CN111727224A - 聚乙烯膜组合物,层压体,及其制造方法 - Google Patents
聚乙烯膜组合物,层压体,及其制造方法 Download PDFInfo
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- CN111727224A CN111727224A CN201880088867.3A CN201880088867A CN111727224A CN 111727224 A CN111727224 A CN 111727224A CN 201880088867 A CN201880088867 A CN 201880088867A CN 111727224 A CN111727224 A CN 111727224A
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- transparent film
- film
- layer
- transparent
- density polyethylene
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Abstract
公开了一种透明膜,其具有含至少50wt%高密度聚乙烯,和任选地小于或等于50wt%的线性低密度聚乙烯的芯层。进一步地,该透明膜可具有与芯层的第一侧相邻的可印刷表层,其中可印刷表层可包括线性低密度聚乙烯或乙烯‑丙烯共聚物,基本上由其组成,或者由其组成。进一步地,透明膜可具有与芯层的第二侧相邻的表层,其中该表层可包括线性低密度聚乙烯或乙烯‑丙烯共聚物,基本上由其组成,或者由其组成。仍然进一步地,可在至少一个方向上取向透明膜,且该透明膜具有至少1200MPa的方向模量。可层压这种透明膜到层压基底,例如双轴取向的聚乙烯单层或多层膜上,以产生具有突出的密封和完整性的层压膜。
Description
相关申请的交叉参考
本申请是PCT申请,其要求2018年2月9日提交的美国临时专利申请序列号62/628,629的优先权,其全部内容通过引用并入于本文。
技术领域
本发明的公开内容涉及用于聚乙烯膜的组合物,结构体和方法,所述聚乙烯膜在包装、包裹和标记应用中包括阻隔保护和提高的密封性能二者。
背景技术
聚乙烯膜广泛用作包装中的密封件。未取向的膜通常具有中等的物理性能且需要结合到其它幅材例如纸、PET、BOPP等上以提供机械强度,或者例如金属化的PET、金属化的BOPP、尼龙或铝箔上以提供阻隔保护。尽管取向常常改进强度,但它也会负面影响密封性能,这对包装来说是不好的。而且,传统的流延或吹塑聚乙烯密封剂膜典型地没有被金属化,这是因为当层压到刚性幅材上时金属粘附性不能很好地粘附以保持完整性。
需要新的多层膜,其具有阻隔保护以及提高的密封性能和包装完整性。此外,需要新型的多层膜,其耐受金属化并提供良好的金属粘附性和金属化的阻隔性能。
发明概述
本发明公开了一种具有芯的透明膜,该芯包含至少50wt%高密度聚乙烯,和任选地小于或等于50wt%线性低密度聚乙烯。进一步地,该透明膜可具有与芯的第一侧相邻的可印刷表层,其中可印刷表层可包括线性低密度聚乙烯或乙烯-丙烯共聚物,基本上由其组成,或者由其组成。进一步地,透明膜可具有与芯的第二侧相邻的表层,其中该表层可包括线性低密度聚乙烯或乙烯-丙烯共聚物,基本上由其组成,或者由其组成。仍然进一步地,该透明膜可在至少一个方向上取向且具有至少1200MPa的方向模量(directional modulus)。可层压这种透明膜到层压基底,例如双轴取向的聚乙烯单层或多层膜上,以产生具有突出的密封和完整性的层压膜。
背景技术
在下面,为了方便起见参考附图使用了方向性术语,例如“上方”,“下方”,“上部”,“下部”,“正面”,“背面”,“顶部”,“底部”等。一般地,“上方”,“上部”,“向上”,“顶部”和类似术语指的是远离地球表面的方向,以及“下方”,“下部”,“向下”,“底部”等术语是指朝向地球表面的方向,但是这仅是出于说明的目的,并且这些术语并不旨在于限制本发明的公开内容。
现描述各种特定的实施方案,变通方案和实施例,其中包括此处为了理解目的而采用的示例性实施方案和定义。尽管以下详细描述给出了特定的优选实施方案,但是本领域技术人员将理解,这些实施方案仅是示例性的,并且可以以其它方式来实践本发明公开内容。为了确定侵权的目的,本发明的范围将涉及任何权利要求,其中包括它们的等同物以及与所列举的等同的要素或限制。
一般地,本申请公开了任选取向(即单轴和/或双轴)的多层聚乙烯(“PE”)膜,其任选地层压到PE基底上,金属化或未金属化的,以便在一些实施方案中产生单一材料层压体,它例如可允许容易的回收,和/或在一些实施方案中与现有的膜及其层压体相比改进了劲度。
如本文中所使用的,“聚合物”可用于表示均聚物、共聚物、互聚物、三元共聚物等。同样,“共聚物”可表示包含两种单体的聚合物或表示包含三种或更多种单体的聚合物。
如本文中所使用的,“中间”被定义为多层膜的一层的位置,其中所述层位于两层其它确定的层之间。在一些实施方案中,中间层可以与两层确定的层中的一层或两层直接接触。在其它实施方案中,附加层也可以存在于中间层与两层确定的层中的一层或两层之间。
如本文中所使用的,“弹性体”定义为基于丙烯的或基于乙烯的共聚物,其可以用力延伸或拉伸至其原始长度的至少100%,并且在去除力后迅速(例如,在5秒钟内)返回其原始尺寸。
如本文中所使用的,“塑性体”定义为密度范围为0.850g/cm3至0.920g/cm3且DSC熔点为至少40℃的基于丙烯或基于乙烯的共聚物。
如本文中所使用的,“实质上不含”定义为是指所参考的膜层在很大程度上但并非全部不存在特定组分。在一些实施方案中,作为标准制造方法的结果在参考层内可以存在少量组分,包括在处理过程中膜碎片的回收和边缘修整。
“基本上由…组成”是指例如,特定的膜层在构成膜层组合物的本体材料内不具有任何大于1wt%或2wt%或3wt%或4wt%或5wt%的其它聚合物,但“基本上由…组成”不排除特定膜层还具有添加剂,例如抗滑剂,防粘连剂,抗氧化剂,颜料,增白剂,空化剂等的可能性,而与什么聚合物或其它材料构成添加剂无关。
芯层
正如本领域技术人员已知的,多层膜的芯层最通常是最厚的层并提供多层结构的基础。在一些实施方案中,芯层包括双轴取向的聚乙烯(“BOPE”),例如高密度聚乙烯膜(“HDPE”)和/或密度大于0.94g/cm3的其它PE,基本上由其组成,或由其组成。在备选的实施方案中,芯层也可以包括其它聚合物,其中包括例如双轴取向的聚丙烯(“BOPP”),双轴取向的聚酯(“BOPET”),双轴取向的聚乳酸(“BOPLA”)及其组合。在又一备选的实施方案中,芯层也可以包含较少量的附加聚合物,所述附加聚合物选自乙烯聚合物、乙烯-丙烯共聚物、乙烯-丙烯-丁烯三元共聚物、弹性体、塑性体,不同类型的茂金属-LLDPE(m-LLDPE)及其组合。
芯层可以进一步包括烃树脂。烃树脂可用于增强或改变挠曲模量,改善可加工性或改善膜的阻隔性能。该树脂可以是与芯聚合物相容的低分子量烃。任选地,该树脂可以被氢化。该树脂的数均分子量可小于5000,优选小于2000,最优选范围为500至1000。该树脂可以是天然的或合成的并且可以具有在60℃至180℃范围内的软化点。
合适的烃树脂包括但不限于石油树脂、萜烯树脂、苯乙烯树脂和环戊二烯树脂。在一些实施方案中,烃树脂选自脂族烃树脂、氢化脂族烃树脂、脂族/芳族烃树脂、氢化脂族芳族烃树脂、脂环族烃树脂、氢化脂环族树脂、脂环族/芳族烃树脂、氢化脂环族/芳族烃树脂、氢化芳族烃树脂、多萜烯树脂、萜烯-酚树脂、松香和松香酯、氢化松香和松香酯、及其组合。
基于芯层的总重量,在芯层中的这类烃树脂的量,无论是单独还是组合,优选小于20wt%,更优选在1wt%至5wt%的范围内。
芯层可进一步包括一种或多种添加剂例如遮光剂、颜料、着色剂、空化剂、增滑剂、抗氧化剂、防雾剂、抗静电剂、填料、防潮添加剂、阻气添加剂,以及它们的组合,如下面进一步详细讨论的。合适的抗静电剂是ARMOSTATTM475(可从Ill.芝加哥的Akzo Nobel商购)。
基于芯层的总重量,空化剂可以以小于30wt%,优选小于20wt%,最优选在2wt%至10wt%的范围内的量存在于芯层中。
优选地,芯层中添加剂的总量占芯层的至多约20wt%,但是一些实施方案可以包括芯层中添加剂的量占芯层的至多约30wt%。
芯层的厚度范围优选为约5μm至100μm,更优选为约5μm至50μm,最优选为5μm至25μm。
衔接层
多层膜的衔接层典型地用于连接多层膜结构的另外两层,例如芯层和密封剂层,并位于这些其它层的中间。衔接层与芯层相比可以具有相同或不同的组成。
在一些实施方案中,衔接层与芯层的表面直接接触。在其它实施方案中,另一层或多层可以在芯层和衔接层之间。衔接层可以包含一种或多种聚合物。另外,该聚合物可包括C2聚合物、马来酸酐改性的聚乙烯聚合物、C3聚合物、C2C3无规共聚物、C2C3C4无规三元共聚物、多相无规共聚物、C4均聚物、C4共聚物、茂金属聚合物、基于丙烯或基于乙烯的弹性体和/或塑性体、丙烯酸乙基-甲基酯(EMA)聚合物、乙烯-乙酸乙烯酯(EVA)聚合物、极性共聚物及其组合。例如,一种聚合物可以是VISTAMAXXTM聚合物等级(可从得克萨斯州Baytown的ExxonMobil化工公司商购),例如VM6100和VM3000等级。或者,合适的聚合物可包括VERSIFYTM聚合物(可从密歇根州米德兰市的Dow化工公司商购)、Basell CATALLOYTM树脂例如ADFLEXTMT100F、SOFTELLTMQ020F,CLYRELLTMSM1340(可从荷兰的Basell聚烯烃公司商购)、PB(丙烯-丁烯-1)无规共聚物,例如Basell PB 8340(可从荷兰的Basell聚烯烃商购)、Borealis BORSOFTTMSD233CF(可从丹麦的Borealis商购)、EXCEEDTM1012CA和1018CA茂金属聚乙烯、EXACTTM5361、4049、5371、8201、4150、3132聚乙烯塑性体、EMCC 3022.32低密度聚乙烯(LDPE)(可从得克萨斯州Baytown的ExxonMobil化工公司购买)。
在一些实施方案中,衔接层可以进一步包含一种或多种添加剂例如遮光剂、颜料、着色剂、空化剂、增滑剂、抗氧化剂、防雾剂、抗静电剂、防粘连剂、填料、防潮添加剂、气体阻隔添加剂及其组合,如下文进一步详细讨论的。
衔接层的厚度范围典型地为约0.50至25μm,优选约0.50μm至12μm,更优选约0.50μm至6μm,和最优选约2.5μm至5μm。然而,在一些较薄的膜中,衔接层的厚度可以为约0.5μm至4μm,或约0.5μm至2μm,或约0.5μm至1.5μm。
表皮层,其中包括可金属化表皮层和可印刷层
在一些实施方案中,表皮层包括选自聚乙烯共聚物或三元共聚物(它可以被接枝或共聚)中的至少一种聚合物,基本上由其组成,和/或由其组成。在一些实施方案中,聚乙烯可包括含酸的部分,所述含酸的部分可以是基于丙烯酸的,基于甲基丙烯酸的,另一种有机酸,或其组合。含酸聚合物中的含酸部分可以是4wt%至20wt%,或6wt%至16wt%,或8wt%至12wt%。作为实例,可使用Exxon Mobil Escor EAA树脂或Dupont Nucrel EAA树脂或Dow Primacor EAA树脂。对于金属化或阻隔性能来说,酸改性的表皮层可含有LLDPE或乙烯乙烯醇基聚合物(“EVOH”),一种合适的EVOH共聚物是EVALTMG176B或XEP 1300(商购于日本的Kuraray有限公司)。
表皮层也可包括加工助剂添加剂,例如防粘连剂,抗静电剂,增滑剂及其组合,如下文进一步详细讨论的。
表皮层的厚度取决于表皮层打算的功能,但范围典型地为约0.20μm至3.5μm,或0.30μm至2μm,或在许多实施方案中,0.50μm至1.0μm。在薄膜实施方案中,表皮层的厚度范围可以是约0.20μm至1.5μm,或0.50μm至1.0μm。
添加剂
存在于膜层中的添加剂可包括但不限于遮光剂、颜料、着色剂、空化剂、增滑剂、抗氧化剂、防雾剂、抗静电剂、防粘连剂、填料、防潮添加剂、气体阻隔添加剂、气体清除剂及其组合。这些添加剂可以以有效量使用,其有效量取决于所需的性能。
合适的遮光剂、颜料或着色剂的实例是氧化铁、炭黑、铝、二氧化钛(TiO2),碳酸钙(CaCO3)及其组合。
空化或引发空隙的添加剂可包括在双轴取向温度下与它向其中添加的层的聚合物材料不相容的任何合适的有机或无机材料,以产生不透明的膜。合适的引发空隙的颗粒的实例是PBT、尼龙、实心或空心的预先形成的玻璃球、金属珠或球、陶瓷球、碳酸钙、滑石粉、白垩或其组合。引发空隙的颗粒的平均直径典型地可以为约0.1至10μm。
用于多层膜的一层或多层表皮层的非迁移性增滑剂可包含聚甲基丙烯酸甲酯(PMMA)。取决于层厚度和期望的滑爽性,非迁移性增滑剂的平均粒度范围可以是约0.5μm至8μm,或1μm至5μm,或2μm至4μm。或者,非迁移性增滑剂如PMMA中的颗粒尺寸可大于包含增滑剂的表皮层的厚度的20%,或大于表皮层的厚度的40%,或大于表层厚度的50%。这种非迁移性增滑剂的颗粒尺寸还可以比表皮层的厚度大至少10%,或者比表皮层的厚度大至少20%,或者比表皮层的厚度大至少40%。通常考虑球形的、颗粒状的非迁移性增滑剂,其中包括PMMA树脂,例如EPOSTARTM(可从日本的Nippon Shokubai有限公司商购)。还已知存在其它商业上合适材料的来源。非迁移性是指这些微粒通常不以迁移性滑爽剂的方式改变整个膜层中的位置。还考虑了常规的聚二烷基硅氧烷,例如粘度为10,000至2,000,000厘沲的硅油或树胶添加剂。
抗静电剂可以包括碱金属磺酸盐、聚醚改性的聚二有机硅氧烷、聚烷基苯基硅氧烷和叔胺。基于层的总重量,此类抗静电剂的用量可以采用约0.05wt%至3wt%的用量范围使用。
合适的抗粘连剂的实例可包括基于二氧化硅的产品,例如44(可从马里兰州Colombia的Grace Davison Products商购),PMMA颗粒例如EPOSTARTM(可从日本的Nippon Shokubai有限公司获得),或聚硅氧烷,例如TOSPEARLTM(可从康涅狄格州威尔顿的GE Bayer Silicones获得)。这种抗粘连剂的有效量占添加抗粘连剂的层的重量的至多约3000ppm。
有用的填料可以包含:细碎的无机固体材料,例如二氧化硅、气相二氧化硅、硅藻土、碳酸钙、硅酸钙、硅酸铝、高岭土、滑石、膨润土、粘土和纸浆。
任选地,非离子或阴离子蜡乳剂可包含在涂层中,即密封层中,以改善抗粘连性和/或降低摩擦系数。例如,密封剂层中可以包括Michem Lube 215,Michem Lube 160的乳剂。可以考虑用在热塑性膜中的任何常规蜡,例如但不限于CarnaubaTM蜡(可从俄亥俄州辛辛那提市的Michelman Corporation购买)。
金属化
表皮层和/或层压基底的外面(即背离芯的一侧)可以在任选地对其进行处理之后进行金属化。可以通过常规方法进行金属化,例如通过沉积金属层(例如铝、铜、银、铬或其混合物)的真空金属化。在金属化之后,可以在真空室的“外部”或“内部”将涂层施加到外部金属化层,以产生以下结构:金属化层/密封剂层/芯/密封剂层/金属化层。在另一个实施方案中,可以在金属表面上施加底漆,然后进行顶涂。
在某些实施方案中,用于金属化的金属是金属氧化物、能够真空沉积、电镀或溅射的任何其它无机材料或有机改性的无机材料例如SiOx,AlOx,SnOx,ZnOx,IrOx,其中x=1或2、有机改性的陶瓷“ormocer”等。沉积层的厚度通常在100至5,000埃的范围内,或优选在300至3000埃的范围内。
表面处理
可以对多层膜的一个或两个外表面进行表面处理以增加表面能,以使该膜能够接受金属化、涂层、印刷油墨、粘合剂和/或层压。可以根据本领域已知的方法之一进行表面处理,其中包括电晕放电、火焰、等离子体、化学处理或借助极化火焰的处理。
打底漆
可以将中间底漆涂层施加到多层膜上。在这种情况下,可以首先通过前述方法之一处理膜,以在其上提供增加的活性粘合剂位点,然后可以随后在如此处理的膜表面上施加底漆材料的连续涂层。这样的底漆材料在本领域中是众所周知的,并且包括例如环氧树脂、聚(乙烯亚胺)(PEI)和聚氨酯材料,美国专利号3,753,769、美国专利号4,058,645和美国专利号4,439,493,其各自通过引用并入本文,公开了此类底漆的用途和应用。底漆提供了与随后的涂料组合物充分且牢固结合的整个粘合活性表面,并且可以通过常规的溶液涂覆方法,例如通过辊涂将其涂覆到膜上。
取向
在某些实施方案中,本文的膜还以双轴取向为特征。膜可以通过本领域已知的任何合适的技术来制造,例如拉幅或吹塑工艺,LISIMTM,和其它。此外,工作条件、温度设置、生产线速度等将根据所用设备的类型和尺寸而变化。尽管如此,这里总体上描述的是制备贯穿本说明书描述的膜的一种方法。在一个特定的实施方案中,使用拉幅法形成膜并使其双轴取向。在拉幅工艺中,可以实现大于100m/min至400m/min或更高的线速度,以及大于2000kg/h至4000kg/h或更高的产量。在拉幅工艺中,将各种材料的片/膜熔融共混并共挤出,例如通过3、4、5、7层模头,将其共挤出成所需的膜结构。直径范围为100mm至300mm或400mm,且长度与直径之比范围为10/1至50/1的挤出机可用于熔融共混熔融层材料,然后将熔体流计量加入模头间隙为0.5或1至上限为3或4或5或6mm的模头中。然后使用空气,水或两者冷却挤出的膜。典型地,将部分浸没在水浴中的单个、大直径辊或设置在20或30至40或50或60或70℃的两个大的冷却辊是合适的冷却装置。挤出膜时,使用气刀和边缘钉扎使熔体和冷却辊之间提供紧密接触。
在拉幅工艺的这一实施方案中的第一冷却步骤的下游,将未取向的膜重新加热至80至100或120或150℃的温度,在一个实施方案中,通过任何合适的方式,例如加热的S-缠绕辊,然后在紧密间隔的差速辊之间通过以实现纵向取向。本领域技术人员可以理解,该温度范围可以根据设备而变化,且特别地取决于组成膜的组分的特性和组成。理想情况下,温度应低于使膜熔化的温度,但温度应足够高以利于纵向取向过程。本文所指的这种温度是指膜温度本身。可以通过使用例如红外光谱法来测量膜温度,其中红外源在处理膜时对准膜;本领域技术人员将理解,对于透明膜,测量实际膜温度将不那么精确。可以根据仪器将膜生产线的加热装置设置在任何合适的加热水平,以达到规定的膜温度。
延长和变薄的膜被送至生产线的拉幅机部分以进行TD定向。在这一点上,片材的边缘被连续链上的机械夹子抓住,并被拉入一个长的、精确控制的热风炉中进行预热步骤。在预热步骤中,膜温度范围为100或110至150或170或180℃。同样,温度将低于将使膜熔化的温度,但温度应足够高以促进横向取向的步骤。接下来,用连续链条上的机械夹子抓住片材的边缘,并将其拉入精确控制的长热风炉中进行横向拉伸。当拉幅机链发散所需的量以在横向拉伸膜时,相对于预热温度,工艺温度降低至少2℃,但典型地不超过20℃,以保持膜温度,从而它不会融化膜。拉伸达到膜横向取向后,将膜在低于熔点的温度下退火,然后将膜从拉伸温度以下冷却至5至10或15或20或30或40℃,然后在修边之前将夹子释放,然后可以进行任选的电晕(coronal),印刷和/或其它处理,然后进行缠绕。
因此,TD取向是通过以下步骤实现的:预加热已经纵向取向的膜,然后在低于膜的熔点的温度下对其进行拉伸和退火,然后在更低的温度下进行冷却步骤。在一个实施方案中,本文所述的膜通过以下方法形成:通过首先将膜预热的方法赋予横向取向,随后相对于预热温度,将工艺温度降低2或3至5至10或15或20℃的范围,在进行薄膜横向取向的同时,随后将温度相对于熔点温度降低5至10或15或20或30或40℃的范围,保持或略微降低(超过5%)拉伸量,以使薄膜退火。后面的步骤赋予本文所述的膜低的TD收缩特性。因此,例如,在预热温度为120℃的情况下,拉伸温度可以为114℃,并且冷却步骤可以为98℃,或者在所公开的范围内的任何温度。如本领域技术人员将理解的,将所述步骤进行足够的时间以影响所需的膜性质。
因此,在某些实施方案中,本文所述的膜以至少5或6或7或8重的TD取向和至少2或3或4重的MD取向被双轴取向。通过如此成形,在某些实施方案中,至少三层(一层芯,两层表皮层,厚度为18-21μm)具有在TD上为100或110至80或90或200MPa范围内的极限拉伸强度;和在其它实施方案中,在MD上具有在30或40至150或130MPa范围内的极限拉伸强度。此外,在某些实施方案中,本文所述的SCS膜具有的MD埃尔门多夫撕裂度大于10或15g,而在其它实施方案中25TD埃尔门多夫撕裂度大于15或20g。
工业适用性
所公开的多层膜可以是独立膜、层压体或网。或者,可以将多层膜密封、涂覆、金属化和/或层压到其它膜结构上。层压基底本身可以是例如在有或无粘合剂辅助下的BOPE或未取向的流延或吹塑PE膜,增加温度和/或压力,水或溶剂等;此外,层压基底可以或者可以没有金属化和/或涂布。可以通过任何合适的方法来制备所公开的多层膜,所述方法包括以下步骤:共挤出根据本描述的说明书和权利要求书的多层膜;取向和制备用于预期用途的膜,例如通过涂布,印刷,纵切,或其它转换方法。
对于某些应用,可能需要将多层膜层压到其它聚合物膜或纸产品上,以用于包装装饰,其中包括印刷和金属化。这些活动通常由最终的终端用户或膜的制作人执行,他们处理膜以供应给最终的终端用户。
所制备的多层膜可以用作柔性包装膜以包装物品或商品,例如食品或其它产品。在一些应用中,膜可以形成袋型包,例如可以用于包装饮料、液体、颗粒或干粉产品。
例举的实施方案
以下是根据前述公开内容的例举生产的膜:
实施例1
实施例2
在实施例1中,使用茂金属LLDPE,但可使用其它类型的LLDPE,而不管是否在非-茂金属化学下形成,例如使用镧系或锕系或茂金属催化。此处,Prime Polymer SP3022的密度和熔体指数分别为0.927g/cm3和1.9。实施例1的芯层包括HDPE,基本上由其组成,或者由其组成,其中NOAV 19A和Exxon HTA108的密度和熔体指数分别为0.962g/cm3和0.72以及0.961g/cm3和0.70。在其它例举的实施方案中,芯层可包括密度为≥0.94g/cm3的PE,基本上由其组成,或者由其组成。
回到实施例2,在膜的表皮层和可印刷层中使用EP共聚物。芯层包括与20wt%的LLDPE结合的HDPE,基本上由其组成,或者由其组成。在其它例举的实施方案中,HDPE可占50,55,60,65,70,75,80,85,90,95,或98wt%结合50,45,40,35,30,25,20,15,10,5或2wt%的LLDPE。在这种混合物中,HDPE和LLDPE的重量百分比的组合可以加合至或者可以没有加合至100,因为芯层可以包括或者可以不包括其它物质。
在纵向上在100℃下将实施例1和2取向4.5倍和在横向上在115℃下取向8-10倍。在拉伸之后,这些膜的厚度均为20μm。在其它实施方案中,膜可以更薄或更厚。
在双轴取向之后,测量实施例1和2的横向性能,其中在下表中描述了结果:
模量(MPa) | 断裂应力(MPa) | 断裂应变(%) | |
实施例1-MD | 1427 | 106 | 263 |
实施例1-TD | 1571 | 117 | 60 |
实施例2-MD | 1245 | 74 | 196 |
实施例2-TD | 1436 | 97 | 83 |
表1
相当地,若前述双轴取向的实施例1和2在表皮层,芯层和可印刷层中含有LLDPE而不是实施例1的LLDPE/HDPE/LLDPE组合物和实施例2的EP共聚物/(HDPE+20%的LLDPE)/EP共聚物(即“LLDPE参考”),则结果将是:
模量(MPa) | 断裂应力(MPa) | 断裂应变(%) | |
LLDPE参考-MD | 299 | 57 | 380 |
LLDPE参考-TD | 500 | 74 | 186 |
表2
在双轴取向实施例1和2并在烘箱内放置7分钟之后,测量在所述温度下的尺寸稳定性,其中在下表中描述了结果:
表3
尺寸稳定性试验牵涉将已知原始尺寸的膜样品置于控温对流烘箱内一定时间段并测量在这种调节之后样品的长度。以%变化形式报道结果。负值表示收缩,而正值表示膨胀。
LLDPE参考以及实施例1和2的雾度分别测量为6%,25%和7%。
模量数据表明具有HDPE芯的膜的机械性能比具有较低模量的那些更硬和/或更加易于印刷。此外,HDPE膜具有良好的尺寸稳定性,这意味着在密封件变形之前层压体可在较宽的温度范围内密封。
通过粘合剂层压将LLDPE参考以及实施例1层压到透明基底,密封剂BOPE膜,和金属化密封剂BOPE膜上。在采用0.75s的停留时间和41N/cm2的夹钳压力下使用Otto Bruger密封设备之后,在层压的组合物/结构体上测量密封强度。在下表中,以g/英寸为单位报到这些密封强度:
80℃ | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ | |
LLDPE参考/金属化BOPE膜 | 140 | 1560 | 1660 | 1040 | 2070 | |
实施例1/金属化BOPE膜 | 190 | 1590 | 1460 | 1160 | 1320 | 2020 |
LLDPE参考/透明BOPE膜 | 0 | 150 | 2120 | 2900 | 3020 | |
实施例1/透明BOPE膜 | 0 | 270 | 2540 | 3260 | 3730 | 2670 |
表4
LLDPE参考/金属化BOPE膜和LLDPE参考/透明BOPE膜显示出在120℃下收缩和在130℃下熔融。实施例1/金属化BOPE膜和实施例1透明BOPE膜显示出在140℃下熔融。
生产袋子。具体地,在130℃下在具有横向和纵向夹钳的垂直形式填充密封(“VFFS”)机上生产袋子。所有PE层压体使用重叠密封,即外部幅材贴着内部幅材密封以形成纵向密封件。气密性是优良的,即当袋子在水下用手推时不存在泄漏。
测试袋子的抗滴落性。具体地,从两米的高度处下落十个450g的袋子。表4中的袋子无一敞开,而若幅材的外侧是PET或BOPP而不是LLDPE参考或实施例1或2的话,则袋子会敞开。
在密闭中,注意到作为外部幅材,在层压体内的实施例1或2比用LLDPE参考制造的袋子更硬。和正如前面建议的,所有-PE层压的袋子可以回收,而用BOPP或PET作为外部幅材和PE作为密封剂幅材制造的袋子是不可回收的。
尽管前述内容针对于公开的发明的例举实施方案,但是在不脱离本发明的基本范围的情况下,可以设计其它和进一步的实施方案,其中公开的组合物、系统和方法的范围由一个或多个权利要求确定。
Claims (20)
1.一种透明膜,其包括:
包含至少50wt%高密度聚乙烯的芯;
与芯的第一侧相邻的可印刷表层;
与芯的第二侧相邻的表层,
其中透明膜在至少一个方向上取向且具有至少1200MPa的方向模量。
2.权利要求1的透明膜,其中该可印刷表层基本上由线性低密度聚乙烯或乙烯-丙烯共聚物组成。
3.权利要求1的透明膜,其中该表层基本上由线性低密度聚乙烯或乙烯-丙烯共聚物组成。
4.权利要求1的透明膜,进一步包括小于或等于50wt%的线性低密度聚乙烯。
5.权利要求1的透明膜,进一步包括一种或多种添加剂。
6.权利要求1的透明膜,进一步包括一层或多层衔接层。
7.权利要求1的透明膜,其中透明膜的厚度小于或等于20μm。
8.权利要求1的透明膜,其中透明膜的雾度小于或等于10%。
9.权利要求1的透明膜,其中透明膜在烘箱内在100℃下7分钟之后的尺寸稳定性小于10%。
10.权利要求1的透明膜,其中透明膜耐受至少70MPa的方向应力。
11.权利要求1的透明膜,其中透明膜耐受至少60MPa的方向应力。
12.权利要求1的透明膜,其中将该透明膜共挤出。
13.权利要求1的透明膜,进一步包括层压基底,其中将透明膜层压到层压基底上以生产层压膜。
14.权利要求13的透明膜,其中层压基底是透明的。
15.权利要求13的透明膜,其中层压基底是未取向膜。
16.权利要求13的透明膜,其中将层压基底金属化。
17.权利要求13的透明膜,其中将层压基底涂布。
18.权利要求13的透明膜,进一步包括在透明膜和层压基底之间的粘合剂。
19.权利要求13的透明膜,其中层压膜在130℃下的密封强度为至少2000g/英寸。
20.权利要求13的透明膜,其中从两米处下落的层压膜的450克袋保持完整。
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