CN108463347A - 具有良好密封性能的双取向的空化线性低密度膜 - Google Patents
具有良好密封性能的双取向的空化线性低密度膜 Download PDFInfo
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- CN108463347A CN108463347A CN201780006450.3A CN201780006450A CN108463347A CN 108463347 A CN108463347 A CN 108463347A CN 201780006450 A CN201780006450 A CN 201780006450A CN 108463347 A CN108463347 A CN 108463347A
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Abstract
本申请公开了用于双轴取向的多层膜的方法，组合物，结构和用途，所述膜可包括含LLDPE，例如mLLDPE的芯层，其中芯层的侧面与第一表层和第二表层相接。这一相同类型(例如，熔融指数，密度，和/或熔融峰)的LLDPE，或者不同类型，或者其共混物可在第一表层和/或第二表层内，其中第一表层位于芯层的第一侧面上，和第二表层位于芯层的第二侧面上，其中与第二侧面相比第一侧面在芯层的相对面上。在100℃下在41N/cm2的压力下在0.75s的停留时间下双轴取向的多层膜的密封强度可以是至少400g/cm。
Description
相关申请的交叉参考
本申请是专利合作条约(PCT)申请，其要求2016年1月21日提交的美国临时专利申请序列号62/281,567的优先权，本文通过参考将其全文引入。
发明领域
本发明的公开内容涉及具有良好密封性能的双取向的、线性低密度膜。
背景技术
流延或吹塑的未取向聚乙烯("PE")或聚丙烯("PP")膜在包装或其他应用中用作密封剂，且可与被印刷的其他网状物，例如纸张，聚对苯二甲酸乙二醇酯("PET")，双轴取向的PP("BOPP")，金属化PET或BOPP，或铝箔结合，以便提供具有刚度和阻隔保护的膜。
密封剂网状物，例如刚才描述的那些常常被着色成白色，以便提供在其上印刷颜色的亮白色基础(base)。使用白色密封剂网状物在印刷白色油墨方面的高成本中起到节约作用。
在PP膜内的固体颗粒或不相容的聚合物可经历取向，以便生产空化(cavitated)BOPP膜。取向过程提高空化。然而，空化的缺点是损害密封强度。
发明概述
本发明公开了用于双轴取向的多层膜的方法，组合物，结构和用途，所述膜可包括芯层，该芯层包含茂金属线性低密度聚乙烯(LLDPE)，例如茂金属线性低密度聚乙烯(mLLDPE)，其中芯层由第一表层和第二表层作为侧面(flanked)。这一相同类型(例如，熔融指数，密度，和/或熔融峰)的LLDPE，例如mLLDPE，或者不同类型，或者其共混物可在第一表层和/或第二表层内，其中第一表层位于芯层的第一侧面上，和第二表层位于芯层的第二侧面上，其中与第二侧面相比，第一侧面在芯层的相对面上。另外，在100℃下，在41N/cm2的压力下，在0.75s的停留时间下，双轴取向的多层膜的密封强度可以是至少400g/cm。
在另一个例举的实施方案中，公开了制造前述双轴取向的多层膜的方法。该方法可包括共挤出前述双轴取向的多层膜的芯层，第一表层和第二表层，然后取向双轴取向的多层膜，在100℃下，在41N/cm2的压力下，在0.75s的停留时间下，其密封强度为至少400g/cm。在额外的实施方案中，前述双轴取向的多层膜可包括在表层和芯层至少一层中间的结合层。
在仍然其他例举的实施方案中，公开了前述双轴取向的多层膜，例如具有和不具有结合层的那些的用途，其中这种用途可以是在包装，贴标签，袋装，或标记应用中。
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"，"前部"，"后部"，"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地球表面的方向，和"以下"，"下部"，"底部"和类似术语是指朝向地球表面的方向，但仅仅是为了阐述性目的，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，其中包括本文为了理解目的采用的例举实施方案和定义。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，本发明的范围将是指任何权利要求，其中包括它们的等价方案和与引述的那些相当的要素或限制。
流延或吹塑的未取向聚乙烯("PE")或聚丙烯("PP")膜在包装或其他应用中用作密封剂，且可与被印刷的其他网状物，例如纸张，聚对苯二甲酸乙二醇酯("PET")，双轴取向的PP("BOPP")，金属化PET或BOPP，或铝箔结合，以便提供具有刚度和阻隔保护的膜。
密封剂网状物，例如刚才描述的那些常常被着色成白色，以便提供在其上印刷颜色的亮白色基础。使用白色密封剂网状物在印刷白色油墨的高成本方面起到节约作用。
在PP膜内固体颗粒或不相容的聚合物可经历取向，以便提供空化BOPP膜，并进而提供具有较低密度，即较高产率或更多平方米/千克膜的白色不透明膜。取向过程提高空化。然而，空化的缺点是损害密封强度。
令人惊奇地，在双取向期间，低密度PE("LLDPE")膜可被空化，并产生具有较低密度的白色不透明膜。这是令人惊奇的，因为LLDPE树脂具有低的结晶度。此外，和与空化BOPP膜相反的是，可生产具有高密封强度，潜在地良好的密封性，和具有在密封期间减少或防止污染的密封性的包装。
在减少的厚度下，新的多层膜提供包装和/或标签热密封性和提高的密封性能(例如，高的密封强度，真空密封，防污染穿透的密封)。消费者受益于在相同或较好性能下减少的包装量。
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"可以指代含两种单体的聚合物或含三种或更多种单体的聚合物。
本文中所使用的"中间"定义为多层膜的一层的位置，其中所述层位于两层其他确定的层之间。在一些实施方案中，中间层可以与两层确定的层中任意一层或两层直接接触。在其他实施方案中，额外的层也可存在于中间层和两层确定的层中任意一层或两层之间。
本文中所使用的"弹性体"定义为在力作用下可延伸或拉伸到其起始长度的至少100％，和一旦移除外力，则快速地(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DSC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部分不存在特定组分，但并不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的碎屑和边角料，小量组分可存在于所提到的层内。
芯层
本领域技术人员已知的是，多层膜中的芯层最常见地为最厚的层，并提供多层结构的基础。在一些实施方案中，芯层基本上由LLDPE组成且基本上不含其他组分。在备选的实施方案中，芯层也可含有较小量选自丙烯聚合物，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的聚合物。尽管绝不限制，但合适的LLDPE的两个实例是：(1)熔融指数为1至3g/10min(在190℃-2.13Kg条件下测量)，密度为0.915至0.930g/cm3和熔融峰为115至135℃的一种。
芯层可进一步包括烃树脂。烃树脂可起到提高或改性弯曲模量的作用，改进加工性，或改进膜的阻隔性能。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。
可适合于本文描述用途的烃树脂包括EMPR 120，104，111，106，112，115，EMFR 100和100A，ECR-373和2101，2203，2520，5380，5600，5618，5690(商购于ExxonMobilChemical Company,Baytown,Tex.)，ARKONTM M90，Ml00，Ml15和M135和SUPER ESTERTM 松香酯(商购于日本Arakawa Chemical Company)；SYLVARESTM苯酚改性的苯乙烯树脂，甲基苯乙烯树脂，苯乙烯化萜烯树脂，ZONATACTM萜烯-芳族树脂，和萜烯酚树脂(商购于ArizonaChemical 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萜烯酚树脂(商购于法国DRT Chemical Company,Landes)；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.)；WINGTACKTMET和EXTRATM(商购于Sartomer of Exton,Pa.)，FORALTM，PENTALYNTM，和PERMALYNTM松香和松香酯(商购于Hercules，现在的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,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(Cavitatingagent)，爽滑剂，抗氧剂，防雾剂，抗静电剂，填料，湿气阻隔添加剂，气体阻隔添加剂，及其组合，正如以下进一步详细讨论的。合适的抗静电剂是ARMOSTATTM475(商购于Akzo Nobel,Chicago，Ill.)
可在芯层内存在用量小于30wt％，优选小于20wt％，最优选范围为2wt％至10wt％的空化剂，基于芯层的总重量。
优选地，芯层内添加剂的总量包括最多约20wt％的芯层，但一些实施方案可包括在芯层内用量最多约30wt％芯层的添加剂。
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。
结合层
典型地使用多层膜中的结合层，将多层膜结构中的两层其他层，例如芯层和密封剂层连接在一起，且位于这些其他层之间。结合层可具有与芯层相比，相同或不同的组成。
在一些实施方案中，结合层与芯层表面直接接触。在其他实施方案中，另一层或多层可以在芯层和结合层的中间。结合层可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，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等级聚合物(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The DowChemical Company,Midland,Mich.)，Basell CATALLOYTM树脂，例如ADFLEXTMT100F，SOFTELLTMQ020F，CLYRELLTMSM1340(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)，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)(商购于ExxonMobil Chemical Company,Baytown,Tex.)。
在一些实施方案中，结合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，抗氧剂，防雾剂，抗静电剂，防粘连剂，填料，湿气阻隔添加剂，气体阻隔添加剂，及其组合，正如以下进一步详细地讨论的。
结合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，结合层的厚度可以是约0.5μm至4μm，或约0.5μm至2μm，或约0.5μm至1.5μm。
表层是任选的，和当存在时，在结合层或芯层的外表面上提供。可以提供表层，改进膜的阻隔性能，加工性，可印刷性，和/或相容性以供金属化，涂布和层压到其他膜或基底上。
在一些实施方案中，表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，或获自Prime Polymer的EvolueTM树脂，或获自Dow的EliteTM树脂。合适的乙烯-丙烯共聚物是Fina 8573(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Chisso Corporation)。对于涂布和印刷功能来说，表层可优选表面处理。为了金属化或阻隔性能，表层可含有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，正如以下更加详细地讨论的。
表层的厚度取决于表层所打算的功能，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，最优选约0.50μm至1.5μm。此外，在较薄的膜的实施方案中，表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，一个或多个涂层，例如用于阻隔，印刷和/或加工的涂层可施加到多层膜的外表面上。例如，涂层可直接在结合层的外表面(即远离芯的那些表面)上，在芯层的任意一面或两面上，或者在别处。这种涂层可包括丙烯酸类聚合物，例如乙烯丙烯酸(EAA)，乙烯丙烯酸甲酯共聚物(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乙烯醇-基涂层，例如PVOH和EVOH包括VINOLTM125或VINOLTM325(二者商购于Air Products,Inc.,Allentown,Pa.)。其他PVOH涂层描述于美国专利No.5,230,963中，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所述处理，以增加其表面能。这一处理可通过使用已知技术，例如火焰处理，等离子体，电晕放电，膜氯化等，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，火焰处理等来实现。尽管有效地使用任何这些技术来预处理膜表面，但通常优选的方法是电晕放电，即包括将膜表面暴露于高压电晕放电下，同时使膜在一对隔开的电极之间穿过的电子处理方法。在膜表面的处理之后，然后向其上施加涂料组合物。
可将涂料组合物作为水-基溶液施加到膜上。可按照任何便利的方式，例如通过照相凹版涂布，辊涂，浸涂，喷涂等，施加涂料组合物到处理过的表面上。可溶通过挤压辊，刮刀等除去过量的水溶液。
添加剂
可存在于多层膜的一层或多层内的添加剂包括，但不限于，遮光剂，颜料，着色剂，空化剂，爽滑剂，抗氧剂，防雾剂，抗静电剂，防粘连剂，填料，湿气阻隔添加剂，气体阻隔添加剂及其组合。可使用有效量的这种添加剂，所述有效量取决于所要求的性能而变化。可在任何层中添加诸如氧气清除剂或气体清除剂之类的添加剂。
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)，聚对苯二甲酸丁二酯(PBT)，滑石，β成核剂及其组合。
空化剂或孔隙-引发添加剂可包括在双轴取向的温度下，与向其中添加的层中的聚合物材料不相容的任何合适的有机或无机材料，以便产生不透明膜。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，金属珠粒或球，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。
爽滑剂可包括较高脂族酸的酰胺，较高脂族酸的酯，蜡，硅油，和金属皂。可基于它向其中添加的层的总重量，使用用量范围为0.1wt％至2wt％的这种爽滑剂。可以有用的爽滑添加剂的一个实例是高分子PDSM(聚二甲基硅氧烷)硅酮胶。
可在多层膜的一层或多层表层中使用的非-迁移的爽滑剂可包括聚甲基丙烯酸甲酯(PMMA)。非-迁移的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，这取决于层厚和所需的爽滑性能。或者，在非-迁移爽滑剂，例如PMMA内颗粒的尺寸比含该爽滑剂的表层的厚度大20％，或者比表层的厚度大40％，或者比表层的厚度大50％。这种非-迁移爽滑剂的颗粒尺寸也可比表层的厚度大至少10％，或者比表层的厚度大至少20％，或比表层的厚度大至少40％。一般地，考虑球形粒状的非-迁移爽滑剂，其中包括PMMA树脂，例如EPOSTARTM(商购于日本Nippon Shokubai Co.,Ltd.)。也已知存在合适的材料的其他商业来源。非迁移是指这些粒子通常在膜层当中不以迁移爽滑剂的方式改变位置。还考虑粘度为10,000至2,000,000厘沲的常规聚二烷基硅氧烷，例如硅油或树胶添加剂。
合适的抗氧剂可包括酚类抗氧剂，例如1010(商购于瑞士的Ciba-GeigyCompany)。通常使用用量范围为0.1wt％至2wt％的这种抗氧剂，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。可使用用量范围为约0,05wt％至3wt％的这种抗静电剂，基于该层的总重量。
合适的防粘连剂的实例可包括二氧化硅-基产品，例如(商购于GraceDavison Products,Colombia,Md,)，PMMA粒子，例如EPOSTARTM(商购于日本的NipponShokubai Co.,Ltd.)，或聚硅氧烷类，例如TOSPEARLTM(商购于GE Bayer Silicones,Wilton,Conn.)。这种防粘连剂包括有效量为最多约3000ppm它向其中添加的层的重量。
有用的填料可包括微细的无机固体材料，例如二二氧化硅，热解法二氧化硅，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。
合适的湿气和气体阻隔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，为了润滑性，可采用用量范围为2wt％至15wt％的含蜡涂料，涂布一层或多层表层，基于表层的总重量。考虑在热塑性膜中有用的任何常规的蜡，例如，但不限于，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。垂直于挤出方向取向被称为横向(TD)取向。可通过首先在MD，接着在TD取向中拉伸或牵伸膜来实现取向。也可通过在膜挤出工艺之后，在此在一个或两个方向上拉幅机取向，从而取向吹塑膜或流延膜。取向可以是按序或同时的，这取决于所需的膜特征。优选的取向比常常在纵向上为挤出宽度的约3至约6倍和在横向上为挤出宽度的约4至约10倍。典型的商业取向工艺是BOPP拉幅工艺，吹塑膜，和LISIM技术。
表面处理
多层膜的一个或两个外表面，尤其密封剂层可以表面处理，以增加表面能，赋予膜接收金属化，涂层，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，化学处理或者借助极化火焰处理，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)。例如，任选地在处理之后，密封剂层和/或表层的外表面可经历金属化。可通过常规方法，例如真空金属化，通过沉积金属层，例如铝，铜，银，铬或其混合物，进行金属化。
打底漆
可将底漆涂层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，在其上提供增加的活性粘合剂位点，且可随后施加连续的底漆材料涂层到如此处理过的膜表面上。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(本文通过参考将其中每一篇引入)公开了使用并施加这种底漆。底漆提供总的粘合活性表面以供对随后施加的涂层组合物彻底和牢固粘结，且可通过常规的溶液涂布方式，例如通过辊施加，施加到膜上。
在某些实施方案中，本文中膜的特征还在于例如通过美国专利No.8,080,294中描述的工序双轴取向，本文引入这一参考文献。可通过本领域已知的任何合适的技术，例如拉幅工艺，双泡工艺，LISIMTM或其他来制造膜。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，但此处通常描述一种在这一公开内容当中所述的膜的制造方法。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，熔融共混并共挤出各种材料的片材/膜例如通过3，4，5，7-层模头成为所需的膜结构。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内。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的下游，通过任何合适的方式，例如加热的S-包卷辊，再加热未取向的片材到60至100或120或150℃的温度，然后在紧密分开的不同速度的辊之间穿过，实现纵向取向。本领域技术人员要理解，这一温度范围可随设备，和尤其随构成膜的各组分的同一性(identity)和组成而变化。理想地，温度低于熔融膜或者引起它变粘并粘附到设备上的温度，但足够高到促进纵向取向工艺。值得注意的是，本文中提到的这一温度是指膜的温度本身。可通过使用例如红外光谱法，测量膜的温度，其中红外源靶向在膜上，当加工膜时；本领域技术人员会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，本领域技术人员可通过已知与膜紧密相邻的空气或辊的温度(这通过任何合适的方式测量)，估计膜的温度。膜生产线的加热方式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，冷却延长并变薄的膜，并穿过到达生产线的拉幅机部分以供TD取向。在这一点处，通过机械钳子，在连续链上夹持片材的边缘并牵引到长的精确控制的热空气烘箱内以供预热步骤。在预热步骤中，膜的温度范围可以是80或110至150或160℃。再者，理想地，温度低于熔融膜，但足够高到促进纵向取向步骤的温度。接下来，通过机械钳子，在连续链上夹持片材边缘，并牵引到长的精确控制的热空气烘箱内以供横向拉伸。拉幅机链(tenterchains)分叉(diverge)所需的量，在足够高到促进横向取向的步骤但足够低到没有熔融膜的温度下，横向拉伸膜。在拉伸到所要求的横向取向之后，冷却膜到比拉伸温度低5至10或15或20或30或40℃的温度，并在任何边缘修整之前，释放机械钳子。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，采用至少5或6或7或8倍TD取向和至少2或3或4倍MD取向，双轴取向本文描述的膜。
在各种实施方案中，基本上不存在空化和/或不透明度诱导剂，是指它们在芯中不以任何可检测量存在。空化和/或不透明度诱导剂的实例包括碳酸钙，滑石，炭黑，粘土，未处理的二氧化硅和氧化铝，氧化锌，云母，石棉，重晶石，碳酸镁及其混合物，以及由聚对苯二甲酸丁二醇酯制造的那些材料，尼龙-6，环烯烃共聚物颗粒，和与芯层材料相不同且在取向期间具有在芯层内生成空腔的尺寸的其他颗粒。
工业实用性
所公开的多层膜可以作为自立式膜，层压体，或网状物。或者，可密封，涂布，金属化，和/或层压多层膜到其他膜结构上。可通过包括下述步骤的任何合适的方法，制备所公开的多层膜：共挤出根据本发明说明书和权利要求的多层膜，取向并例如通过涂布，印刷，切开(slitting)或其他转化方法，制备膜以供打算用途。
对于一些应用来说，可期望层压多层膜到其他聚合物膜或纸张产品上，为的是例如包装装饰，其中包括印刷和金属化。典型地最终的用户或者通过加工膜为了供应最终用户的膜转化者，进行这些活动。
所制备的多层膜可用作挠性包装膜，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，例如可用于包装饮料，液体，颗粒或干粉产品。也可在标签应用中，在农业或园艺应用中，或者各种其他应用中使用所制备的多层膜。
实验
作为非限制性实例，在中试车间线上制造两个双轴取向的LLDPE膜，其中表1是为了无色/透明的非空化结构和表2是为了空化结构。
表1
1-例如，LLDPE类型：MI＝1.9，ρ＝0.927g/cm3，Tm＝127℃(mLLDPE)
2-例如，LLDPE类型：MI＝3.8，ρ＝0.913g/cm3，Tm＝113℃(mLLDPE)
表2
1-例如，mLLDPE类型：MI＝1.9，ρ＝0.927g/cm3，Tm＝127℃(mLLDPE)
2-例如，mLLDPE类型：MI＝3.8，ρ＝0.913g/cm3，Tm＝113℃(mLLDPE)
3-例如，Schulman Polybatch FCC 7310HD
针对表1和2的无色和空化膜，测量下述性能，并在下表3中报道。
表3
因此，数据表明可使用CaCO3颗粒作为空化剂，空化LLDPE双取向膜，以便生产白色不透明的膜，其具有比非-空化状态下的相同LLDPE膜低的密度，并提供对光的阻隔。
现回到表4，报道了来自表1和2的膜的密封性能。使用标准试验方法ASTM F2029，在41N/cm2的压力和0.75s的停留时间下，在从80℃至150℃的温度范围内，在层压体上使用具有卷边钳的Otto Brugger密封计。数据表明空化的双取向LLDPE膜维持高的密封强度，而双取向的空化PP膜产生弱的密封，因为在空化芯上密封剂表皮的粘附性差，正例如在美国专利No,8,815,377中所解释的。相当的空化BOPP样品将得到低于1000g/英寸的密封强度，这相当于根据有效数字，密封强度为400g/cm。根据相应g/英寸测量结果内有效数字的数值，将图2中报道的g/英寸测量结果转化并以g/cm报道。
表4
鉴于前述，可由以上描述的膜，形成各种袋，包装，小袋(例如自立式，垂直填充-和-密封，水平填充-和-密封等)，膜，层压体，和其他结构，其中这种膜可具有任何阶段的产品(例如食品，饮料)，所述产品要求具有必不可少的完整度和/或对水，氧气或其他污染物的阻隔的密封。
尽管前面涉及所公开的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，想出其他和进一步的实施方案，其中所公开装置，体系和方法的范围由一个或多个权利要求确定。
Claims (20)
1.一种双轴取向的多层膜，它包含：
含线性低密度聚乙烯(LLDPE)的芯层，其中芯层由第一侧面和第二侧面作为侧面；
位于第一侧面上的含LLDPE的第一表层；和
位于第二侧面上的含LLDPE的第二表层，
其中双轴取向的多层膜具有在100℃下在41N/cm2的压力下在0.75s的停留时间下至少400g/cm的密封强度。
2.权利要求1的双轴取向的多层膜，进一步包含一种或多种空化剂。
3.权利要求2的双轴取向的多层膜，其中双轴取向的多层膜的密度等于或低于0.8g/cm3。
4.权利要求1的双轴取向的多层膜，进一步包含一种或多种阻隔添加剂。
5.权利要求1的双轴取向的多层膜，其中在芯层、第一表层和第二表层的每一个中，该LLDPE与彼此相比是相同或不同的类型。
6.权利要求1的双轴取向的多层膜，进一步包含一个或多个结合层。
7.权利要求1的双轴取向的多层膜，其中一个或多个结合层中每一层包括一种或多种聚合物，其任选地包含LLDPE，其中在芯层、第一表层和第二表层的每一个中，该LLDPE与彼此相比是相同或不同的类型。
8.权利要求6的双轴取向的多层膜，进一步包含一种或多种空化剂。
9.权利要求1的双轴取向的多层膜，其中在130℃下密封强度为至少1500g/cm。
10.权利要求1的双轴取向的多层膜，其中在130℃下密封强度为至少2000g/cm。
11.权利要求1的双轴取向的多层膜，其中芯层包括至少80wt％的LLDPE。
12.权利要求1的双轴取向的多层膜，进一步包括金属化层、底漆、涂层、印刷油墨、层压层或其组合。
13.权利要求1的双轴取向的多层膜，进一步包括对双轴取向的多层膜中任何层的表面处理。
14.权利要求1的双轴取向的多层膜，在芯层内进一步包括烃树脂。
15.权利要求1的双轴取向的多层膜，其中LLDPE包括茂金属线性低密度聚乙烯。
16.权利要求1的双轴取向的多层膜，其中双轴取向的多层膜具有至少40％的透光率。
17.权利要求1的双轴取向的多层膜，其中在第一表层内的第一类型LLDPE不如在第二表层内的第二类型LLDPE致密。
18.一种方法，包括共挤出权利要求1的芯层、第一表层和第二表层，和在共挤出之后的取向，其中双轴取向的多层膜具有在100℃下在41N/cm2的压力下在0.75s的停留时间下至少400g/cm的密封强度。
19.权利要求1的双轴取向的多层膜在包装、贴标签、袋装或标记应用中的用途。
20.权利要求7的双轴取向的多层膜在包装、贴标签、袋装或标记应用中的用途。
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| EP4116093A1 (en) * | 2021-07-09 | 2023-01-11 | Trioworld Landskrona AB | Sustainable multilayer film comprising recycled polyethylene useful in food packaging |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20180272671A1 (en) | 2018-09-27 |
| EP3405344B1 (en) | 2023-06-07 |
| EP3405344A4 (en) | 2019-06-19 |
| WO2017127808A1 (en) | 2017-07-27 |
| EP4163111A1 (en) | 2023-04-12 |
| EP3405344C0 (en) | 2023-06-07 |
| EP3405344A1 (en) | 2018-11-28 |
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