CN1655929A - 未取向聚丙烯包装膜 - Google Patents
未取向聚丙烯包装膜 Download PDFInfo
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Abstract
一种含高结晶聚丙烯、标准聚丙烯和成核剂的未取向的膜。所述的膜具有在如食品包装和棉栓外包装的应用所要求的物理性质,包括良好的可撕性、刚性和记忆性。此外,所述的未取向的膜的成本合理,因为该膜无需经拉伸或取向步骤就能获得这些物理性质,而用于食品包装和棉栓外包装的常规聚丙烯膜则需要进行膜的拉伸或取向。
Description
技术领域
本发明涉及包装膜,特别是未取向包装膜。所述包装膜配制成具有刚性、记忆,和诸如食品包装和棉栓外包装的应用所要求的易撕开。
发明背景
本发明涉及包装膜,特别是易撕开,但同时保护膜内的产品不受污物、灰尘、湿气或其它污染物污染的包装膜。这样的膜的典型用途包括,例如糖果包装、棉栓外包装、冰淇淋包装和快餐食品单独包装。但是,应当知道的是,本发明的膜可以有许多别的用途。本包装膜有一最优化模量,使膜保持其形状。例如,用这种膜作为硬糖果的包装时,用这种膜包裹硬糖块,伸出的膜边缘再绞合,记忆和割线模量(secant modulus)是使膜能保持其位置,防止硬糖果从包装中脱出,直到用外力才能取出膜内糖块所要求的特性。
透明度根据这一要求,制造双轴向取向聚丙烯(BOPP)膜,由于产品的刚性、强度、透明度和防湿性能,在包装工业,特别是食品的包装上占有重要位置。当前,这一市场份额占生产出的BOPP膜的70%。通常,这些膜是用所谓拉幅过程生产出的多层结构。其生产工艺是聚合物在挤出机中熔融并均化,熔体过滤,带入缝形模头或环形模头,挤出形成单层或多层熔体膜。用缝形模头挤出,熔体帘流流涎在一冷辊筒上结晶。用环形模头挤出时,膜经空气骤冷形成固体膜。膜再进行纵向和横向取向和拉伸。拉伸过程是一个典型的三步过程,如EP-0116457B1中所述。拉伸后,膜冷却到室温,再两边修整。如果需要,膜可进行表面处理。然后把膜卷绕,并按顾客要求包装。BOPP膜与应用相关的性质主要由双轴向取向和聚合物的组成决定。然而,双轴向取向的生产过程有许多缺点。首先,该过程涉及使用昂贵的设备,并在制造过程中引入附加的工序,因此造成效率低和成本高的生产工艺。第二,由于膜加工过程中的应力作用,在生产过程中,膜很容易破裂例如膜撕裂很敏感。
已开发几种现有技术膜来代替BOPP膜。这样一种膜是用包含聚丙烯共聚物、含有4个或更多碳原子的α烯烃和乙烯的树脂层涂层涂覆聚合物膜制造的。由于存在乙烯和聚丙烯组分的结晶性,制成的膜的撕裂性差。并且,膜需要树脂层层合到聚合物膜上,这能进一步降低膜的可撕性。
另一种先有技术的BOPP取代膜的制备是使膜仅在一个方向上取向。但是,这一工艺使用过时的膜取向设备,虽然它去掉了一个加工步骤,但是保留的取向步骤仍然费时,昂贵并增加加工故障的次数。
还有一种现有技术BOPP取代膜,涉及在膜中加上y弱线,或膜本身刻痕。或者在包装的每一端封口加上一排凹口。但是,由于附加设备的成本和附加的制造步骤,这样生产的包装膜比较昂贵。另外,在撕裂线超过被包产品的地方,大量包装材料被浪费,从而增加加工成本。
再有一种先有技术包装膜涉及加入撕裂带。撕裂带是一种窄的支撑材料带,沿被包产品的包装膜内周边粘合,终止于两边各加凹口的凸出物上。当凸出物被提升和牵拉时,由于开切口和牵拉力,撕裂开始沿牵拉方向延长。但是,加上凸出物也增加了成本。
因此,需要提供一种有优良刚性,屈服时拉伸伸长低,良好的死褶特性和优良的可撕性的合理成本的包装膜。
发明概述
本发明的一个目的是提供一种包装膜,它不要求取向却具有优良可撕性和刚性。
本发明的另一个目的是提供一种防水包装膜,其透明度增加,有足够的死摺特性。
本发明是一种未取向的包装膜,它包含标准聚丙烯和熔体流动速率为20g/10min或更大的高结晶聚丙烯(hcPP)。hcPP通常用于如注塑这样的应用,如美国专利6,162,887中描述的。该专利参考结合于此。高结晶聚丙烯可用来增加膜的刚性和结晶度。虽然所有的聚丙烯膜随着老化,结晶度有些提高,这是hcPP的固有特性,高结晶度使本发明的膜易撕裂。可将成核剂加入膜组成中,以获得所需的死褶或记忆特性并增加刚性。因为不需要二次或随后的取向加工步骤,本发明的包装膜的成本较先有技术的包装膜有合理。
本包装膜可以是单层膜或多层膜。在多层的实施方案中,含标准均聚聚丙烯,但不含hcPP的表层可包封芯层,该芯层包含hcPP和标准均聚聚丙烯树脂。因为较高结晶的芯层处于两个较低结晶的层之间,膜更易加工,且增加了耐久性。另一种多层膜有一芯层和两个表层,三个层都含hcPP树脂。
每一层内hcPP树脂含量依所需膜的性质而变。例如,所有的膜层可含相同量的hcPP树脂。结果,这些层有相似或相同的粘度,无需加工助剂可同时在标准共挤出设备上共挤出。
从下面对较好实施方案的详细描述,并结合附图,能更好地理解本发明的另一些目的和优点。
附图简述
图1是含不同数量hcPP的四个样品膜沿纵向的伸长性质图。
图2是三层膜的实施方案截面图。
图3是另一个三层膜的实施方案截面图。
较好的实施方案详述
本发明是未取向的刚性包装膜,用于象食品包装或糖果包装这样的应用。膜的组成使膜呈刚性,易撕裂,不需要膜进行拉伸或取向。此膜含高结晶聚丙烯(hcPP),常规丙烯和成核剂。此膜也可包含色母料和膜加工添加剂。
本发明的膜,未经取向或拉伸,能达得与从双轴向取向聚丙烯制得的膜的物性相似的物理性能。加入膜内的hcPP量要足以使膜达到用于如食品包装和棉栓外包装这些应用所需的刚性和可撕性。撕裂可用膜在破裂前的百分伸长率测定,如用ASTM D 882测定,和用裤型撕裂(撕裂扩展)测定如用ASTM D 1938测定。刚度或模量可以割线模量测定,它是应力与应变之比,在一定范围该比值不变。另外说明,割线模量表示膜变形一定量所需的力。
本发明的膜较好有足够的结晶度,使膜在纵向伸长小于或等于350%时破裂。更好的,膜在纵向伸长小于约200%时破裂,最好在纵向伸长小于100%破裂。更好的是最后的膜在纵向伸长约15%或小于15%。另外,此膜较好的裤型撕裂小于约100g,使膜一旦被穿刺就能容易地撕裂。本发明的膜也有足够的刚性或割线模量,使能用于如食品包装或棉栓外包装的最终用途。另外说明,此膜有足够的刚性,使膜能形成固定住产品的包装,并能在产品周围保持其形状。虽然割线模量值依测试设备不同变化,膜在纵向的割线模量值最好是大于或等于约200,000psi。
选择hcPP的量,使膜未经取向或拉伸就具有要求的物理性质。膜中hcPP树脂含量较好大于膜重量的15%。较好的,hcPP量在膜重的约30%至90%范围,更好是约35%至约65%,使膜的伸长值小于100%。hcPP的量更好是膜重的约40%至50%。
如图1所示,是四个样品膜的纵向伸长值图,随着hcPP量的增加,膜伸长值急速下降。测试结果和膜的具体组成结合实施例1-4讨论。
如本领域所理解的,可采用几种方法测定聚丙烯的结晶度。例如聚丙烯的结晶度可用溶于二甲苯中的聚丙烯的重量百分数表征。膜中的hcPP可溶于二甲苯的重量较好为约0.5重量%至1重量%。hcPP较好是丙烯均聚物。或者hcPP可以是丙烯和α-烯烃如乙烯的共聚物。但是,优选hcPP均聚物,因为加入如乙烯的共聚单体可降低膜的结晶度。结晶度的降低使膜的易撕性减小。
hcPP的熔体流动速率至少约20g/10min,特别要大于20g/10min。更好的,HcPP的熔体流动速率大于约30g/10min。hcPP的熔体流动速率最好为30g/10min至约50g/10min。一个特别优选的例子,hcPP的熔体流动速率为40g/10min。先有技术的双轴向取向膜使用熔体流动速率小于约12g/10min的结晶聚丙烯,如在美国专利号6,060,139中披露的,该专利参考结合于此。采用高熔体流动速率hcPP使加工困难,因为当熔融时,hcPP的粘性小于其他低熔体流动速率的聚丙烯。可是,虽然加工难,这种高熔体流动速率的hcPP提供本发明的膜无需取向就具备所需要的刚性和可撕性。合适的hcPP树脂包括核化均聚物hcPP,如以商品名HuntsmanP946K-033(从Huntsman Corporation得到)和Fina EOD-9601与Fina NO1146(二者可从Atofina Chemicals,Inc.得到)出售的树脂。
本发明的膜还包含标准聚丙烯,以使膜保持足够的柔性和耐久性,从而易于加工并适于最终应用。标准聚丙烯的二甲苯中溶解量约为2重量%至约4重量%。聚丙烯的熔体流动速率为约2g/10min至约20g/10min熔体流动速率,最好约8g/10min至约18g/10min。合适的聚丙烯包括均聚物聚丙烯,如以商品名Huntsman11S12A熔体流动速率购自Huntsman Corporation,其熔体流动速率12g/10min;Amoco10-6721,熔体流动速率购自BP p.l.c,其熔体流动速率7g/10min;ExxonMobil PP4683E1,熔体流动速率购自Exxon Mobil Corporation,熔体流动速率9g/10min;和Union Carbide DX5E66,熔体流动速率购自Dow Chemical Company,熔体流动速率8.8g/10min。本发明的膜较好含有高至膜重量的约85%的常规聚丙烯,更好约15%至约70%,取决于获得要求的物理性质所需膜内hcPP和膜添加剂量。
聚丙烯较好是丙烯均聚物。均聚物聚丙烯缺少能改变本发明膜的结晶度的乙烯或其它单体。另外,聚丙烯可与少量乙烯或C3-C10α-烯烃共聚。例如,本发明膜可包含无规聚丙烯共聚物(“RCP”)。如本领域所理解的,RCP是与乙烯共聚的丙烯,乙烯量宜为聚丙烯重量的约2%至约4%。测定聚丙烯熔体流动速率的方法披露于TheWiley Encyclopedia of Packaging Technology(Aaron L.Brody et al.eds.,2ndEd.1997)P.677;制造聚丙烯的方法披露于Kirk-Othmer Concise Encyclopedia ofchemical Technology PP.1420-21(Jacgueline I.Kroschwitz et al.eds.,4thEd.1999),该书参考结合于此。
本发明的膜可包含添加剂,如成核剂、防粘连化合物、抗静电剂、润滑剂和稳定剂,以有助于加工和/或改善膜的物理性质。本发明的膜较好包含至少一种成核剂,以增加结晶度和死褶或记忆特性。本发明膜可包含二种或多种成核剂的混合物,以提供膜所需的性质。此外,成核剂的微细粒子通常会改善膜的光学性质。
加入膜内的成核剂数量依所需的模量和记忆性质而变化。虽然本发明膜可包含任何适量的成核剂,但优选的量是膜重量的约5%。本发明膜最好包含膜重量的约0.1%至约4%的成核剂。
合适成核剂的例子包括滑石粉、各种二氧化硅、碳黑、高岭土、脂族一元酸或二元酸或芳基烷基酸的盐、芳香族羧酸或脂环羧酸的碱金属或铝盐、双苯亚甲基山梨醇、苯甲酸盐、有机磷酸钠盐和上述盐的游离酸。成核剂通常以粉末或粉末混合物、悬浮液或溶液、或母料形式加入。不管用哪种方法,成核剂宜预先分散处理。合适的成核剂包括以商品名Plastolyn 2349(购自Eastman Chemical Corporation)和Milliken 8C41-10(购自Milliken & Company)出售的成核剂。成核剂Plastolyn2539是氢化烃类树脂和聚烯烃的塑料添加剂。成核剂Millliken 8C41-10是熔体流动速率10g/10min的无规共聚聚丙烯中的基于山梨醇的澄清剂的10%浓缩物。其它合适的成核剂包括以商品名Ciba Irgaclear D,Ciba Sodiun Benzoate和CibaIrgaclear DM(购自Ciba Specialty Chemicals Corporations);和ABM-107与ABM 101(购自Riverdale Color)出售的成核剂。一些成核剂如以商品名Milliken8C41-10,Ciba Irgaclear D和Ciba Irgaclear DM出售的那些,也能提高膜的透明度。
本发明膜还可包含高达约30重量%的碳酸钙添加剂。碳酸钙添加剂可用于使膜不透明。较好的碳酸钙添加剂是60%碳酸钙与聚丙烯的共混物,它以商品名Standridge 01SAM06162出售。在包含一个芯层和二个表层的膜的实施方案中,碳酸钙添加剂可包含在芯层或表层内。或者,碳酸钙添加剂可包含在芯层和至少一个表层内。
虽然所有的聚丙烯膜随着老化都会形成一定程度的结晶度,已发现,加入碳酸钙添加剂加速结晶过程。没加碳酸钙添加剂的本发明的膜在送至购买者之前,通常要老化几天到一周。然而,含碳酸钙添加剂的本发明的膜在制造过程中或制造刚完成就显示结晶性。因此,制得的含碳酸钙添加剂的膜几乎立刻送至购买者。
将膜层卷到一个辊筒上时,膜层会结合在一起。膜卷在辊筒上时,防粘连剂有助于保持膜层分开。但是,高浓度的防粘连剂可造成膜的雾化。膜较好的还包含约0.1%至约5%的防粘连剂。合适的防粘连剂的例子包括无机添加剂,如二氧化硅、碳酸钙、硅酸镁、硅酸铝、磷酸钙,和有机添加剂如聚酰胺、聚酯和聚碳酸酯。合适的防粘连剂包括以商品名Ampacet 10126出售的防粘连剂,它是低密度聚乙烯,加有20%防粘连剂。
膜还可包含外润滑剂。外润滑剂减小摩擦系数、减少或消除膜与制膜设备的热金属部件的粘结。内润滑剂在各聚合物链之间提供润滑作用,在加工过程中产生内部滑移从而促进热稳定,减少膜的熔融破损。外润滑剂的例子包括聚乙烯蜡、芥酸酰胺和乙烯双油酸酰胺(EBO)。硬脂酸是内润滑剂的一个例子。钙/锌皂类热稳定剂是加工助剂,可作为内润滑剂和外润滑剂。合适的润滑剂包括以商品名Ampacet 10090(购自Ampacet Corporation),Techmer PM11458E4(购自TechmerPM,LLC)和Polyfil SSC0500(购自Polyfil Corporation)出售的滑爽剂。
着色剂也可加入包装膜中。着色剂较好的加入量可高达约30%。典型的着色剂包括二氧化钛和碳酸钙。在多层膜的情况,着色剂最好包含在芯层以避免模具咬模。芯层包含一定百分率的着色剂可降低芯层中HcPP的百分率。为了保持膜所需的刚性和可撕性,由着色剂从芯层取代的hcPP的量可包含在表层内。
本发明的膜可采用本领域熟知的常规挤出或共挤出方法挤出为单层膜或多层膜。在挤出机中用于每层的聚合物树脂熔融并与添加剂混合。树脂然后通过缝形模头挤出(或在多层膜情况共挤出)。
本发明的一个芯层夹于两个表层之间的三层膜的实施方案示于图2。图2所示的膜用A/B/A结构表示,其中两个表层相同。膜的具体组成和层的厚度结合下面的
实施例讨论。
另外,如图3所示,本发明的膜用A/B/C表示,C层不同于A层。一个实施方案中,A层由聚丙烯均聚物和少量hcPP形成,C层是热封层。热封层较好含有低熔点聚合物,其熔点约50℃或更低为好,其量至多是热封层重量的约20%,更好是热封层重量的约5%至约10%。合适的聚合物包括乙烯乙酸乙烯酯、甲基丙烯酸乙酯和金属茂。热封层较好的还包含为热封层重量的约80%至约95%的均聚聚丙烯。
在多层情况,每一表层厚度以不超过膜的总厚度的约30%为宜。每一表层厚度最好不超过膜厚度的约20%。芯层厚度至少是膜厚度的约40%为宜,最好是膜厚的至少约60%。膜的其它实施方案可包含多于三个的层。一个实施方案的膜有五层,用结构A/D/B/D/A代表。
在多层情况,芯层所含hcPP的量宜大于表层。在某些实施方案中,一个或两个表层可不包含高结晶聚丙烯。含有至少一个无hcPP的表层会使膜更耐久,因为它保护结晶的易撕裂的芯层。同样,表层含有少于芯层的hcPP,也提供某种保护并增加耐久性。
或者,表层和芯层可含有等量的hcPP。如上面讨论的,有相似或相同粘度的膜层的共挤出,无需加入加工助剂来增加或降低树脂的粘度,可同时在标准共挤出设备上共挤出。因此,含有相似或等量的hcPP的场合可有良好的加工效率。
本发明的膜的厚度最大约4密耳。膜厚度超过约1密耳,hcPP对膜的可撕性和刚性的影响最突出。厚度约0.4密耳至约1密耳的膜,需要有较高含量的hcPP和成核剂,以获得所需的刚性和可撕性。
本发明的包装膜符合FDA对食品接触应用的规章要求。另外,包装膜在常规挤出设备上,熔融温度为215-255℃时进行加工。
如上所述,本发明的膜具有的物理性质包括优良的可撕性、刚性和记忆性,适合于食品包装和棉栓外包装。此外,本发明膜的成本合理,因为这些膜无需对用于食品包装和棉栓外包装的常规聚丙烯膜进行拉伸或取向步骤,就具有要求的物理性质。
实施例
测试的实施例具有下面表A-F列出的组成。下面列出的实施例的组成中,hcPP是核化的高结晶聚丙烯均聚物,熔体流动速率为40g/10min,以商品名FinaEOD-9601出售。在下面实施例中,聚丙烯指的是标准均聚聚丙烯,熔体流动速率为8.8g/10min,以商品名Union Carbide DX5E766出售。下表中列出的防粘连剂是在低密度聚乙烯中20%防粘连剂的混合物,以商品名Ampacet 10126出售。下面列出的成核剂是一种氢化烃树脂和聚烯烃的塑料添加剂,以商品名Plastolyn 2539(“Plastolyn”)出售。芥酸酰胺滑爽剂是5%的芥酸酰胺在低密度聚乙烯中的滑爽剂,以商品名Ampacet 10090出售。下面实施例中使用的其它树脂具体如下。下面所用的“Milliken”指在无规共聚聚丙烯中的山梨醇成核剂,以商品名Milliken8C41-10出售。
实施例1-4
实施例1-4是结构为A/B/A的三层膜样品,相应的膜厚度列于下表A。
表A
A/B/A厚度 | A层 | B层 | 总hcPP% | |
实施例1 | 10%/80%10% | 94%聚丙烯2%防粘连剂2%成核剂2%芥酸酰胺滑爽剂 | 98%聚丙烯2%成核剂 | 0% |
实施例2 | 25%/50%25% | 14%hcPP2%防粘连剂2%成核剂2%芥酸酰胺滑爽剂 | 14%hcPP84%聚丙烯2%成核剂 | 14% |
实施例3 | 17.5%/65%17.5% | 94%聚丙烯2%防粘连剂2%成核剂2%芥酸酰胺滑爽剂 | 68%hcPP30%聚丙烯2%成核剂 | 44.2% |
实施例4 | 25%/50%25% | 72%hcPP16%聚丙烯2%防粘连剂2%成核剂2%芥酸酰胺滑爽剂 | 98%hcPP2%成核剂 | 88% |
实施例1-4的四个样品膜按上面列出的组分制备,并测定数种物理性质,列于表B
表B
性质 | ASTM测试# | 单位 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
%hcPP | 0 | 14 | 44.2 | 88 | ||
厚度 | D2103 | 密耳耳 | 1.42 | 1.43 | 1.22 | 1.43 |
纵向伸长 | D882 | % | 761 | 352 | 6 | |
纵向伸长@屈服 | D882 | % | 10 | 7 | 8 | 6 |
纵向裤型撕裂 | D1938 | 克 | 71 | 65 | 61 | 53 |
纵向带/厚 | D2103 | 密耳 | 1.4 | 1.43 | 1.22 | 1.42 |
纵向割线模量 | D882 | Psi | 219,100 | 229,500 | 239,300 | 294,100 |
横向伸长 | D882 | % | 473 | 7 | 8 | 5 |
横向伸长@屈服 | D882 | % | 7 | 7 | 7 | 5 |
横向裤型撕裂 | D1938 | 克 | 190 | 170 | 144 | 134 |
横向带/厚 | D2103 | 密耳 | 1.42 | 1.4 | 1.24 | 1.43 |
横向割线模量 | D882 | Psi | 190,600 | 215,700 | 223,000 | 262,200 |
雾度 | D1003 | % | 10.4 | 11 | 12.1 | 8.79 |
光泽度(向内) | D2457 | % | 52.9 | 49.3 | 45.3 | 54 |
光泽度(向外) | D2457 | % | 53.3 | 49 | 45.5 | 53.4 |
如表B所示,实施例3和实施例4的含大于14%hcPP的样膜,在纵向和拉伸方向的伸长值很低,使膜容易撕裂。另外,实施例3和实施例4具有比实施例1和实施例2低的裤型撕裂值,表明较高的hcPP含量也降低了抗撕裂扩展。实施例3和实施例4在纵向和横向的割线模量值也都高于220,000。相反,实施例1和实施例2的伸长值高于350%,割线模量值小于实施例3和实施例4。由此可见,含有大于膜重量的约15%的hcPP提供低的伸长百分数,使膜易撕裂。表B的数据显示,与成核剂结合的hcPP的量大于15%,能提供优良的刚性和可撕性。但是,当hcPP的百分数上升超过约40%时,伸长百分数在约6%至约11%之间。
实施例5-6
制备组成列于表1的实施例3的样品膜,并与实施例5和实施例6比较。除了使用的hcPP和成核剂,实施例5和实施例6的组成与实施例3相同。实施例5和实施例6含有的hcPP,其熔体流动速率为20g/10min。成核剂是Milliken成核剂。实施例3和实施例5-6是三层膜,可用结构A/B/A代表,相应的厚度是17.5/65/17.5。测定了实施例3和实施例5-6的物理性质并列于表C。
表C
性质 | ASTM测试# | 单位 | 实施例3 | 实施例5 | 实施例6 |
树脂熔体流动速率 | 40 | 20 | 20 | ||
厚度 | D2103 | 密耳 | 1.34 | 1.40 | 1.51 |
纵向伸长 | D882 | % | 9 | 353 | 225 |
纵向伸长@屈服 | D882 | % | 7 | 7 | 7 |
纵向裤型撕裂 | D1938 | 克 | 53 | 67 | 99 |
纵向带/厚 | D2103 | 密耳 | 1.38 | 1.41 | 1.46 |
纵向割线模量 | D882 | Psi Psi | 245,800 | 215,321 | 203,876 |
横向伸长 | D882 | % | 8 | 5 | 6 |
横向伸长@屈服 | D882 | % | 7 | 5 | 6 |
横向裤型撕裂 | D1938 | 克 | 154 | 165 | 166 |
横向带/厚 | D2103 | 密耳 | 1.36 | 1.40 | 1.47 |
横向割线模量 | D882 | Psi | 228,800 | 203,144 | 193,357 |
雾度 | D1003 | % | 11.2 | 4.7 | 5.12 |
光泽度(向内) | D2457 | % | 52.5 | 76.5 | 74.2 |
光泽度(向外) | D2457 | % | 52.6 | 74.9 | 74.0 |
如表C列出的测试结果所示,含20熔体流动速率的hcPP的膜比含等量的40熔体流动速率的hcPP的膜有较低的刚性和较高的伸长值和裤型撕裂值。例如,实施例5的纵向伸长是352%,实施例6是225%,而实施例3则是9%。增加20熔体流动速率的hcPP和成核剂的量,将会提高含熔体流动速率为约20g/10min的hcPP膜的刚性和可撕性。
实施例7-10
制备含不同数量和不同类型的成核剂的实施例7-10的样品膜,测试物理性质,列于下面的表E。实施例7-10的组成,除下面表D表示的成核剂的类型和数量外,与上面表A标示的实施例3的组成相同。
表D
成核剂 | 百分数 | |
实施例7 | 0% | |
实施例8 | Milliken | 4% |
实施例9 | Plastolyn | 2% |
实施例10 | Plastolyn | 4% |
表E
性质 | ASTM测试# | 单位 | 实施例7 | 实施例8 | 实施例9 | 实施例10 |
厚度 | D2103 | 密耳 | 1.44 | 1.35 | 1.34 | 1.41 |
雾度 | D1003 | % | 9.9 | 4.3 | 11.2 | 8.5 |
光泽度(向内) | D2457 | % | 59.0 | 80.5 | 52.5 | 64.5 |
光泽度(向外) | D2457 | % | 60.4 | 80.9 | 52.6 | 63.7 |
纵向伸长 | D882 | % | 10 | 7 | 9 | 8 |
纵向伸长@屈服 | D882 | % | 8 | 7 | 7 | 7 |
纵向裤型撕裂 | D1938 | 克 | 92 | 70 | 53 | 51 |
纵向带/厚 | D2103 | 密耳 | 1.43 | 1.37 | 1.38 | 1.41 |
纵向割线模量 | D882 | Psi | 226,000 | 230,900 | 245,800 | 241,400 |
横向伸长 | D882 | % | 9 | 7 | 8 | 7 |
横向伸长@屈服 | D882 | % | 8 | 6 | 7 | 6 |
横向裤型撕裂 | D1938 | 克 | 143 | 146 | 154 | 148 |
横向带/厚 | D2103 | 密耳 | 1.42 | 1.36 | 1.36 | 1.39 |
横向割线模量 | D882 | Psi | 204,600 | 239,800 | 228,800 | 218,300 |
表E表明,成核剂提高了膜的刚性,如实施例8-10中较高的割线模量值所示。成核剂也降低裤型撕裂值,该值衡量一旦膜被穿刺撕裂扩展的难易程度。另外,表E中的数据表明,Milliken牌成核剂使膜具有较低的百分雾度值,从而提高了未加着色剂颜料的普通膜的透明度。
结晶性实施例
制备了含不同量的hcPP和成核剂的数种样品膜。用先有技术的双轴向取向聚丙烯(“BOPP”)的一个样品膜也进行了测试。然后样品膜在三个不同温度进行评价:熔融开始的温度,最高熔融温度和最高重结晶温度。使用差热扫描量热计测定每个膜的熔融和重结晶曲线,就得到结果。熔融曲线包括膜开始熔化的“开始”温度和膜完全熔化的“最高”温度。优选具有高熔点的膜,因为高熔点说明包装膜的结晶度和模量高,易撕裂且防渗性能高。重结晶最高点指示膜重结晶成它的原先形态的温度。
表F
膜类型 | hcPP% | 成核剂% | 成核剂 | 厚度密耳 | 开始温度℃ | 最高温度℃ | 重结晶最高点 |
hcPP | 44 | 0 | - | 1.41 | 157.828 | 166.147 | 130.633 |
hcPP | 44 | 2 | Milliken | 1.38 | 159.446 | 164.850 | 129.966 |
hcPP | 44 | 4 | Milliken | 1.45 | 158.661 | 165.100 | 132.133 |
hcPP | 44 | 2 | Plastolyn | 1.22 | 157.001 | 163.516 | 130.466 |
hcPP | 44 | 4 | Plastolyn | 1.46 | 156.345 | 165.913 | 129.800 |
hcPP | 44 | 2 | Plastolyn | 2 | 156.222 | 166.016 | 129.633 |
hcPP | 44 | 2 | Plastolyn | 1 | 157.724 | 163.266 | 130.133 |
hcPP | 88 | 2 | Plastolyn | 1.43 | 161.382 | 166.350 | 130.300 |
hcPP | 14 | 2 | Plastolyn | 1.43 | 160.248 | 164.183 | 126.966 |
hcPP | 0 | 2 | Plastolyn | 1.41 | 156.062 | 160.183 | 113.466 |
hcPP | 0 | - | - | - | 151.233 | 156.183 | 110.633 |
表F显示,含hcPP的膜的熔点高于标准BOPP膜的熔点,事实证实,hcPP膜在约156℃至约160℃的温度范围开始熔融,约160℃至约166℃完全熔融;而标准BOPP膜在151℃开始熔融,到156℃完全熔融。因此,含hcPP的膜具有较高结晶度,从而具有优良的撕裂性质,提高了可撕性。这个结论符合由图1-4所示数据得出的结论。
表F也表明,成核剂的存在一般增加包装膜的结晶度。但是,成核剂的类型对结晶度几乎没有影响。而且,厚度对结晶度几乎没有影响。
最后,表F表明,熔点随hcPP量的增加而升高。因此,膜内所含hcPP的重量百分数越大,结晶度越高,导致提高膜的可撕性、刚性、透明度和防渗性能。
对本领域技术人员而言,在不偏离本发明的根本原则下可以对本发明上述实施方案的细节进行变动,是显而易见的。
Claims (23)
1.一种未取向的膜,包含:
熔体流动速率大于30g/10min的高结晶聚丙烯,
成核剂,
聚丙烯。
2.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯量和成核剂量足以使膜具有需要的记忆性、模量和可撕性,使膜能保持形状,并易于撕裂,无需对膜进行取向就可达到需要的记忆性、模量和可撕性。
3.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯量和成核剂量足以使膜在按照ASTM D 882测定的伸长率小于350%时破裂,并能使膜具有在一个方向用ASTM D 882测定的割线模量大于约200,000psi,并且无需对膜进行取向,所述膜就具有大于约200,000psi割线模量和能在伸长率小于350%时破裂。
4.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯的量至少是膜重量的15%。
5.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯的量在膜重量的约30%至约90%的范围。
6.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯的量为膜重量的约40%至约50%的范围。
7.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯的熔体流动速率为约30g/10min至约50g/10min。
8.如权利要求1所述的膜,其特征在于,所述高结晶聚丙烯的熔体流动速率为约40g/10min。
9.如权利要求1所述的膜,其特征在于,所述成核剂的量为小于膜重量的约5%。
10.如权利要求1所述的膜,其特征在于,所述聚丙烯是熔体流动速率为约8g/10min至约20g/10min的均聚聚丙烯。
11.如权利要求1所述的膜,其特征在于,所述的膜在按照ASTM D 882测定的伸长率小于约350%时破裂。
12.如权利要求1所述的膜,其特征在于,所述的膜在按照ASTM D 882测定的伸长率小于约100%时破裂。
13.一种未取向的膜,包含:
一层芯层,包含高结晶均聚聚丙烯、聚丙烯和成核剂芯层,所述高结晶均聚聚丙烯的熔体流动速率至少为20g/10min;
二层表层,包含聚丙烯和熔体流动速率至少为20g/10min的高结晶均聚聚丙烯。
14.如权利要求13所述的膜,其特征在于,所述的高结晶均聚聚丙烯的量至少是膜重量的约15%。
15.如权利要求13所述的膜,其特征在于,所述的成核剂的量为膜重量的约0.1%至约2%。
16.如权利要求13所述的膜,其特征在于,所述的两个表层中至少有一个还含熔体流动速率至少为20g/10min的高结晶均聚聚丙烯。
17.如权利要求13所述的膜,其特征在于,所述的芯层含有着色剂。
18.一种包装,包括:
经成形以包住产品的膜,所述的膜是由熔体流动速率至少为20g/10min的高结晶聚丙烯、成核剂和聚丙烯形成的,
所述的膜在成形为包装膜之前未取向,
和所述的包装膜容易被撕开,并具有足够的记忆性和刚性以保持包装内产品周围的形状。
19.如权利要求18所述的膜,其特征在于,所述高结晶聚丙烯的量至少为膜重量的15%。
20.如权利要求18所述的膜,其特征在于,所述高结晶聚丙烯的量为膜重量的约30%至约90%的范围。
21.如权利要求18所述的膜,其特征在于,所述的膜在按照ASTM D 882测定的伸长率小于约100%时破裂。
22.如权利要求18所述的膜,其特征在于,所述的膜的厚度在约0.4密耳至约2密耳范围。
23.如权利要求18所述的膜,其特征在于,所述的膜的厚度在约1密耳至约2密耳范围。
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EP (1) | EP1513682A4 (zh) |
CN (1) | CN1655929A (zh) |
AU (1) | AU2003225035A1 (zh) |
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Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
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US6825276B2 (en) * | 2001-04-17 | 2004-11-30 | Pliant Corporation | Nonoriented stiff packaging film with superior tear properties |
KR101113341B1 (ko) | 2002-10-15 | 2012-09-27 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 올레핀 중합용 다중 촉매 시스템 및 이로부터 제조된중합체 |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US20040175464A1 (en) * | 2003-03-07 | 2004-09-09 | Blemberg Robert J. | Multilayer structures, packages, and methods of making multilayer structures |
US20040175466A1 (en) * | 2003-03-07 | 2004-09-09 | Douglas Michael J. | Multilayer barrier structures, methods of making the same and packages made therefrom |
US7601285B2 (en) * | 2003-12-31 | 2009-10-13 | Boston Scientific Scimed, Inc. | Medical device with varying physical properties and method for forming same |
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US20070080485A1 (en) * | 2005-10-07 | 2007-04-12 | Kerscher Christopher S | Film and methods of making film |
CN101070363B (zh) * | 2006-05-12 | 2010-08-04 | 贵州省材料技术创新基地 | 一种透明聚丙烯的制备方法 |
JP5275227B2 (ja) | 2006-05-16 | 2013-08-28 | チバ ホールディング インコーポレーテッド | 単層及び多層インフレートフィルム |
US8041024B2 (en) * | 2006-10-17 | 2011-10-18 | International Business Machines Corporation | Method and system for telephone number change notification and tracking |
US8000458B2 (en) * | 2006-11-10 | 2011-08-16 | International Business Machines Corporation | Method and system for verifying incoming telephone numbers |
US8014512B2 (en) * | 2007-04-18 | 2011-09-06 | International Business Machines Corporation | Method and system for user interaction within a queue |
US20080286547A1 (en) * | 2007-05-18 | 2008-11-20 | Hubbard Michael A | Polypropylene films with enhanced moisture barrier properties, process for making and composition thereof |
US8945702B2 (en) * | 2007-10-31 | 2015-02-03 | Bemis Company, Inc. | Barrier packaging webs having metallized non-oriented film |
GB0811991D0 (en) * | 2008-07-01 | 2008-08-06 | Scalar Technologies Ltd | Authentication apparatus and methods |
GB2462995B (en) * | 2008-09-02 | 2012-11-14 | Excelsior Technologies Ltd | Improved food packaging for use in microwave ovens |
CN102574322B (zh) * | 2009-08-04 | 2014-06-25 | 三菱瓦斯化学株式会社 | 容器的制造方法 |
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EP2603548A1 (en) | 2010-08-12 | 2013-06-19 | Borealis AG | Easy tear polypropylene film without notch |
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CZ306740B6 (cs) * | 2010-10-05 | 2017-06-07 | Basf Se | Způsob přípravy nukleovaného semikrystalického polyolefinu |
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US10251770B2 (en) | 2014-01-03 | 2019-04-09 | Hollister Incorporated | Lubricated valve for ostomy pouch |
EP3609702A1 (en) | 2017-04-12 | 2020-02-19 | Dow Global Technologies LLC | Multilayer films containing a slip agent |
CN110628107B (zh) * | 2018-06-22 | 2022-12-02 | 中国石油天然气股份有限公司 | 薄膜开口剂、改性乙丙橡胶膜及用于形成其的组合物 |
WO2022235930A1 (en) * | 2021-05-05 | 2022-11-10 | Superior Plastics Extrusion Co. Inc. Dba Impact Plastics | Modification of polypropylene resins with nucleating agents to enhance mechanical and barrier properties of films |
KR20240017193A (ko) * | 2022-07-28 | 2024-02-07 | 에스케이이노베이션 주식회사 | 개봉성이 확보된 폴리에틸렌계 적층 포장재 및 이의 제조방법 |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3773609A (en) | 1970-09-19 | 1973-11-20 | Chisso Corp | Process for preparing film of crystalline propylene polymer having good heat sealability at low temperature |
US4410582A (en) | 1980-12-10 | 1983-10-18 | Toray Industries, Inc. | Multi-layered polyolefin laminated film |
US4585817A (en) | 1984-06-11 | 1986-04-29 | Mobil Oil Corporation | Crystallizable polyolefin composition having increased crystallization temperature and rate of crystallization |
US4786562A (en) | 1986-07-11 | 1988-11-22 | Sumitomo Chemical Company, Limited | Polypropylene multi-layer film |
US4908278A (en) | 1986-10-31 | 1990-03-13 | Minnesota Mining And Manufacturing Company | Severable multilayer thermoplastic film |
US4870134A (en) | 1987-05-27 | 1989-09-26 | Shell Oil Company | Film, sheet and laminate capable of forming easy-open packagings |
JP2641242B2 (ja) | 1988-04-01 | 1997-08-13 | 大倉工業株式会社 | 多層熱収縮性フイルム |
US4944990A (en) | 1988-06-16 | 1990-07-31 | Mobil Oil Corporation | Oriented white opaque multilayer heat sealable film and method of forming same |
US5066543A (en) | 1990-02-28 | 1991-11-19 | Shell Oil Company | Film, sheet and laminate capable of forming easy-open packagings |
JPH03286859A (ja) | 1990-04-03 | 1991-12-17 | Toray Ind Inc | 三層積層フィルム |
JP3016880B2 (ja) | 1991-02-01 | 2000-03-06 | 三菱化学株式会社 | フィルム成形用高結晶性ポリプロピレン |
DE59207030D1 (de) | 1991-05-28 | 1996-10-10 | Hoechst Ag | Siegelbare, opake, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
US5310584B1 (en) | 1992-04-14 | 1999-02-16 | Amoco Corp | Thermoformable polypropylene-based sheet |
DE59408824D1 (de) | 1993-01-25 | 1999-11-25 | Hoechst Trespaphan Gmbh | Biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4311950A1 (de) | 1993-04-10 | 1994-10-13 | Hoechst Ag | Opake, matte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP3267735B2 (ja) | 1993-04-15 | 2002-03-25 | 三菱化学株式会社 | 二軸延伸複層フィルム |
DE4318031A1 (de) | 1993-05-29 | 1994-12-01 | Hoechst Ag | Harzhaltige, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4337250A1 (de) | 1993-09-27 | 1995-03-30 | Hoechst Ag | Biaxial orientierte Polypropylenfolie mit verbesserten Eigenschaften hinsichtlich Mechanik und Barriere |
US6106938A (en) | 1994-12-22 | 2000-08-22 | Sumitomo Chemical Company, Ltd. | Polypropylene composition and laminated and oriented film therefrom |
US5674630A (en) | 1995-05-08 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Polymer compositions and cast films |
EP0745638A1 (de) | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit verbessertem Weiterreisswiderstand |
KR100277378B1 (ko) * | 1995-11-24 | 2001-01-15 | 고또오 슈운기찌 | 프로필렌조성물및그제조방법과폴리프로필렌조성물및성형품 |
US5689935A (en) | 1996-03-11 | 1997-11-25 | Recot, Inc. | Product package having reliable openability |
JP3813263B2 (ja) | 1996-06-07 | 2006-08-23 | 株式会社プライムポリマー | 易引裂性キャストフィルム |
EP0854155A4 (en) | 1996-07-31 | 2002-01-02 | Japan Polyolefins Co Ltd | HIGH CRYSTALLINITY POLYPROPYLENE |
US6576306B2 (en) * | 1996-09-04 | 2003-06-10 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
DE19815046A1 (de) * | 1998-04-03 | 1999-10-14 | Borealis Ag | Polyolefinfolien und Polyolefinbeschichtungen von Substraten |
US6303233B1 (en) | 1998-04-06 | 2001-10-16 | Mobil Oil Corporation | Uniaxially shrinkable biaxially oriented polypropylene film |
US20010055692A1 (en) | 1999-03-17 | 2001-12-27 | Michael T. Heffelfinger | Multi-layer film with core layer of syndiotactic polypropylene |
US6306518B1 (en) * | 1999-05-19 | 2001-10-23 | Montell Technology Company Bv | High surface gloss, co-extruded sheets from propylene polymer materials |
DE60137341D1 (de) * | 2000-08-22 | 2009-02-26 | Exxonmobil Chem Patents Inc | Polypropylen filme |
US6825276B2 (en) * | 2001-04-17 | 2004-11-30 | Pliant Corporation | Nonoriented stiff packaging film with superior tear properties |
-
2002
- 2002-04-17 US US10/126,051 patent/US6825276B2/en not_active Expired - Fee Related
-
2003
- 2003-04-17 AU AU2003225035A patent/AU2003225035A1/en not_active Abandoned
- 2003-04-17 MX MXPA04010229A patent/MXPA04010229A/es active IP Right Grant
- 2003-04-17 EP EP03721740A patent/EP1513682A4/en active Pending
- 2003-04-17 WO PCT/US2003/011931 patent/WO2003089243A1/en not_active Application Discontinuation
- 2003-04-17 CN CNA038116537A patent/CN1655929A/zh active Pending
- 2003-04-17 CA CA002482861A patent/CA2482861A1/en not_active Abandoned
-
2004
- 2004-09-10 US US10/937,957 patent/US7087314B2/en not_active Expired - Fee Related
- 2004-09-10 US US10/937,956 patent/US20050031886A1/en not_active Abandoned
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US20050037186A1 (en) | 2005-02-17 |
US7087314B2 (en) | 2006-08-08 |
WO2003089243A1 (en) | 2003-10-30 |
US20030054161A1 (en) | 2003-03-20 |
US20050031886A1 (en) | 2005-02-10 |
MXPA04010229A (es) | 2005-07-27 |
EP1513682A4 (en) | 2009-07-29 |
EP1513682A1 (en) | 2005-03-16 |
CA2482861A1 (en) | 2003-10-30 |
AU2003225035A1 (en) | 2003-11-03 |
US6825276B2 (en) | 2004-11-30 |
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