CN105492328B - 热激活收缩膜 - Google Patents

热激活收缩膜 Download PDF

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CN105492328B
CN105492328B CN201480048313.2A CN201480048313A CN105492328B CN 105492328 B CN105492328 B CN 105492328B CN 201480048313 A CN201480048313 A CN 201480048313A CN 105492328 B CN105492328 B CN 105492328B
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polymer
film
shrink film
film according
low
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CN105492328A (zh
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H·T·彭
A·薛
Y·帕蒂尔
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Avery Dennison Corp
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Abstract

公开了具有以下的掺混物的可收缩膜层：(i)具有高玻璃化转变温度的一种或多种聚合物，和(ii)具有低玻璃化转变温度的一种或多种聚合物。还公开了制备这种膜层的方法。

Description

热激活收缩膜
发明背景
收缩膜具有许多用途，包括作为产品标签和用于包装。本发明进一步提供收缩膜的实施方式以及也提供用于制备收缩膜的方法。
发明内容
在一种实施方式中，本发明包括具有至少第一可收缩膜层的收缩膜。该可收缩膜层包括具有高玻璃化转变温度的可收缩聚合物和具有低玻璃化转变温度的可收缩聚合物的掺混物。
在另一种实施方式中，本发明包括用于制备可收缩膜的方法。该方法包括制备包括具有高玻璃化转变温度的可收缩聚合物和具有低玻璃化转变温度的可收缩聚合物的掺混物，和由所述掺混物形成膜。
以下描述阐释了本发明的一种或多种实施方式并且用来解释本发明的原理和示例性实施方式。
附图简述
图1是示例性膜的烘箱收缩值的图；和
图2是示例性膜的DMA收缩曲线的图。
发明内容
现在将详细参考本发明的示例性实施方式，在附图中图解其一个或多个实施例。通过解释本发明的方式而不是通过限制本发明的方式，提供每个实施例。本领域技术人员将显而易见，本发明可做出改进和变型，而不背离其范围和精神。例如，图解或描述为一种实施方式的部分的特征可用于另一种实施方式，以获得更进一步实施方式。因此，由于落在所附权利要求书和其等同的范围内，本发明旨在涵盖这种改进和变型。
如本领域所理解，收缩膜是当加热至收缩引发温度时在至少一个方向上收缩的膜。在一些实施方式中，当暴露于收缩引发温度时，本发明的收缩膜可仅在纵向上收缩。在其他实施方式中，当暴露于收缩引发温度时，收缩膜可替代地或另外地在横向(transversedirection)(也称为横向(cross direction))上收缩。在仍其他实施方式中，当暴露于收缩引发温度时，本发明的收缩膜可仅在纵向上收缩，并且可在横向上生长(或扩张)。
在一些实施方式中，本发明包括由使用(i)和(ii)的掺混物制备的至少一个可收缩层组成的膜：(i)至少一种具有高玻璃化转变温度(Tg)的可收缩聚合物，和(ii)至少一种具有低Tg的可收缩聚合物。在一些特定实施方式中，本发明的膜可具有使用(i)和(ii)制备的至少一个膜层：(i)至少一种具有高玻璃化转变温度的环状烯烃共聚物(COC)，和(ii)至少一种具有低玻璃化转变温度的COC。如本文所使用，高Tg表示在约85℃至约165℃的范围中的玻璃化转变温度并且低Tg表示低于约85℃的玻璃化转变温度。以上范围可包括其中每个间断值和每个间断范围。
一种或多种具有高Tg的可收缩聚合物和一种或多种具有低Tg的可收缩聚合物的任何结合落在本发明的范围中。在一些具体实施方式中，具有高Tg的聚合物可包括具有Tg在约85℃至约160℃的范围中的聚合物。在其他实施方式中，具有约90℃至约155℃的Tg的聚合物可用作高Tg聚合物。另外，在一些具体实施方式中，具有约-100℃至约85℃的Tg的聚合物可用作低Tg聚合物。在一些实施方式中，具有约-60℃至约85℃的Tg的聚合物可用作低Tg聚合物。在又其他实施方式中，具有Tg在约-40℃至83℃的范围中的聚合物可用作低Tg聚合物。在仍其他实施方式中，具有范围在约-35℃至约82℃中的Tg的聚合物可用作低Tg聚合物。在又其他实施方式中，具有小于约80℃的Tg的聚合物可用作低Tg聚合物。以上范围中的每个可包括其中每个间断值和每个间断范围。
高和低Tg聚合物的任何合适的掺混物可用于本发明的具体实施方式。在一些实施方式中，可收缩层可包括按重量计约1％至约99％的具有高玻璃化转变温度的可收缩聚合物和按重量计约1％至约99％的具有低玻璃化转变温度的可收缩聚合物，每种包括其中每个间断范围。在一些实施方式中，可收缩层可包括按重量计约10％至约80％的具有高玻璃化转变温度的可收缩聚合物和按重量计约20％至约90％的具有低玻璃化转变温度的可收缩聚合物。
举例来说，在一些实施方式中，一种或多种高Tg COC聚合物和一种或多种低TgCOC聚合物可掺混在可收缩层中。在其他实施方式中，高Tg COC可与低Tg聚烯烃掺混以形成可收缩层。在仍其他实施方式中，具有高Tg的聚苯乙烯可与具有低Tg的苯乙烯嵌段共聚物，诸如苯乙烯乙烯丁烯苯乙烯聚合物(SEBS)、苯乙烯乙烯/丙烯苯乙烯(SEPS)聚合物、苯乙烯丁二烯(SBR)、苯乙烯-乙烯/丙烯-苯乙烯(SEPS)和聚(苯乙烯-丁二烯-苯乙烯)聚合物(SBS)掺混以形成可收缩层。另外地，在一些实施方式中，可收缩层可包括与低Tg PETG和/或低Tg聚对苯二酸亚乙酯(PET)掺混的高Tg的乙二醇改性的聚对苯二酸亚乙酯(PETG)和/或聚碳酸酯。以上实施方式旨在阐释本发明的特定实施方式，而不限制其范围。
另外，虽然在玻璃化转变温度的背景中讨论了本文的实施方式，本发明还包括替代地其中可收缩层聚合物掺混物基于热变形温度(heat deflection temperature)(也称作热变形温度(heat distortion temperature))(HDT)的实施方式。在这点上，这种可收缩层可包括(i)至少一种具有高热变形温度的聚合物诸如COC和(ii)至少一种具有低热变形温度的聚合物诸如COC的掺混物。如本文所使用，高热变形温度包括高于约75℃的温度，和低热变形温度包括在约75℃处或低于其的温度。
具有高Tg聚合物和低Tg聚合物的掺混物的本发明的可收缩层可任选地包括其他组分。举例来说，在一些实施方式中，该可收缩层可包括一种或多种另外的聚合物材料，诸如线型低密度聚乙烯或低密度聚乙烯。另外，如果期望，这种层还可包含其他组分，诸如颜料、填料、稳定剂、光保护剂或其他合适的改性剂。这些膜层还可包含防粘连剂、助滑添加剂和抗静电剂。有用的防粘连剂包括无机颗粒，诸如粘土、滑石、碳酸钙和玻璃。用于本发明的助滑添加剂包括聚硅氧烷、蜡、脂肪酰胺、脂肪酸、金属皂和微粒，诸如二氧化硅、合成无定形二氧化硅和聚四氟乙烯粉末。用于本发明的抗静电剂包括碱金属磺酸盐、聚醚改性的聚二有机硅氧烷、聚烷基苯基硅氧烷和叔胺。
在一些实施方式中，本发明的可收缩层可包括按重量计约5％至约50％的半晶状聚合物。举例来说，这种半晶状聚合物可包括烯烃聚合物，诸如线型低密度聚乙烯、低密度聚乙烯和其他聚乙烯。在一些具有高和低Tg COC聚合物的掺混物的可收缩层的实施方式中，该可收缩层可包括具有密度在约0.90g/cc至约0.94g/cc的范围中的一种或多种半晶状聚合物。在其他实施方式中，具有高和低Tg COC聚合物的掺混物的可收缩层可包括具有密度在约0.905g/cc至约0.935g/cc的范围中的半晶状聚合物。在仍其他实施方式中，具有高和低Tg COC聚合物的掺混物的可收缩层可包括具有密度在约0.91g/cc至约0.93g/cc的范围中的半晶状聚合物。
本发明的膜可以是具有高和低Tg聚合物的掺混物的单层膜，或在其他实施方式中，可以是多层膜，其中至少一层使用高和低Tg聚合物的掺混物制备。在一些实施方式中，具有至少一种高Tg聚合物和一种低Tg聚合物的可收缩层可构成多层膜的总厚度的至少约5％。在一些实施方式中，具有至少一种高Tg聚合物和一种低Tg聚合物的掺混物的可收缩层可构成多层膜的总厚度的约2％至约30％。在其他实施方式中，这种高Tg和低Tg掺混的可收缩层可构成多层膜的总厚度的约5％至约25％。另外，在一些实施方式中，诸如在以下讨论的样品F-H中，多层膜可具有包括高和低Tg掺混物的第一收缩层和不包括高和低Tg掺混物的至少第二收缩层。
在本发明的一些多层膜实施方式中，其他层可包括，举例来说，表层、粘结层、核心层、印刷层和粘合层。在一些实施方式中，核心可包括聚合材料，诸如聚烯烃树脂或其掺混物。例如，在本发明的一些实施方式中，核心层可由低密度聚乙烯、线型低密度聚乙烯、中密度聚乙烯、乙烯基醋酸乙酯、聚丙烯和其掺混物组成。在一些实施方式中，核心层可另外地或可替代地由高弹体和/或塑性体组成。在一些实施方式中，核心层可用其他非烯烃材料诸如苯乙烯乙烯丁烯苯乙烯(SEBS)、聚(苯乙烯-丁二烯-苯乙烯)(SBS)、聚(苯乙烯-异戊二烯-苯乙烯)(SIS)、和其他相似组分制备。
根据本发明的一些方面，以下样品提供了一些示例性实施方式。如以下显示，样品A-E是具有可收缩层的膜，该可收缩层具有高Tg COC(表示为TOPAS 5013)和低Tg COC(表示为TOPAS 8007)，并且每个样品的高Tg COC与低Tg COC的重量比不同。另外，样品F-H显示膜表层的实施方式的示例性组成，其中粘结层包括高Tg COC和低Tg COC的掺混物。同样地，这些样品之间的粘结层中的高Tg聚合物与低Tg聚合物的重量比不同。样品I-J使用高Tg聚苯乙烯(表示为聚苯乙烯EA3400并且具有约102℃的Tg)和低Tg苯乙烯乙烯丁烯苯乙烯聚合物(SEBS)(表示为Kraton G2832并且具有-42℃的Tg)。最后，样品K使用高Tg PETG(表示为FX100，其作为Tritan Copolyester FX100可购自Eastman，并且具有110℃的Tg)，和样品L使用FX100和低Tg PETG(表示为SKC，其作为Skygreen K2012可购自SK Chemicals，并且具有82℃的Tg)。如以下数据所反映，层百分比是反映层的厚度比的体积百分比。
如表I中的某些实施例所使用，低Tg聚合物是Topas COC 8007(其具有75℃的HDT/B)，和高Tg聚合物是Topas COC 5013(其具有130℃的HDT/B)，其中二者均可购自TopasAdvanced Polymers，Inc。另外，使用的低密度聚乙烯产品可表示为Dowlex LDPE(其具有0.918g/cm3的密度)和Dow Elite 6111(其具有0.912g/cm3的密度，并且是具有乙烯-辛烯共聚物的增强的聚乙烯树脂)，其二者均可购自Dow Chemical Company。此外，Versify 2300是具有0.867g/cm3的密度的高弹体，并且也购自Dow Chemical Company。示出的防粘连剂以商标名Crystal Clear 102077 Antiblock Additive PE MB可购得，其可购自AmpacetCorporation。关于样品K和L，如上所提到，高Tg材料是PETG(表示为FX100，其作为TritanCopolyester FX100购自Eastman，并且具有110℃的Tg)，并且样品L使用FX100和低Tg PETG(表示为SKC，其作为Skygreen K2012购自SK Chemicals，并且具有82℃的Tg)。
在表I中的其他实施例中，聚苯乙烯是高Tg聚合物，和EA3400表示购自AmericanStyrenics，LLC的聚苯乙烯产品，和SEBS是低Tg聚合物，其中G2832表示Kraton G2832，其是购自Kraton Polymers的苯乙烯-乙烯/丁烯-苯乙烯(SEBS)嵌段共聚物。另外，LDPE表示低密度聚乙烯，特别是购自Dow Chemical Company的Dowlex LDPE 722，Septon 2004表示以商标名Septon 2004购自Kuraray CO.，Ltd.的苯乙烯乙烯丙烯苯乙烯嵌段共聚物，Amplify3351表示以商标名Amplify 3351购自Dow Chemical Company的马来酐接枝聚合物，Huntsman LDPE PE1017表示以商标名PE1017购自Huntsman Corporation的低密度聚乙烯，Dowlex LDPE 722表示以商标名Dowlex LDPE 722购自Dow Chemical Company的低密度聚乙烯，和Engage 8842表示购自Dow Chemical Company的聚烯烃高弹体。本领域技术人员容易理解，表I中化合物的以上具体提及实质上仅是示例性的，并且除这些组分以外或替代这些组分，可使用具有合适特性的其他组分。
还测试了样品A-L的MD烘箱收缩率、DMA收缩曲线和多种光学特性。通过对样品的4″×4″膜部分进行穿孔，测试MD烘箱收缩率。对于每个样品，将不同部分放置在烘箱中，其为以下数据中列出的温度之一。该部分被加热五分钟，并且然后测量以确定在每个方向上的尺寸变化(收缩或生长)。以下报告值是从原始部分的纵向上的收缩百分比。通过在流变仪中放置一条样品，并且在张力方向上施加小负载至条带以避免卷曲，进行DMA收缩测试。然后以3℃/min的速率施加热。监测该条带，并且记录以下数据，其提供作为温度的函数的尺寸变化。使用以下步骤测试光学特性。对于光泽度，依据标准ASTM D2457，在60°处测量塑料膜的镜面光泽度。依据标准ASTM D2457，通过测量从光源穿过塑料膜的所得光测定透射比、雾度和清晰度。
虽然以上样品指示层百分比范围，但是在膜上进行的实际测试具有以下层百分比：
样品A-E
表层总计25％(每侧12.5％)
核心层总计75％
样品F-H
表层总计10％(每侧5％)
粘结层总计20％(每侧10％)
核心层总计70％
样品I-J
表层总计25％(每侧12.5％)
粘结层总计14％(每侧7％)
核心层总计61％
样品K-L
表层总计25％(每侧12.5％)
核心层总计75％
如以上结果所指示，基于高Tg聚合物与低Tg聚合物的比例，膜的收缩特性可能不同。此外，如图1中所显示，收缩引发温度是高Tg聚合物与低Tg聚合物之比的非线性函数。因此，通过改变可收缩层中高Tg聚合物与低Tg聚合物的比例，在具体实施方式中可调节收缩引发温度。通常，如在图中所显示，通常观察到，高Tg组分的增加获得收缩引发温度的升高。另外，如通过样品K和样品L的对照所显示，与样品K的高Tg PETG层相比，高Tg PETG和低TgPETG的样品L中掺混的表层(在这种情况下，约82℃的低Tg)导致改变膜的激活温度。
认识到该相关性，在本发明的一些实施方式中，通过可收缩膜层中高Tg聚合物与低Tg聚合物的比例可控制膜的收缩引发温度。例如，通过膜层中这种组分的掺混，收缩引发温度可被调节至期望的水平。结果，由测试具有高Tg聚合物与低Tg聚合物的不同比例的不同膜层，使用外推法，可外推数据以确定需要的比例，以实现膜的某个收缩引发温度。本发明的这种实施方式使得膜被制备为具有合适的收缩引发温度，其可避免膜在正常储存或运输温度下不期望的收缩。
本领域技术人员可实践本发明的这些和其他改进和变化，而不背离本发明的精神和范围，其在所附权利要求书中被更具体地阐释。另外，应当理解，不同实施方式的方面可整体或部分互换。此外，本领域技术人员将认识到，以上描述仅是举例来说，并且它不旨在限制本发明，如在所附权利要求书中所进一步描述。因此，所附权利要求书的精神和范围不应被限制为本文包含的版本的示例性描述。

Claims (18)

1.具有至少第一可收缩膜层的收缩膜，其包括以下的掺混物：
具有在85℃至165℃的范围中的高玻璃化转变温度的可收缩聚合物，和
具有小于85℃的低玻璃化转变温度的可收缩聚合物，
所述第一可收缩膜层中所述具有高玻璃化转变温度的可收缩聚合物和所述具有低玻璃化转变温度的可收缩聚合物的重量比在50:50至1:99的范围中。
2.根据权利要求1所述的收缩膜，其中所述高玻璃化转变温度在90℃至160℃的范围中。
3.根据权利要求1或2所述的收缩膜，其中所述低玻璃化转变温度在-60℃至84℃的范围中。
4.根据权利要求1所述的收缩膜，其中所述收缩膜是单层膜或多层膜。
5.根据权利要求4所述的收缩膜，其中所述收缩膜是多层膜，并且第二可收缩膜层包括具有高玻璃化转变温度的可收缩聚合物和具有低玻璃化转变温度的可收缩聚合物。
6.根据权利要求1所述的收缩膜，其中所述收缩膜包括高弹体。
7.根据权利要求1所述的收缩膜，进一步包括核心层。
8.根据权利要求7所述的收缩膜，其中所述核心层由聚烯烃组成。
9.根据权利要求7所述的收缩膜，其中所述核心层由选自以下的材料组成：低密度聚乙烯、线型低密度聚乙烯、中密度聚乙烯、乙烯基醋酸乙酯、聚丙烯、高弹体、塑性体、苯乙烯乙烯丁烯苯乙烯、聚(苯乙烯-丁二烯-苯乙烯)、聚(苯乙烯-异戊二烯-苯乙烯)(SIS)、乙二醇改性的对苯二酸酯(PETG)、聚对苯二酸亚乙酯(PET)和其掺混物。
10.根据权利要求1所述的收缩膜，其中所述膜是多层膜，并且包括至少一种高Tg聚合物和一种低Tg聚合物的掺混物的层构成多层膜总厚度的至少约5％。
11.根据权利要求1所述的收缩膜，其中所述膜是多层膜，并且包括至少一种高Tg聚合物和一种低Tg聚合物的掺混物的层构成所述膜总厚度的约2％至约30％。
12.根据权利要求1所述的收缩膜，其中所述具有高玻璃化转变温度的可收缩聚合物是环状聚烯烃共聚物，并且所述具有低玻璃化转变温度的可收缩聚合物是环状聚烯烃共聚物。
13.根据权利要求12所述的收缩膜，其中所述低玻璃化转变温度环状聚烯烃共聚物具有75℃的热变形温度HDT/B。
14.根据权利要求1所述的收缩膜，其中所述具有高玻璃化转变温度的可收缩聚合物是乙二醇改性的对苯二酸酯(PETG)，并且所述具有低玻璃化转变温度的可收缩聚合物是乙二醇改性的对苯二酸酯(PETG)。
15.根据权利要求1所述的收缩膜，其中所述第一可收缩膜层进一步包括选自低密度聚乙烯或线型低密度聚乙烯的一种或多种额外的聚合物。
16.制备可收缩膜的方法，其中所述方法包括：
制备在权利要求1至3任一项中指示的掺混物，和
由所述掺混物形成膜。
17.根据权利要求16所述的方法，其中所述膜是由所述掺混物制备的单层膜或多层膜。
18.根据权利要求16或17所述的方法，其中所述膜通过挤出形成。
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