CN109070565A - 具有改进的密封性能的双取向的线性低密度聚乙烯膜 - Google Patents
具有改进的密封性能的双取向的线性低密度聚乙烯膜 Download PDFInfo
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- CN109070565A CN109070565A CN201780024254.9A CN201780024254A CN109070565A CN 109070565 A CN109070565 A CN 109070565A CN 201780024254 A CN201780024254 A CN 201780024254A CN 109070565 A CN109070565 A CN 109070565A
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Abstract
公开了打算提供高品质密封的用于多层膜的组合物,方法和用途,所述密封具有充足的密封强度以供在包装和其他应用中使用,同时与常规的未取向聚烯烃膜和网状物材料的常规组合相比,更加成本合算和更高产率。该膜包括具有芯层,表面表皮层,和密封剂表皮层的LLDPE的多层结构。芯层进一步包括爽滑剂,同时表皮层进一步包括防粘连剂。任选的实施方案可包括介于芯层和表皮层之间的衔接层,或者可在芯层或衔接层中的一层或多层内包括颜料。可以对表面表皮层进行表面处理(例如电晕放电处理),以改进对涂布或金属化的适用性。
Description
相关申请的交叉参考
本申请是要求2016年4月18日提交的美国临时专利申请序列号62/324,069优先权的专利合作条约(PCT)申请,其内容在本文中通过参考全文引入。
发明领域
本发明的公开内容涉及一种具有良好的密封性能的双取向的线性低密度膜。
背景技术
流延或吹胀的未取向的聚乙烯("PE")或聚丙烯("PP")膜在包装或其他应用中广泛地用作密封剂。
这种膜通常具有普通的物理性能,和因此与其他纤网材料,例如纸张,聚对苯二甲酸乙二醇酯("PET"),双轴取向("BO")的聚丙烯("PP"),聚酰胺,例如尼龙,铝箔或其他材料结合,以便提供例如增强的阻挡保护,刚度和印刷品质。
然而,结合这些膜与纤网材料的需求会增加这些膜的厚度,这也会降低来自给定量的聚合物的产率(和因此增加的制造成本)。
本发明的公开内容提供新的多层膜和方法,其兼有低的膜厚和在含有例如流体、油、粉末或纤维(在其他情况下,它们可能会干扰密封形成)的包装、袋子或其他容器的密封区域内增强的密封性能,例如高的密封强度,高品质的气密密封,和显著的污染中的密封性(Seal-Through-Contamination)。而且,这些新的多层膜转化成减少量的包装和材料成本,同时提供相同或改进的性能。
发明概述
在各种实施方案中,公开了多层膜,典型地具有改进的密封性能的聚合物膜,其包括芯层,任选地在芯的一面或两面上的中间的一层或多层衔接层,在芯的至少一面(或若存在的话,衔接层)上的密封剂层,和在一些实施方案中,包括在(任选地在其间具有衔接层的)芯的两面上的密封剂层。一层可以被处理和金属化,且任选地具有聚合物涂层,该聚合物涂层有或无底漆,和/或表皮层。
附图简述
图1描绘了与标准的基准膜(30DLOR)相比,若干公开实施方案的密封强度的试验结果。
详细说明
为了方便起见,在提到附图中,使用以下的方向性术语,例如“以上”,“以下”,“上部”,“下部”,“前面”,“后面”,“顶部”,“底部”等。一般地,“以上”,“上部”,“向上”,“顶部”和类似术语是指远离任何包装内容物的方向,和“以下”,“下部”,“向下”,“底部”和类似术语是指朝向任何包装内容物的方向,但仅仅为了阐述性目的意指,和这些术语并不意味着限制本发明的公开内容。
现描述各种具体的实施方案,变体和实施例,其中包括为了理解目的,本文采用的例举的实施方案和定义。尽管下述详细说明给出了具体的优选实施方案,但本领域技术人员要理解,这些实施方案仅仅是例举,和可按照其他方式实践本发明的公开内容。为了确定侵权的目的,本发明的范围是指任何权利要求,其中包括它们的等价范围,和与引述的那些相当的要素或限制。
可使用本文中所使用的“聚合物”指代均聚物,共聚物,互聚物,三元共聚物等。同样,“共聚物”可以表示包括两种单体的聚合物或者表示包括三种或更多种单体的聚合物。
本文所使用的“中间”定义为多层膜中一层的位置,其中所述层位于两层其他识别层之间。在一些实施方案中,中间层可以与两层识别层中任意一层或这两层直接接触。在其他实施方案中,额外的层也可存在于中间层和两层识别层之一或二者之间。
本文中所使用的“弹性体”定义为在力量下可延长或拉伸到其起始长度的至少100%,且一旦移除力量,则快速(例如在5秒内)恢复到其起始尺寸的丙烯-基或乙烯-基共聚物。
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和熔点为至少40℃的丙烯-基或乙烯-基共聚物。
本文中所使用的“基本上不含”定义为是指所提到的膜层大多数,但并非完全不存在特定组分。在一些实施方案中,作为标准制造方法的结果,其中包括在加工期间回收膜碎屑和边角料,小量组分可存在于所提到的层内。
已发现,以下例举的共挤出的双轴取向的线性低密度聚乙烯(LLDPE)膜的某些实施方案可在降低的厚度下提供增强的密封。可例如在双取向生产线,例如在美国专利No.8,080,294(本文通过参考将其引入)中描述的生产线上生产这种膜。在表1-4中列出的下述实例中,注意膜的厚度为30μm,但其他实施方案可具有变化的厚度,且可以落在例如10μm至120μm范围内。
电晕处理的表面
表1-参考例
电晕处理的表面
表2-样品1电晕处理的表面
表3-样品2电晕处理的表面
表4-样品3电晕处理的表面
表5-样品4
在前述实例中,在各种共挤出层当中LLDPE树脂就物理性能,例如熔体指数,密度,熔融峰等等可以相同或不同。在一个实施方案中,密封剂一侧的表皮层和衔接层中的LLDPE可具有比芯层和/或面向外的表皮层和衔接层中的LLDPE高的熔体指数和低的密度,以便提高密封剂一侧的层的热密封性能并避免因密封引起的视觉变形和流变学缺陷。由于类似的原因,密封剂表皮层包括较大浓度的防粘连剂,例如沸石和/或硅酸盐(可使用其他防粘连剂,正如随后讨论的)。
在芯层中,使用一种或多种茂金属-催化的LLDPE,通常因为m-LLDPE改进了双取向的加工性。然而,在密封剂层、衔接层或表皮层中,可使用m-LLDPE,齐格勒-纳塔(ZN-LLDPE),或其他LLDPE。后面的段落提供关于物理性能和其他密封剂特征可接受范围的细节。
关于实施例,为了确保基于表面上相同或至少类似LLDPE树脂的供应商不发生变化,运行样品1和2。此处样品1的下部衔接层和表皮层不同于样品2的下部衔接层和表皮层;在其他情况下这些样品膜是相同的。在这两种样品膜之间没有出现对比的密封性,阻挡效率和外观差别。
样品3的着色层使用15%的Ampacet TiO2母料,其中该母料是Ampacet 110359C,它是在LDPE载体内70%的TiO2。尽管TiO2是颜料,但在其他实施方案中,可替代地使用非-白色颜料或者与白色颜料结合使用。相反,除了着色以外,空化剂,例如CaCO3可赋予消费者所期望的所需的白色-不透明性能且仍然提供具有降低的密度和非凡的密封强度的薄膜。
大多数前述实施例在一层或多层内显示出迁移性爽滑剂。关于迁移性爽滑剂的备选,可使用非迁移性爽滑剂,正如样品4中一样。当进行如此时,通常将非迁移性爽滑剂置于一层或多层密封剂层内而不是芯层内。在本发明公开内容的随后提供了爽滑剂的进一步的讨论。
现回到图1,进行试验,其中使用溶剂-基粘合剂,例如Henkel的或Dow的AdcoteTM 575S,将所公开的膜样品粘附到聚酯("PET")基底上,并使用具有卷边钳(crimpjaw)设定的Otto Bruger密封器热密封以施加经0.75秒的停留时间的41N/cm2的压力。(自然地,压力和停留时间的变化对于密封强度做图来说可以不同)。在这些条件下,针对基准实施例,即获自Norfilm的30DLOR(基于LLDPE-C8和LDPE的共混物的吹胀薄膜,熔体指数为0.9g/10min(在190℃和2.13Kg条件下测量),和密度为0.923g/cm3),测量密封强度,单位g/英寸。
在图1中阐述了参考样品,样品1和样品3的性能。与参考和基准实例相比,样品1和样品3的实例在低温下显示出改进的密封强度。
在其他例举的实施方案中,可层压所公开的膜到吹胀的聚烯烃膜,例如PE上,以便生产赋予可回收优势的PE层压体。在其他例举的实施方案中,层压体可以是PP,丙烯-基聚合物,聚乙烯-基聚合物,其混合物,尼龙及它们的组合。
基于本发明的公开内容,诸如包装,袋子,标签,标记,水平-形成-填充-和-密封(horizontal-form-fill-and-seal)("HFFS")的容器,垂直-形成-填充-和-密封(vertical-form-fill-and-seal)("VFFS")的容器,盖子,小袋,直立式囊袋,外包装等等(即,通常为“用具)之类的结构可以由消费者可接受的所公开的组合物和膜形成。在一种特定的情况下,在VFFS包装机上制造袋子。在这一生产中,纵向肋片的密封温度和横向锯齿的密封温度为140℃。在每一生产的袋子中,填充350g聚丙烯树脂粒料。从2米处下落10个袋子,然后评价,在表6中阐述了其结果。在这一试验中,与参考实施例相比,样品1和3显示出好得多的抗袋子下落性,且性能接近于基准实施例。
实施例 | 在2m下落之后(10个袋子中)完整的袋子数 |
参考例/PET | 0 |
样品1/PET | 9 |
样品3/PET | 9 |
30DLOR/PET(基准) | 10 |
表6-下落试验结果
还在污染中的密封条件下测量密封强度。此处,用咖啡粉,牛奶或油污染膜,然后在使用经0.75秒的停留时间产生41N/cm2压力的具有卷边钳的Otto Bruger密封器上密封之后,测量密封强度。表7中阐述的结果表明样品1和3维持高的密封强度,甚至在用液体或粉末污染之后。
实施例 | 无污染物 | 咖啡粉 | 牛奶 | 油 |
参考例/PET | 0 | 0 | 0 | 0 |
样品1/PET | 9 | 9 | 9 | 9 |
样品3/PET | 9 | 9 | 9 | 9 |
30DLOR/PET(基准) | 10 | 10 | 10 | 10 |
表7-污染中的密封性试验结果
芯层
正如本领域技术人员已知的,多层膜的芯层最常见地为最厚的层且提供多层结构的基础。在一些实施方案中,芯层基本上由线性低密度聚乙烯("LLDPE")组成且基本上不含其他组分。在备选的实施方案中,芯也可含有比较小量的选自丙烯聚合物,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,塑性体及其组合中的额外聚合物。尽管绝不限制,但合适的LLDPE的实例是熔融指数为1至4g/10min(在190℃和2.13Kg条件下测量),密度为从0.915或更低至0.930g/cm3和熔融峰为90至138℃的那些。
芯层或衔接层或二者可进一步包括烃树脂。烃树脂可起到提高或改性弯曲模量,改进加工性或改进膜的阻挡性能的作用。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以小于5000,优选小于2000,最优选范围为500至1000。该树脂可以是天然或合成树脂且软化点范围可以是60℃至180℃。
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,聚萜烯树脂,萜烯-苯酚树脂,松香和松香酯,氢化松香和松香酯,及其组合。
如本文描述的可以适于使用的烃树脂包括EMPR 120,104,111,106,112,115,EMFR100和100A,ECR-373和2101,2203,2520,5380,5600,5618,5690(商购于ExxonMobil Chemical Company,Baytown,Tex.);ARKONTM M90,M100,Ml15和M135和SUPERESTERTM松香酯(商购于日本Arakawa Chemical Company);SYLVARESTM苯酚改性的苯乙烯,甲基苯乙烯树脂,苯乙烯化萜烯树脂,ZONATACTM萜烯-芳族树脂,和萜烯苯酚树脂(商购于Arizona Chemical Company,Jacksonville,Fla.);SYLVATACTM和SYLVALITETM松香酯(商购于Arizona Chemical Company,Jacksonville,Fla.);NORSOLENETM脂族芳族树脂(商购于法国Cray Valley);DERTOPHENETM萜烯苯酚树脂(商购于DRT Chemical Company,Landes,法国);EASTOTACTM树脂,PICCOTACTMC5/C9树脂,REGALITETM和REGALREZTM芳族和REGALITETM脂环族/芳族树脂(商购于Eastman Chemical Company,Kingsport,Tenn.);WINGTACKTM ET和EXTRATM(商购于Sartomer,Exton,Pa.);FORALTM,PENTALYNTM,以及PERMALYNTM松香和松香酯(商购于Hercules,现在Eastman Chemical Company,Kingsport,Tenn.);QUINTONETM酸改性的C5树脂,C5/C9树脂,和酸改性的C5/C9树脂(商购于日本Nippon Zeon);和LXTM混合芳族/脂环族树脂(商购于Neville Chemical Company of Pittsburgh,Pa.);CLEARONTM氢化萜烯芳族树脂(商购于日本Yasuhara);和PICCOLYTETM(商购于Loos&Dilworth,Inc.,Bristol,Pa.)。可在美国专利No.5,667,902中找到其他合适的烃树脂,本文通过参考将其引入。前述实例仅仅是阐述性的且绝不限制。
在芯层内或者单独或者结合的这种烃树脂的用量优选小于20wt%,更优选范围为1wt%至5wt%,基于芯层的总重量。
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,爽滑剂,抗氧化剂,防雾剂,抗静电剂,填料,湿气阻挡添加剂,气体阻挡添加剂,及其组合,正如以下进一步详细地讨论的。合适的抗静电剂是ARMOSTATTM 475(商购于Akzo Nobel ofChicago,Ill.)。
空化剂可以存在于芯层内,其用量小于30wt%,优选小于20wt%,最优选范围为2wt%至10wt%,基于芯层的总重量。
优选地,在芯层内添加剂的总量占芯层的最多约20wt%,但一些实施方案可在芯层内包括占芯层用量最多约30wt%的添加剂。
芯层的厚度范围优选为约5μm至100μm,更优选约5μm至50μm,最优选5μm至25μm。
衔接层
典型地使用多层膜中的衔接层,以连接多层膜结构中的两层其他层,例如芯层和密封剂层,且置放在这些其他层中间。衔接层可以具有与芯层相比,相同或不同的组成。
在一些实施方案中,衔接层与芯层表面直接接触。在其他实施方案中,另一层或另外的多层可以在芯层和衔接层的中间。衔接层可以包括一种或多种聚合物。另外,该聚合物可包括C2聚合物,C3聚合物,C2C3无规共聚物,C2C3C4无规共聚物,多相无规共聚物,C4均聚物,C4共聚物,茂金属聚合物,丙烯-基或乙烯-基弹性体和/或塑性体,或其组合。例如,一种聚合物可以是VISTAMAXXTM聚合物等级(商购于ExxonMobil Chemical Company,Baytown,Tex.),例如VM6100和VM3000等级。或者,合适的聚合物可包括VERSIFYTM聚合物(商购于TheDow Chemical Company,Midland,Mich.),Basell CATALLOYTM树脂,例如ADFLEXTM T100F,SOFTELLTM Q020F,CLYRELLTM SM1340(商购于荷兰Basell Polyolefins),PB(丙烯-丁烯-1)无规共聚物,例如Basell PB 8340(商购于荷兰Basell Polyolefins),Borealis BORSOFTTMSD233CF(商购于丹麦Borealis),EXCEEDTM 1012CA和1018CA茂金属聚乙烯,EXACTTM 5361,4049,5371,8201,4150,3132聚乙烯塑性体,EMCC 3022.32低密度聚乙烯(LDPE)(商购于ExxonMobil Chemical Company,Baytown,Tex.)。
在一些实施方案中,衔接层可以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,爽滑剂,抗氧化剂,防雾剂,抗静电剂,抗粘连剂,填料,湿气阻挡添加剂,气体阻挡添加剂,及其组合,正如以下进一步详细地讨论的。
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,衔接层的厚度可以是约0.5μm至4μm,或0.5μm至2μm,或0.5μm至1.5μm。
表皮层是任选的,和若存在的话,则在衔接层或芯层的外表面上提供。可提供表皮层,改进膜的阻挡性能,加工性,印刷性,和/或相容性以供金属化,涂布和/或层压到其他膜或基底上。
在一些实施方案中,表皮层包括选自聚乙烯聚合物或共聚物,聚丙烯聚合物或共聚物,乙烯-丙烯共聚物,乙烯-丙烯-丁烯("EPB")三元共聚物,丙烯-丁烯共聚物,乙烯-乙烯醇聚合物及其组合中的至少一种聚合物。优选地,聚乙烯聚合物是LLDPE,例如获自ExxonMobil Chemicals的ExceedTM树脂,或者获自Prime Polymer的EvolueTM树脂,或者获自Dow的EliteTM树脂。合适的乙烯-丙烯共聚物是Fina8573(商购于Fina Oil Company,Dallas,Tex.)。合适的EPB三元共聚物是Chisso 7510和7794(商购于日本ChissoCorporation)。对于涂布和印刷功能来说,表皮层可优选表面处理。对于金属化或阻挡性能来说,表皮层可含有LLDPE或乙烯乙烯醇基聚合物("EVOH")。合适的EVOH共聚物是EVALTMG176B或XEP 1300(商购于日本的Kuraray Company Ltd.)。
表皮层也可包括加工助剂添加剂,例如防粘连剂,抗静电剂,爽滑剂及其组合,正如以下进一步详细地讨论的。
表皮层的厚度取决于表皮层所打算的功能,但典型地范围为约0.50μm至3.5μm,优选约0.50μm至2μm,和在许多实施方案中,最优选为约0.50μm至1.5μm。此外,在较薄的膜实施方案中,表皮层的厚度范围可以是约0.50μm至1.0μm,或0.50μm至0.75μm。
涂层
在一些实施方案中,一层或多层涂层,例如用于阻挡,印刷和/或加工的涂层可施加到多层膜的外表面上。例如,涂层可直接在芯层的任意一面或两面上的衔接层的外表面上(即远离芯的那些表面),或在别处。这种涂层可包括丙烯酸类聚合物,例如乙烯丙烯酸(EAA),乙烯丙烯酸甲酯(EMA),聚偏二氯乙烯(PVdC),聚(乙烯基)醇(PVOH)和EVOH。可通过乳液或溶液涂布技术或者通过共挤出和/或层压,施加涂层。
可适合于与多层膜一起使用的PVdC涂层是迄今为止在膜制造操作中用作涂层的任何已知的PVdC组合物,例如在美国专利No.4,214,039,美国专利No.4,447,494,美国专利No.4,961,992,美国专利No.5,019,447,和美国专利No.5,057,177中描述的任何PVdC材料,本文通过参考将其引入。
适合于与多层膜一起使用的已知的乙烯醇-基涂层,例如PVOH和EVOH包括VINOLTM125或VINOLTM 325(二者均商购于Air Products,Inc.,Allentown,Pa.)。在美国专利No.5,230,963中描述了其他PVOH涂层,本文通过参考将其引入。
在施加涂料组合物到合适的基底上之前,膜的外表面可如本文中所描述的处理,以增加其表面能。这一处理可通过使用已知技术实现,例如火焰处理,等离子体,电晕放电,膜氯化,例如将膜表面暴露于气态氯气下,用氧化剂,例如铬酸处理,热空气或蒸汽处理,和火焰处理等。尽管这些技术中任何一种有效地用于预处理膜表面,但频繁地优选的方法是电晕放电,电子处理方法(其包括当使膜在一对隔开的电极之间穿过时,将膜表面暴露于高电压的电晕放电下)。在膜表面处理之后,向其上施加涂料组合物。
可作为水-基溶液施加涂料组合物到膜上。可以以任何方便的方式,例如通过照相凹版涂布,辊涂,浸涂,和喷涂等,施加涂料组合物到处理过的表面上。可通过挤压辊,和刮刀等除去过量水溶液。
添加剂
可在多层膜的一层或多层中存在的添加剂包括,但不限于,遮光剂,颜料,着色剂,空化剂,爽滑剂,抗氧化剂,防雾剂,抗静电剂,防粘连剂,填料,湿气阻挡添加剂,气体阻挡添加剂及其组合。可使用有效量的这种添加剂,所述有效量可随所要求的性能而变化。可在任何层内添加添加剂,例如氧气清除剂或气体清除剂。
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),聚对苯二甲苯丁二醇酯(PBT),滑石,β成核剂,及其组合。
空化或孔隙-引发添加剂可包括在双轴取向温度下,与它加入其中的层内聚合物材料不相容的任何合适的有机或无机材料,以便生成不透明膜。合适的孔隙-引发颗粒的实例是PBT,尼龙,实心或中空的预成形玻璃球,金属珠或球,陶瓷球,碳酸钙,滑石,白垩或其组合。孔隙-引发颗粒的平均直径典型地可以是约0.1至10μm。
爽滑剂可包括高级脂肪酸酰胺,高级脂肪酸酯,蜡,硅油,和金属皂。可使用用量范围为0.1wt%至2wt%的这种爽滑剂,基于它向其中添加的层的总重量。可能有效的爽滑添加剂的实例包括高分子量的聚二甲基硅氧烷("PDMS"),硅油或硅胶。
在多层膜的一层或多层表皮层中使用的非迁移性爽滑剂可包括聚甲基丙烯酸甲酯(PMMA)。非迁移性爽滑剂可具有范围为约0.5μm至8μm,或1μm至5μm,或2μm至4μm的平均粒度,这取决于层的厚度和所需的爽滑性能。备选地,在非迁移性爽滑剂,例如PMMA内粒子的尺寸可以大于含有该爽滑剂的表皮层厚度的20%,或者大于表皮层厚度的40%,或者大于表皮层厚度的50%。这种非迁移性爽滑剂的颗粒尺寸也可以至少大于表皮层厚度的10%,或者至少大于表皮层厚度的20%,或者至少大于表皮层厚度的40%。一般地,考虑球形、粒状的非迁移性爽滑剂,其中包括PMMA树脂,例如EPOSTARTM(商购于日本的Nippon ShokubaiCo.,Ltd.)。还已知存在合适材料的其他商业源。非迁移性意味着这些粒子通常没有以迁移性爽滑剂的方式改变其在膜层当中的位置。还考虑常规的聚二烷基硅氧烷,例如粘度为10,000至2,000,000厘沲的硅油或硅胶添加剂。
合适的抗氧化剂可包括酚类抗氧剂,例如1010(商购于瑞士的Ciba-Geigy Company)。这种抗氧剂的用量范围通常为0.1wt%至2wt%,基于它向其中添加的层的总重量。
抗静电剂可包括碱金属磺酸盐,聚醚改性的聚二有机基硅氧烷,聚烷基苯基硅氧烷,和叔胺。这种抗静电剂的用量范围可以是约0.05wt%至3wt%,基于该层的总重量。
合适的防粘连剂的实例可包括氧化硅-基产品,例如44(商购于Grace Davison Products,Colombia,Md.),PMMA粒子,例如EPOSTARTM(商购于日本的NipponShokubai Co.,Ltd.),或聚硅氧烷,例如TOSPEARLTM(商购于GE Bayer Silicones,Wilton,Conn.)。这种防粘连剂包括它向其中添加的层的重量最多约3000ppm的有效量。
有用的填料可包括微细的无机固体材料,例如氧化硅,热解法氧化硅,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。
合适的湿气和气体阻挡添加剂可包括有效量的低分子量树脂,烃树脂,尤其石油树脂,苯乙烯树脂,环戊二烯树脂和萜烯树脂。
任选地,可用含蜡的涂料涂布一层或多层表皮层以供润滑,其用量范围为2wt%至15wt%,基于表皮层的总重量。任何常规的蜡,例如,但不限于,考虑在热塑性膜中有用的CarnaubaTM蜡(商购于Michelman Corporation,Cincinnati,Ohio)。
取向
实施方案包括可能的单轴或双轴取向多层膜。在挤出方向上取向被称为纵向(MD)取向。垂直于挤出方向的取向被称为横向(TD)取向。可通过首先MD接着TD取向,拉伸或牵拉膜,来实现取向。也可在膜挤出工艺随后,再次通过在一个或两个方向上拉幅机取向来取向吹胀薄膜或流延薄膜。取向可以是按序或同时的,这取决于所需的膜特征。优选的取向比通常为在纵向上是挤出宽度的约3至约6倍,和在横向上是挤出宽度的约4至约10倍。典型的商业取向工艺是BOPP拉幅工艺,吹胀薄膜,和LISIM技术。
表面处理
多层膜的外表面之一或二者,和尤其密封剂层可以表面处理,以增加表面能,使得膜接受金属化,涂布,印刷油墨和/或层压。可根据本领域已知的方法之一,其中包括电晕放电,火焰,等离子体,化学处理,或者通过极化火焰处理,从而进行表面处理。
金属化
可金属化多层膜的外表面(即远离芯的一面)和任选地之后涂布。例如,在任选地处理之后,密封剂层和/或表皮层的外表面可以经历金属化。可通过常规的方法,例如真空金属化,通过沉积金属层,例如铝,铜,金,银,锌,铬或其混合物,或任何其他金属化技术,例如电镀或溅射,进行金属化。典型地,根据ANSI/NAPM IT2.19的标准工序,施加金属层到1.5至5.0或优选1.8至4.0的光学密度(OD)。
在某些实施方案中,金属是氧化物,能真空沉积,电镀或溅射的任何其他无机材料,或有机改性的无机材料,例如SiOx,AlOx,SnOx,ZnOx,IrOx,有机改性的陶瓷“ormocer”等。此处整数x是1或2。沉积层的厚度范围典型地为100至5,000埃,或优选300至3000埃。
打底漆
打底涂层可施加到多层膜的任何表面上。在这一情况下,可首先通过前述方法之一处理膜,在其上和如此处理的膜表面上提供增加的活性粘合位点,随后可施加底漆材料的连续涂层。这种底漆材料是本领域公知的,且包括例如环氧和聚(乙烯亚胺)(PEI)材料。美国专利No.3,753,769,美国专利No.4,058,645和美国专利No.4,439,493(它们各自通过参考引入)公开了这种底漆的使用和施加。底漆提供总体粘合性活性表面以供对随后施加的涂料组合物彻底和牢固的粘结,且可通过常规的溶液涂布方式施加,例如通过辊施加。
在某些实施方案中,本文中膜的特征还在于双轴取向,在本文中通过参考将其引入。可通过本领域已知的任何合适的技术,制造膜,例如拉幅工艺,双泡工艺,LISIMTM或其他。进一步地,操作条件,温度设置,线速度等将随所使用的设备的类型和尺寸而变化。尽管如此,但此处一般地描述了在本发明公开内容当中描述的一种制造膜的方法。在一个特别的实施方案中,形成膜并使用“拉幅”方法双轴取向。在拉幅工艺中,熔融共混,并例如通过3,4,5,7-层模头,共挤出各种材料的片材/膜成所需的膜结构。可使用挤出机熔融共混熔融层材料,然后将熔融的物流计量到模头中。然后使用空气,水或二者,冷却挤出的片材。
在拉幅工艺的这一例举的实施方案中,第一冷却步骤下游是通过任何合适的方式,例如加热的S-缠绕辊,再加热未取向的片材到60至100或120或150℃的温度,然后在紧密隔开的不同速度的辊之间穿过,以实现纵向取向。本领域技术人员要理解,这一温度范围可以随设备,和尤其随构成膜的组分的同一性和组成而变化。理想地,温度将低于熔融膜,或者引起它变得对设备粘性和粘附,但足够高到促进纵向取向工艺的温度。值得注意的是,本文中提到的这种温度是指膜的温度本身。可例如通过红外光谱法,测量膜的温度,所述红外源的目标为正在加工的膜;本领域技术人员要理解,测量实际的膜温度可能不精确和/或完全准确。在这一情况下,已知通过任何合适的方式测量的与膜紧密相邻的空气或辊的温度,本领域技术人员可估计膜的温度。膜生产线的加热设备可设定在任何合适的加热水平下,这取决于仪器,以实现所述或所需的膜温度。
随后,冷却变长和变薄的膜并穿过生产线的拉幅机部分以供TD取向。在这一点处,通过在连续链上的机械夹子夹持片材边缘并推入到长的精确控制的热空气烘箱内以供再加热步骤。在再加热步骤中,膜的温度范围可以是80或110至150℃或160℃。再者,温度理想地低于熔融膜但足够高到促进横向取向步骤的温度。接下来,通过在连续链上的机械夹子夹持片材边缘并推入到长的精确控制的热空气烘箱内以供横向拉伸。拉幅机链分开(diverge)所需量,在足够高到促进横向取向步骤但足够低到使膜没有熔融的温度下在横向上拉伸膜。在拉伸到所要求的横向取向之后,然后冷却膜到比拉伸温度低5至10或15或20或30或40℃,并在任何边缘修整之前释放机械夹子。之后,可发生任选的电晕或任何其他处理,接着缠绕。
因此,在某些实施方案中,本文描述的膜双轴取向至少5或6或7或8倍TD取向和至少2或3或4倍MD取向。
在各种实施方案中,基本上不存在空化和/或不透明诱导剂,这意味着他们在芯层内不宜任何可检测量存在。空化和/或不透明诱导剂的实例包括碳酸钙,滑石,炭黑,粘土,未处理的氧化硅和氧化铝,氧化锌,云母,重晶石,碳酸镁及其混合物,以及由聚对苯二甲酸丁二酯,尼龙-6,环烯烃共聚物粒子制造的那些材料和相不同于芯层材料且具有在取向期间在芯层内产生空腔的尺寸的其他粒子。
工业实用性
所公开的多层膜可以是独立的膜,层压体或网状物。或者,多层膜可以密封,涂布,金属化和/或层压到其他膜结构,例如本文讨论的那些上。所公开的多层膜可通过任何合适的方法制备,该方法包括根据本说明书的描述和权利要求共挤出多层膜,例如通过涂布,印刷,狭缝涂布或其他转化方法取向并制备膜以供打算用途的步骤。
对于一些应用来说且如前所讨论的,可期望层压多层膜到其他聚合物膜或纸产品上,其目的例如是包装装饰,其中包括印刷和金属化。典型地由最终用户或加工膜用以供应给最终用户的膜加工者进行这些活动。
所制备的多层膜可用作挠性包装膜,以包装制品或物品,例如食品或其他产品。在一些应用中,可将膜形成为小袋类型的包装,例如可以用于包装饮料,液体,粒子或干粉产品。
鉴于前述内容,各种袋子,包装,小袋(例如,直立袋,垂直填充-和-密封袋,水平填充-和-密封袋等),膜,层压体和其他结构可由以上描述的膜形成,其中它们可以具有任何状态(phase)的产品(例如食品,饮料),所述产品要求具有必不可少的完整性和/或对水和/或氧气渗透阻挡的密封并具有低的厚度。
尽管前面涉及所公开发明的例举实施方案,但可在没有脱离本发明的基本范围情况下修订其他和进一步的实施方案,其中所公开的装置,体系和方法的范围通过一个或多个权利要求确定。
Claims (20)
1.一种双轴取向的多层膜,它包括:
含线性低密度聚乙烯的芯层;
含线性低密度聚乙烯和第一防粘连剂的表面表皮层;
含线性低密度聚乙烯和或者第二防粘连剂或者与表面表皮层相比浓度更大的第一防粘连剂的密封剂表皮层;
介于表面表皮层和芯层之间的第一衔接层,第一衔接层包括线性低密度聚乙烯;和
介于密封剂表皮层和芯层之间的第二衔接层,第二衔接层包括线性低密度聚乙烯。
2.权利要求1的膜,其中该膜的总厚度为10μm至120μm。
3.权利要求1的膜,其中芯层、密封剂表皮层、第二衔接层或其组合进一步包括爽滑剂。
4.权利要求1的膜,其中对表面表皮层进行电晕放电处理、火焰处理、极化火焰处理、等离子体处理、化学处理或其组合。
5.权利要求1的膜,其中表面表皮层进一步包括着色剂。
6.权利要求1的膜,其中表面表皮层或第一衔接层中的至少一层进一步包括着色剂。
7.权利要求1的膜,其中芯层、第一衔接层、和表面表皮层包括第一线性低密度聚乙烯,和第二衔接层和密封剂表皮层包括第二线性低密度聚乙烯,和其中第一线性低密度聚乙烯的熔体指数低于第二线性低密度聚乙烯和密度大于第二线性低密度聚乙烯。
8.权利要求1的膜,其中芯层中的线性低密度聚乙烯是茂金属催化的线性低密度聚乙烯。
9.权利要求1的膜,其中芯层、第一衔接层、第二衔接层或其组合进一步包括最多20wt%的烃树脂。
10.权利要求1的膜,其中芯层进一步包括抗氧化剂、防雾剂、抗静电剂、防粘连剂、湿气阻挡添加剂、气体阻挡添加剂或其组合。
11.权利要求1的膜,其中表面表皮层或密封剂表皮层中的至少一层用包括乙烯丙烯酸、乙烯丙烯酸甲酯共聚物、聚偏二氯乙烯、聚乙烯醇、乙基乙烯醇或其组合的聚合物涂布。
12.权利要求3的膜,其中芯包括爽滑剂和爽滑剂是迁移性爽滑剂。
13.权利要求3的膜,其中密封剂表皮层包括爽滑剂,其中第二爽滑剂是非迁移性爽滑剂。
14.权利要求1的膜,其中表面表皮层或密封剂表皮层中的至少一层被金属化。
15.权利要求1的膜,其中芯层的厚度为5μm至100μm。
16.权利要求1的膜,其中第一和第二衔接层的厚度各自为0.5μm至25μm,以及表面表皮层和密封剂表皮层的厚度各自为0.5μm至3.5μm。
17.权利要求1的膜,其中通过包括共挤出和膜取向的工艺生产该膜。
18.权利要求1的膜,其中使用溶剂-基粘合剂将该膜粘附到聚酯基底上。
19.权利要求1的膜,其中将该膜层压到含聚乙烯、聚丙烯、尼龙或其组合的聚烯烃膜上。
20.权利要求1的膜,其中该膜形成包装、袋子、标签、标记、水平形成-填充-和-密封容器、垂直形成-填充-和-密封容器、盖子、小袋、囊袋、外包装或其组合。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US201662324069P | 2016-04-18 | 2016-04-18 | |
US62/324,069 | 2016-04-18 | ||
PCT/US2017/028181 WO2017184633A1 (en) | 2016-04-18 | 2017-04-18 | Bi-oriented, linear, low-density, polyetheylene film with improved sealing properties |
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CN109070565A true CN109070565A (zh) | 2018-12-21 |
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CN201780024254.9A Pending CN109070565A (zh) | 2016-04-18 | 2017-04-18 | 具有改进的密封性能的双取向的线性低密度聚乙烯膜 |
Country Status (7)
Country | Link |
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EP (1) | EP3419825B1 (zh) |
CN (1) | CN109070565A (zh) |
CA (1) | CA3021927A1 (zh) |
ES (1) | ES2826431T3 (zh) |
MX (1) | MX2018010408A (zh) |
PL (1) | PL3419825T3 (zh) |
WO (1) | WO2017184633A1 (zh) |
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WO2017127808A1 (en) * | 2016-01-21 | 2017-07-27 | Jindal Films Americas Llc | Bi-oriented, cavitated, linear, low-density film with good sealing properties |
US11518154B2 (en) | 2020-01-27 | 2022-12-06 | Exxonmobil Chemical Patents Inc. | Barrier films for packaging |
CN116583542A (zh) | 2020-12-08 | 2023-08-11 | 埃克森美孚化学专利公司 | 具有长链支化的高密度聚乙烯组合物 |
WO2024013255A1 (de) * | 2022-07-13 | 2024-01-18 | Rkw Se | Polyolefinische verpackungsfolie |
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- 2017-04-18 EP EP17786488.1A patent/EP3419825B1/en active Active
- 2017-04-18 CN CN201780024254.9A patent/CN109070565A/zh active Pending
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Also Published As
Publication number | Publication date |
---|---|
EP3419825A1 (en) | 2019-01-02 |
EP3419825A4 (en) | 2019-10-09 |
WO2017184633A1 (en) | 2017-10-26 |
PL3419825T3 (pl) | 2021-01-25 |
EP3419825B1 (en) | 2020-08-19 |
CA3021927A1 (en) | 2017-10-26 |
ES2826431T3 (es) | 2021-05-18 |
MX2018010408A (es) | 2018-11-29 |
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