CN101304876A - 取向多层收缩标签 - Google Patents
取向多层收缩标签 Download PDFInfo
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Abstract
本发明涉及一种多层取向收缩薄膜,包括至少一个包含聚苯乙烯材料的表层和至少一个包含聚烯烃层的中心层。所述薄膜主要在纵向或横向择优取向。这些薄膜理想地适合用作收缩标签,该标签可作为CD收缩套使用或者用于连续轧制过程。所述薄膜理想地具有小于1.0g/cm3的总密度,从而方便循环处理。
Description
技术领域
本发明涉及取向收缩多层薄膜,其包括至少一个包含非晶态玻璃状聚合物材料,例如聚苯乙烯材料的表层和至少一个包含聚烯烃层的中心层。所述薄膜主要在纵向或横向择优取向。这些薄膜理想地适合用作收缩标签,该标签可作为CD收缩套使用或者用于连续轧制过程。所述薄膜理想地具有小于1.0g/cm3的总密度,从而方便使用含水浮选分离技术进行循环处理。
背景技术和发明内容
收缩标签通常分成两类:随卷随缩(roll-on shrink-on,ROSO)标签和套管式标签(sleeve-type label)(套管标签)。ROSO标签是环绕容器包裹的薄膜片。套管标签是管状结构的,通过套在容器上而环绕于容器。加热环绕容器的收缩标签可使标签收缩并与容器相贴合。
为了与容器相贴合,每种类型的标签必须在环绕容器周向延伸的方向优先进行收缩(即在一个方向比在另一个方向收缩程度更大)。ROSO薄膜定位在容器上,薄膜的纵向(MD)环绕容器周向进行延伸。由于优先纵向取向(MDO),因此ROSO薄膜主要沿薄膜的纵向(MD)进行收缩。相比之下,套管标签通常定位在容器上,标签的横向(transversedirection)(TD)(也称作横向(cross direction)或″CD″)环绕容器周向进行延伸。由于优先横向取向(TDO),因此套管标签主要沿薄膜的横向(TD)进行收缩。
对ROSO标签的特别需求超过套管标签,因为ROSO标签所需加工较少且制备成本较低。由于在连续卷材加工时在取向膜上印刷,使得ROSO标签通常呈卷状。相比之下,套管标签,尽管也呈卷状,但在轧制成卷状前需要印刷、切割、粘合进套管,套管标签相对于ROSO标签,其生产过程复杂化并增加了生产成本。此外,由于与用于ROSO标签的纵向取向膜相比,设备成本相对较高,用于套管标签的横向取向薄膜往往更昂贵。另外,在容器上应用ROSO标签通常比应用套管标签加工得更快。
尽管ROSO标签在生产速度上具有优势,但套管标签历史上已经在环绕容器的收缩程度上具有优势。套管标签环绕容器周围的收缩通常至多70百分比(%)。相比之下,历史已表明,通常的ROSO薄膜环绕容器周围的收缩最高仅约20%。对于ROSO标签,需要在纵向上的收缩大于25%,更优选大于约50%。通常的ROSO标签收缩较低主要是由于:(1)对于薄膜,主要使用取向聚丙烯(OPP),一种结晶聚合物,和(2)限制允许作用在粘胶接缝(glue seam)上的应力,该粘胶接缝使得标签环绕容器固定在适当位置(包裹)——作用在粘胶接缝上的应力过大将引起标签在容器上移位,或者在极端情况下,引起胶接接头失效,标签不再环绕容器包裹。因此,对于薄膜,观察到的收缩张力是用于确定其是否适合用作ROSO标签的一个重要因素,通常优选较低的收缩张力。套管标签,没有胶接接头或者具有在用于容器前已很大程度固化的胶接接头,在收缩过程中能够容忍更大程度的应力。
套管标签历史上享有更大程度的收缩,因此能比ROSO标签更好地与容器***贴合。但是,考虑到ROSO标签的生产优势,需要识别适合制备ROSO标签的取向膜,其能比当前的ROSO标签(即,更可与套管标签相比较的)环绕容器周向收缩至更大的程度,但是又无损于标签胶接接头的失效。
聚苯乙烯(PS)有时用于制备收缩标签用薄膜,因为PS相对于PP经电晕处理(对于提供适合于印刷的聚合物薄膜表面是必要的)后在时间延长期间仍保持较高的表面能。因此,与PP薄膜不同,PS薄膜的电晕处理可以在生产期间进行,而不是仅在印刷标签前进行。
聚苯乙烯基收缩标签薄膜经常包含高抗冲聚苯乙烯(HIPS)组分以提高标签韧性(例如,抗撕裂性)。但是,在通常的HIPS范围中的橡胶粒子具有大于一个微米的平均粒子大小(见,例如美国专利(USP)6897260,第4栏,第26-27行)。大橡胶粒子倾向于降低标签薄膜的透明度,干扰使用薄膜进行背面印刷(印刷在标签薄膜邻近容器的面上使其透过薄膜是可读的),以及干扰透过标签观察容器或产品。通常的HIPS还包含以HIPS总重计大于7%的橡胶。高浓度橡胶会阻碍薄膜的可印刷性(printability),降低薄膜的透明度,减少尺寸稳定性并不合需要地增加最终薄膜的凝胶量。
与共聚多酯和聚氯乙烯(PVC)薄膜相比,使用PS薄膜方便瓶子和标签的循环利用,因为较低的密度使得标签更易与较高密度(例如,聚酯)瓶子分离。若收缩薄膜的密度小于1.0g/cc将更有利于循环利用,因为这将允许浮选分离技术。
此外,较低密度的薄膜有利于提供较高的薄膜产量,或者更大面积/lb的薄膜。较高密度的标签备料,例如共聚多酯或PVC薄膜,不具有相似的优点。
需要一种适用于ROSO或收缩套管标签的取向多层薄膜。
2005年7月28日提交的美国临时申请60/703385,在此引入其全部内容作为参考,教导了一种适于用作ROSO标签的双轴取向聚苯乙烯基薄膜,其包含的HIPS橡胶粒子大小和橡胶浓度比通常HIPS的低。需要提供一种收缩薄膜,其表现出比60/703385中教导的薄膜更小的收缩张力。还需要收缩膜的总密度小于约1g/cm3,以方便在循环过程中采用浮选技术将标签与瓶子分离。
因此,一方面,本发明是一种取向多层收缩膜,其包括至少一个包含非晶态玻璃状聚合物,例如聚苯乙烯材料的表层和至少一个包含聚烯烃层的中心层。所述多层膜可以在纵向择优取向,例如使用一组MDO轧辊;或者在横向,例如使用拉幅机法(tenter frame process)。非晶态玻璃状聚合物材料优选聚苯乙烯材料,如现有技术中通常已知的,其可以是通用聚苯乙烯(GPPS)或者可以包括其他苯乙烯类材料以赋予耐久性和韧性。这些其他材料包括例如高抗冲聚苯乙烯材料、苯乙烯类嵌段共聚物,例如K-树脂(获自Chevron Phillips)、SBS(苯乙烯丁二烯苯乙烯三嵌段共聚物)、SIS(苯乙烯异戊二烯苯乙烯)、SEBS(苯乙烯乙烯-丁烯苯乙烯三嵌段共聚物)和/或其组合。当需要高抗冲聚苯乙烯时,薄膜优选包含一种高抗冲聚苯乙烯,其与通常的HIPS相比具有更小的橡胶粒子和更低的橡胶浓度,从而使薄膜获得韧性而不阻碍薄膜的可印刷性、透明度或接触透明度。在至少一个中心层所用的聚烯烃,视预期应用的需要,优选能被选来控制薄膜的收缩张力和薄膜的收缩。
另一方面,本发明的多层膜还包括在聚烯烃层和聚苯乙烯表层之间的一个或多个结合层。
另一方面,本发明是一种包括第一或第二方面所述多层薄膜的收缩标签,其中该薄膜在一面或两面有印刷。
附图说明
图1是显示样品3-1和3-2薄膜的MD收缩数据的图。
图2是显示样品3-1和3-2薄膜的CD收缩数据的图。
图3是显示样品4-1至4-4和5薄膜的MD收缩数据的图。
图4是显示样品4-1至4-4和5薄膜的CD收缩数据的图。
发明详述
本发明的取向多层收缩薄膜包括至少一个包含非晶态玻璃状聚合物的表层和至少一个包含聚烯烃层的其他层。非晶态玻璃状聚合物材料优选聚苯乙烯材料。本发明的多层薄膜优选在反面包括第二表层,其包含非晶态玻璃状聚合物材料和包含中心层的聚烯烃层。第二表层优选的材料与第一表层的相同。任选地,多层薄膜可以包括在表层和聚烯烃层之间的一个或多个结合层。
A、表层
表层包括非晶态玻璃状聚合物。非晶态玻璃状聚合物具有超出室温的玻璃化转变温度(根据采用动态力学热分析所测的tan(δ)曲线上适当的峰值确定)并且基本上是非晶态的(即利用如宽角X-射线衍射所确定的结晶度小于约10重量%)。非晶态玻璃状聚合物包括聚苯乙烯材料(例如GPPS、HIPS、K RESIN、SIS、SBS、SEBS)以及PETG、非晶态PET、非晶态PLA或者PVC。当使用GPPS作为非晶态玻璃状聚合物材料时,需要GPPS的Mw(重均分子量)大于100,000g/mol,优选150,000g/mol或更大,更优选200,000g/mol或更大。还需要GPPS的Mw(重均分子量)小于约350,000g/mol,优选小于约320,000g/mol。Mw可以根据现有技术中已知的凝胶渗透色谱确定。需要GPPS的熔体流动速率(MFR)为1或更大,优选1.2克每10分钟(克/10分钟)或更大,并需要20克/10分钟或更小,优选10克/10分钟或更小。聚苯乙烯的MFR根据ASTM方法D1238(在200℃下5千克重量)确定。
适宜的GPPS的例子包括STYRONTM 663通用聚苯乙烯(STYRON是The Dow Chemical Company的商标)、STYRON 668和STYRON685D。
如果需要较大的延性和/或韧性,则一个或两个表层可以包括其他材料,例如HIPS、SBS、K-resin、SIS、SEBS等。这些另外的材料优选用以保持光学透明度。2005年7月28日提交的名称为“IMPROVEDRUBBER MODIFIED MONOVINYLDENE AROMATIC POLYMERSAND THEMOFORMED ARTICLES(改进的橡胶改性单亚乙烯基芳族聚合物及其制品)”的美国专利申请11/191817中描述了适用于本发明的一个或多个表层的一类特别有用的HIPS,在此引入其全部内容作为参考。
非晶态玻璃状聚合物表层可以包含其他添加剂,例如矿物油或其他增塑剂,以及其他现有技术中通常已知的添加剂。这些材料包括例如无机填料、导电填料、颜料、抗氧化剂、酸清除剂、阻燃剂、紫外线吸收剂、如硬脂酸锌的操作助剂、助挤剂、滑爽添加剂、渗透改性剂、抗静电剂、防结块添加剂和其他热塑性聚合物。
也考虑到所述表层可以包括其他非晶态玻璃状聚合物,例如PETG(聚对苯二甲酸乙二酯,G)、非晶态PET(聚对苯二甲酸乙二酯)、非晶态PLA(聚乳酸)。聚氯乙烯(PVC)和/或其组合。这些材料倾向于具有较高的密度,这将导致薄膜的总密度大于1g/cm3,使得薄膜出于循环利用的考虑而较少受到优选。
也考虑到在一个或两个表层中可以使用两种或更多非晶态玻璃状聚合物的组合。
所述表层优选占本发明多层薄膜重量的10重量%至80%,更优选10%至70%,更优选20%至50%,最优选30%至50%。
B)聚烯烃层
本发明的多层薄膜还包括含聚烯烃材料的第二层。优选的聚烯烃材料包括聚乙烯均聚和共聚物以及聚丙烯均聚和共聚物。这些包括低密度聚乙烯、线性低密度聚乙烯、很低(或超低)密度聚乙烯、聚乙烯塑性体和高弹体,例如均匀支化的线性乙烯聚合物和基本线性乙烯聚合物、中等密度聚乙烯和高密度聚乙烯)、均聚物聚丙烯(″hPP″)无规共聚物聚丙烯(″RCP″)和丙烯基塑性体和高弹体,例如WO 03/040442中所描述的那些,在此引入其全部内容作为参考,及其组合。最优选的是聚烯烃塑性体和高弹体,特别是聚乙烯塑性体和高弹体以及聚丙烯塑性体和高弹体,包括WO03/040442和2005年8月19日提交的美国申请60/709688中所描述的丙烯基塑性体和高弹体(在此引入上述每个专利的全部内容作为参考——这些材料中的一些可从The DowChemical Company以商品名VersifyTM购得),和由ExxonMobil Chemicalcompany以商品名VistamaxxTM销售的丙烯基塑性体和高弹体。聚烯烃中心层的密度优选小于0.920g/cm3,更优选小于0.90g/cm3,更优选小于约0.89g/cm3,最优选小于约0.88g/cm3。
可以选择聚烯烃组分以提供适当的熔点和结晶度,从而控制薄膜的收缩张力。优选地,所选聚烯烃树脂(或共混物)的熔点为150℃以下,更优选小于135℃,还更优选小于120℃,最优选小于100℃。
所述聚烯烃组分还可以有利地包括现有技术中通常已知的多种添加剂。这些材料包括例如无机填料、导电填料、颜料、抗氧化剂、酸清除剂、阻燃剂、紫外线吸收剂、操作助剂、助挤剂、滑爽添加剂、渗透改性剂、抗静电剂、防结块添加剂和其他热塑性聚合物。
所述聚烯烃层优选占本发明多层薄膜重量的20重量%至90%,更优选30%至90%,还更优选50%至80%,且还更优选50%至70%。
C)结合层
本发明的多层薄膜还可以任选地包括一个或多个结合层。结合层有利于帮助确保在玻璃状非晶态聚合物层与内部或中心聚烯烃层之间的良好粘合。当在表层使用聚苯乙烯材料时用作结合层的适宜聚合物包括SEBS和SEPS嵌段共聚物及其制剂、EVA、SBS、SIS、K-树脂及其组合。
所述结合层还可以有利地包括现有技术中通常已知的多种添加剂。这些材料包括例如无机填料、导电填料、颜料、抗氧化剂、酸清除剂、阻燃剂、紫外线吸收剂、操作助剂、助挤剂、滑爽添加剂、渗透改性剂、抗静电剂、防结块添加剂和其他热塑性聚合物。
所述结合层,如果有的话,优选占整个多层薄膜的5重量%至15重量%。
整个薄膜
优选用于各层的树脂存在在多层薄膜中,使得薄膜按照ASTMD-792所确定的总密度小于1.0g/cm3,更优选小于0.98g/cm3。
本发明的薄膜是取向的,这是指它们具有单轴取向或双轴取向,其择优取向为纵向(MD)或横向(CD)。择优取向是指在纵向或横向的取向比在其他方向的大。在MD或CD的取向度为至少2x,优选至少3x,最优选至少4x,这取决于所需的收缩方向。本发明取向收缩薄膜的收缩张力在135℃下通常大于约50psi,优选大于100psi。尽管薄膜的MDO比率通常为20或更小,但MDO比率没有明确的上限。MDO比率大于20的薄膜的风险为,在ROSO标签应用中以高作用力环绕容器收缩以致环绕瓶子固定标签的粘胶接缝减弱或失效。这对于在收缩套管应用中的TDO比率也是真实的。
使用纵向长10厘米、横向长2.5厘米的样品测定纵向取向ROSO标签的MDO比率。将样品置于热油浴中,在最高熔融树脂的熔点以上以及在表层的玻璃化转变温度以上保持30秒(ASTM D2732)。然后再次测量纵向尺寸。热前与热后的纵向尺寸比率对应于MDO比率。
使用横向长10厘米、纵向长2.5厘米的样品测定横向取向收缩套管标签的TDO比率。将样品置于热油浴中,保持在最高熔融树脂的熔点以上以及在表层的玻璃化转变温度以上30秒(ASTM D2732)。然后再次测量横向尺寸。热前与热后的横向尺寸比率对应于TDO比率。
本发明的多层薄膜可以在取向步骤之前采用如下的方法常规制备:流延薄膜法、吹塑薄膜法、挤压贴胶法或层压法,并优选流延薄膜法。
可以选择用于薄膜生产工艺拉伸/取向过程中的薄膜温度,以帮助控制收缩张力。薄膜拉伸温度优选为100℃至150℃,更优选为120℃至135℃。
当需要MD取向时,使用一组MDO轧辊即可方便地实现。当需要CD取向时,使用拉幅机法即可方便地实现。这些及其他用以实现取向的步骤是现有技术中众所周知的。
特别是当本发明的多层薄膜用于ROSO标签时,该薄膜的收缩张力应小于约500psi,更优选小于400psi,更优选小于300psi,最优选小于约250psi。套管标签能容忍较高的收缩张力,例如大于1100psi,甚至大于1400psi。收缩张力按照ASTM D-2838确定。
本发明的薄膜需要表明在正常的收缩标签应用温度(例如对于ROSO为110℃至140℃,对于套管为110℃至130℃)下,在择优取向方向(温度120℃至130℃下取向时)的收缩为20%或更多,优选30%或更多,更优选40%或更多,还更优选50%或更多,更优选60%或更多,甚至还更优选在取向方向为70%或更多。20%以下的收缩往往不合需要地限制薄膜与容器***相贴合的程度。尽管收缩程度的上限是未知的,但它在100%以下。
需要地,薄膜表明在正常的收缩标签应用温度(例如对于ROSO为110℃至140℃,对于套管为110℃至130℃)下,在与择优取向相反的方向(温度120℃至130℃下取向时)的收缩为30%或更少,优选20%或更少,更优选10%或更少,还更优选5%或更少。应该理解“小于5%”的收缩也包括增长,尽管增长应该得到最小化。
在标签工业的一些应用中,需要透明度(特别是接触透明度)和透彻度(transparency)以从标签定位处非模糊地观察到产品。还需要高透明度和透彻度用于“反向”印刷标签,其中印刷定位在标签与容器之间,且消费者通过标签观察印刷。通常地,本发明的薄膜在膜厚为2.0密耳(50□m)时,其透明度值为10或更高,优选15或更高,更优选20或更高,更优选25或更高,还更优选30或更高。按照ASTM方法D-1746确定透明度。
雾度值还提供了对薄膜透明度的一种度量,低雾度值对应于高透明度。本发明薄膜的雾度值可以为任何可能的值。但是,本发明的一个优点在于能够获得具有高透明度和低雾度值的取向薄膜。本发明的薄膜在膜厚为2.0密耳(50□m)时,其雾度值通常为20或更低,优选小于15,更优选10或更低,仍更优选8或更低,还更优选6或更低,最优选4或更低。按照ASTM方法D-1003确定雾度值。
为了在高的线速度下适当分配ROSO标签,本发明多层薄膜的刚性在其他原因中是重要的。在择优取向方向取向的多层薄膜的刚性应该至少为约5Gurley,通常可以高至150Gurley。更经常地,取向的多层薄膜的刚性根据TAPPI Gurley刚性试验T543pm测量为20至70Gurley。
虽然所述薄膜可以具有任何所需的厚度,但本发明薄膜的总厚度通常为1密耳(25μm)或更高,优选1.5密耳(38μm)或更高,通常为4密耳(100μm)或更低,优选3密耳(76μm)或更低。薄膜厚度小于1密耳(25μm)时,在加工和处理过程中切割薄膜往往是相当困难的。大于4密耳(100μm)的厚度在技术上是能达到的,但在经济上通常是不合需要的。本发明薄膜需要的收缩张力或取向释放应力(ORS)为500psi(2758kPa)或更小,优选小于400psi,更优选小于300psi,最优选小于约250psi。收缩张力按照ASTM D-2838确定。ORS是对加热收缩过程中薄膜所受应力的一种度量。需要的是降低ROSO薄膜的ORS值。ROSO薄膜通常至少有一端粘合至容器,环绕该容器薄膜得以应用。具有高ORS值的标签在收缩过程中能将足够的应力应用到环绕容器固定标签的粘胶接缝上,从而损害(damage)或损坏(break)该接缝。降低ORS值减少了接缝线(薄膜-薄膜)在收缩过程中受损害或损坏的可能性。
本发明的薄膜可在任何应用中使用,这得益于其在纵向或横向的热触发收缩。所述薄膜可特别用作ROSO标签。为了将本发明的薄膜转化成本发明的ROSO标签,将薄膜切成所需宽度,并电晕处理薄膜的一面(以任何顺序),然后在薄膜电晕处理的一面进行印刷。印刷能定位于薄膜的“背”面上以产生反向印刷的标签。薄膜的背面靠着容器定位,在ROSO标签应用中,当薄膜环绕容器时透过薄膜观察背面的印刷。通常采用现有技术中可用的任何方法在连续卷材加工时进行这些步骤。
本发明的薄膜和标签还有利地具有通过薄膜或标签的穿孔。穿孔最需要位于薄膜紧邻最窄部分的部分或者薄膜应用于ROSO时环绕容器的部分。穿孔允许气体逸出,否则气体倾向于陷在标签与容器之间,由此使得标签更紧地与容器贴合。本发明的薄膜和标签可以包含沿薄膜表面均匀分布的穿孔或者包含特别紧邻薄膜(或标签)区域的穿孔,该区域与薄膜(或标签)环绕容器定位的最窄部分相一致。可以在任何时候对本发明薄膜和标签的穿孔进行打孔;但是,为了方便ROSO标签的印刷,需要在印刷后对薄膜和标签进行打孔。
以下实施例用于举例说明本发明,并不用于确定本发明的全部范围。
实施例
实施例1和2中,使用多层流延薄膜生产线制备了两个多层流延薄膜。每个薄膜具有A/B/C/B/A结构,其中A层为包含非晶态玻璃状聚合物材料的表层,B层为结合层,C层为聚烯烃层。薄膜的组成如下:
实施例1:表层,每个占薄膜总结构的约25重量%,由StyronTM 668GPPS(密度=1.05g/cc,MFR=5.5克/10分钟(5kg/200℃))制得。结合层,每个占薄膜总结构的约12重量%,由KRATON G1730M(密度=0.90g/cc,MI=13克/10分钟(5kg/230℃))制得。中心层是WO 03/040442中所描述的一类开发的丙烯塑性体,其含5重量%的乙烯,熔体流动速率为8克/10分钟(ASTM D1238,230℃,2.16kg),密度为0.888g/cc。中心层占总结构的约26%。薄膜的计算密度为约0.974gm/cc。在取向步骤前的平均总膜厚为约112微米。
实施例2:表层,每个占薄膜总结构的约21重量%,由StyronTM 668GPPS制得。结合层,每个占薄膜总结构的约12重量%,由KRATONG1730M制得。中心层是WO 03/040442中所描述的一类开发的丙烯塑性体,其含5重量%的乙烯,熔体流动速率为8克/10分钟(ASTM D1238,230℃,2.16kg),密度为0.888g/cc。中心层占总结构的约34%。薄膜的计算密度为约0.961gm/cc。在取向步骤前的平均总膜厚为约124微米。
每个实施例的薄膜挤出条件示于表I:
这些流延薄膜可以采用Bruckner Karo IV装置在下面表II所示条件下进行拉伸。薄膜在所示的拉伸条件下进行拉伸而无撕裂或破裂。薄膜在共混模式下显得非常稠厚的(起皱的),表明它们具有标签应用所需的极好刚性。收缩标签薄膜的拉伸条件和收缩性能如下所述。收缩采用ASTM D2732(热油浴)测定,浸渍时间约20秒。收缩张力采用ASTM D2838测定。
表II
实施例 | 拉伸方向 | 拉伸温度(℃) | 拉伸比率 | 预热时间(秒) | 拉伸率(%/分钟) | 最终厚度(密耳) | 收缩张力(PSI)在135℃下 | 收缩在135℃下 |
1 | MD | 130 | 4x | 40 | 1000 | 1.05 | 150 | 75 |
2 | MD | 130 | 4X | 40 | 1000 | 1.25 | 140 | 75 |
2 | CD | 130 | 4X | 40 | 1000 | 1.2 | 55 | 75 |
1 | CD | 130 | 4X | 40 | 200 | 1.0 | 70 | 75 |
1 | MD | 130 | 5X | 40 | 50 | 0.8 | 206 | 79 |
1 | CD | 130 | 5X | 40 | 50 | 0.8 | 95 | 78 |
2 | MD | 130 | 5X | 40 | 50 | 0.9 | 210 | 79 |
2 | CD | 130 | 5X | 40 | 50 | 0.9 | 79 | 74 |
上述数据表明使用本发明的薄膜组合物可以得到在纵向或横向具有极好收缩的收缩标签薄膜。按照需要,本发明薄膜的收缩张力在所有实施例中也是低的,小于250psi。
实施例3:制备了另一个五层结构。在该挤出***中由挤出机A和C提供表层,每个表层占薄膜总结构的15重量%。这些层通过将70%STYRON 668 GPPS和30%K-树脂苯乙烯-丁二烯共聚物DKll(获自Chevron Phillips)干混制得。每个结合层占薄膜总结构的10重量%,由挤出机D提供。结合层由KRATON G1730M制得。中心层占薄膜总结构的50重量%,由该***中的挤出机B提供。中心层是WO 03/040442中所描述的一类开发的丙烯塑性体,其含5重量%的乙烯,熔体流动速率为8克/10分钟(ASTM D1238,230C,2.6kg),密度为0.888g/cc。
采用变速轧辊在纵向进行取向,从而赋予如样品3-1和3-2中所列的多种取向程度。
加工条件列于表III中。
表III
样品3-1和3-2中所得薄膜的收缩数据如图1和2所示。
这些样品的薄膜性能示于表IV中。
表IV
样品3-1 | 样品3-2 | ||
ASTM试验法 | |||
平均透明度 | D1746 | 94.7 | 96.7 |
平均Elmendorf撕裂度-类型B(恒定半径)-横向 | D1922 | 36.8 | 110.0 |
平均厚 度类型B-横向(密耳) | 1.7 | 2.3 | |
平均Elmendorf撕裂度-类型B(恒定半径)-纵向 | D1922 | 14.0 | 14.0 |
平均厚度 类型B-纵向 | 1.8 | 1.7 | |
平均光泽45度 | D2457 | 108.8 | 102.0 |
平均雾度 | D1003 | 1.9 | 2.1 |
张力-横向 | D882 | ||
平均%伸长(%) | 159.0 | 23.9 | |
平均极限张力(psi) | 2931.8 | 2309.6 | |
平均屈服应力(psi) | 2901.7 | 2309.6 | |
张力-纵向 | D882 | ||
平均%伸长(%) | 22.2 | 30.3 | |
平均极限张力(psi) | 5842.2 | 5162.4 | |
平均屈服应力(psi) | 4602.6 | 4407.9 | |
收缩张力(psi) | 105C | 547 | 360 |
收缩张力(psi) | 135C | 535 | 400 |
实施例4和5制备了另一系列的5层结构。在该挤出***中由挤出机A和C提供表层,每个表层占薄膜总结构的15重量%。这些层通过将70%STYRON 668 GPPS和30%K-树脂苯乙烯-丁二烯共聚物DKll(获自Chevron Phillips)干混制得。每个结合层占薄膜总结构的10重量%,由挤出机D提供。结合层由KRATON G1730M制得。中心层占薄膜总结构的50重量%,由该***中的挤出机B提供。中心层是WO 03/040442中所描述的一类开发的丙烯塑性体,其含5重量%的乙烯,熔体流动速率为8克/10分钟(ASTM D1238,230C,2.6kg),密度为0.888g/cc。
对于实施例5,中心层是WO 03/040442中所描述的一类开发的丙烯塑性体,其含9重量%的乙烯,熔体流动速率为8克/10分钟(ASTMD1238,230C,2.6kg),密度为0.876g/cc。
薄膜首先通过MDO轧辊,并有意诱导少许的取向,然后利用拉幅机在薄膜的横向进行取向。还研究了多种程度的取向及取向的变化温度。
这些材料的加工条件示于表V中:
表V
收缩性能示于图3和4中。
由这些材料所得薄膜的性能示于表VI中:
表VI
ASTM方法 | 样品4-1 | 样品4-2 | 样品4-3 | 样品4-4 | 样品5 | |
平均透明度 | D1746 | 99.1 | 98.2 | 98.7 | 99.0 | 98.0 |
平均Elmendorf撕裂度类型B(恒定半径)-横向 | D1922 | 28.2 | 36.8 | 25.4 | 5.2 | 17.0 |
平均厚度类型B-横向 | 1.6 | 1.4 | 1.2 | 1.2 | 1.3 | |
平均Elmendorf撕裂度-类型B(恒定半径)-纵向 | D1922 | 11.8 | 7.2 | 5.2 | 30.8 | 20.2 |
平均厚度 类型B-纵向 | 1.3 | 1.4 | 1.2 | 1.3 | 1.2 | |
平均光泽45度 | D2457 | 107.8 | 95.8 | 108.7 | 91.9 | 105.6 |
平均雾度 | D1003 | 1.3 | 3.1 | 1.4 | 4.3 | 1.3 |
张力-横向 | D882 | |||||
平均%伸长(%) | 35.5 | 27.9 | 29.3 | 20.3 | 13.6 | |
平均极限张力(psi) | 8065.6 | 12390.4 | 8151.3 | 13833.1 | 4716.2 | |
平均屈服应力(psi) | 5691.3 | 5084.1 | 5417.8 | 13833.1 | 4675.0 | |
张力-纵向 | D882 | |||||
平均%伸长(%) | 5.9 | 5.9 | 5.6 | 29.2 | 6.7 | |
平均极限张力(psi) | 4621.1 | 4187.3 | 4293.9 | 4425.3 | 2820.7 | |
平均屈服应力(psi) | 4621.0 | 4187.3 | 4293.9 | 4425.3 | 2820.7 | |
收缩张力(psi) | 105C | 333 | 1212 | 567 | 1338 | 167 |
收缩张力(psi) | 135C | 350 | 1098 | 473 | 1433 | 40 |
由实施例4和5可见,改变拉幅机箱内的取向温度影响收缩张力(样品4-2和4-4在较低温度下进行)。
另外,将中心材料改变成较低密度材料也能减少收缩张力(样品5)。
Claims (23)
1、一种多层取向收缩薄膜,其包括至少一个包含非晶态玻璃状聚合物材料的表层和至少一个包含聚烯烃层的中心层。
2、根据权利要求1所述的多层薄膜,其中,所述非晶态玻璃状聚合物是聚苯乙烯材料。
3、根据权利要求1所述的多层薄膜,其中,所述薄膜的总密度小于1.0g/cm3。
4、根据权利要求3所述的多层薄膜,其中,所述薄膜的总密度小于0.98g/cm3。
5、根据权利要求1所述的多层薄膜,其中,所述薄膜在纵向或横向择优取向。
6、根据权利要求5所述的多层薄膜,其中,在一个方向的取向至少是相反方向的两倍。
7、根据权利要求5所述的多层薄膜,其中,在一个方向的取向至少是相反方向的三倍。
8、根据权利要求1所述的多层薄膜,其中,所述薄膜的收缩张力小于500psi。
9、根据权利要求1所述的多层薄膜,其中,所述薄膜的收缩张力小于250psi。
10、根据权利要求1所述的多层薄膜,其还包括在至少一个表层与至少一个中心层之间的结合层。
11、根据权利要求2所述的多层薄膜,其中,所述聚苯乙烯材料包括GPPS、HIPS、SBS、SIS、SEBS或K-树脂中的一种或多种。
12、根据权利要求11所述的多层薄膜,其中,所述聚苯乙烯材料包括平均橡胶粒子大小小于约1微米的HIPS。
13、根据权利要求1所述的多层薄膜,其中,所述非晶态玻璃状聚合物材料包括PETG、非晶态PET、非晶态PLA或者PVC中的一种或多种。
14、根据权利要求1所述的多层薄膜,其中,所述聚烯烃材料包括一种或多种低密度聚乙烯、线性低密度聚乙烯、很低(或超低)密度聚乙烯、聚乙烯塑性体和高弹体,例如均匀支化的线性乙烯聚合物和基本线性乙烯聚合物、中等密度聚乙烯和高密度聚乙烯)、均聚物聚丙烯(″hPP″)无规共聚物聚丙烯(″RCP″)或丙烯基塑性体和高弹体。
15、根据权利要求14所述的多层薄膜,其中,所述聚烯烃材料是塑性体或高弹体。
16、根据权利要求15所述的多层薄膜,其中,所述聚烯烃材料是丙烯基塑性体或高弹体。
17、根据权利要求10所述的多层薄膜,其中,所述结合层包括SEBS、SEPS、EVA、SBS、SIS或K-树脂中的一种或多种。
18、根据权利要求10所述的多层薄膜,其中,所述非晶态玻璃状聚合物表层占整个薄膜的10重量%至80重量%,聚烯烃内层占整个薄膜的20重量%至90重量%,结合层占整个薄膜的0至15重量%。
19、一种包括上述权利要求任一项所述多层薄膜的收缩标签。
20、根据权利要求19所述的收缩标签,其中,所述收缩标签是随卷随缩(ROSO)标签。
21、根据权利要求19所述的收缩标签,其中,所述收缩标签是套管式标签。
22、根据权利要求20所述的收缩标签,其特征在于所述标签在135℃下在择优取向的方向收缩大于40%。
23、根据权利要求21所述的收缩标签,其特征在于所述标签在135℃下在择优取向的方向收缩大于40%。
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- 2006-11-02 WO PCT/US2006/042816 patent/WO2007058783A1/en active Application Filing
- 2006-11-02 KR KR1020087014274A patent/KR20080074177A/ko not_active Application Discontinuation
- 2006-11-02 CN CN201310578892.9A patent/CN103692746B/zh not_active Expired - Fee Related
- 2006-11-02 BR BRPI0620471-6A patent/BRPI0620471A2/pt not_active IP Right Cessation
- 2006-11-02 JP JP2008540076A patent/JP5427411B2/ja not_active Expired - Fee Related
- 2006-11-02 AU AU2006315832A patent/AU2006315832A1/en not_active Abandoned
- 2006-11-02 DE DE200660016160 patent/DE602006016160D1/de active Active
- 2006-11-02 RU RU2008123819A patent/RU2415014C2/ru not_active IP Right Cessation
- 2006-11-02 CN CNA2006800422914A patent/CN101304876A/zh active Pending
- 2006-11-02 AT AT06827376T patent/ATE477113T1/de not_active IP Right Cessation
- 2006-11-02 CA CA 2628427 patent/CA2628427A1/en not_active Abandoned
- 2006-11-02 EP EP06827376.2A patent/EP1951524B2/en active Active
- 2006-11-02 US US12/093,891 patent/US8541077B2/en active Active
- 2006-11-02 ZA ZA200804210A patent/ZA200804210B/xx unknown
- 2006-11-14 AR ARP060104984 patent/AR057578A1/es not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104640702A (zh) * | 2012-07-17 | 2015-05-20 | Upm拉弗拉塔克公司 | 一种标签面材 |
CN104859241A (zh) * | 2015-04-29 | 2015-08-26 | 安徽顺彤包装材料有限公司 | 一种食品包装复合薄膜及其制作工艺 |
CN108297511A (zh) * | 2018-01-30 | 2018-07-20 | 江苏光辉包装材料有限公司 | 一种用于流延拉伸热收缩标签膜及其制备方法 |
CN108299575A (zh) * | 2018-01-30 | 2018-07-20 | 江苏光辉包装材料有限公司 | 一种耐高温氯化聚丙烯及其制备方法以及应用 |
Also Published As
Publication number | Publication date |
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CA2628427A1 (en) | 2007-05-24 |
WO2007058783A1 (en) | 2007-05-24 |
EP1951524A1 (en) | 2008-08-06 |
KR20080074177A (ko) | 2008-08-12 |
JP2009515733A (ja) | 2009-04-16 |
DE602006016160D1 (de) | 2010-09-23 |
AU2006315832A1 (en) | 2007-05-24 |
ZA200804210B (en) | 2009-09-30 |
RU2008123819A (ru) | 2009-12-27 |
BRPI0620471A2 (pt) | 2011-11-08 |
EP1951524B2 (en) | 2014-08-20 |
RU2415014C2 (ru) | 2011-03-27 |
AR057578A1 (es) | 2007-12-05 |
EP1951524B1 (en) | 2010-08-11 |
US20090220757A1 (en) | 2009-09-03 |
ATE477113T1 (de) | 2010-08-15 |
US8541077B2 (en) | 2013-09-24 |
JP5427411B2 (ja) | 2014-02-26 |
CN103692746B (zh) | 2017-04-12 |
CN103692746A (zh) | 2014-04-02 |
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