CN101573228B - 用于薄膜金属层形成的成核层 - Google Patents
用于薄膜金属层形成的成核层 Download PDFInfo
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- CN101573228B CN101573228B CN200780048674.7A CN200780048674A CN101573228B CN 101573228 B CN101573228 B CN 101573228B CN 200780048674 A CN200780048674 A CN 200780048674A CN 101573228 B CN101573228 B CN 101573228B
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Abstract
本发明公开了一种导电膜,其在柔性聚合物支承体上通过如下方式形成:涂敷种子层到所述柔性聚合物支承体,并且在所述种子层上涂敷可延展的、透射可见光的金属层,所述种子层包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或它们的混合物(包括混合型氧化物)。所述种子层氧化物有利地促进随后以更均匀或更致密方式涂敷的金属层的沉积,或促进连续金属层的更早形成(即,以较薄的涂敷厚度)。所得的膜具有高的可见光透射比和低的电阻。
Description
相关申请的交叉引用
本专利申请要求2006年12月28日提交的临时专利申请No.60/882,389的提交日的优先权,该专利的公开内容以引用方式并入本文中。
技术领域
本发明涉及具有高可见光透射比和低电阻的导电膜。这些膜适用于例如电磁干扰(EMI)屏蔽和汽车应用。
背景技术
光学膜结合在多种应用中。有时候这些膜采用薄的金属(例如银)层。光学膜用于柔性基底上的多种构造中以获得有益的特性。对于光学膜代表性的用途包括阳光控制膜、EMI屏蔽膜、窗膜和导电膜。这些膜通常需要高的可见光透光率,并且如果被金属化,需要低的电阻率。
在导电金属层中的透光率和电阻率之间存在成比例的关系。这种关系使得形成既具有高可见光透光率又具有低电阻率的膜的通常目标是微妙的平衡,因为改变无论哪个特性的性能都会不利地影响另一个特性。当形成金属层时,金属可以在其沉积时凝聚。这可以导致非均匀的膜,并且可能需要涂敷相对厚的金属层从而得到高度导电的膜或有效的屏蔽膜。这种凝聚或岛状物的形成使得透光率减弱并且引起电阻率增加。
具有高透光率和高导电率的柔性光学膜一直是需要的,并且用于制备这类膜的方法也一直是需要的。
发明内容
在一个方面,本发明提供一种在柔性聚合物支承体上形成导电膜的方法,该方法包括在柔性聚合物支承体上形成种子层以及在种子层上涂敷可延展的、透射可见光的金属层,该种子层包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或它们的混合物(包括混合型氧化物和掺杂型氧化物)。
在第二方面,本发明提供一种导电膜,包括柔性聚合物支承体;在支承体上的种子层,包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或它们的混合物(包括混合型氧化物和掺杂型氧化物);以及在种子层上的可延展的、透射可见光的金属层。
在第三方面,本发明提供一种制备玻璃制品的方法,包括组装玻璃材料层和导电、透射可见光的膜。膜在种子层的上具有透射可见光的金属层,该种子层在柔性聚合物支承体上包括氧化镓、氧化铟、氧化镁、氧化锌或它们的混合物(包括混合型氧化物和掺杂型氧化物)。玻璃材料和膜粘合在一起成为一体的制品。
本发明所公开的膜和制品当形成时或当经受弯曲、挠曲、拉伸、变形操作或暴露于腐蚀性环境时,提供对于剥离、断裂或腐蚀增加的抵抗力,同时仍然保持足够的导电率和良好的EMI屏蔽性能。在一个实施例中,金属层在膜的大部分区域上(例如在其中需要EMI屏蔽、加热或类似功能的膜的部分上)是基本上连续的。在一些实施例中,金属层可以在整个膜上完全连续;并且在其他实施例中,可以图案化金属层以限定有限数目的孔、洞或通道用于所需的功能(例如,提供一个或多个频率选择表面或截然不同的导电路径)。
本发明的这些方面以及其它方面在下面的具体实施方式中将显而易见。然而,在任何情况下,以上概述都不应理解为是对要求保护的主题的限制,该主题仅受所附权利要求书的限定,并且在审查期间可以进行修改。
附图说明
图1A-1E是示例性本发明所公开的膜的示意性剖视图。
图2是用于制备下面描述的膜的装置的示意图。
图3是没有种子层或在二氧化钛或氧化锌种子层上沉积的薄的银层膜的透光率和表面电阻率的图形表示。
图4是示出在多种溅射功率电平下使用氧化锌种子层和银金属层制备的实施例的透射比的坐标图。
图5是示出使用氧化锌种子层制备的实施例的透射比和反射的坐标图。
图6是示出使用二氧化钛种子层制备的对比膜的透射比和反射的坐标图。
在附图的多张图中类似的参考符号表示类似的元件。附图中的元件未按比例绘制。
具体实施方式
单词“一”、“一个”和“该”与“至少一种”可互换地使用,是指一种或多种所描述的元件。通过在本发明所公开的涂覆制品中对于多种元件的位置使用例如“顶上”、“上”、“最上”、“下面”等取向单词,我们是指元件相对于水平设置的、面向上的支承体的相对位置。并不预期膜或制品在其制造期间或者之后在空间中应该具有任何具体取向。
术语“复杂弯曲”当用于表面或制品时是指表面或制品从单点开始在两个不同的、非线性方向弯曲。
术语“共聚物”包括无规和嵌段共聚物两者。
术语“交联的”当用于聚合物时是指聚合物具有通过共价化学键(通常通过交联分子或基团)结合在一起以形成网状聚合物的聚合物链。一般来讲交联聚合物的特征在于不溶性,但是在存在合适溶剂的情况下可以为可溶胀的。
术语“可延展的”当用于金属层时是指当结合透射可见光的膜时可以在面内方向拉伸至少约3%,而没有电连续性损耗并且没有在金属层的表面中形成可见的不连续性(如肉眼在约0.25米的距离处检测的)的层。
术语“反射红外光的”当用于支承体、层、膜或制品时是指支承体、层、膜或制品在约700nm至约4,000nm的波长区域中在至少100nm宽的带中反射至少约50%的光(例如,在接近法线角处约6°入射角处测量)。
术语“光”是指太阳辐射。
术语“金属”包括纯金属和金属合金。
术语“非平面”当用于表面或制品(例如,玻璃或其他玻璃材料的)时是指表面或制品具有连续、间歇、单向或复杂弯曲。
术语“光学厚度”当用于层时是指层的物理厚度乘以其面内折射率。
术语“光学透明的”当用于膜或层合的玻璃制品时是指通过肉眼在约1米的距离处检测,在膜或制品中没有视觉上可见的失真、模糊或缺陷。
术语“聚合物”包括均聚物和共聚物,以及可以在可混溶共混物中例如通过共挤出或通过反应(包括,例如酯交换反应)形成的均聚物或共聚物。
术语“可见光透射比”或“透射可见光的”当用于支承体、层、膜或制品时是指支承体、层、膜或制品在550nm处具有大于50%的可见光透射比。
术语“没有显著的断裂或折痕”当用于层合玻璃制品中的膜时是指通过肉眼在约1米,优选地约0.5米的距离处检测,在膜中没有视觉不连续性。
术语“没有显著的褶皱”当用于层合玻璃制品中的膜时是指使用肉眼在约1米,优选地约0.5米的距离处检测,没有由平滑膜表面的收缩得到的小的脊和沟。
参见图1A,可用作例如EMI屏蔽的示例性膜在110总体地示出。膜110包括透射可见光的塑料膜(由例如聚对苯二甲酸乙二醇酯(“PET”)制成)形式的柔性支承体112和在支承体112上的叠层。叠层包括在支承体112上的成核氧化物种子层114(由例如氧化锌制成)、在种子层114上的可延展的金属层116(例如由银或银合金制成)以及在层116上的保护性聚合物层122(由例如交联丙烯酸酯制成)。保护性聚合物层122限制了对叠层的损坏并且还可以改变叠层的光学特性。如果需要可以通过任选的电极124使层116接地。种子层114、金属层116和保护性聚合物层122每个都是透射可见光的(正如膜110作为整体也是),并且优选地至少金属层116和保护性聚合物层122是连续的。种子层114不必是连续的并且可以比层116或122薄得多。例如,种子层114可以为一系列作为有助于更均匀或更致密重叠层116沉积的成核位点的小的岛状物。
在图1B中,另一个示例性膜在120总体地示出。膜120与膜110相似,但在支承体112和种子层114之间包括聚合物底层132(由例如交联丙烯酸酯制成)。底层132有助于平滑在支承体112中的表面粗糙和其他缺陷,并且有助于更平滑的层116的最后沉积。底层132还可以改变叠层的光学特性。
在图1C中,第三示例性膜在130总体地示出。膜130与膜110相似,但包括法布里-珀罗(Fabry-Perot)干涉叠层126以及在支承体112上硬质涂层134。叠层126包括第一透射可见光的金属层116、透射可见光的聚合物间隔层(spacing layer)118和第二透射可见光的金属层120。可以选择层116和120以及居间聚合物间隔层118的厚度以使得层116和120部分反射并部分透射。间隔层118的光学厚度为用于透射光的所需通带中心波长的约1/4至1/2。波长在通带内的光主要通过层116和120透射。波长在通带上或下的光主要由116和120反射。例如,可以选择金属层116和120以及间隔层118的厚度以使得膜透射可见光和反射红外光。硬质涂层134具有比例如图1B中的层132的聚合物底层更大的硬度(如使用例如铅笔硬度测试在暴露的硬质涂层上测定的)。即使硬质涂层134埋在叠层126和保护性聚合物层122的下面,相比于使叠层涂敷在较软的聚合物底层132或涂敷在支承体112上的制品,出人意料地硬质涂层134可以赋予叠层126改善的耐久性(如例如通过提高的耐磨性或在制品130上进行的铅笔硬度测试所表明的)。硬质涂层134还可以改变叠层的光学特性。硬质涂层134有利地包括填充剂颗粒136(由例如高折射率颗粒(例如氧化锌纳米颗粒)制成),相比于没有这种颗粒而制成的制品,当正确选择时其可以增加穿过制品130的可见光透光率。
在图1D中,另一个示例性膜在140总体地示出。膜140与膜130相似,但是包括透明的聚合物底层132而不是硬质涂层134。
在图1E中,又一个示例性膜在160总体地示出。膜160与膜140相似,但包括在聚合物层118和薄的金属层120之间的种子层115(由例如氧化锌制成),和在聚合物底层132下面的硬质涂层134。可以省略层132和134的任何一个或两个,或它们的顺序可以颠倒。
可以采用多种可透射可见光的支承体。在一个实施例中,支承体在550nm处具有至少约70%的可见光透光率。示例性的支承体包括但不限于柔性塑性材料,包括热塑性膜,例如聚酯(例如PET或聚萘二甲酸乙二醇酯)、聚丙烯酸酯(例如,聚甲基丙烯酸甲酯)、聚碳酸酯、聚丙烯、高或低密度聚乙烯、聚砜、聚醚砜、聚氨酯、聚酰胺、聚乙烯醇缩丁醛、聚氯乙烯、聚偏二氟乙烯、聚硫化亚苯和环烯聚合物(例如,得自Topas Advanced Polymers公司的TOPASTM和得自Zeon化工公司的ZEONORTM);以及热固性膜,例如纤维素衍生物、聚酰亚胺、聚酰亚胺苯并噁唑和聚苯并噁唑。支承体还可以为多层光学膜(“MOF”),例如在美国专利No.7,215,473B2中描述的那些。由PET和MOF制成的支承体是优选的。支承体可以具有多种厚度,例如,约0.01至约1mm的厚度。然而例如当需要自支承制品时,支承体可以相对更厚。此类自支承制品还可以通过如下步骤制备:在薄的、柔性支承体上形成本发明所公开的对照膜,并且将柔性支承体层合或者说是结合到更厚的、不可挠曲或较少挠曲的补充支承体(例如玻璃或塑料板)上。
涂敷的层的平滑度、连续性或粘合力中的一种或多种可以通过支承体的正确预处理而增大。在一个实施例中,预处理方案涉及在存在反应性或非反应性气氛(例如,空气、氮气、氧气或如氩气的惰性气体)的情况下支承体的放电预处理(例如,等离子体、辉光放电、电晕放电、介质阻挡放电或大气压放电)、化学预处理或火焰预处理。这些预处理可有助于确保重叠层的支承体的表面接受随后涂敷的层。在另一个实施例中,支承体被有机支承涂层(例如聚合物底层132或硬质涂层134的一种或两种)涂敷,可任选地然后使用等离子体进一步预处理或进行上述描述的其他预处理中的一个。当采用时,有机底层优选地基于一个或多个交联丙烯酸酯聚合物。如果有机底层为硬质涂层或包括硬质涂层,则硬质涂层优选地基于含无机氧化物颗粒的分散体的涂层组合物,例如在美国专利No.5,104,929(Bilkadi)中描述的组合物。3M 906耐磨涂层(得自3M公司)是优选的硬质涂层组合物。可以使用多种技术,包括溶液涂敷、辊涂(例如,凹版辊涂)或喷涂(例如,静电喷涂)涂敷一层或多层有机底层,然后使用(例如)UV辐射交联。有机底层(并且还希望有机间隔层和聚合物保护层)优选地通过闪蒸和气相沉积可辐射交联的单体或低聚物(例如,丙烯酸酯单体或低聚物),随后就地(使用例如电子束装置、UV光源、放电装置或其他合适的设备)交联来涂敷,如在上述提到的美国专利No.7,215,473B2和美国专利No.6,818,291B2、6,929,864B2、7,018,713B2以及在其中引用的文献中描述的。有机支承体涂层的所需化学组成和厚度部分将取决于支承体的性质。对于PET和MOF支承体,支承体涂层可以例如由丙烯酸酯单体或低聚物形成并且可以例如具有足以提供连续层的厚度(例如,几纳米至最多约2微米)。还可以调节底层的厚度以提高膜的光学特性,例如,增加穿过叠层的透光率并最小化叠层的反射率。成核氧化物种子层对支承体的粘合力可以通过在有机支承体涂层中包括粘合促进添加剂或抗腐蚀添加剂进一步提高。适合的粘合促进添加剂或抗腐蚀添加剂包括硫醇、酸(例如羧酸或有机磷酸)、三唑、染料以及润湿剂。一种具体的粘合促进添加剂,双-巯基乙酸乙二醇酯在美国专利No.4,645,714中描述。有利的是,添加剂存在的量足够提供增加的种子层粘合力,而不会引起种子层不适当地氧化或其他降解。
在一层或多层成核氧化物种子层中可以采用多种氧化物。在涂敷的多个种子层的情况下,它们可以是相同或不同的,有利地是相同的。种子层氧化物有利地促进随后以更均匀或更致密形式涂敷的金属层的沉积,或促进连续金属层的更早形成(即,以较薄的涂敷厚度)。合适氧化物的选择可以取决于所选的支承体和相邻的金属层,并且正常情况下将凭经验做到。代表性的种子层氧化物包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡以及它们的混合物(包括混合型氧化物和掺杂型氧化物)。例如,种子层可以包含氧化锌或掺杂有铝或氧化铝的氧化锌。可以使用在膜金属化领域中采用的技术形成一层或多层种子层,所述技术例如溅射(例如,平面或旋转的磁控溅射);蒸镀(例如,电阻或电子束蒸镀);化学气相沉积法;金属有机CVD(MOCVD);等离子体增大、辅助、或活化的CVD(PECVD);离子溅射;等。种子层可以便利地例如通过溅射种子层氧化物或就地通过溅射氧化的气氛中的前体金属直接形成。溅射靶还可以包括金属(例如,铝、铟、锡或锌)或氧化物(例如,氧化铝、氧化铟、氧化铟锡、氧化锡或氧化锌)以使得溅射靶更导电。示例性的溅射靶包括氧化锌∶氧化铝、氧化锌∶氧化镓、氧化锌∶氧化锡、氧化铟∶氧化锌、氧化铟∶氧化锡、氧化铟∶氧化锡∶氧化锌、铟∶锌、铟∶锡、铟∶锡∶锌、氧化铟镓锌或Zn(1-x)MgxO∶Al、MgIn2O(4-x)。其具体实例包括99∶1和98∶2的氧化锌∶氧化铝、95∶5的氧化锌∶氧化镓、93∶7的氧化锌∶氧化镓、90∶10的氧化铟∶氧化锌、90∶10和95∶5的氧化铟∶氧化锡、约76∶24至约57∶43的铟∶锌和90∶10的铟∶锡。多个种子层可以具有相同或不同的厚度,并且优选地每一个足够厚以使得随后涂敷的金属层是均匀的,具有最小的光吸收。优选地一层或多层种子层足够薄以确保所得的膜和采用膜的制品具有期望程度的可见光透光率。例如,一层或多层种子层的物理厚度(相对于光学厚度)可以为小于约20nm,小于约10nm,小于约8nm,小于约5nm,小于约4nm或小于约3nm。一层或多层种子层的物理厚度还可以为大于0nm,至少0.5nm或至少1nm。在一个实施例中,一层或多层种子层的物理厚度大于0并且小于约5nm。在第二实施例中,一层或多层种子层的物理厚度大于0并且小于约4nm。在第三实施例中,一层或多层种子层的物理厚度大于0并且小于约3nm。
在一层或多层金属层中可以采用多种金属。当采用多个金属层时,它们可以是相同或不同的并且有利地是相同的。示例性的金属包括银、铜、镍、铬、贵金属(例如,金、铂或钯)以及它们的合金。可以使用类似于上述提到的用于种子层的那些膜金属化领域中的技术,并且对于非贵金属使用非氧化大气环境形成金属层。一层或多层金属层足够厚以便为连续的,并且足够薄以确保本发明公开的膜和采用膜的制品具有期望程度的可见光透光率。金属层通常将比下面的种子层厚。在一个实施例中,一层或多层金属层的物理厚度将为约5至约50nm。在另一个实施例中,金属层厚度为约5至约15nm。在第三实施例中,金属层厚度为约5至约12nm。
如果需要,另外的交联聚合物间隔层(例如层118)和另外的金属层(例如层120)可以涂敷到第一金属层上。例如,包含3、4、5或6个金属层的叠层可以提供用于某些应用的期望特性。在一个具体的实施例中,膜可以具有包含2至6个金属层的叠层,其中金属层中的每一个具有设置在金属层之间的交联聚合物间隔层。
在图1C-1E中示出的交联聚合物间隔层118位于第一金属层116和第二金属层120或第二成核种子层115之间,并且可以由多种有机材料形成。如果需要,可以使用传统涂敷方法(例如辊涂(例如,凹版辊涂)或喷涂(例如,静电喷涂))涂敷间隔层。间隔层优选地使用(例如)类似当使用交联的有机底层时所采用的那些技术交联。交联的有机间隔层比非交联的有机间隔层具有若干优点。在形成或层合过程期间,交联的有机间隔层将不会如非交联有机间隔层一样明显地随着加热而熔融和软化,并且因此不太可能在温度和压力的同时影响下流动、变形或显著变薄。交联的有机间隔层是高度耐溶剂的,而非交联的有机间隔层可以被包括在汽车流体(例如汽油、油、透射流体和窗户清洗剂)中发现的那些溶剂溶解或明显地软化。与由相似聚合物加工得到的非交联有机间隔层相比,交联的有机间隔层还可以具有期望的物理特性,例如较高的模量和硬度、在应变时较好的弹性恢复或较好的回弹性。优选地间隔层在下面的金属层上就地交联。间隔层优选地通过涉及闪蒸、汽相沉积和交联单体或低聚物的方法形成,如在上述提到的美国专利No.6,818,291B2、6,929,864B2、7,018,713B2以及7,215,473B2和其中引用的文献中描述的。可挥发的(甲基)丙烯酸酯优选地用于此类方法,可挥发的丙烯酸酯是尤其优选的。通过冷却支承体可以提高涂敷效率。特别优选的单体包括多官能(甲基)丙烯酸酯,单独使用或与其他多官能或单官能(甲基)丙烯酸酯结合使用,例如二丙烯酸己二醇酯、丙烯酸乙氧基乙酯、丙烯酸苯氧基乙酯、(一)丙烯酸氰基乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸十八烷基酯、丙烯酸异癸酯、丙烯酸月桂酯、丙烯酸β-羧乙酯、丙烯酸四氢糠基酯、丙烯酸二腈酯、丙烯酸五氟苯基酯、丙烯酸硝基苯基酯、丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、(甲基)丙烯酸2,2,2-三氟甲酯、二丙烯酸二乙二醇酯、二丙烯酸三乙二醇酯、二甲基丙烯酸三乙二醇酯、二丙烯酸三丙二醇酯、二丙烯酸四乙二醇酯、二丙烯酸新戊二醇酯、丙氧基化的二丙烯酸新戊二醇酯、二丙烯酸聚乙二醇酯、二丙烯酸四乙二醇酯、双酚A环氧二丙烯酸酯、二甲基丙烯酸1,6-己二醇酯、三羟甲基丙烷三丙烯酸酯、乙氧基化的三羟甲基丙烷三丙烯酸酯、丙氧基化的三羟甲基丙烷三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、三丙烯酸季戊四醇酯、丙烯酸苯硫基乙酯、丙烯酸萘氧基乙酯、得自UCB化工公司的IRR-214环状二丙烯酸酯、得自Rad-Cure有限公司的环氧丙烯酸酯RDX80095,以及它们的混合物。多种其他可固化的材料可以包含在间隔层中,例如,丙烯酰胺、乙烯基醚、乙烯基萘、丙烯腈、以及它们的混合物。间隔层物理厚度部分取决于其折射率,部分取决于本发明所公开的膜的所需光学特性。优选的光学厚度为用于透射光的所需通带中心波长的约1/4至1/2。对于在阻隔红外线的干涉叠层中的应用,交联有机间隔层可以(例如)具有为约1.3至约1.7的折射率,约75至约275nm(例如,约100至约150nm)的光学厚度以及约50至约210nm(例如,约65至约100nm)的相应物理厚度。可以采用光学建模以选择合适的层厚度。
任何另外的金属层的平滑度和连续性以及它们对下面层(例如,对交联聚合物间隔层)的粘合力优选地在涂敷重叠金属层之前通过合适地预处理下面的层而增大,或通过在下面的层中包括合适的添加剂而增大。示例性的预处理包括上述的支承体预处理,例如间隔层的等离子体预处理。
本发明所公开的膜的最上层可任选地为合适的保护层,例如层122。多种有机材料可用于形成聚合物保护层。如果需要,可以使用传统的涂敷方法(例如辊涂(例如,凹版辊涂)或喷涂(例如,静电喷涂))涂敷保护层。保护层优选地使用(例如)类似于当使用交联的有机底层时可以采用的那些技术交联。保护层还可以单独形成并使用层合涂敷。优选地保护层使用上述闪蒸、汽相沉积和交联单体或低聚物形成。用于此类保护层的示例性的单体或低聚物包括可挥发的(甲基)丙烯酸酯。保护层还可以包含粘合促进添加剂。示例性的添加剂包括上述间隔层添加剂。如果本发明所公开的膜在机械吸能材料例如聚乙烯缩丁醛(“PVB”)的片之间层合,则可以选择保护层的折射率以最小化在界面处由机械吸能材料和本发明所公开的膜之间的折射率的任何差值引起的反射。还可以后处理保护层以提高保护层对机械吸能材料的粘合力。示例性的后处理包括上述支承体预处理。在一个实施例中,可以采用等离子体后处理本发明所公开的膜的两侧。
多种功能层或元件可以加入到本发明所公开的膜中以改变或提高它们的物理或化学特性,尤其是在至少一个膜表面。此类层或涂层可以包括(例如)使膜在制造过程中更易于处理的低摩擦涂层或滑颗粒;当膜紧邻另一层膜或表面放置时,向膜添加扩散特性或者抑制光耦合或牛顿环的颗粒;粘合剂,例如压敏粘合剂或热熔粘合剂;促进对邻近层的粘合力的底漆;用于当膜以粘合剂辊形式使用时的低粘合力背胶材料;以及允许通过一层或多层金属层的一层或多层的电流、电压感测或电容感测的电极。功能层或涂层还可以包括抗粉碎、抗侵入或抗刺穿-撕裂的膜和涂层(例如,在公布的PCT专利申请No.WO01/96115A1中描述的功能层)。另外的功能层或涂层还可以包括减振或吸声膜层,例如在美国专利No.6,132,882和5,773,102中描述的那些,和提供保护或改变膜对液体(例如水或有机溶剂)或对气体(例如氧气、水蒸气或二氧化碳)的透射特性的阻挡层。这些功能部件可以结合到膜最外层中的一层或多层,或它们可以涂敷为单独的膜或涂层。针对一些应用,可能有利的是,通过例如将染色的膜层层合到膜、将着色的涂层涂敷到膜的表面或在用于制备膜的一个或多个材料中包括染料或颜料来改变本发明所公开的膜的外观或性能。染料或颜料可以在光谱的一个或多个选择区域(包括红外、紫外或可见光谱的部分)中吸收。染料或颜料可以用于补充本发明所公开的膜的特性,尤其是膜透射一些频率而反射其他频率的情况下。在本发明所公开的膜中可以采用的尤其可用的着色层在美国专利No.6,811,867B1中有所描述。该层可以层合、挤出涂敷或共挤出为膜上的表皮层。颜料装填量可以在约0.01和约1.0重量%之间变化,以根据需要更改可见光透光率。还期望加入UV吸收覆盖层,以保护当暴露于UV辐射时可能不稳定的膜的任何内层。可以加入到本发明所公开的膜中的其他功能层或涂层包括(例如)防静电涂层或膜;阻燃剂层;UV稳定剂层;耐磨材料或硬涂层材料层;光学涂层;防雾材料;磁或磁光涂层或膜;液晶板;电致变色或电致发光板;感光乳剂;棱镜膜;以及全息膜或图像。另外的功能层或涂层在例如美国专利No.6,368,699、6,352,761和6,830,713中有所描述。本发明所公开的膜可以用例如油墨或其他印刷标记(例如用于显示产品标识、取向信息、广告、警告、装饰或其他信息的那些)处理。多种技术可以用于在本发明所公开的膜上印刷,包括网版印刷、喷墨印刷、热转移印刷、凸版印刷、橡皮版印刷、柔性版印刷、打点印刷、激光印刷等等,并且可以使用多种类型的油墨,包括单组分和双组分油墨、氧化干燥和UV干燥的油墨、溶解的油墨、分散的油墨和100%油墨系统。
当设置有电极时,本发明公开的膜可以用于(例如)天线、电磁干扰(EMI)屏蔽的目的,以及用于电热膜应用,例如玻璃、车辆窗户和显示器的除雾(de-fogging,de-misting)、除霜或除冰。电热膜应用可能需要显著的载流能力,但当需要可见光透射率时必须采用非常薄的(因此非常脆的)金属或金属合金层。电热膜应用公开于美国专利No.3,529,074、4,782,216、4,786,783、5,324,374和5,332,888中。电热膜在车辆安全玻璃(例如汽车、飞机、火车或其他车辆的挡风玻璃、背光源、天窗或侧窗)中是尤其受关注。有利的是,在低压下用于此类制品的金属层具有低的电阻,例如,小于或等于约20欧姆每平方的电阻。例如,金属层可以具有约5欧姆每平方至约20欧姆每平方的电阻,约7.5欧姆每平方至约15欧姆每平方的电阻,或约7.5欧姆每平方至约10欧姆每平方的电阻。
沿着法向轴测量,本发明所公开的膜和包括本发明所本公开的膜的制品优选地在光谱可见部分的透光率(可见光透射比)Tvis为至少约60%。在另一个实施例中,膜的可见光透射比为至少约70%。在又另一个实施例中,膜的可见光透射比为至少约75%。
本发明所公开的膜可以接合或层合到多种多样的基底。典型的基底材料包括玻璃材料,例如玻璃(其可以被绝缘、回火、层合、退火或热增强)和塑料(例如聚碳酸酯和聚甲基丙烯酸甲酯)。膜可以接合非平面基底,特别是具有复杂弯曲的那些。期望的是,膜为可延展的并且能够在层合和脱气过程中贴合上述非平面基底,而没有显著的断裂或折痕。本发明所公开的膜可以在足以有助于膜在没有显著褶皱情况下贴合非平面基底的条件下被取向并可选地热定型。当膜将要层合到的非平面基底具有已知的形状或弯曲时,并且尤其当基底具有已知的极复杂弯曲时,这是尤其可用的。通过单独地控制膜在每个面内方向的收缩,可以使得膜在层合期间(例如在压料辊层合或压热处理期间)以控制的方式收缩。例如,如果膜将要层合到的非平面基底具有复杂弯曲,那么可以定制膜在每个面内方向的收缩以匹配在那些方向的基底的具体弯曲特性。具有最大收缩的面内膜方向可以对准具有最小曲率(即,最大的曲率半径)的基底的维度。除了或取代根据曲率半径的表征曲率,如果需要还可以使用其他量度(例如由基底的主表面限定的几何表面测量的凸起或凹陷区域的深度)。对于层合到典型的非平面基底而言,膜收缩在两个面内方向可以大于约0.4%,在至少一个面内方向大于约0.7%,或在至少一个面内方向大于约1%。在一个实施例中,限制总体膜收缩以降低边缘分层或“抽出(pull-in)”。因此,膜收缩在每个面内方向可以小于约3%,或在每个面内方向小于约2.5%。收缩特性主要由下列因素控制:例如采用的膜或基底材料以及膜拉伸比率、热定型温度、停留时间和内束(相对于最大导轨设定测量的在拉幅热定型区的导轨间距的降低)。涂层还可以改变膜收缩特性。例如,底漆涂层可以降低横向(“TD”)收缩约0.2%至约0.4%并且增加纵向(“MD”)收缩约0.1至约0.3%。取向和热定形设备可以广泛地变化,并且理想的方法定形在各情况下实验地确定。关于用于制备具有目标收缩特性的制品的技术的进一步细节在美国专利No.6,797,396中有所描述。关于用于制备采用MOF支承体的制品以及用于制备采用一层或两层玻璃的层合物的技术的进一步细节在美国专利No.7,189,447B2中有所描述。
可以便利地用于制造本发明所公开的膜的装置170的实例在图2中示出。动力卷轴161a和161b使支承体162穿过装置170来回移动。温度控制的旋转筒163以及惰轮163a和163b载着支承体162通过等离子体预处理器164、种子金属或种子金属氧化物溅射涂敷器165、金属溅射涂敷器166、蒸发器167以及电子束交联装置168。液态单体或低聚物169从贮存器171提供到蒸发器167。在通过装置170的第一次操作中,第一成核氧化物种子层(例如层114)、第一金属层(例如层116)和(如果需要的话)有机间隔层(例如层118)可以涂敷到支承体162或在其上形成。当刚涂敷的支承体162从卷轴161b重新卷绕回到卷轴161a上时,有机间隔层可以起到限制对第一金属层的损坏的暂时保护层的作用。通过装置170的第二次操作可以用于涂敷或形成第二成核氧化物种子层(例如层115)、第二金属层(例如层120)和聚合物保护层(例如层122)。装置170可以封闭在合适的室(图2中未示出)中,并且保持在真空下或提供有合适的惰性气氛以使得氧气、水蒸气、粉尘和其他大气污染物不会干扰各种预处理、涂敷、交联和溅射步骤。活性气体(例如,氧气或水蒸气)还可以引入到装置170(或可以从支承体或从室本身中排气)以形成故意干扰,例如将金属层转变为氧化物层。
在以下的实例中对本发明进行进一步说明,其中除非另外指明,所有份数、百分比和比率均按重量计。
实例1
将一卷0.05mm(2密耳)厚的PET基底加载入类似于图2中示出的滚筒式真空室。基底在30.5m/min(100ft/min)线速度下向前运动,并且在以8.6×10-3托的压力提供的、250sccm的氩气和180sccm的氧气气氛在4.0kW下通过反应磁控溅射锌涂敷。依次地,在同次操作中,在以2.8×10-4托的压力提供的、40sccm氩气的气氛中在8kW下使用银磁控溅射基底。膜为可透射可见光以及反射红外光的,并且在550nm下呈现77.1%的透光率。电特性在下面的表1中示出。使用DELCOMTM电导系数监控器(德康仪器有限公司(Delcom Instruments,Inc.))测量传导性,并且片的电阻率作为测量的传导性值的倒数计算。膜具有11.5欧姆/平方的片电阻率。
比较例1
将一卷0.05mm厚的PET基底加载入实例1的真空室。基底在30.5m/min线速度下向前运动,并且在以2.8×10-4托的压力提供的、40sccm的氩气气氛中在8kW下用磁控溅射银涂敷。所得的膜在550nm处的透光率为66.2%并且具有18.7欧姆/平方的片电阻率。在没有种子层存在情况下制备的这种膜比实例1的膜具有更低的可见光透光率和更低的电导率。
比较例2
将一卷0.05mm厚的PET基底加载入实例1的真空室。基底在33.5m/min(110ft/min)线速度下向前运动,并且在以8.1×10-4托的压力提供的、10sccm的氩气气氛中在2.8kW下用磁控溅射钛涂敷。由于金属钛的高吸气趋势,认为种子层通过与室内附带的或支承体贡献的氧气反应形成二氧化钛。依次地,在同次操作中,在以1.2×10-3托提供的、140sccm的氩气气氛中在8kW下用银磁控溅射基底。膜在550nm处呈现64.9%的透光率。片电阻率为10.5欧姆/平方。使用钛溅射靶而不是锌靶制备的这种膜比实例1和比较例1的膜具有更低的可见光透光率。
表1
膜特性
图3比较了上述制备的一系列样品在550nm处的透光率对片电阻率。使用有叠加的十字的未填充矩形框,示出类似于实例1的膜制备的样品。使用未填充的菱形符号,示出类似于比较例1的膜制备的样品。使用填充(即,变黑的)的矩形框,示出类似于比较例2的膜制备的样品。图3示出总体来看根据实例1制备的样品比其他样品具有改善的透光率和导电性。
实例3
使用实例1的方法,但是用18.3m/min(60ft/min)的线速度和98∶2的氧化锌∶氧化铝种子层溅射靶,用氧化锌∶氧化铝成核种子层在1、4和8kW下磁控溅射PET基底,然后用银在2、3、4、5、6、8和10kW下磁控溅射PET基底。所得膜的光学特性在图4中示出,曲线A、B和C分别对应于1、4和8kW种子层功率电平,并且沿着每个单独曲线的点对应于增加的银功率电平。较高的银功率电平(并且对于多个运行,较高的种子功率电平)对应于较低的透光率水平。
实例4
PET支承体用光学叠层涂敷,光学叠层以丙烯酸酯/ZnO/Ag/丙烯酸酯/ZnO/Ag/丙烯酸酯的叠层构造按顺序包含交联的丙烯酸酯底层、第一氧化锌成核种子层、第一银金属层、交联的丙烯酸酯间隔层、第二氧化锌成核种子层、第二银金属层和交联的丙烯酸酯保护层。交联的丙烯酸酯层都使用64%IRR214丙烯酸酯(UCB化工公司)、28%丙烯酸正月桂酯和8%双-巯基乙酸乙二醇酯的混合物制备并且使用美国专利No.6,818,291B2的一般方法涂敷。氧化锌和银层使用实例1的一般方法涂敷。所得膜的透光率/反射曲线在图5中示出。在对比项中,使用用比较例2的一般方法涂敷的二氧化钛种子层制备相似的膜。所得膜的透光率/反射曲线在图6中示出。通过比较图5和图6可以看到,图5的光学叠层比图6的光学叠层一般来讲呈现更好的光学特性。
本文中引用的所有参考文献明确地以全文引用的方式并入本公开。已经对本公开涉及的示例性实施例进行了讨论,并涉及到了本公开范围内的可能的变型。在不脱离本公开的范围情况下本公开中的这些和其他变型和修改形式对于本领域的技术人员将显而易见,并且应该理解,本公开和下面示出的权利要求书不应限定于本文所述的示例性实施例。
Claims (25)
1.一种在柔性聚合物支承体上形成导电膜的方法,该方法包括:
a)在所述柔性聚合物支承体上形成不连续种子层,所述种子层包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或者含有它们的混合型氧化物或掺杂型氧化物的混合物;以及
b)在所述不连续种子层上沉积可延展的、透射可见光的金属层,其中所述导电膜可以在面内方向拉伸至少3%,而没有电连续性损耗并且没有在金属层的表面中形成通过肉眼在0.25米的距离处检测的可见的不连续性。
2.根据权利要求1所述的方法,还包括在所述支承体和所述不连续种子层之间形成有机支承体涂层。
3.根据权利要求1所述的方法,其中所述不连续种子层包括氧化锌。
4.根据权利要求1所述的方法,其中所述不连续种子层使用包括氧化锌:氧化铝、氧化铟:氧化锌、氧化铟:氧化锡、氧化铟:氧化锡:氧化锌、铟:锌、铟:锡、氧化铟镓锌、Zn(1-x)MgxO:Al或MgIn2O(4-x)的溅射靶而形成。
5.根据权利要求1所述的方法,其中所述金属层包括银。
6.根据权利要求1所述的方法,还包括:
c)在所述金属层上形成第二不连续种子层,所述第二不连续种子层包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或者含有它们的混合型氧化物或掺杂型氧化物的混合物;以及
d)在所述第二不连续种子层上沉积第二可延展的、透射可见光的金属层。
7.根据权利要求6所述的方法,还包括在所述金属层之间形成聚合物间隔层从而得到阻隔红外线的法布里-珀罗叠层。
8.根据权利要求1所述的方法,其中所述不连续种子层的物理厚度大于0并且小于5nm,并且所述金属层的物理厚度为5至50nm。
9.根据权利要求1所述的方法,其中所述膜的可见光透射比为至少70%并且片电阻率小于20欧姆每平方。
10.一种导电膜,包括柔性聚合物支承体;在所述支承体上的不连续种子层,所述种子层包括氧化镓、氧化铟、氧化镁、氧化锌、氧化锡或者含有它们的混合型氧化物或掺杂型氧化物的混合物;以及在所述种子层上的可延展的、透射可见光的金属层,其中所述导电膜可以在面内方向拉伸至少3%,而没有电连续性损耗并且没有在金属层的表面中形成通过肉眼在0.25米的距离处检测的可见的不连续性。
11.根据权利要求10所述的膜,还包括在所述支承体和所述不连续种子层之间的有机支承体涂层。
12.根据权利要求10所述的膜,其中所述不连续种子层包括氧化锌。
13.根据权利要求12所述的膜,其中所述氧化锌掺杂有铝或氧化铝。
14.根据权利要求10所述的膜,其中所述不连续种子层包括氧化铟:氧化锌、氧化铟:氧化锡、氧化铟镓锌、Zn(1-x)MgxO:Al或MgIn2O(4-x)。
15.根据权利要求10所述的膜,还包括在所述金属层上的第二不连续种子层和在所述第二不连续种子层上的第二金属层。
16.根据权利要求15所述的膜,其中所述金属层被聚合物间隔层分开并且提供阻隔红外线的法布里-珀罗叠层。
17.根据权利要求15所述的膜,还包括第三、第四、第五或第六不连续种子层和在所述第二金属层上的第三、第四、第五或第六金属层,其中所述金属层被聚合物间隔层分开并且提供阻隔红外线的法布里-珀罗叠层。
18.根据权利要求10所述的膜,其中所述不连续种子层的物理厚度大于0并且小于5nm,并且所述金属层的物理厚度为5至50nm。
19.根据权利要求10所述的膜,其中所述膜的可见光透射比为至少70%并且片电阻率小于20欧姆每平方。
20.根据权利要求10所述的膜,其中所述膜的片电阻率为7.5至15欧姆每平方。
21.一种包括根据权利要求10所述的膜的电装置。
22.一种用于制备玻璃制品的方法,该方法包括:
a)将玻璃材料层和膜组装,所述膜包括柔性聚合物支承体;在所述支承体上的不连续种子层,所述不连续种子层包括氧化镓、氧化铟、氧化镁、氧化锌或它们的混合物;以及在所述不连续种子层上的可延展的、透射可见光的导电金属层,其中所述膜可以在面内方向拉伸至少3%,而没有电连续性损耗并且没有在金属层的表面中形成通过肉眼在0.25米的距离处检测的可见的不连续性;以及
b)将所述玻璃材料和膜粘合在一起成为一体的制品。
23.根据权利要求22所述的方法,其中所述玻璃材料包括玻璃并且所述玻璃制品还包括在所述膜和所述玻璃之间的吸能层。
24.根据权利要求22所述的方法,其中所述不连续种子层包括氧化锌、氧化铟:氧化锌、氧化铟:氧化锡、Zn(1-x)MgxO:Al、MgIn2O(4-x)或氧化铟镓锌。
25.根据权利要求22所述的方法,还包括在所述金属层上的至少第二不连续种子层以及在所述第二种子层上的至少第二金属层,并且其中所述金属层被聚合物间隔层分开并且提供阻隔红外线的法布里-珀罗叠层,所述不连续种子层的物理厚度大于0并且小于5nm,并且所述金属层的物理厚度为5至50nm。
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JP2010514597A (ja) | 2010-05-06 |
EP2125361B1 (en) | 2019-01-23 |
CN101573228A (zh) | 2009-11-04 |
KR101511799B1 (ko) | 2015-04-13 |
US20100089621A1 (en) | 2010-04-15 |
JP5519293B2 (ja) | 2014-06-11 |
US9822454B2 (en) | 2017-11-21 |
BRPI0721299A2 (pt) | 2014-03-25 |
BRPI0721299B1 (pt) | 2018-07-24 |
KR20090104006A (ko) | 2009-10-05 |
EP2125361A1 (en) | 2009-12-02 |
WO2008083308A1 (en) | 2008-07-10 |
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