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CN103154101A - 热收缩性聚酯薄膜 - Google Patents

热收缩性聚酯薄膜 Download PDF

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CN103154101A
CN103154101A CN201180049530XA CN201180049530A CN103154101A CN 103154101 A CN103154101 A CN 103154101A CN 201180049530X A CN201180049530X A CN 201180049530XA CN 201180049530 A CN201180049530 A CN 201180049530A CN 103154101 A CN103154101 A CN 103154101A
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金成度
吴泰炳
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Abstract

本发明涉及一种热收缩性聚酯薄膜，其热收缩起始温度为60℃以下、玻璃化转变温度为77℃以下、并且60℃的热收缩率为2%以上。由于该热收缩性聚酯薄膜与现有薄膜相比，玻璃化转变温度及热收缩起始温度低，因此适合用作高密度聚乙烯（HDPE）容器等的标签。

Description

热收缩性聚酯薄膜
技术领域
本发明涉及一种用作外部包装材料等的热收缩性聚酯薄膜，尤其涉及一种适合用作高密度聚乙烯（HDPE）容器标签的热收缩性聚酯薄膜。
背景技术
为了在玻璃瓶或塑料瓶上标记名称及内容物的信息等，一直以来使用多种标签。以往大部分是将纸质标签用胶水贴附于玻璃瓶或塑料瓶上使用，但最近为了引起消费者的注意而实施多样的印刷或是为了记入更多的信息而采用全裹卷标（full wrapping），因此热收缩性薄膜正受瞩目。
热收缩性薄膜是指利用在拉伸取向后在一定的温度以上时重新收缩为拉伸前形态的特性，用于多种形态的容器包装上的薄膜。
高密度聚乙烯（HDPE）容器主要用于生活用品（洗发液，润肤露等）方面，从特性上HDPE与其他物质相比具有热膨胀系数高，特别是从50℃开始膨胀的特点。由于HDPE的这种特性，当使用从70℃就开始收缩的现有聚酯类热收缩薄膜时，因热收缩薄膜在收缩机中收缩前，HDPE容器就先开始膨胀，因此热收缩薄膜会根据膨胀的HDPE容器完成标签贴附。但是在贴附完成后，HDPE容器的温度达到常温时，HDPE容器会再次收缩，结果使热收缩薄膜不能紧密地贴附在HDPE容器上，会变松。
因此，需要开发出一种在应用于HDPE等容器时，具有优异的粘附性的新型热收缩性聚酯薄膜。
发明内容
本发明的目的在于，提供一种适合用作高密度聚乙烯（HDPE）容器等的标签的热收缩性聚酯薄膜。
根据上述目的，本发明提供一种热收缩起始温度为60℃以下、玻璃化转变温度（Tg）为77℃以下、并且60℃的热收缩率为2%以上的热收缩性聚酯薄膜。
上述热收缩性聚酯薄膜优选为65℃的热收缩率为15%以上，70℃的热收缩率为42%以上，80℃的热收缩率为70%以上。
这种热收缩性聚酯薄膜可由1种2价酸（diacid）成分和3种二醇（diol）成分进行无规共聚而成。
此外，本发明的另一目的在于，提供一种由上述热收缩性聚酯薄膜制成的容器标签。
本发明的热收缩性聚酯薄膜的玻璃化转变温度（Tg）低于现有的薄膜，热收缩起始温度为60℃以下，因此适合用作HDPE容器等的标签。
下面，更加具体地说明本发明。
本发明的热收缩性聚酯薄膜可以由1种2价酸成分和3种二醇成分进行无规共聚而成。
根据本发明的一个优选实施例，上述热收缩性聚酯可由作为上述2价酸成分的A1）和作为上述二醇成分的B1）、B2）以及B3）进行无规共聚而成；所述A1）为对苯二甲酸和对苯二甲酸二甲酯中的一种，所述B1）为乙二醇，所述B2）为新戊二醇和环己烷二甲醇中的一种，所述B3）为在主链的轴上的碳原子数为3个以上的直链二醇。
此时，上述二醇成分中的B3）成分优选为选自二乙二醇、1,3-丙二醇、1,4-丁二醇及1,5-戊二醇。
此外，上述二醇成分中的B1）至B3）的含量优选含量如下：B1）为60～90mol%，B2）为5～30mol%，以及B3）为1～20mol%。更优选为，B1）为60～85mol%，B2）为10～25mol%，以及B3）为1～15mol%。
其结果为构成薄膜的高聚物可以具有包括下述甲至丙的重复单元的无规共聚物的结构。
Figure BDA00003043626200031
在上述式中，x、y及z为各个单元结构的重复数。
具有上述组成的本发明薄膜的热收缩起始温度为60℃以下，例如55℃至60℃为宜。
这是因为薄膜的玻璃化转变温度（Tg）低于现有（约78～80℃）的温度，所以本发明薄膜的玻璃化转变温度为77℃以下，例如为70℃至77℃，更优选为70℃至75℃。
其结果，使得本发明的薄膜显示出不同于现有薄膜的热收缩率，具体为：在水箱中进行10秒钟热处理时，对于横向的热收缩率优选为：60℃为2%以上，65℃为15%以上，70℃为42%以上，以及80℃为70%以上。更优选为，上述热收缩率60℃为2～10%，65℃为15～40%，70℃为42～60%，以及80℃为70～75%。
本发明的热收缩性聚酯薄膜可由下述方法制备而成，该方法包括：a）将1种2价酸和3种二醇进行混合及聚合反应，从而获得无规共聚树脂的步骤；b）熔融上述共聚树脂，进行挤出，从而获得未拉伸片材的步骤；以及c）将上述未拉伸片材沿横向拉伸，进行热定型的步骤。
在上述步骤b）中熔融挤出温度优选为260℃至285℃。
此外，在上述步骤c）中的拉伸比为3.5倍至4.5倍。热定型温度优选为65℃至95℃。
这样制得的薄膜厚度优选为20μm至90μm。
本发明还提供一种由本发明的热收缩性聚酯薄膜制成的容器标签。
上述容器卷标优选为用作高密度聚乙烯（HDPE）容器的标签。此时，由于收缩起始温度低于现有的收缩起始温度，因此在HDPE容器等上实施贴附时，在HDPE容器完全膨胀之前，就会热收缩，从而贴附在容器上，因此，在贴附完成后，即使在常温下HDPE容器进行收缩，也能够维持标签的粘附性。
具体实施方式
下面通过实施例对本发明进一步进行详细说明，下述实施例仅是例示本发明，但下列实施例并不限定本发明的内容。
实施例1至3及比较例1和2：热收缩性聚酯薄膜的制备
如下表1中所记载，通过改变组成并制备各个共聚聚酯树脂后，将该树脂进行熔融挤出，然后沿横向拉伸及进行热定型，从而分别制得了厚度为40μm的热收缩性聚酯薄膜。此时，聚合反应条件及其它工序条件采用了本发明所属技术领域通常使用、并且熟知的聚酯薄膜的标准制备方法。
表1
根据下列试验方法，对上述实施例及比较例中制备的薄膜进行评价，其结果如下表2所示。
试验例1：热收缩率
将试样沿着待测定试样的方向裁剪，使长度为300mm，并且沿着待测定试样方向的垂直方向裁剪，使宽度为15mm，从而裁剪出长度为300mm，宽度为15mm的试样。然后在维持要测定的温度的恒温水箱中，进行10秒钟热处理后，利用长度通过下列公式进行了计算。
收缩率（%）=[（300-热处理后的剩余试样的长度（mm）/300]×100
试验例2：HDPE容器的不合格率（粘附性评价）
将上述实施例及比较例制得的各个薄膜贴附于100个HDPE容器上后，将用手推时标签因变松而起皱的情况作为不合格处理，将100个当中的贴附不合格的容器数用百分率表示，以此为基础进行了如下评价。
良好：不合格率不到5%
不合格：不合格率5%以上
试验例3：玻璃化转变温度（Tg）
使用示差扫描量热计（differential scanning calorimetry，Q100，TA公司）分别测定了各个薄膜的玻璃化转变温度。
表2
Figure BDA00003043626200051
如从上述表2中可知，本发明的实施例制备的热收缩性聚酯薄膜的收缩起始温度为60℃以下，因此在贴附到HDPE容器上后，也能够维持粘附性，但与此相反，超出了本发明范围的比较例制备的薄膜，由于其收缩起始温度高，因此在贴附后变松。
以上述实施例为中心，对本发明进行了说明，但这只不过是对本发明的例示，本领域的技术人员应当知道，本领域技术人员可在本发明权利要求书中限定的范围内对本发明实施多种变形及等同的其他实施例进行实施。

Claims (11)

1.一种热收缩性聚酯薄膜，其特征在于，所述热收缩性聚酯薄膜的热收缩起始温度为60℃以下、玻璃化转变温度为77℃以下，并且60℃的热收缩率为2%以上。
2.根据权利要求1所述的热收缩性聚酯薄膜，其特征在于，所述热收缩性聚酯薄膜65℃的热收缩率为15%以上，70℃的热收缩率为42%以上，80℃的热收缩率为70%以上。
3.根据权利要求1所述的热收缩性聚酯薄膜，其特征在于，所述热收缩性聚酯薄膜是由1种2价酸成分和3种二醇成分进行无规共聚而成。
4.根据权利要求1所述的热收缩性聚酯薄膜，其特征在于，所述热收缩起始温度为55℃至60℃，玻璃化转变温度为70℃至77℃，并且具有下列热收缩特性：
60℃热收缩率：2%至10%；
65℃热收缩率：15%至40%；
70℃热收缩率：42%至60%；以及
80℃热收缩率：70%至75%。
5.根据权利要求3所述的热收缩性聚酯薄膜，其特征在于，所述热收缩性聚酯是由作为所述2价酸成分的A1）和作为所述二醇成分的B1）、B2）以及B3）进行无规共聚而成；所述A1）为对苯二甲酸和对苯二甲酸二甲酯中的一种，所述B1）为乙二醇，所述B2）为新戊二醇和环己烷二甲醇中的一种，所述B3）为在主链的轴上的碳原子数为3个以上的直链二醇。
6.根据权利要求5所述的热收缩性聚酯薄膜，其特征在于，所述二醇成分中的B3）成分选自二乙二醇、1,3-丙二醇、1,4-丁二醇及1,5-戊二醇。
7.根据权利要求5所述的热收缩性聚酯薄膜，其特征在于，所述二醇成分中的B1）至B3）的含量如下：B1）为60～90mol%，B2）为5～30mol%，以及B3）为1～20mol%。
8.根据权利要求5所述的热收缩性聚酯薄膜，其特征在于，所述二醇成分中的B1）至B3）的含量如下：B1）为60～85mol%，B2）为10～25mol%，以及B3）为1～15mol%。
9.根据权利要求1所述的热收缩性聚酯薄膜，其特征在于，所述热收缩性聚酯薄膜为沿横向单轴拉伸的薄膜。
10.一种由权利要求1所述的热收缩性聚酯薄膜制成的容器标签。
11.根据权利要求10所述的容器卷标，其特征在于，所述容器卷标为高密度聚乙烯容器的卷标。
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