导电膜。不用聚合物粘合剂或在可光成像组合物中形成透明导电网络。在玻璃和聚对苯二甲酸乙二酯(PET)支持物上涂布所述透明导电膜。
美国专利申请公布2009/0130433A1描述了按如下方式形成的透明导电膜:涂布银纳米线以形成网络,然后在外涂布一层氨酯丙烯酸酯聚合物粘合剂。
待解决的问题:
为了使基于银的透明导体具有实际用途,重要的是当经受环境条件时,这些基于银的透明导体是长期稳定的。
由于空气中少量化学物质的反应而产生的任何大气腐蚀将诱导金属纳米线表面的不期望的化学反应,从而影响基于金属纳米线的透明导体的导电性和性能。众所周知,当与大气接触时,腐蚀或“锈蚀”容易发生在银金属表面,因为硫化氢与银反应导致银表面的硫化:
2Ag+H2S→Ag2S+H2
因为硫化银的导电性比银金属的导电性低很多,所以当与大气接触时,基于银纳米线的导体可逐渐失去导电性。
与和空气接触的裸露金属线形成对比,聚合物基质中的银纳米线更稳定,因为聚合物的存在减慢硫化氢(或其它腐蚀剂)向银纳米线表面的扩散。然而,重要的是甚至当纳米线被嵌入聚合物基质中时,使银纳米线表面稳定以防止硫化过程。
美国专利申请公布2008/0286447提出使用芳族三唑和其它含氮化合物作为用于基于银纳米线的透明导体的腐蚀抑制剂。还提出长链烷基硫代化合物为适用的腐蚀抑制剂。
有用的是发现用于透明导电膜的抗腐蚀剂,所述透明导电膜包含聚合物粘合剂中的银纳米线的无规网络,可使用普通涂布技术从水性或有机溶剂涂布所述聚合物粘合剂。
发明概述
我们已经发现,某些1,2-二嗪化合物特别可用作抗腐蚀剂以针对基于银纳米线的透明导电膜与腐蚀剂(诸如硫化氢)的不利反应对此类导电膜的无规网络进行稳定。
在一个实施方案中,本发明提供透明导电制品,其包含:
已涂布于其上的透明支持物;
包含分散于聚合物粘合剂中的银纳米线的无规网络的透明导电膜;和
一种或多种具有一般结构(I)或(II)的1,2-二嗪化合物;
其中,R1、R2、R3和R4独立地为:氢、包含多达20个碳原子的取代或未取代的烷基、包含多达10个碳原子的取代或未取代的芳基、包含多达10个碳、氧、氮或硫原子的取代或未取代的杂芳基、卤素原子(F、Cl、Br或I)、羟基(OH)、硫醇基(SH)、包含多达20个碳原子的取代或未取代的烷氧基、氨基(NR5R6)(其中R5和R6独立地为氢、包含多达20个碳原子的烷基或包含多达10个碳原子的芳基)、硫醚基(SR7)(其中R7是包含多达20个碳原子的烷基或包含多达10个碳原子的芳基)、亚砜基(SOR7)、砜基(SO2R7)、羧酸基(COOH)或羧酸的盐(CO2 -M+)(其中M+是阳离子(诸如金属阳离子、季铵阳离子或季鏻阳离子))、甲酰胺基(CONR5R6)、酰氨基(NR5COR7)、酰基(COR7)、酰氧基(OCOR7)或磺酰氨基(SO2NR5R6),
或者(R1和R2)或(R2和R3)或(R3和R4)与1至5个碳、氮、硫和/或氧原子连接在一起形成脂环或芳环。
在另一个实施方案中,本发明提供透明导电制品,其包含:
已涂布于其上的透明聚对苯二甲酸乙二酯支持物;
包含银纳米线的无规网络的透明导电膜,所述银纳米线的纵横比为20至3300,以足以提供500ohm/sq或更低的表面电阻率和在约350nm至约1100nm的整个光谱范围至少70%的透射比的量分散于聚合物粘合剂中;和
由以下一种或多种结构表示的1,2-二嗪化合物:
其中R1、R2、R3和R4为如上所述。
在另外的实施方案中,本发明还提供用于形成透明导电制品的方法,其包括:
制备银纳米线在1,2-二嗪化合物和聚合物粘合剂的溶液中的分散体;
其中1,2-二嗪化合物具有一般结构(I)或(II);
其中R1、R2、R3和R4为如上所述。
将银纳米线在1,2-二嗪化合物和聚合物粘合剂的溶液中的分散体涂布在透明支持物上;以及
干燥支持物上的涂层,从而形成银纳米线的无规网络。
发明详述
定义:
术语“导电层”或“导电膜”是指包含分散于聚合物粘合剂中的银纳米线的网络层。
术语“导电的”是指导电性。
术语“制品”是指“导电层”或“导电膜”在支持物上的涂层。
术语“涂布重量(coating weight)”、“涂层重量(coat weight)”和“覆盖率”是同义的,并且通常以每单位面积的重量或摩尔表示,诸如g/m2或mol/m2。
术语“透明的”意指能够透射可见光而没有显著的散射或吸收。
“雾度”是使光在所有方向均匀扩散的大角度散射。它是偏离入射光大于平均2.5度的透射光的百分比。雾度降低对比度并且产生乳白色或朦胧的外观。雾度的数值越低,材料的模糊度越小。
术语“有机溶剂”意指“在使用温度下为液体的材料,其化学式包含一个或多个碳原子”。
术语“水性溶剂”意指一种材料,在使用温度下为液体,其在均相溶液中的组合物包含最大比例的水(即,至少50重量%的水)。
术语“水可溶”意指溶质与水形成均相溶液,或其中水为主要组分的溶剂混合物。
术语“一个”或“一种”是指“至少一种”所述组分(例如,本文所述的抗腐蚀剂、纳米线和聚合物)。
另外,本文件引用的所有出版物、专利和专利文件的全部内容均以引用的方式并入本文,如单独通过引用的方式并入一样。
银纳米线:
银纳米线是赋予导电膜和使用导电膜制备的制品以导电性的主要组分。透明导电膜的导电性主要由以下控制:a)单根纳米线的导电性、b)终端间的纳米线的数量和c)纳米线之间的连通性。低于一定的纳米线浓度(也称为渗滤阈值),终端间的导电性是零,因为纳米线被隔开太远而不提供连续的电流通路。高于这个浓度,存在至少一个可用的电流通路。当提供更多的电流通路时,层的总体电阻将下降。然而,当提供更多的电流通路时,由于纳米线的光吸收使导电膜的透明度(即,光透射百分比)下降。同样,当导电膜中银纳米线的数量增加时,由于由银纳米线引起的光散射使透明膜的雾度增加。相似的效果将出现在用导电膜制备的透明制品中。
在一个实施方案中,银纳米线的纵横比(长度/宽度)为约20至约3300。在另一个实施方案中,银纳米线的纵横比(长度/宽度)为约500至约1000。长度为约5μm至约100μm(微米)且宽度为约30nm至约200nm的银纳米线是适用的。宽度为约50nm至约120nm且长度为约15μm至约100μm(微米)的银纳米线也适用于构建透明导电网络膜。
可通过本领域已知的方法制备银纳米线。具体地,可通过在多元醇(例如,乙二醇或丙二醇)和聚(乙烯吡咯烷酮)的存在下银盐(例如,硝酸银)的液相还原来合成银纳米线。根据(例如)Ducamp-Sanguesa,C.等,J.of Solid State Chemistry,(1992),100,272-280;Xia,Y.等,Chem.Mater.(2002),14,4736-4745,和Xia,Y.等,Nano Letters,(2003),3(7),955-960中描述的方法,可大规模生产尺寸均匀的银纳米线。
聚合物粘合剂:
对于透明导电膜的实际制造过程,重要的是具有导电组分(诸如银纳米线)和在涂布溶液中的聚合物粘合剂二者。聚合物粘合剂溶液发挥双重作用,作为分散剂以促进银纳米线的分散和作为增粘剂以使银纳米线涂布分散体稳定,从而在涂布过程的任何时间点都不发生银纳米线的沉降。还期望具有在单涂布分散体中的银纳米线和聚合物粘合剂。这简化了涂布过程并且使得一次涂布成功,并且避免了首先涂布裸露银纳米线以形成不牢固且易碎的膜,随后在外涂布聚合物以形成透明导电膜的方法。
为了使透明导电膜适用于各种装置应用,同样重要的是透明导电膜的聚合物粘合剂为任选透明且柔性的,但仍然具有高机械强度、良好的硬度、高热稳定性和光稳定性。这需要待用于透明导电膜的聚合物粘合剂的Tg(玻璃化转变温度)大于透明导电膜的使用温度。
本领域已知透明、任选清澈的聚合物粘合剂。合适的聚合粘合剂的实例包括但不限于:聚丙烯酸化物,诸如聚甲基丙烯酸酯(例如,聚(甲基丙烯酸甲酯))、聚丙烯酸酯和聚丙烯腈、聚乙烯醇、聚酯(例如,聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯和聚萘二甲酸乙二醇酯);具有高芳香性的聚合物,诸如酚醛树脂或甲酚-甲醛聚苯乙烯、聚乙烯甲苯、聚乙烯二甲苯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚醚酰胺、聚硫化物、聚砜、聚苯撑和聚苯基醚;聚氨酯(PU);聚碳酸酯;环氧树脂;聚烯烃(例如聚丙烯、聚甲基戊烯和环烯烃);丙烯腈-丁二烯-苯乙烯共聚物(ABS);纤维素制品;硅酮和其它含硅聚合物(例如聚倍半硅氧烷和聚硅烷);聚氯乙烯(PVC);聚醋酸乙烯酯;聚降冰片;合成橡胶(例如EPR、SBR、EPDM)和含氟聚合物(例如,聚偏二氟乙烯;聚四氟乙烯(TFE)或聚六氟丙烯);氟烯烃和碳氢化合物烯烃(hydrocarbon olefin)的共聚物(例如,)和无定形碳氟化合物聚合物或共聚物(例如,由Asahi GlassCo.开发的或由Du Pont开发的AF)聚乙烯醇缩丁醛;聚乙烯醇缩醛、明胶;多糖和淀粉。
在某些实施方案中,为了在聚合物涂布溶液中分散和稳定银纳米线,有利的是使用具有高氧含量的聚合物粘合剂。含氧基团,诸如羟基和羧酸基,具有与银纳米线表面结合的强亲和力并且促进分散和稳定。许多富氧聚合物还在通常用于制备有机溶剂涂布材料的极性有机溶剂中具有良好的溶解性,而其它富氧聚合物在水中或通常用于制备水性溶剂涂布材料的水性溶剂混合物中具有良好的溶解性。
在某些实施方案中,当用于制备从有机溶剂涂布的基于银纳米线的透明导电膜时,纤维素酯聚合物,诸如醋酸丁酸纤维素(CAB)、醋酸纤维素(CA)或醋酸丙酸纤维素(CAP)优于其它富氧聚合物粘合剂,所述有机溶剂诸如2-丁酮(甲乙酮,MEK)、甲基异丁酮、丙酮、甲醇、乙醇、2-丙醇、醋酸乙酯或其混合物。它们的使用产生其中所涂布膜的光透射比和导电性极大提高的透明导电膜。另外,这些纤维素酯聚合物的玻璃化转变温度为至少100℃并且提供具有高机械强度、良好硬度、高热稳定性和光稳定性的透明、柔性膜。
纤维素酯聚合物可以干燥透明导电膜的约40至约90重量%存在。优选地,它们以干燥膜的约60至约85重量%存在。在一些构造中,可使用纤维素酯聚合物和一种或多种另外聚合物的混合物。这些聚合物应该与纤维素聚合物相容。所谓相容意指当被干燥时,聚合物形成透明、单相混合物。另外一种或多种聚合物可提供另外的益处,诸如促进与支持物的粘附和改进硬度和耐擦伤性。如上所述,所有聚合物的总重量%是干燥透明导电膜的约40至约95重量%。优选地,所有聚合物的总重量是干燥膜的约60至约85重量%。聚酯聚合物是适用的另外聚合物的实例。
在其它实施方案中,也可使用水溶性聚合物粘合剂,诸如聚乙烯醇、明胶、聚丙烯酸、聚酰亚胺。也可使用其它水可分散乳胶聚合物,诸如含有(甲基)丙烯酸单元的聚丙烯酸酯和聚甲基丙烯酸酯。从水性溶液涂布在制造过程中对环境有益并且减少挥发性有机化合物的排放。
使用水溶性聚合物,诸如聚乙烯醇或明胶作为基于银纳米线的透明导体的粘合剂产生膜透射比和导电性都极大改善的上好透明导电膜。使用聚氨酯聚合物粘合剂的水性分散体制备的类似透明导电膜显示较不理想的透射比和导电性。当向聚合物溶液中添加聚合物交联剂时,使用聚乙烯醇或明胶聚合物粘合剂制备的透明导电膜也表现极佳的透明度、耐擦伤性和硬度。根据本发明制备的透明导电膜提供在约350nm至约1100nm的整个光谱范围内至少70%的透射比和500ohm/sq或更低的表面电阻率。
包含银纳米线和水溶性聚合物粘合剂的透明导电制品也表现极佳的透明度、高耐擦伤性和硬度。另外,当被支持的聚酯预涂布明胶底涂层时,使用这些聚合物粘合剂制备的透明导电膜具有对聚在苯二甲酸乙二酯(PET)支持物上良好的粘附。
水溶性聚合物粘合剂以干燥透明导电膜的约40至约95重量%存在。优选地,它们以干燥膜的约60至约85重量%存在。
在一些构造中,多达50重量%的明胶或聚乙烯醇聚合物粘合剂可被一种或多种另外聚合物代替。这些聚合物应该与明胶或聚乙烯醇聚合物粘合剂相容。所谓相容意指当干燥时,所有聚合物形成透明、单相混合物。另外的一种或多种聚合物可提供另外的益处,诸如促进与支持物的粘附和改进硬度和耐擦伤性。水溶性丙烯酸聚合物特别优选为另外的聚合物。这类聚合物的例子是聚丙烯酸和聚丙烯酰胺,和其共聚物。如上所述,所有聚合物的总重量%是干燥透明导电膜的约50至约95重量%。优选地,所有聚合物的总重量是干燥膜的约70至约85重量%。
若需要,具有这些聚合物粘合剂的透明导电膜对支持物的耐擦伤性和硬度可通过使用交联剂来交联聚合物粘合剂而改善。异氰酸酯是用于含有自由羟基的纤维素酯聚合物的典型交联剂的实例。乙烯砜是用于明胶粘合剂的典型交联剂的实例。
抗腐蚀剂:
抗腐蚀剂是化学化合物,当添加至透明导电膜时,其改善对于由大气中的一种或多种化学物质与膜中的一种或多种组分的反应而导致的大气腐蚀的构造稳定性。该反应导致膜的导电性和/或物理完整性受损。当用在透明导电膜中时,抗腐蚀剂应该是无色且无味的,并且应该对使用透明导电膜的环境中的热、光和湿度的条件稳定。
对于基于银纳米线的导电膜,具有含有N、O或S的官能团的化学化合物是可能适用的抗腐蚀剂,因为这些官能团具有与银纳米线表面的配位能力。认为配位与这些化合物复合并且使银表面钝化以阻止大气气体与银表面的反应。然而,事实上,许多此类化合物当与银纳米线表面结合时,将显著降低所得导电膜的导电性。显然,这些化合物的绝缘效果阻止纳米线接触点处的电子“流”。因此,重要的是鉴定一类将提供对透明导电膜的抗腐蚀保护而不引起导电性的显著降低和其它负面影响的化合物。
我们已发现1,2-二嗪化合物在掺入含有银纳米线的膜时提供抗腐蚀特性。所述1,2-二嗪化合物具有一般结构(I)或(II)。
其中,R1、R2、R3和R4独立地为:氢、包含多达20个碳原子的取代或未取代的烷基、包含多达10个碳原子的取代或未取代的芳基、包含多达10个碳、氧、氮或硫原子的取代或未取代的杂芳基、卤素原子(F、Cl、Br或I)、羟基(OH)、硫醇基(SH)、包含多达20个碳原子的取代或未取代的烷氧基、氨基(NR5R6)(其中R5和R6独立地为氢、包含多达20个碳原子的烷基或包含多达10个碳原子的芳基)、硫醚基(SR7)(其中R7是包含多达20个碳原子的烷基或包含多达10个碳原子的芳基)、亚砜基(SOR7)、砜基(SO2R7)、羧酸基(COOH)或羧酸的盐(CO2 -M+)(其中M+是阳离子(金属阳离子或季铵阳离子或季鏻阳离子))、甲酰胺基(CONR5R6)、酰氨基(NR5COR7)、酰基(COR7)、酰氧基(OCOR7)或磺酰氨基(SO2NR5R6),
或者(R1和R2)或(R2和R3)或(R3和R4)与1至5个碳、氮、硫和/或氧原子连接在一起形成脂环或芳环。
在另一个实施方案中,R1、R2、R3和R4是氢、卤素、羟基、包含1至6个碳原子的烷基、包含6个碳原子的芳基、包含1至6个碳原子的烷氧基,或(R1和R2)或(R2和R3)或(R3和R4)与4个碳原子连接在一起形成稠和的苯并环。
在另一个实施方案中,R1、R2、R3和R4是氢、氧、溴、羟基、包含1至4个碳原子的烷基、包含6个碳原子的芳基、包含1至4个碳原子的烷氧基,或(R2和R3)与4个碳原子连接在一起形成稠和的苯并环。
具有结构(I)和(II)的1,2-二嗪化合物的非限制性实例包括:
导电膜的涂布:
用于透明银纳米线膜的基于有机溶剂的涂布制剂可通过使各种组分与一种或多种聚合物粘合剂在适当的有机溶剂体系中混合来制备,所述有机溶剂体系通常包括一种或多种溶剂,诸如甲苯、2-丁酮(甲乙酮,MEK)、甲基异丁酮、丙酮、甲醇、乙醇、2-丙醇、醋酸乙酯、乳酸乙酯、四氢呋喃或其混合物。甲乙酮是特别适用的涂布溶剂。用于透明银纳米线膜的水性涂布制剂可通过使各种组分与水中或水与水易混溶剂(诸如丙酮、甲醇、乙醇、2-丙醇或四氢呋喃或其混合物)的混合物中的一种或多种聚合物粘合剂混合来制备。可通过使用各种涂布程序涂布所述制剂来制备含有银纳米线的透明膜,所述涂布程序诸如钢丝缠绕刮棒式涂布、浸渍涂布、气刀涂布、帘幕涂布、斜板式涂布、狭缝模具式涂布、辊式涂布、凹版涂布或挤出涂布。可将表面活性剂和其它涂布助剂掺入涂布制剂中。
在一个实施方案中,银纳米线的涂布重量约20mg/m2至约500mg/m2。在另一个实施方案中,银纳米线的涂布重量约20mg/m2至约200mg/m2。在另一个实施方案中,银纳米线的涂布重量约30mg/m2至约120mg/m2。透明导电涂层的适用的涂层干燥厚度是约0.05μm至约2.0μm,并且优选约0.1μm至约0.5μm。
涂布和干燥后,透明导电膜应具有小于1,000ohms/sq并且优选小于500ohm/sq的表面电阻率。
涂布和干燥后,透明导电膜应具有尽可能高的透射比%。至少为70%的透射比是适用的。至少为80%并且甚至至少90%的透射比是更加适用的。
特别适用的是透射比为至少70%且表面电阻率小于500ohm/sq的膜。
根据本发明的透明导电膜提供在约350nm至约1100nm的整个光谱范围内至少70%的透射比和小于500ohm/sq的表面电阻率。
透明支持物:
在一个实施方案中,将导电材料涂布在支持物上。支持物可以是刚性的或柔性的。
适当的刚性基底包括,例如玻璃、聚碳酸酯、丙烯酸树脂等。
当将导电材料涂布在柔性支持物上时,支持物优选地是具有任何期望的厚度并且由一种或多种聚合材料组成的柔性、透明的聚合膜。需要支持物在导电层的涂布和干燥过程中表现尺寸稳定性并且具有与覆盖层适当的粘附特性。用于制备此类支持物的适用的聚合材料包括聚酯[诸如聚(对苯二甲酸乙二酯)(PET)和聚(萘二甲酸乙二酯)(PEN)]、醋酸纤维素和其它纤维素酯、聚乙烯醇缩醛、聚烯烃、聚碳酸酯和聚苯乙烯。优选的支持物由具有良好热稳定性的聚合物组成,诸如聚酯和聚碳酸酯。也可对支持物材料进行处理或退火以减少收缩且促进尺寸稳定性。可也使用透明多层支持物。
将导电膜涂布到支持物上:
可通过使用各种涂布程序将上述制剂涂布到透明支持物上来制备透明导电制品,所述涂布程序诸如钢丝缠绕刮棒式涂布、浸渍涂布、气刀涂布、帘幕涂布、斜板式涂布、狭缝模具式涂布、辊式涂布、凹版涂布或挤出涂布。
或者,可通过将如上所述制备的透明导电膜层压到透明支持物上来制备透明导电制品。
在一些实施方案中,可将包含两种或更多种聚合物的单相混合物的“载体”层制剂直接涂敷到支持物上并且从而位于支持物和银纳米线层之间。载体层的作用是促进支持物与含有银纳米线的透明聚合物层的粘附。载体层制剂可与透明导电银纳米线层制剂顺序涂敷或同时涂敷。优选的是所有涂层可同时涂敷到支持物上。载体层通常被称为“粘附促进层”、“夹层”或“中间层”。
如上所述,在一个实施方案中,银纳米线的涂布重量是约20mg/m2至约500mg/m2。在其它实施方案中,银纳米线的涂布重量是约20mg/m2至约200mg/m2。也涵盖其中银纳米线以约30mg/m2至约120mg/m2涂布的实施方案。
涂布和干燥后,透明导电制品应具有小于1,000ohms/sq并且优选小于500ohm/sq的表面电阻率。
类似地,在透明支持物上涂布和干燥后,透明导电制品应具有尽可能高的光透射比。至少为70%的透射比是适用的。至少为80%并且甚至至少90%的透射比是更加适用的。
特别优选的是透射比为至少70%且表面电阻率为小于500ohm/sq的制品。
提供以下实施例以说明本发明的实践,并且不旨在由此限制本发明。
用于实验和实施例的材料和方法:
除非另外指明,在以下实施例中使用的所有材料易于从标准商业来源获得,诸如Aldrich Chemical Co.(Milwaukee,Wisconsin)。除非另外指明,所有百分比是按重量计。使用以下另外的方法和材料。
新癸酸铋是新癸酸的铋盐。
CAB 171-15是可从Eastman Chemical Co.(Kingsport,TN)获得的醋酸丁酸纤维素树脂。其玻璃化转变温度为161℃。
Mayer Bar是1/2英寸直径型号303不锈钢涂布棒并可从R.D.Specialties,Inc.(Webster,NY)获得。
MEK是甲乙酮(或2-丁酮)。
银纳米线根据文献描述的程序制备(Wiley,B.;Sun,Y.;Xia,Y.Langmuir,21,(18),8077,2005)。所制备的银纳米线显示直径为80至140nm,并且长度为10至50μm。
THDI是Desmodur N-3300(2,2,4-三甲基六亚甲基二异氰酸酯)。它是六亚甲基二异氰酸酯的三聚物,并且可从Bayer Material Science(Pittsburgh,PA)获得。
BHTT是4-苯甲基-1,2,4-三唑-3-硫醇。其具有如下所示的结构(C-1)。
BZT是苯并三唑。其具有如下所示的结构(C-2)。
MMBI是2-巯基-4(5)-甲基苯并咪唑。其具有如下所示的结构(C-3)。
4-MPA是4-甲基邻苯二甲酸。其具有如下所示的结构(C-4)。
PMT是1-苯基-1H-四唑-5-硫醇(苯基-巯基-四唑)。其具有如下所示的结构(C-5)。
TCPA是四氯邻苯二甲酸。其具有如下所示的结构(C-6)。
PHZ是酞嗪(结构I-1)。
PAZ是酞嗪酮(结构II-3)。
Cl-PHZ是1,4-二氧酞嗪(结构I-3)。
Bu-PHZ是6-异丁基酞嗪(结构I-4)。
PYZ是哒嗪(结构I-2)。
聚合物预混合溶液的制备:
通过混合以下材料来制备醋酸丁酸纤维素聚合物预混合溶液:
透明银纳米线涂层的制备
向按如上所示制备的1.46g聚合物预混合溶液中加入0.12g 2-丙醇中的银纳米线分散体(~5.0%银纳米线)和含有如表1所示的抗腐蚀化合物的0.015g溶液。
将所得的分散体在滚轴混合器中混合10分钟以获得均匀的分散体。用10号Mayer棒将分散体涂布在4-mil(102μm)清晰的聚对苯二甲酸乙二酯支持物上。将所得的涂层在220°F(104℃)烘箱中干燥6分钟以得到适合测试的透明导电膜。
与硫化氢(H2S)接触时的表面电阻率的测量:
使用从Electronic Design To Market,Inc.(Toledo,OH)获得的R-CHEK型号RC2175表面电阻率测量计来测量导电样品涂层的表面电阻率。
涂布后立即测量导电样品涂层的表面电阻率以提供初始值。
然后将导电样品涂层放置在容积约4升的封闭、气密室中。将含有硫代乙酰胺溶液(100g水中0.20g硫代乙酰胺)的瓶子放置在室中并打开。将测试室封闭并且使样品在室中与H2S接触几天。硫代乙酰胺是用于产生低浓度硫化氢气体的方便来源(Journal of ChemicalEducation,32,474,1955),并且如果需要,可通过改变溶液中的硫代乙酰胺浓度来调节气密室中的硫化氢的浓度。定期检查样品的电阻率以监控由于银纳米线涂层与硫化氢气体反应导致的膜电阻率的变化,所述硫化氢气体由硫代乙酰胺的分解产生。该测试使样品加速腐蚀。
加速腐蚀测试结果示出在下表II中,证明与硫代乙酰胺溶液室中的硫化氢接触几天后,不含抗腐蚀化合物的透明导电膜的导电性迅速恶化,比较例Comp-1。
对于几种测试的芳香族化合物,它们中的一些含有氮或硫基团,当将这些化合物加入到导电膜制剂(Comp-2、Comp-3和Comp-4)时,观察到差的初始膜导电性。这些化合物不适于用作透明导电膜的抗腐蚀剂。
对于一些其它化合物,当加入到导电膜制剂中时,所得膜的初始导电性没有显著改变。然而,这些化合物不提供任何抗腐蚀效果,因为在经历H2S加速测试后,这些样品的导电性由初始值显著变化,Comp-5、Comp-6和Comp-7。
对于含有本发明1,2-二嗪化合物的导电膜样品,Inv-1至Inv-5,在H2S环境中测试8天后,没有显著影响样品的导电性。这些结果证明通过向包含银纳米线的透明导电膜构造中加入1,2-二嗪化合物提供显著的稳定性改善。
已具体根据某些优选的实施方案详细描述了本发明,但是将理解的是可在本发明的精神和范围内实现改变和修改。
Claims (21)
1.一种透明导电制品,其包含:
已涂布于其上的透明支持物;
包含分散于聚合物粘合剂中的银纳米线的无规网络的透明导电膜;和
一种或多种具有一般结构(I)或(II)的1,2-二嗪化合物;
其中,R1、R2、R3和R4独立地为:氢;包含多达20个碳原子的取代或未取代的烷基;包含多达10个碳原子的取代或未取代的芳基;包含多达10个碳、氧、氮或硫原子的取代或未取代的杂芳基;卤素原子(F、Cl、Br或I);羟基(OH);硫醇基(SH);包含多达20个碳原子的取代或未取代的烷氧基;氨基(NR5R6),其中R5和R6独立地为氢、包含多达20个碳原子的烷基或包含多达10个碳原子的芳基;硫醚基(SR7),其中R7是包含多达20个碳原子的烷基或包含多达10个碳原子的芳基;亚砜基(SOR7);砜基(SO2R7);羧酸基(COOH)或羧酸的盐(CO2 -M+),其中M+是阳离子(诸如金属阳离子、季铵阳离子或季鏻阳离子);甲酰胺基(CONR5R6);酰氨基(NR5COR7);酰基(COR7);酰氧基(OCOR7)或磺酰氨基(SO2NR5R6),
或者(R1和R2)或(R2和R3)或(R3和R4)与1至5个碳、氮、硫和/或氧原子连接在一起形成脂环或芳环。
2.根据权利要求1所述的透明导电制品,其中所述透明支持物是柔性透明聚合物膜。
3.根据权利要求1所述的透明导电制品,其中所述银纳米线以足以提供小于1000ohm/sq的表面电阻率的量存在。
4.根据权利要求1所述的透明导电制品,其中所述银纳米线的纵横比为约20至约3300。
5.根据权利要求1所述的透明导电制品,其中所述银纳米线以约20mg/m2至约500mg/m2的量存在。
6.根据权利要求1所述的透明导电制品,其在约350nm至约1100nm的整个光谱范围内的透射比为至少70%并且表面电阻率为500ohm/sq或更低。
7.根据权利要求1所述的透明导电制品,其中所述聚合物粘合剂包含水溶性聚合物。
8.根据权利要求7所述的透明导电制品,其中所述水溶性聚合物包含明胶、聚乙烯醇或其混合物。
9.根据权利要求8所述的透明导电制品其还包含多达50重量%的一种或多种另外的水溶性聚合物。
10.根据权利要求9所述的透明导电制品,其中所述另外的水溶性聚合物中的一种或多种是聚丙烯酸聚合物。
11.根据权利要求1所述的透明导电制品,其中所述聚合物粘合剂包含有机溶剂可溶性聚合物。
12.根据权利要求11所述的透明导电制品,其中所述有机溶剂可溶性聚合物粘合剂包含纤维素酯聚合物。
13.根据权利要求11所述的透明导电制品,其中所述有机溶剂可溶性聚合物粘合剂包含醋酸纤维素、醋酸丁酸纤维素或醋酸丙酸纤维素或其混合物。
14.根据权利要求12所述的透明导电制品,其中所述纤维素酯聚合物的玻璃化转变温度为至少100℃。
15.根据权利要求11所述的透明导电制品,其还包含多达50重量%的一种或多种另外的有机溶剂可溶性聚合物。
16.根据权利要求12所述的透明导电制品,其中所述另外的聚合物中的一种或多种是聚酯聚合物。
17.根据权利要求1所述的透明膜导电制品,其中
R1、R2、R3和R4是氢、卤素、羟基、包含1至6个碳原子的烷基、包含6个碳原子的芳基、包含1至6个碳原子的烷氧基。
或者(R1和R2)或(R2和R3)或(R3和R4)与4个碳原子连接在一起形成稠和的苯并环。
19.根据权利要求1所述的透明导电制品,其还包含位于所述透明支持物和所述透明导电膜之间的透明聚合物层。
21.一种用于形成透明导电制品的方法,其包括:
制备银纳米线在1,2-二嗪化合物和聚合物粘合剂的溶液中的分散体;
其中所述1,2-二嗪化合物具有一般结构(I)或(II);
其中,R1、R2、R3和R4独立地为:氢;包含多达20个碳原子的取代或未取代的烷基;包含多达10个碳原子的取代或未取代的芳基;包含多达10个碳、氧、氮或硫原子的取代或未取代的杂芳基;卤素原子(F、Cl、Br或I);羟基(OH);硫醇基(SH);包含多达20个碳原子的取代或未取代的烷氧基;氨基(NR5R6),其中R5和R6独立地为氢、包含多达20个碳原子的烷基或包含多达10个碳原子的芳基;硫醚基(SR7),其中R7是包含多达20个碳原子的烷基或包含多达10个碳原子的芳基;亚砜基(SOR7);砜基(SO2R7);羧酸基(COOH)或羧酸的盐(CO2 -M+),其中M+是阳离子(诸如金属阳离子、季铵阳离子或季鏻阳离子);甲酰胺基(CONR5R6);酰氨基(NR5COR7);酰基(COR7);酰氧基(OCOR7)或磺酰氨基(SO2NR5R6);
或者(R1和R2)或(R2和R3)或(R3和R4)与1至5个碳、氮、硫和/或氧原子连接在一起形成脂环或芳环;
将银纳米线在1,2-二嗪化合物和聚合物粘合剂的溶液中的所述分散体涂布在透明支持物上;以及
干燥所述支持物上的涂层以形成银纳米线的无规网络。
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CN105593313A (zh) * | 2013-09-27 | 2016-05-18 | 东进世美肯株式会社 | 含有金属纳米线的导电性涂布组合物及利用其的导电性膜的形成方法 |
CN105593313B (zh) * | 2013-09-27 | 2018-02-13 | 东进世美肯株式会社 | 含有金属纳米线的导电性涂布组合物及利用其的导电性膜的形成方法 |
CN104037263A (zh) * | 2014-05-29 | 2014-09-10 | 晶澳太阳能有限公司 | 一种太阳能电池片栅线硫化处理工艺 |
CN104867541A (zh) * | 2015-04-16 | 2015-08-26 | 浙江科创新材料科技有限公司 | 一种透明导电薄膜及其制备方法 |
CN104910402A (zh) * | 2015-04-28 | 2015-09-16 | 中科院广州化学有限公司南雄材料生产基地 | 基于纳米银线改性和紫外光固化制备透明导电薄膜的方法 |
CN106782768A (zh) * | 2016-08-15 | 2017-05-31 | 中山大学 | 一种纳米金属线透明导电薄膜及其制备方法 |
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EP2547735B1 (en) | 2016-03-16 |
KR20130038812A (ko) | 2013-04-18 |
CN102939346B (zh) | 2015-12-02 |
JP5496408B2 (ja) | 2014-05-21 |
EP2547735A1 (en) | 2013-01-23 |
JP2013522845A (ja) | 2013-06-13 |
WO2011115603A1 (en) | 2011-09-22 |
US20130004765A1 (en) | 2013-01-03 |
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