CN1088426C - 耐热压敏胶结构体 - Google Patents

耐热压敏胶结构体 Download PDF

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CN1088426C
CN1088426C CN96190711A CN96190711A CN1088426C CN 1088426 C CN1088426 C CN 1088426C CN 96190711 A CN96190711 A CN 96190711A CN 96190711 A CN96190711 A CN 96190711A CN 1088426 C CN1088426 C CN 1088426C
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R·H·曼
E·I·孙
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Avery Dennison Corp
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Abstract

这里提供了耐热性压敏胶标签、胶带和类似结构体，它包括层压到压敏胶和防粘衬里上的耐热性面材。在一个实施方案中，面材是交联的聚烯烃。在另一个实施方案中，面材是两层或多层聚合物材料的一元共挤出物，其中外层是耐热性聚合物如尼龙6。该耐热性结构体可用于可进行电子照相印刷的标签和胶带。

Description

耐热压敏胶结构体
本发明涉及压敏胶结构体的耐热性聚合物面材，和尤其涉及交联聚烯烃膜和共挤塑加工的多层聚合物膜，这些膜适合用作压敏胶标签和胶带的电子照相印刷面材。
发明背景
纸张和塑料膜两者都曾广泛地用作电子照相印刷机和复印机，包括目前全世界在办公室和家庭使用的“激光印刷机”中的印刷媒介。US专利4,770,931，4,900,654，5,055,371和5,104,731描述了可进行电子照相印刷的聚合物膜的几个实例。
在一个典型的电子照相成像方法中，通过以下方法将图像印刷(或复印)到纸张或耐热膜基材上：(1)在黑暗中将电荷均匀地沉积在光电导鼓上；(2)将该鼓暴露于光图案，从而产生潜影区；(3)通过向潜影区添加调色剂颗粒使该图案显影；(4)在纸张或其它介质通过转鼓时将调色剂颗粒转移到纸张或其它介质上；(5)加热使调色剂颗粒熔化在纸张上；和(6)清洗光电导鼓。US专利4,071,362，4,526,847，4,621,009，4,935,288，5,104,721和5,135,261描述了可与耐高温基材(通常为聚酯膜)一起使用的用于调色剂固定的涂料。
虽然各种材料可用作压敏胶标签和胶带的面材，但不是所有的这类材料适合于大范围的压延、印刷和目前在标签和胶带工业中使用的其它加工步骤，包括电子照相印刷。有涂层的漂白牛皮纸是最廉价和最常用的标签材料。然而，近年来，对聚合物标签面材有强烈的需求。聚合物膜一般不象纸标签那样容易撕裂，并通常更适合于高速贴标签方法。还有，聚合物膜标签用于塑料容器上是优选的，因为它们一般它们更具柔性和能够更好地与容器贴合，和不太容易形成褶皱和皱纹。
塑料膜基材也适合用作可进行电子照相印刷的压敏胶标签面材。必要的是，在电子照相印刷应用中使用的标签面材必须能够承受在熔化过程中遇到的高温。在典型的电子照相复印机或印刷机中，熔化机构包括加热辊和/或熔化棒，它们的温度高达400F°。一般情况，通过电子照相印刷机标签或标签片材仅仅简单地与熔化棒相遇，刚好在它离开印刷机之前。然而，如果标签在熔化棒下方通过时该印刷机“阻塞”，这一相遇能够持续较长时间。在这种情况下，如果标签面材没有足够的耐热性，即熔点或玻璃化转变温度没有超过熔化棒的温度，它趋向于熔化和***，引起纸张通路的污染和较长的停机清洗时间。在一些情况中，面材的分离(物理破坏)引起标签结构脱层，使粘合剂暴露于熔化器，和损坏熔化器。
由于其易印刷性和高耐热性，聚氯乙烯膜通常用作标签面材，包括例如在超市货架做标记用标签、鼓式标签和铭牌上使用的可进行电子照相印刷的面材。聚酯膜也广泛地用作电子照相印刷介质和用作可印刷的耐高温标签的面材。
聚烯烃类，如聚乙烯和聚丙烯，一般比聚氯乙烯对环境更加友好，并比聚酯便宜，已发现可用作某些应用中的标签面材。例如，US专利No.5,064,893描述了具有改进的模切性的碳酸钙填充聚乙烯标签面材。然而，迄今聚烯烃还没有用作电子照相印刷操作中乙烯基类材料或聚酯的替代物，因为它们在电子照相印刷机阻塞时在熔化棒下趋向于熔化和***。
所以，可以看出，目前需求能够承受在电子照相印刷机和复印机中遇到的高温，但比聚氯乙烯对环境更友好的和比聚酯标签便宜的一种压敏胶标签结构体。
改进聚烯烃膜的耐热性的一个途径是让它交联，通过加热、辐射(例如，紫外线或电子束辐射)或加热和辐射兼用。欧洲专利申请No.0,490,854 A2描述了使用紫外线辐射制造交联聚乙烯的方法和装置。US专利3,741,253，3,953,557，4,031,162，4,064,296，4,224,262，4,278,738，4,576,993，4,797,235，4,957,790，5,035,955，5,089,352和5,106,545描述了交联的热收缩性膜。US No，4,891,173，5,006,378，5,043,204和5,145,728描述了透明、防潮、取向、交联的聚乙烯膜。难以置信的是，虽然几十年以前就知道交联的聚乙烯，很显然，迄今还没有人将交联的聚烯烃用作压敏胶标签的面材，该标签适合用于电子照相印刷方法中。
本发明概述
本发明提供耐热性压敏胶标签、胶带和类似结构体，它们适合于电子照相印刷。该结构体具有不含聚氯乙烯和一般比聚酯电子照相印刷介质便宜的聚合物面材。
在本发明的一个方面，将一种或多种聚烯烃膜交联，优选通过电子束辐射，制得耐热性标签或胶带面材。然后按照普通方法用该面材制造耐热性压敏胶标签和胶带。
在本发明的另一个方面，通过共挤出几个聚合物层，包括耐热性外层，制得耐热性标签或胶带面材。通过使用廉价的聚烯烃或其它聚合物作为面材的内层，和使用仅仅一较薄的耐热性材料如聚酯或交联烯烃的外层，最大程度地降低了共挤出的多层聚合物面材的成本。按照普通方法从该面材制得耐热性压敏胶标签和胶带。
本发明详述
根据本发明提供一种新型的耐热性压敏胶结构体。该结构体可以是标签、胶带、贴花膜或类似制品，一般包括耐热性面材的较薄的片材或膜材，粘附于面材的第一表面的至少一部分的压敏胶，和以可松脱方式固定在压敏胶上的防粘层。该面材为所有形式的标记、设计图案和其它标志提供了可印刷表面，并使结构体具有一定厚度和强度。压敏胶使结构体发粘，和防粘面在结构体的运输、贮存和加工(例如压延)过程中保护粘合剂。
在本发明的第一个示例性实施方案中，面材包括一层或多层聚合物材料，包括至少一种交联聚烯烃的外层，该外层是“耐热性的”。对于本公开的目的来说，如果材料在升高的温度(在典型的电子照相印刷机熔化装备线，如在大多数激光印刷机和类似机器中可发现的加热辊和/或熔化棒中遇到)下暴露时没有熔化和***(即经历明显的机械破坏和破裂)，则该材被认为是“耐热性的”。当然有许多牌号和型号的这类机器，所有机器的“平均”熔化棒温度还不确定。然而，现已清楚的是许多商业激光印刷机具有熔化机构，该机构可升温至约175-200℃，或高达约400℃的温度。这里描述的“耐热性”面材在暴露于这一温度时，至少在从“阻塞”电子照相印刷机或复印机的纸路中清除由这类材料构成的压敏胶结构体所需要的短时间内不会熔化和***。
适合用作耐热性外层(或甚至整个面材)的代表性、但非排他性的一类聚烯烃包括聚乙烯，聚丙烯，聚丁烯(例如聚1-丁烯)，乙烯共聚物(如线性低密度聚乙烯，以及乙烯和另一种或多种共聚用单体，如己烯、丁烯，辛烯等，的其它共聚物)，丙烯共聚物，丁烯共聚物，和它们的相容性共混物。对于本公开物的目的，如果两种聚合物材料能够紧密共存和具有永久物理结合力而没有明显的聚合物分离现象，则认为它们是“相容性”。在宏观水平上存在多相的聚合物共混物被认为是不相容的。
在该实施方案的一个最简单的实例中，面材是交联聚烯烃或聚烯烃共混物的单一挤出层。例如，通过使用交联的高密度聚乙烯(HDPE)和交联线性低密度聚乙烯(LLDPE)面材已经制造耐热性压敏胶结构体。
在本发明的稍复杂的实例中，面材包括一元共挤出物：聚合物材料(典型是热塑性聚合物和/或聚合物共混物)的几个共挤出层基本上永久地相互粘合在一起。一元共挤出物的外层包括上述交联聚烯烃或聚烯烃共混物。共挤出物的其它层或多个层是对于一种或多种所需性能，例如强度、模量、成本等，进行选择的聚合物。适合用作面材的其它层或多个层的代表性、但非排他性的一类聚合物材料包括聚烯烃，聚酯，尼龙，聚苯乙烯，丁腈橡胶，其它可挤塑的热塑性塑料，和它们的相容性共混物。
通过同时挤出几种热塑性进给料，其中至少一种是将要变成面材的耐热性外层的可交联的聚烯烃或聚烯烃共混物，可以制备多层面材。能够使用任何合适类型的共挤出模头，例如包括通常用来制备在食品包装和其它应用中使用的多层膜的Cloren“vane(叶片)”模头。
取决于用来形成共挤出的面材的具体聚合物材料，在一些实施方案中，有利的是还同时挤出一种或多种将要变成那些共挤出层之间的“连接”层的进给料。尤其，当共挤出时，在两种层的材料相互之间没有充分地粘附在一起时，“连接”层(与它们)一起挤出并在它们之间，将它们以基本上永久单一的状态保持在一起。例如，尼龙6和聚乙烯能够共挤出形成基本上永久性的、单一的共挤出物，即通过同时将尼龙6，聚乙烯，和对两种材料有良好亲和力的聚合物如改性聚乙烯或乙烯-乙酸乙烯酯共聚物挤出。这一聚合物变成尼龙6和聚乙烯两层之间的“连接”层。一般来说，  “连接”层材料的选择至少部分地取决于所要结合或“连接”在一起的材料的各种性能，例如包括材料的极性/非极性性质，模量，流动性能等。
在所述单层和多层实施方案中，面材在被挤出后按照普通方法加以交联。优选地，通过使用普通的电子束产生器，如范德格拉夫高压电子产生器，由电子束辐射进行交联。其它各种电子加速器是已知的并能够用来将聚烯烃外层交联。
由面材接收的电子束辐射剂量能够作为表面剂量形式和作为吸收剂量形式来测量。为了测量表面剂量，将剂量测量仪放置于或接近于暴露在辐射源(在这种情况下是电子束产生器)的面材表面上。为了测量吸收剂量，使用两个剂量测量仪，一个放置在面材表面上方，与辐射源处在同一侧，和另一测量仪放置在面材下方。
在实验室挤出的聚乙烯和聚丙烯的单层膜中，通过让挤出的聚合物膜暴露于约5-30兆拉德(Mrad)之间，优选约20兆拉德的表面剂量，或暴露于约2-20兆拉德之间，优选约10兆拉德的吸收剂量，一般获得一种充分交联了的具有“耐热性”的聚烯烃膜聚合物。然而，应该指出的是，通过将化学交联剂掺入熔融的聚合物材料中，使面材外层具有“耐热性”所需要的电子束辐射的最低剂量能够减少。事实上，对于一些易遭受电子束诱发的断链作用的聚烯烃，如聚丙烯，重要的是，包含化学交联剂以获得所需水平的聚合物交联。合适的交联剂的非限制性实例包括单官能度单体如丙烯酸酯和甲基丙烯酸酯。
聚烯烃面材的电子束辐射不仅使面材交联，而且似乎还提高面材的模切性，据信它部分地取决于面材的拉伸应变。对用不同电子束辐射剂量辐射的挤出聚烯烃膜面材的几个样品进行试验后表明，在电子束剂量和被辐射聚烯烃膜的拉伸应变之间存在反比关系。即，随着电子束辐射剂量的增加，聚烯烃面材的拉伸应变下降。
在本发明的又一个实施方案中，面材包括多个聚合物材料共挤出层，包括耐热性聚合物如尼龙6、聚甲基戊烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、共聚酯(如Kodar Thermx可结晶共聚酯6761，由Eastman Chemical Co.(伊斯特曼化学公司)销售)、聚酰胺、聚酰亚胺和具有足够高的熔点或玻璃化转变温度的其它聚合物(但聚氯乙烯除外)的外层。其它挤出层的聚合物材料是从它们的物理性能(例如强度、模量等)和/或成本来选择。这类聚合物材料的非限制性实例包括聚烯烃，聚酯，尼龙，聚苯乙烯，丁腈橡胶，其它可挤出的热塑性塑料，和它们的相容性共混物。
通过用传统方法同时将两种或多种聚合物材料进给料经合适的挤出模头(如上述Cloren“叶片”模头)挤出(其中至少一种是耐热性的)，可制得共挤出的聚合物膜面材。若有必要确保两层之间的粘附力，正如以上所讨论的那样，可将一个或多个“连接”层能够包含在共挤出的面材内。
在本发明的一些实施方案中，有利的是在一层或多层面材中包括一种或多种填料，以改进面材或赋予面材所需性能。例如，填料如碳酸钙、云母、滑石、二氧化钛、氧化铝和类似物可包含在挤出前的聚合物材料的熔体中，以赋予该膜以不透明性、强度和/或其它性能。各种填料在挤出聚合物膜中的引入已描述在US专利No.4,713,273，它被引入本文供参考。
还应指出的是，在本发明的一些实施方案中，理想的是在交联前将挤出的聚合物膜热拉伸，为的是使膜产生纵向取向(MDO)。这一热拉伸的有用实例见于US专利No.4,713,273中。在其它应用中，有益的是在交联之前将挤出的膜双轴取向。热塑性塑料膜的双轴取向(如MDO)是众所周知的。挤出膜的拉伸能够改进面材的机械强度，包括它的模量和强度。
在本发明的一些实施方案中，面材固有的静电性能有利于在用该面材制造的标签、胶带和其它结构体上进行电子照相印刷。在其它实施方案中，理想的是用一种或多种涂料涂敷挤出面材的外层以改进电子照相印刷过程中油墨和/或调色剂固着性。这类涂料的例子可在一些以上指出的专利中找到。或者(或在一些情况下，共同地)，面材的耐热性外表面能够按照普通方式进行电晕处理，以改进面材的印刷性。
本发明提供了耐热性压敏胶标签、胶带和类似结构体，它们是通过使用本工业领域中众所周知的方法，将面材层压在压敏胶和防粘衬里上而从上述面材制得的。能够使用丙烯酸系，橡胶/树脂基，和其它类型的压敏胶，这取决于该结构体的最终用途和该结构体所要进行的加工步骤(例如层压加工)。压敏胶能够用作溶剂基涂料，水乳液，热熔体，或其它涂料，这取决于使用的具体粘合剂。当有必要改进面材和粘合剂之间的粘附力时，可使用常规的粘结剂。
类似地，防粘面具有常规的和众所周知的性质，并包括，例如，硅氧烷涂敷过的防粘衬里(例如用于标签和贴花膜)，自卷绕压敏胶带的低粘性背侧，或自卷绕胶带的内衬。在另一个实施方案中，防粘面包括由上述面材制造的用低粘性材料如硅氧烷聚合物涂敷过的柔性背衬。
下面的实施例为本发明提供了非限制性说明。在每种情况下，制得挤出或共挤出聚合物膜面材，用电子束辐射(仅仅实施例1)，层压到压敏胶和防粘衬里上，切成一定的尺寸，和供给激光印刷机，然后故意让它阻塞以试验该结构体的耐热性。每一样品的耐热性根据通过/失败比例来分类。试验样品的标准如下：
·通过：在暴露于加热熔化棒的区域中面材没有发生分离(破裂)，而是保持连续。在该暴露于熔化棒的区域中的面材或接近该区域的面材的拉伸或变形被认为可接受，只要面材没有发生分离(破裂)。
·失败：在熔化器的热作用下发生面材分离。当面材分离时，它趋向于自卷曲，暴露粘合剂，和粘附于熔化器。部分面材会撕裂并粘附于熔化器。
对由阻塞试验引起的面材的分离或变形程度的肉眼观察结果可用来在通过和失败两类中评判样品(仅仅实施例1)，使用0-5的评判级别。低于2的样品显示出分离并被认为无用；高于2的那些都不分离；具有5级别的样品显示出最佳总体质量，有最低程度的变形和仅仅轻微的褶皱变形。
实施例1
使用具有1英寸螺杆直径和25∶1长径比的Killion挤出机，挤出高密度聚乙烯(HDPE)和线性低密度聚乙烯(LLDPE)膜的几个样品。所有的膜都是大约3密耳厚。第二种样品通过使用轮带驱动的范德格拉夫高压电子产生器，用电子束辐射一个样品的全部。不同样品接受不同剂量的辐射，它以表面剂量的形式测量。通过将挤出的、辐射过的膜(和一个没有辐射的样品)层压到由约20g/m2的Flexcryl RE-49粘合剂(由Air Product & Chemical，Inc.(气体产品和化学公司)，Allentown，PA制造)组成的压敏胶和76磅(每“令”)硅氧烷涂敷过的防粘衬里上，制得标签结构体。将每一个样品切成2″×10″矩形，粘贴到8.5″×11″纸片上，并放置在IBM Lexmark 4029台面激光印刷机的纸槽里。然后每一样品自动进给通过印刷机，一直到样品直接与熔化器接触为止。在此时，打开机盖，让样品在熔化器下方阻塞，样品在被取出之前与熔化器接触5秒钟。在从激光印刷机中取出后，每一样品经肉眼检查在熔化器接触处的表面缺陷，并以上规定的级别来评判。结果示于表I。
                                  表I
面材(聚烯烃) 电子束剂  量(Mrad) 被试验样品的编号# 通过/失败 等级(0-5) 评价
HDPE 0 1 失败 0 面材的明显分离
HDPE 5 2 失败 0 面材的完全分离
HDPE 10 2 通过 3 变形和褶皱；没有分离
HDPE 15 2 通过 3 稍比10Mrad HDPE样品变形大
HDPE 20 2 通过 4 轻微褶皱
LLDPE 5 2 失败 1 变形和分离
LLDPE 10 2 通过 3 变形和褶皱，没有分离
LLDPE 15 2 通过 5 小变形，稍褶皱
LLDPE 20 3 通过 5 小变形，稍褶皱
实施例2
通过使用Killion供料机构和Extrusion Die，Inc.的六英寸宽的膜/片模头加热至500F°，将尼龙6，高密度聚乙烯(HDPE)，和一连接层Plexar360(由Quantum Chemical Corp.(量子化学公司)，Cincinnati，OH制造的基于LLDPE的材料)共挤出制得多层耐热性聚合物面材。使用长径比25∶1的Killion 3/4英寸挤出机将尼龙6挤出；使用长径比25∶1的Killion 1英寸挤出机将HDPE挤出；和使用长径比25∶1的Brabender 3/4英寸挤出机挤出连接层。共挤出膜大约2.5密耳厚，大约80％的厚度属于HDPE，10％的厚度属于尼龙6和10％的厚度属于连接层。挤出膜用作面材，以便通过将面材层压到由约20g/m2的Flexcryl RE-49粘合剂(由Air Product &Chemical，Inc.(气体产品和化学公司)制造)组成的压敏胶和76磅(每“令”)硅氧烷涂敷过的防粘衬里上来制备标签结构体。将每一个样品切成2″×10″矩形，粘贴到8.5″×11″纸片上，并放置在IBM Lexmark 4029台面激光印刷机的纸槽里。然后每一片自动进给通过印刷机，一直到样品直接与熔化器接触为止。在此时，打开机盖，让样品在熔化器下方阻塞，样品在被取出之前与熔化器接触3-10秒钟。在从激光印刷机中取出后，每一样品经肉眼检查在熔化器接触处的表面缺陷，并以上规定的级别来评判。结果示于表II。
                                 表II
面材 被试验样品的编号# 暴露时间(秒) 通过/失败 评价
尼龙/连接层/HDPE 4 3 通过 一些变形
  尼龙6/连接层/HDPE     2     10   通过 明显变形

Claims (10)

1、一种用于电子照相印刷的耐热性压敏胶结构体，包括：
耐热性面材，该面材包括一层或多层聚合物材料，其中包括至少一种交联聚烯烃的外层；
粘附于与所述外层相对的面材的表面的至少一部分的压敏胶；和
以可松粘合方式固定在压敏胶上的防粘面。
2、根据权利要求1的耐热性压敏胶结构体，其中面材的静电性能有利于在结构体上电子照相印刷。
3、根据权利要求1的耐热性压敏胶结构体，进一步包括在面材上的有利于在结构体上电子照相印刷的涂层。
4、权利要求1的耐热性压敏胶结构体，其中至少一种交联聚烯烃是选自聚乙烯、聚丙烯、聚丁烯、乙烯共聚物、丙烯共聚物，丁烯共聚物和它们的相容性共混物。
5、根据权利要求1的耐热性压敏胶结构体，其中交联聚烯烃是交联的高密度聚乙烯。
6、根据权利要求1的耐热性压敏胶结构体，其中交联的聚烯烃是交联的低密度聚乙烯。
7、根据权利要求1的耐热性压敏胶结构体，其中交联的聚烯烃是交联的线性低密度聚乙烯。
8、根据权利要求1的耐热性压敏胶结构体，其中交联的聚烯烃是用电子束产生交联的聚烯烃。
9、根据权利要求4的耐热性压敏胶结构体，其中至少一种交联的聚烯烃是电子束交联的聚烯烃或聚烯烃共混物。
10、根据权利要求8的耐热性压敏胶结构体，其中面材进一步包括一层或多层聚合物材料，它们中每一层是在交联之前随聚烯烃一起共挤出。
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WO1996039297A1 (en) 1996-12-12
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AU6262396A (en) 1996-12-24
US5830571A (en) 1998-11-03

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