CN102869501A - 非pvc薄膜和非pvc薄膜层压材料 - Google Patents
非pvc薄膜和非pvc薄膜层压材料 Download PDFInfo
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Abstract
本发明涉及非PVC薄膜和薄膜层压材料,用于销售、广告活动,特别是室外或其它环境影响的促销和安全应用。在一个示例性实施方式中,薄膜包括两层,顶层和底层。所述顶层是氨基甲酸乙酯丙烯酸杂化聚合物,所述底层是基于非PVC的聚合物。薄膜可以是透明的、半透明的、清澈的或具有其它期望的光学特性。
Description
相关申请的交叉引用
本申请要求2010年3月4日提交的美国临时专利申请号61/310,378的优先权,其以其全部通过引用被并入本文。
发明领域
本发明处于对于小版式和大版式图形薄膜和呈现、广告媒体、促销媒介、静态视觉通讯、车辆和产品包装和其它商业应用使用的非PVC薄膜和非PVC薄膜层压材料的领域。薄膜可以是清澈的、透明的、半透明的或具有其它期望的光学特性。
发明背景
聚氯乙烯(PVC)薄膜已广泛用于许多促销和广告活动如过去的室外图形应用。这样的应用包括标志、旗帜、快速的销售图形、建筑和墙壁覆盖、消费者产品标签和其它压敏产品。然而,存在对使用基于PVC的产品的环境和健康影响的渐增了解,近年来这已显著增加。目前,存在从消费者销售、促销和广告产品流中减少或甚至消除基于PVC的产品的动向。
室外销售和图形应用的薄膜理想地应具有以下特点中的至少一些:印刷适性(printability)、耐久性、保色性(color retention)和抗划伤性。共形性(conformability)和适当的机械性能如拉伸伸长率和拉伸强度对应用过程也是优选的。非适应的薄膜,即不具有足够的伸长率或柔性的薄膜,不可遵循它被应用到的对象或表面的轮廓,在表面和薄膜之间产生气泡或空隙。不足的伸长性质可使薄膜难于应用到表面上,例如具有弯曲、角、脊和其它非平面构型的那些表面,但是太大的伸长率可使薄膜变形和潜在地引起印刷的标记扭曲。当被拉伸时如当薄膜正被应用到非平面表面时,具有低拉伸强度的薄膜可引起薄膜容易断裂。
由于新的PVC替代薄膜正在发展,该薄膜中的一些在一个方面如印刷适性具有优良性能,但是关于其它性质如室外耐久性,缺乏足够的功能性来使薄膜受到要求高的广告和促销市场的欢迎。解决上述问题的一个可能的方法是利用多层薄膜层压材料,每层提供一个或多个期望的性质,以便层压材料具有需要的所有期望的性质。
当用作薄膜层压材料最外面的保护层,或只是用作给定表面的保护薄膜时,良好的室外耐久性和在许多情况下光学透明性也是需要的,以便下面印刷层上的标记可看得见。
因此,存在用于室外图形和其它销售和消费者使用应用的基于非PVC的透明薄膜和非PVC薄膜层压材料的需要。
发明概述
下面描述的本发明的实施方式不是意欲是详尽的或将本发明限制到以下详细的描述中公开的精确形式。而是,选择和描述实施方式,以便本领域技术人员可理解和了解本发明的原理和实施。
本发明涉及基于非PVC的薄膜产品,其具有与常规的PVC提供物相似的性质,其适合与销售促销、图形、品牌运动和其它基于印刷或图像通信的发端联系使用。
在目前描述的发明的一个示例性实施方式中,非PVC薄膜——其可以是清澈的、透明的、半透明的或具有其它期望的光学特性——由聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或氨基甲酸乙酯丙烯酸杂化聚合物构成。
在目前描述的发明的另一个示例性实施方式中,非PVC透明薄膜包括顶层和底层。顶层包括聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或氨基甲酸乙酯丙烯酸杂化聚合物。底层包括基于乳剂的、基于溶剂的或基于挤出型非PVC的聚合物。
在目前描述的发明的另一个示例性实施方式中,提供非PVC薄膜层压材料,其包括顶层、底层、粘合剂层和基底。顶层包括氨基甲酸乙酯丙烯酸杂化聚合物。底层具有基于非PVC乳剂的聚合物。基底层具有印刷或成像的标记或图形。
在目前描述的发明的另外一个示例性实施方式中,广告图形被呈现并包括具有在其上提供的促销标记的表面、具有前面和后面的透明薄膜,后面与表面接触,前面暴露于大气(例如空气)或非大气(例如冰)。薄膜包括第一层和基本上在第一层下面的第二层和在第二层下面与第一层相对的粘合剂层。薄膜的第一层包括氨基甲酸乙酯丙烯酸杂化聚合物,第二层包括基于非PVC乳剂的聚合物。
根据以下详细的描述,本发明的其它特征和优势对本领域技术人员将变得明显。然而,应当理解,各个实施方式和具体实施例的详细描述——虽然指示本发明的优选和其它实施方式——通过例证而不是限制的方式被给出。可进行本发明范围内的许多改变和修改而不背离其精神,本发明包括所有这样的修改。
附图简述
通过参考以下本发明目前优选的示例性实施方式的更详细的描述联合附图,本发明的这些以及其它目的和优势将被更完全地了解和理解,其中
图1是根据本发明的薄膜的一个示例性实施方式的截面图解;
图2是图解制备根据本发明的薄膜的一个实施方式的示例性制造方法的框图;
图3是图解制备根据本发明的薄膜的一个实施方式的另一个制造方法的流程图;
图4是根据本发明的薄膜的一个示例性实施方式的截面图解;
图5是根据本发明的薄膜层压材料的另外示例性实施方式的截面图解;
图6图解根据本发明的应用到表面上的广告图形的示例性实施方式的顶视图;和
图7图解根据本发明的广告图形卷的示例性实施方式。
除非另外指出,上面图的图解不必按比例绘制。
发明详述
本文件中公开的装置和方法通过实例和参考图而被详细描述。除非另外指明,图中同样的数字表示对贯穿图中相同的、相似的或相应的元件的参考。应当理解,可对公开和描述的实例、排列、构型、组分、元件、装置、方法、材料等进行修改,并且该修改对具体应用可以是期望的。在本公开中,具体形状、材料、技术、排列等的任何确定或与呈现的具体实施例相关,或仅仅是这样的形状、材料、技术、排列等的一般描述。具体细节或实施例的识别不意欲,并不应被解释为强制性的或限制性的,除非特别地像这样指定。装置和方法的选择实例在下文中公开和参考图被详细描述。
本发明涉及用于室外图形应用、广告、促销和其它销售活动的薄膜和薄膜层压材料。更具体地,本发明涉及用于这样的应用的非PVC透明薄膜和非PVC薄膜层压材料。薄膜和薄膜层压材料提供适当的室外耐久性、抗划伤性、光泽、共形性、拉伸伸长率和拉伸强度。
在本发明的一个示例性实施方式中,具有适合用于室外图形应用的性质的单层透明薄膜由聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或聚氨酯丙烯酸杂化聚合物构成。
在本发明的另一个示例性实施方式中,多层透明薄膜提供适合用于室外图形应用的性质。多层薄膜具有至少两层。第一层由聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或氨基甲酸乙酯丙烯酸杂化聚合物构成。该第一层的厚度可以是约0.3密耳(7.6微米)至约2密耳(50.8微米)。其它层为全部构造提供另外的机械强度、改善的粘着、改善的共形性和减少的成本。层数可基于对产品的最终要求、成本限制和处理设备的获得性来确定。这样的其它层可由乳剂聚合物、溶剂聚合物或挤出型聚合物制成。合适的聚合物包括——没有限制——丙烯酸聚合物、苯乙烯丙烯酸聚合物、醋酸乙烯酯乙烯共聚物和聚烯烃。这样的其它层的厚度可以是约0密耳至约2密耳。乳剂聚合物的实例包括——没有限制——从BASF,Ludwigshafen,Germany获得的JONCRYL 617A JONCRYL 1987、JONCRYL 98、JONCRYL FLX5000、ACRONALNX4612X和ACRONAL OPTIVE 410;和来自Wacker Chemicals,Munich,Germany的VINNAPAS EF 811或其组合。
在本发明的另一个示例性实施方式中,非PVC透明薄膜包括顶层和底层。顶层由聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或聚氨酯丙烯酸杂化聚合物构成。底层包括基于非PVC乳剂的聚合物。 一般而言,基于非PVC的聚合物可以是基于乳剂的聚合物、基于溶剂的聚合物和/或挤出型聚合物。在某些实施方式中,基于非PVC的聚合物是丙烯酸聚合物。
如本文所用,术语“图形”指在一些表面上视觉可感觉的呈现,其意欲为商标、图解、招待、通知、广告、布告和销售产品、服务、项目等等。
现在参考图,其中图1提供根据目前描述的发明制备的示例性薄膜的断面图。薄膜100具有两层。薄膜可以是透明的、半透明的、清澈的或具有其它期望的光学特性。在一个示例性实施方式中,顶层102是氨基甲酸乙酯丙烯酸杂化聚合物。底层104在目前描述的实施方式中是强化聚合物层。
另外,薄膜层可具有至少一种加入到任何一层或两层的添加剂,或两种加入到一层或两层的添加剂。如果包括中间层(参见图4),添加剂还可存在于中间层。添加剂选自紫外线稳定剂、自由基清除剂、交联剂、增稠剂、流动和均化剂、流变学改性剂、表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料、共溶剂或其组合。
顶层102的氨基甲酸乙酯丙烯酸杂化聚合物是在分子水平混合的氨基甲酸乙酯聚合物和丙烯酸聚合物的组合。为了环保,顶层102优选由水性分散相产生,虽然产生氨基甲酸乙酯丙烯酸杂化聚合物的其它方法也可以使用。通常,有两种方法来制备这样的杂化聚合物分散体。在第一种方法中,制备聚氨酯分散体。然后将丙烯酸单体加入到聚氨酯分散体中。丙烯酸聚合物在存在聚氨酯分散体的情况下形成。在第二种方法中,形成聚氨酯预聚物。然后将丙烯酸单体加入到预聚物中。氨基甲酸乙酯和丙烯酸聚合同时完成。关于这些方法有许多出版物。例如,美国专利号Honig的3,684,758;Kaizerman的4,198,330;Loewrigkeit的4,644,030;和Tien的5,594,065详细描述上述方法。出版物、专利和专利申请在各处被引入该公开。本文引用的所有参考文献在此通过引用被并入。
根据上面描述的方法制备的氨基甲酸乙酯丙烯酸杂化聚合物分散体已被发现由于通过利用上述过程而发生的分子水平混合,当与两种聚合物的简单混合物相比时显示较好的机械性能。为了甚至更环保地制备制剂,即欲减少对其它制剂的环境影响,氨基甲酸乙酯丙烯酸杂化聚合物分散体可被进一步改善,以不含N-甲基吡咯烷酮(NMP)——通常在其它应用中用作处理溶剂的成分。
用于本发明的组合物的合适的氨基甲酸乙酯丙烯酸杂化聚合物分散体是具有脂肪族丙烯酸单体和脂肪族聚氨酯组分的那些分散体。由于产生的薄膜产品将用于室外环境,薄膜将暴露于水分,如露水、雨或雪;温度偏差;光和可影响薄膜性能的其它情况。例如,水分可引起薄膜组分或其上的图象褪色和薄膜自身变白。因此,需要保持亲水单体和其它组分的适当平衡,以当暴露于这样的情况时使该薄膜获得需要的抵抗力。单体和其它组分还应当被选择,以被平衡,以获得需要的拉伸性质、粘合阻力、抗划伤性、透明性和光泽。例如,存在于氨基甲酸乙酯丙烯酸杂化聚合物中的丙烯酸的量控制该顶层的拉伸性质。
用于本发明的合适的氨基甲酸乙酯丙烯酸杂化分散体在来自Air Products,Allentown,Pennsylvania的商品名HYBRIDUR下获得,包括HYBRIDUR 870;HYBRIDUR 570;HYBRIDUR 580;HYBRIDUR 878和来自DSM NeoResins,ofWaalwijk,The Netherlands的NEOPAC R9000。
可将紫外线屏蔽剂和自由基清除剂加入到顶层以改善室外耐久性。适合该应用的紫外线屏蔽剂通常是基于苯并三氮唑的化合物或在需要的区域能吸收紫外线能量的其它化合物。商业上可获得的紫外线吸收剂包括——没有限制——来自BASF,Ludwigshafen,Germany的TINUVIN 400 DW、TINUVIN 292;和来自Clariant;Muttenz,Switzerland的HOSTAVIN 3310。紫外线屏蔽剂的量可以在约0%至约5%的范围内。
还可将自由基清除剂可加入到薄膜顶层以改善顶层的耐候性。合适的自由基清除剂包括但不限于来自BASF,Ludwigshafen,Germany的TINUVIN 1130、TINUVIN 123DW;和来自Clariant,Muttenz,Switzerland的HOSTAVIN 3065。自由基清除剂的量可以在约0%至约5%的范围内。
其它紫外线屏蔽系统也可用于改善该薄膜的耐气候性。这些包括纳米大小的氧化锌和氧化铈或其组合,其可用于获得薄膜需要的抗紫外线性。合适的纳米金属氧化物包括但不限于来自BYK Additives of Altana,Wesel,Germany的NANOBYK 3840、NANOBYK 3810。添加剂的总量可以在约0%至约10%的范围内。
继续讨论图1提供的层压材料,底层104具有聚合物层,该聚合物层改善整个薄膜100的拉伸性质,其还可减少整个薄膜的成本。这样的强化聚合物层的实例包括——没有限制——基于乳剂的聚合物、基于溶剂的聚合物和挤出型聚合物。合适的聚合物包括——没有限制——丙烯酸聚合物、苯乙烯丙烯酸聚合物、醋酸乙烯酯乙烯共聚物和聚烯烃。也可将紫外线稳定剂和自由基清除剂加入到底层中。添加剂合在一起可以在全部制剂的约0%至约5%的范围内。
当丙烯酸聚合物用于底层104时,丙烯酸聚合物可以与顶层102中使用的丙烯酸聚合物相同或不同。脂肪族和芳香族丙烯酸均可适于包含在底层中。合适的丙烯酸聚合物包括具有优良的粘合阻力、拉伸性质和透明度的丙烯酸乳剂,如从BASF,Ludwigshafen,Germany获得的JONCRYL 617A。
顶层102的厚度可以在约0.5密耳至约5密耳的范围内。底层104的厚度可以在约0.5密耳(12.7微米)至约5密耳(127微米)的范围内。当顶层102的厚度太薄时,薄膜的耐化学性、抗划伤性和室外耐久性可受损害。当底层104的厚度太薄时,整个薄膜的拉伸性质可不足。与上述相反,当顶层和底层102、104分别太厚时,构建物的厚度还可影响薄膜的共形性。
薄膜100可利用对这样的目的合适的任何方法产生。在一个实施方式中,首先通过本领域技术人员熟知的技术将薄膜组合物沉积到可移去的支撑物或载体层上。这样的技术的实例包括冲模涂布(die coating)、刮刀涂布、帘式涂布和逆转辊涂布。在组合物已干燥之后可分离可移去的支撑物。示例性的可移去的支撑物可选自硅化带、剥离纸和剥离薄膜如PET或其它合适的材料。
制备根据本发明的薄膜的示例性方法显示在图2的框图200中。在步骤205启动工艺之后,下一步骤210要提供顶层组分和可移去的支撑物。接下来,在步骤215,混合顶层组分以形成顶层组合物。顶层组合物包括聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物或氨基甲酸乙酯丙烯酸杂化分散体以及自由基清除剂和紫外线屏蔽剂至少之一。接下来,在步骤220,用顶层组合物涂布可移去的支撑物,如通过槽冲模涂布(slot die coating)、帘式涂布或其它可接受的方法。在步骤225,干燥顶层组合物。干燥可通过利用受热的或周围空气环境、固化或通过其它合适的方法而发生。在步骤230,提供底层组分。在步骤235,混合底层组分以形成底层组合物。底层组合物包括乳剂聚合物或溶剂聚合物以及自由基清除剂和紫外线屏蔽剂至少之一。在步骤240,在顶层上涂布底层组合物,如通过槽冲模涂布。在步骤245,干燥底层组合物。可选地,在进行下一个步骤之前,将薄膜与压敏粘合剂(PSA)涂布的剥离衬里进一步层压。在步骤250,将可移去的支撑物从干燥的两层薄膜去除或分离。分离或去除可通过利用用于将薄膜与载体或支撑物层分离的剥离刀片或小刀来完成。可选地,在尖角处通过载体分离薄膜,以便薄膜可被容易地从载体或支撑物拾起。薄膜卷起并备用。可选地,可将薄膜切成和分成相等大小或不同长度的片材或部分。该方法在步骤255结束。
顶层和底层基本上彼此共同延伸,即,将边和/或面对齐和并列。当然,可能顶层可以以图案施加到底层上,以便层互相不完全并列。
在本发明的另一个实施方式中,顶层和底层组合物可被同时涂布到可移去的支撑物上。图3中的流程图300显示这样的示例性工艺。在步骤305开始之后,下一步骤310要提供顶层组分、底层组分和可移去的支撑物。接下来,在步骤315,混合顶层组分以形成顶层组合物。基本上同时,混合底层组分以形成底层组合物。接下来,在步骤320,利用双冲模同时涂布顶层组合物和底层组合物,顶层组合物接触可移去的支撑物,底层组合物接触顶层组合物。另外,顶层和底层可分开形成,然后通过常规器械被挤出或涂布到支撑物或载体上。在步骤325,干燥涂布的组合物。可选地,在进行下一步骤之前将薄膜进一步与涂布PSA的剥离衬里层压。干燥组合物之后,在步骤330中将可移去的支撑物或载体层从干燥的两层薄膜去除。可将薄膜卷起并备用或根据具体应用的需要而铺开。然后通过常规的方法如通过喷墨和静电印刷技术,薄膜可被印刷或成像或可选地,薄膜可被施加到先前可以已被印刷或成像的另一个基底上。该方法在步骤335结束。
除了上述以外,可用漆膜或其它材料进一步外涂布薄膜以提供光泽外观。该步骤可发生在薄膜形成过程期间、印刷之后或生产工艺已结束完成之后的材料收集之后。
本发明的薄膜可用于与图形或其它信息操作性结合。如本文所用,操作性结合包括将薄膜施加到图形或信息——包括作为薄膜的部分或作为另外的层如印刷层或先前印刷的层的图形或信息——上,或将图形或信息施加到薄膜上。
薄膜可用作室外应用、建筑和运输型广告活动等等的可印刷的介质。薄膜还可用作将被层压到对象上的保护性薄膜,如电子装置、建筑、艺术或美学元件、向后反射的汽车牌照、向后反射的标牌薄膜、名牌、标签、汽车外部和内部部分等等的保护性层压材料。另外的示例性应用可包括安全标志、图形显示、政府规定的显示、军事应用或在室外环境中需要保护的表面。
薄膜还可包括粘合剂层。粘合剂可以是压敏粘合剂、胶水和光学透明的任何其它类型的粘合剂,并且当用于接触印刷的标记时,将不影响印刷的标记。粘合剂可被图案涂布,并可针对特定性质如持久性、可移去性或可复位性等等而被选择。粘合剂可以是无规共聚物粘合剂或嵌段共聚物粘合剂。无规共聚物粘合剂包括基于丙烯酸和/或甲基丙烯酸共聚物、α-烯烃共聚物、硅氧烷共聚物、氯丁二烯/丙烯腈共聚物等等的那些无规共聚物粘合剂。嵌段共聚物粘合剂包括基于线性嵌段共聚物(即,A-B和A-B-A型)、分支嵌段共聚物、星状嵌段共聚物、接枝或放射状嵌段共聚物等等的那些嵌段共聚物粘合剂和天然和合成橡胶粘合剂。有用的压敏粘合剂的描述可在Encyclopedia of Polymer Science and Engineering,Vol.13.Wiley-Interscience Publishers(New York,1988)中找到。有用的压敏粘合剂的另外描述可在Encyclopedia of PolymerScience and Technology,Vol.1,Interscience Publishers(New York,1964)中找到。
当使用压敏粘合剂时,剥离衬里可用于保护粘合剂,避免与非预期的表面不注意的接触。可利用适于所选粘合剂的任何剥离衬里。对于压敏粘合剂,剥离衬里可以是,例如,涂布的纸或薄膜、和超级压光纸(calendared paper)。适于剥离衬里的涂料包括,例如,硅氧烷基和氟基材料、或具有期望的剥离性质的任何其它材料,例如,蜡和氨基甲酸酯。
图4显示本发明的一个实施方式。薄膜400具有顶层402、底层404、中间层406和剥离衬里408。在应用时,可将剥离衬里剥落以暴露粘合剂表面。薄膜可通过粘合剂层附加到要保护的表面。中间层可包括粘合剂层、粘结涂布层或粘附促进层。
薄膜还可用作较大的薄膜层压材料的部分。图5显示薄膜层压材料的一个实施方式的横断面视图。薄膜层压材料500由顶层502、底层504、粘合剂层506、油墨层510和下面的基底层512组成。虽然被称作油墨层,但是油墨可不必形成连续的层。多种可印刷的材料可用作下面的基底层。优选基于非PVC的可印刷的材料以制备整个基于非PVC的薄膜层压材料。国际专利申请PCT/US08/84812描述利用非PVC组合物产生的多种薄膜,并以其全部通过引用被并入。油墨或调色剂固定涂层,如聚乙烯醇可加入以增加对层压材料的印刷固定性。
图6显示根据本发明的施加到表面的广告图形薄膜的示例性实施方式的顶视图。通过利用粘合剂将具有广告图形614的薄膜层压材料布置到表面616上。
图7显示根据本发明的薄膜层压材料700的卷的示例性实施方式。
另外的组分,如增稠剂、流动和均化剂、流变学改性剂可加入到顶部和底部制剂中的每一个以获得期望的涂布质量。合适的增稠剂的实例包括——没有限制——来自Dow Chemicals,Midland,Michigan的ACRYSOL RM-2020 NPR、TM8W和UCARPOLYPHOBE 115 TR。合适的流动和均化剂的实例包括——没有限制——来自Dupont的ZONYL FS300;来自Omnova Solutions的Polyfox PF-156A;和来自MasonChemical Company的Masurf和具有相似化学性质的其它流动和均化剂。两层中的掺入百分比均可以在0%至10%改变。另外的粘度调节剂可包括在制剂中,以将粘度改变到期望的水平和/或赋予期望的流动特性。这些可以是基于氨基甲酸乙酯的碱可溶胀的缔合增稠剂。如来自Arkema Emulsion Systems的UCAR polyphobe 102或来自Elementis的Rheolate 350的产品是可在制剂中使用的一般实例。两层中的掺入百分比均可以在0%至10%改变。其它组分,如水或异丙醇(IPA)也可以以约0%至约10%加入到制剂中。
交联剂可加入到顶层制剂以改善该薄膜层的机械性能。合适的交联剂的实例包括——没有限制——来自DSM Neo Resins,Waalwijk,The Netherlands的基于聚氮丙啶的CX-100;来自Dow Chemicals,Midland,Michigan的UCARLINK XL-25SE、ERL-4221、ERL-4234;和来自Momentive Performance Materials Inc.,Waterford,New York的COATOSIL 1770、SILQUEST A-187。
没有限制,其它添加剂,例如,本领域技术人员已知的表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料和共溶剂可加入到顶层和底层中每一个的组合物中。
试验方法
厚度
利用获自Testing Machines Inc.in Ronkonkoma,NY的TMI Model 49-70 PrecisionMicrometer测量薄膜厚度。将样品置于上基准面和下基准面之间。上基准面在样品顶部,测量厚度并显示在数字指示仪上。
CIE L*a*b*颜色空间
该试验用于描述样品的颜色。该3维颜色空间系统由国际照明委员会(CIE)开发,并将L*限定为表示颜色的亮度,在0(黑色)至100(白色)之间。在该系统中,a*表示沿着红色(洋红色)/绿色轴的颜色位置,其中负值表示绿色,正值表示红色或洋红色,b*表示沿着蓝色/黄色轴的颜色位置,其中负值表示蓝色,正值表示黄色。该试验利用获自X-Rite,Inc.,Grand Rapids,Michigan的COLOR I 5台式分光光度计进行。该试验方法是TAPPI T524 om-94。
加速老化
加速老化试验通过将试验样品暴露于光、水分和温度极限来模拟材料长期室外暴露的损伤效应。测试并观察样品的耐光性(褪色)和耐气候性(破裂、灰化、卷曲、收缩等)。来自Atlas Material Testing Technology LLC in Chicago,IL的Atlas CI65A XenonArc老化试验机用于该试验。
首先将具有白色、黄色、洋红色、青色和黑色的条纹的印刷图案印刷在可印刷的基底上。然后将本发明的薄膜——其可以是透明的、半透明的、清澈的或具有其它期望的光学特性——层压到印刷层上,以通过利用压敏粘合剂来制备薄膜层压材料。在放置在老化试验机中之前先测试样品的CIE L*a*b*颜色空间。允许样品在老化试验机中老化指定量的时间。将样品从老化试验机中取出,进行CIE L*a*b*颜色空间读取和观察收缩、灰化、破裂等的任何改变。如果2000小时之后没有看得见的改变,并且由ΔE表示的L*、a*和b*合在一起的改变小于10,那么给予样品通过等级。利用以下公式计算ΔE值:
光泽
利用来自BYK Gardner USA in Columbia,MD的BYK Gardner Micro-TRI-Gloss光泽计来测量光泽。通用的测量角60°用于测量。通常,可接受的光泽读数是80或更高。
拉伸强度和拉伸伸长率
利用来自Instron Co.in Canton,MA的Instron Model 5542来测试薄膜的拉伸伸长率和拉伸强度。改良的ASTM D882用于测定本发明的薄膜的拉伸强度和伸长百分比。操作如下:
1.以机器方向切出1英寸x4英寸(25.4mmx101.6mm)样本。
2.在两个末端距离末端1英寸(25.4mm)紧握薄膜,因此紧握之间的间隔是2英寸(50.8mm)。
3.设置十字头速度每分钟12英寸(“ipm”)(每分钟304.8mm)。
4.获得拉伸强度,其是拉伸应力乘以薄膜厚度的结果。在断裂时的拉伸强度是在断裂时出现的最大应力乘以薄膜厚度。
5.机器报告伸长%。
标准需要180%的最小最终伸长率和每平方英寸0.5磅(“psi”)(6,895 N/m2)的最小拉伸强度。薄膜上压敏粘合剂(PSA)的存在或缺乏没有明显改变薄膜的强度和/或伸长率。因此,不论下面的实例中的薄膜包括PSA与否,均利用相同的薄膜但没有PSA层进行拉伸伸长率试验。
铆钉试验
将大约2.5英寸(63.5mm)x2.5英寸(63.5mm)的试验样品施加到来自Frontier TankCenter in Richfield,Ohio的刷有油漆的4英寸(101.6mm)x12英寸(304.8mm)铝板上。11.4mm(直径)X3.3mm(高度)X7.62mm(轴直径)(0.45"(直径)X0.13"(高度)X0.3"(轴直径))的扁铆钉头均匀地分布在铝板上。进行应用以最小化形成任何褶皱,特别是在这些铆钉头周围。利用针刺释放陷入的空气,而具有硬毛的刷子和塑料的橡皮滚子用于得到铆钉周围的薄膜的最佳共形性。将样品在环境状态存放24小时。测量和记录铆钉周围的薄膜的升高部分的直径。然后将样品置于来自Atlas Electric DevicesCo.in Chicago,Illinois的利用UVB 313灯泡的Atlas Ci5000 Xenon Arc老化试验机1000小时。然后取出样品并再次测量铆钉周围升高的薄膜的直径。当直径改变小于0.0625英寸(1.58mm)时,给予样品通过等级。
收缩试验
用来自Avery Dennison Corporation in Pasadena,CA的商品名S8072的压敏粘合剂以每平方米约30克(gsm)的涂层重量涂布试验样品。然后将样品附着到来自Q-LabCorporation of Cleveland,OH的干净的铝板。将样品在环境状态存放24小时。在薄膜上以纵向(machine direction,MD)和横向(cross-machine direction,CD)制备5英寸(127mm)网状线。然后将样品在160°F(71°C)老化48小时。测量MD和CD上的尺度改变。如果两个方向上的收缩都小于0.33%,那么给予样品通过等级。
实施例
以下实施例中使用的化学药品以及关于每一个的功能、制造和地点的信息列在表1中。
表1
表2列出用于产生顶层的制剂的五个实施例。
表2
实施例1至5:顶层组合物
表3列出用于产生底层的制剂的两个实施例。
实施例6至7:底层组合物
表3
实施例编号 | JONCRYL 617A | TINUVIN 292 | TINUVIN 1130 | 总计 |
% | % | % | % | |
6 | 99.0 | 0.50 | 0.50 | 100 |
7 | 98.65 | 0.675 | 0.675 | 100 |
表4列出利用实施例5作为顶层、实施例7作为底层以每层各种厚度产生的薄膜的五个实施例。
实施例8至12:薄膜
表4
实施例编号 | 顶层厚度(密耳) | 底层厚度(密耳) |
8 | 0.75 | 0.75 |
9 | 1 | 0.5 |
10 | 1 | 1 |
11 | 1.33 | 0.66 |
12 | 2 | 0.5 |
实施例13对照
将HYBRIDUR 870自身制成薄膜。当薄膜厚度是约1.7密耳(43微米)时,拉伸伸长率是80%。当薄膜厚度是约2.4密耳(61微米)时,拉伸伸长率是大约150%。当进行老化试验机试验时,薄膜显示大量收缩。
已测试了实施例8至12的各种性质。已测试了薄膜的薄膜厚度、在60度的光泽和拉伸伸长率。对于抗划伤性和收缩试验,每个样品用约30gsm来自Avery DennisonCorporation in Pasadena,CA的商品名S8072的压敏粘合剂涂布。对于加速老化和铆钉测试,将涂有粘合剂的样品进一步层压到可印刷的薄膜上。PCT申请PCT/US08/84812中,可印刷的薄膜是实施例编号29B,该申请以其全部通过引用被并入本文。
表5列出每个样品测量的性质。所有实施例已通过加速老化试验,具有在60度高于90的光泽,和高于200的拉伸伸长率。所有样品已通过抗划伤性试验、铆钉测试和收缩试验。
表5
实施例13三层薄膜
利用HYBRIDUR 870作为顶层、JONCRYL 617 A作为中间层和VINNAPAAS EF811作为第三层而产生三层薄膜。每层可以是约0.5密耳(12.7微米)至约2密耳(50.8微米)厚。
实施例14-17
表6列出用于产生顶层的制剂的四个另外的实施例。
表6
实施例18-22
表7列出用于产生底层的制剂的五个另外的实施例。
表7
本文提到的所有的专利、公开的申请和文章在此以其全部通过引用被并入。
说明书,包括权利要求、摘要和附图中公开的所有特征,和公开的任何方法或工艺中的所有步骤,可以以任何组合来进行组合,除了这样的特征和/或步骤中至少一些互相排斥的组合。说明书,包括权利要求、摘要和附图中公开的每个特征可由用于相同、相等或相似目的的备选特征替代,除非另外明确说明。因此,除非另外明确说明,公开的每个特征只是普通系列的相等或相似特征中的一个实例。
为了说明的目的提供本发明的前述详细的描述,它不意欲是穷尽的或将本发明限制到公开的具体实施方式。实施方式可提供不同的能力和益处,取决于用于实现本发明主要特征的结构。因此,本发明的范围只由以下权利要求来限定。
Claims (27)
1.光学上透明的保护性薄膜,包括:
顶层;和
基本上与所述顶层共同延伸的底层,和
其中所述顶层选自聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物和氨基甲酸乙酯丙烯酸杂化聚合物;和
所述底层由基于非PVC的聚合物构成。
2.如权利要求1所述的薄膜,其中所述基于非PVC的聚合物选自基于乳剂的聚合物、基于溶剂的聚合物和挤出型聚合物。
3.如权利要求1所述的薄膜,其中所述基于非PVC的聚合物是丙烯酸聚合物。
4.如权利要求1所述的薄膜,进一步包括:
粘合剂层,和
其中所述粘合剂层与所述底层接触。
5.如权利要求1所述的薄膜,进一步包括在所述薄膜的所述顶层和底层中至少之一中的至少一种添加剂。
6.如权利要求5所述的薄膜,其中所述至少一种添加剂选自紫外线稳定剂、自由基清除剂、交联剂、增稠剂、流动和均化剂、流变学改性剂、表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料、共溶剂、水、异丙醇和其组合。
7.薄膜层压材料,包括:
顶层;
底层;
中间层;
基底层,和
其中所述顶层选自聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物和氨基甲酸乙酯丙烯酸杂化聚合物;
所述底层包括基于非PVC的聚合物;
并且所述基底层具有在其上印刷或成像的标记。
8.如权利要求7所述的薄膜层压材料,其中所述中间层选自粘合剂层、粘结涂布层或粘附促进层。
9.如权利要求7所述的薄膜层压材料,进一步包括在所述薄膜的所述顶层、中间层和底层中至少之一中的至少一种添加剂。
10.如权利要求9所述的薄膜层压材料,其中所述至少一种添加剂选自紫外线稳定剂、自由基清除剂、交联剂、增稠剂、流动和均化剂、流变学改性剂、表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料、共溶剂、水、异丙醇和其组合。
11.广告或信息图形,包括:
具有在其上提供的促销标记的表面;
具有前面和后面的薄膜,所述后面与所述表面接触;
所述薄膜包括第一层和基本上在所述第一层下面的第二层以及在所述第二层下面与所述第一层相对的粘合剂层;和
其中所述第一层包括氨基甲酸乙酯丙烯酸杂化聚合物,所述第二层包括基于非PVC的聚合物。
12.广告或信息图形,包括:
表面;
粘合剂层;
具有前面和后面的可印刷的基底,所述后面面对所述表面并与所述粘合剂层接触,所述前面具有在其上提供的促销标记;
具有顶层和底层的透明薄膜,所述底层面对所述可印刷的基底的所述前面;和
其中所述顶层选自聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物和氨基甲酸乙酯丙烯酸杂化聚合物;和
所述底层包括基于非PVC的聚合物。
13.如权利要求12所述的广告图形,其中所述表面选自建筑、运输、艺术、美学、安全装置、道路标志、汽车外部和内部、军事、安全装置道路标志、外部汽车和其组合。
14.如权利要求12所述的广告图形,其中所述粘合剂层包括选自持久的粘合剂、可移去的粘合剂、可复位的粘合剂和其组合的粘合剂。
15.如权利要求12所述的广告图形,其中所述促销标记选自α和/或数字字符、图像和其组合。
16.如权利要求12所述的广告图形,其中在所述第一层和第二层之一上提供基底层。
17.如权利要求16所述的广告图形,其中所述基底层包括油墨层。
18.如权利要求12所述的广告图形,进一步包括在所述薄膜的所述顶层和底层中至少之一中的至少一种添加剂。
19.如权利要求18所述的广告图形,其中所述至少一种添加剂选自紫外线稳定剂、自由基清除剂、交联剂、增稠剂、流动和均化剂、流变学改性剂、表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料、共溶剂、水、异丙醇和其组合。
20.一卷或一张图形广告薄膜,包括:
具有至少第一层和第二层的薄膜,所述第一层包括氨基甲酸乙酯丙烯酸杂化聚合物,所述第二层包括基于非PVC乳剂的聚合物;和
所述第一和第二层之一被与广告标记操作性结合地提供。
21.如权利要求20所述的一卷或一张图形广告薄膜,其中所述薄膜进一步包括在所述第一层和第二层之一上提供的粘合剂层。
22.如权利要求21所述的一卷或一张图形广告薄膜,其中在所述粘合剂层上提供剥离层。
23.如权利要求20所述的一卷或一张图形广告薄膜,其中所述薄膜进一步包括在所述第一层和第二层之一上提供的基底层。
24.如权利要求23所述的一卷或一张图形广告薄膜,其中所述基底层包括印刷层。
25.如权利要求20所述的一卷或一张图形广告薄膜,进一步包括在所述薄膜的所述第一层和第二层中至少之一中的至少一种添加剂。
26.如权利要求25所述的一卷或一张图形广告薄膜,其中所述至少一种添加剂选自紫外线稳定剂、自由基清除剂、交联剂、增稠剂、流动和均化剂、流变学改性剂、表面活性剂、消泡剂、分散剂、湿润剂、染料、颜料、共溶剂和其组合。
27.用于室外环境的透明薄膜,包括选自聚氨酯、聚氨酯丙烯酸共聚物、聚氨酯丙烯酸混合物和氨基甲酸乙酯丙烯酸杂化聚合物的聚合物。
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EP2542409A1 (en) | 2013-01-09 |
US20120088054A1 (en) | 2012-04-12 |
CN102869501B (zh) | 2016-05-18 |
BR112012022175A2 (pt) | 2016-10-25 |
ES2712893T3 (es) | 2019-05-16 |
PL2542409T3 (pl) | 2019-05-31 |
MX2012010210A (es) | 2012-10-03 |
MX344924B (es) | 2017-01-11 |
JP6434547B2 (ja) | 2018-12-05 |
AU2011222600A1 (en) | 2012-10-04 |
JP2013521162A (ja) | 2013-06-10 |
KR20130037670A (ko) | 2013-04-16 |
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RU2012142182A (ru) | 2014-04-10 |
WO2011109692A1 (en) | 2011-09-09 |
US20140017433A1 (en) | 2014-01-16 |
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