CN106867222A - 一种全降解抗拉抗撕食品包装膜 - Google Patents

一种全降解抗拉抗撕食品包装膜 Download PDF

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CN106867222A
CN106867222A CN201710093408.1A CN201710093408A CN106867222A CN 106867222 A CN106867222 A CN 106867222A CN 201710093408 A CN201710093408 A CN 201710093408A CN 106867222 A CN106867222 A CN 106867222A
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parts
layer
mass fraction
tear
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CN106867222B (zh
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陈
陈一
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Tianjin Renyi Industrial Co ltd
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Abstract

本发明涉及一种全降解抗拉抗撕食品包装膜，由三层复合得到，从上到下依次为抗拉层、抗撕层和抗菌层，其中抗拉层、抗撕层采用双层熔融共挤成膜，抗菌膜采用高温流延在双层共挤膜上覆膜，该复合膜拥有优异的抗拉和抗撕性，且具有良好的抗菌效果，膜环保，可实现基本全降解，可广泛应用于环保包装膜领域。

Description

一种全降解抗拉抗撕食品包装膜
技术领域
本发明涉及一种复合包装膜的制备方法，尤其涉及一种具有优异抗拉抗撕性的、及具有抗菌效果的全降解多层复合食品包装膜的制备方法。
背景技术
塑料材料虽然拥有较优异的性能和广泛的适用性，但其来源于石油产品且无法降解，在资源危机和环境污染越发严重的今天，寻找性能优良且可再生的替代材料则成为目前材料领域研究的重中之重。尤其是在膜制备领域，当前的商品发展导致包装材料的用量剧烈增加，尤其是膜材料，作为最轻便的包装材料，被广泛应用，同时也造成了大量的白色污染，发展具有优异性能的，可降解的膜材料具有非常大的经济和社会效益。
在目前的可降解材料中，淀粉因其便宜的价格和广泛的来源已被深入研究并通过改性与复合制备了多种生活与工业用品，如淀粉基膜、淀粉餐具等。但淀粉有其天然的缺陷，它的力学性能差，性能不稳定，只能运用于对力学性能要求低的领域。但生物聚酯的出现改变了这一现状，如聚乳酸、聚己内酯、其他生物聚酯、生物质基聚氨酯等，其中典型的如聚乳酸，聚乳酸（PLA）是脂肪族聚酯，以聚乳酸（2-羟基丙酸）为基本结构单元。PLA可通过发酵玉米等天然原料制得，也可采用聚乳酸缩聚制得。PLA 及其终端产品可在堆肥条件下自然分解成为CO2和水，降低了固体废弃物排放量，是一种绿色环保的生物来源材料。其次，如PHA (聚羟基脂肪酸酯)类， PRS(聚丁二酸丁二醇酯) 、PGA (聚乙醇酸) 、PCL (聚己内酯)等也具有良好的力学性能。生物降解聚酯由于自身的生物降解性、肌体组织相容性、与其他类生物降解材料(如淀粉、纤维等)相比的良好力学性能和工艺性能，已成为目前最有发展前途的生物降解材料，并已被广泛运用于包装、纺织、组织工程及药物缓释领域。然而，要使得其成为替代传统塑料的新一代材料，生物降解聚酯发展面临必须解决的问题。首先，生物降解聚酯与其他生物降解材料相比虽然有相当优势，然而，高分子材料其广泛的应用领域对生物降解聚酯的性能提出了挑战。通过生物法合成的生物降解聚酯一般脆性很高，很难单独直接满足一般的使用要求；而化学合成法制得的脂肪族聚酯大多相对分子质量较低，很难单独作为塑料制品使用。可见，生物降解聚酯的性能已成为制约其发展的首要因素。所以，各种不同的改性方法均被用于生物质聚酯的改性研究，如化学的共聚法，物理的共混法等，其改性产物已基本达到纤维和板材的实用要求，已有较多的相关产品面世。而对于膜材料而言，聚酯膜材料研究得最多的仍是聚聚乳酸膜，聚聚乳酸由于本身的脆性特性，导致其膜在受力后非常容易破裂，各种改性也在此基础上进行，如CN103467941B公开的一种透明高韧性聚乳酸膜及其制备方法，CN105199348A公开的一种高强度高韧性耐热聚乳酸基膜材料的制备方法等，均是采用不同物质的共混从而提高单一膜的性能。而针对其他生物质聚酯制备的可降解膜材料研究仍较少，通过多层配合的方式，结合不同层的特性叠加，来实现包括更好的强度、韧性、或其他的功能性如阻隔性、抗菌性等无疑是一种非常简单而实用的方法。
发明内容
本发明的目的是为了克服生物质单层膜脆性大，力学性能差且功能性单一的缺陷，提供一种具有优异强度、抗撕裂性及具有抗菌效果的多层复合膜的制备方法。
本发明的目的是通过以下技术方案实现的：
一种全降解抗拉抗撕食品包装膜，由3层复合得到，从上到下依次为抗拉层、抗撕层和抗菌层。
进一步，所述抗拉层为以聚己内酯-聚三亚甲基碳酸酯共聚物、聚乳酸-聚己内酯共聚物、聚羟基丁酸酯和羟磷灰石为主料，加入少量防水剂、抗氧剂、润滑剂复配挤出而成。其中，聚己内酯-聚三亚甲基碳酸酯共聚物的质量份数介于35-65份之间，聚乳酸-聚己内酯共聚物的质量份数介于25-45份之间，聚羟基丁酸酯的质量份数介于10-20份之间，羟磷灰石的质量份数介于5-10份之间。防水剂的质量份数介于3-6份之间，抗氧剂的质量份数介于2-4份之间，润滑剂的质量份数介于3-6份之间。
进一步，所述防水剂为水溶性丙烯酸酯类共聚物。
进一步，所述抗氧剂为抗氧剂 264，BHT，168，1010中的一种或几种任意比例混合。
进一步，所述抗拉层中，聚己内酯-聚三亚甲基碳酸酯共聚物的分子量介于150000-300000之间，其中聚己内酯和聚三亚甲基碳酸酯的摩尔比例介于30：70-70：30之间。
进一步，所述聚乳酸-聚己内酯共聚物的分子量介于200000-400000之间，其中聚乳酸和聚己内酯的摩尔比例介于80：20-50：50之间。
进一步，所述聚羟基丁酸酯的分子量介于100000-200000之间。
进一步，所述抗撕层为以羟基丁酸戊酸共聚酯、端羟基超支化聚酯为主料，加入少量催化剂辛酸亚锡、纳米片层蒙脱土、加工助剂复配挤出而成。其中，羟基丁酸戊酸共聚酯的质量份数介于65-85份之间，端羟基超支化聚酯的质量份数介于10-20份之间，催化剂辛酸亚锡的质量份数介于0.8-1.6份之间，纳米片层蒙脱土的质量份数介于3-6份之间，加工助剂的质量份数介于3-6份之间。
进一步，所述羟基丁酸戊酸共聚酯的分子量介于80000-150000之间。
进一步，所述端羟基超支化聚酯为长链脂肪族超支化聚酯，其羟值为20-50/mol，羟值为500-650，酸值小于30，分子量介于2000-5500之间，分子量分布介于1-1.3之间。
进一步，所述抗撕膜中由于有催化剂的存在，羟基丁酸戊酸共聚酯、端羟基超支化聚酯的端基将发生一定程度的缩聚，从而进一步提高材料的相容性和性能。
进一步，所述加工助剂为硬脂酸钙、聚乙烯蜡、石蜡中的一种。
进一步，所述抗菌层为部分醇解PVA、PVA接枝聚甲基丙烯酸酯、羧甲基壳聚糖为主料，加入少量增塑剂、表面活性剂、纤维素类增稠剂复配流延成膜。其中，部分醇解PVA的质量份数介于50-75份之间，PVA接枝聚甲基丙烯酸酯的质量份数介于20-45份之间，羧甲基壳聚糖的质量份数介于10-20份之间，增塑剂的质量份数介于3-6份之间，表面活性剂的质量份数介于4-8份之间，纤维素类增稠剂的质量份数介于0.5-1.2份之间。
进一步，所述抗菌层中部分醇解PVA的醇解度为60%-88%之间，聚合度介于1500-4000之间。
进一步， PVA接枝聚甲基丙烯酸酯的接枝度按质量比介于5-15%之间，分子量介于10000-25000之间，可采用自由基聚合进行制备，也可以采用市售产品。
进一步，所述羧甲基壳聚糖为N，O-羧甲基壳聚糖，其取代度介于1-1.5之间。
进一步，所叙述表面活性剂为阴离子表面活性剂。
进一步，所述纤维素类增稠剂为甲基纤维素、羧甲基纤维素中的一种。
进一步，所述三层复合膜的制备方式为：其中抗拉层、抗撕层采用熔融双层共挤成膜，抗菌层为通过以抗拉层、抗撕层复合层为基膜，在其上进行流延成膜。
进一步，所述抗拉层、抗撕层均采用熔融共挤出成膜，所述抗拉层的挤出加工温度介于215-230℃之间，抗撕层的挤出加工温度介于210-220℃之间，抗菌层的流延加工温度介于80-90℃之间。
进一步，所述抗拉层的厚度介于0.05-0.15mm之间，所述抗撕层的厚度介于0.08-0.16mm之间，所述抗菌层的厚度介于0.05-0.1mm之间。
进一步，本发明的有益效果在于，复合膜由三层共挤，每层提供不同的性能，其中抗拉层具有优异的拉伸性能和弹性，且由于不同改性共聚物的存在和良好相容导致了良好的综合膜性能，抗撕膜由于多支链和缩聚反应的发生，导致分子链在两个方向上排布和固定，形成了优异的抗撕性能，且抗拉层和抗撕层由于本身分子结构的类似和共挤出，形成了结合性良好的双层膜，抗拉和抗撕性能互补和传导，最终得到了优异的力学性能。抗菌层采用流延方式复膜在抗撕膜内，其本身也具有良好的力学性能和抗菌性，最终三层膜形成了整体的优异性能。
具体实施方式
以下将详细描述本发明的示例性实施方法。但这些实施方法仅为示范性目的，而本发明不限于此。
实施例1
一种全降解抗拉抗撕食品包装膜，由三层复合得到，从上到下依次为抗拉层、抗撕层和抗菌层。其中，所述抗拉层的厚度为0.1mm，所述抗撕层的厚度为0.12mm，所述抗菌层的厚度为0.08mm。
所述抗拉层为以聚己内酯-聚三亚甲基碳酸酯共聚物、聚乳酸-聚己内酯共聚物、聚羟基丁酸酯和羟磷灰石为主料，加入少量防水剂、抗氧剂、润滑剂复配挤出而成。其中，聚己内酯-聚三亚甲基碳酸酯共聚物的质量份数为55份，聚乳酸-聚己内酯共聚物的质量份数为32份，聚羟基丁酸酯的质量份数为16份之间，羟磷灰石的质量份数为8份。防水剂的质量份数为4份，抗氧剂的质量份数为3份，润滑剂的质量份数为4份。
所述防水剂为水溶性丙烯酸酯类共聚物。
所述抗氧剂为抗氧剂 264。
所述抗拉层中，聚己内酯-聚三亚甲基碳酸酯共聚物的分子量介于200000-250000之间，其中聚己内酯和聚三亚甲基碳酸酯的摩尔比例为55：45。
所述聚聚乳酸-聚己内酯共聚物的分子量介于250000-350000之间，其中聚乳酸和己内酯的摩尔比例介于60：40之间。
所述聚羟基丁酸酯的分子量介于100000-200000之间。
所述抗撕层为以羟基丁酸戊酸共聚酯、端羟基超支化聚酯为主料，加入少量催化剂辛酸亚锡、纳米片层蒙脱土、加工助剂复配挤出而成。其中，羟基丁酸戊酸共聚酯的质量份数为70份，端羟基超支化聚酯的质量份数为16份，催化剂辛酸亚锡的质量份数为1份，纳米片层蒙脱土的质量份数为4份，加工助剂的质量份数为4份。
所述羟基丁酸戊酸共聚酯的分子量介于100000-120000之间。
所述端羟基超支化聚酯为长链脂肪族超支化聚酯，其羟值为42/mol，羟值为520，酸值小于20，分子量介于4800之间，分子量分布为1.2。
所述加工助剂为硬脂酸钙。
所述抗菌层为部分醇解PVA、PVA接枝聚甲基丙烯酸酯、羧甲基壳聚糖为主料，加入少量增塑剂、表面活性剂、纤维素类增稠剂复配流延成膜。其中，部分醇解PVA的质量份数为65份，PVA接枝聚甲基丙烯酸酯的质量份数为32份，羧甲基壳聚糖的质量份数为15份，增塑剂的质量份数为4.5份，表面活性剂的质量份数为6份，纤维素类增稠剂的质量份数为0.8份。
所述抗菌层中部分醇解PVA的醇解度为80%，聚合度为1788。
PVA接枝聚甲基丙烯酸酯的接枝度按质量比接入5-15%之间，分子量介于15000-20000之间。
所述羧甲基壳聚糖为N，O-羧甲基壳聚糖，其取代度为1.2。
所叙述表面活性剂为十二烷基苯磺酸钠。
所述纤维素类增稠剂为羧甲基纤维素。
所述三层复合膜的制备方式为：其中抗拉层、抗撕层采用熔融双层共挤成膜，抗菌层为通过以抗拉层、抗撕层复合层为基膜，在其上进行流延成膜。
所述抗拉层、抗撕层均采用熔融共挤出成膜，所述抗拉层的挤出加工温度介于215-230℃之间，抗撕层的挤出加工温度介于210-220℃之间，抗菌层的流延加工温度为85℃。
具体性能如表1所示。
实施例2
一种全降解抗拉抗撕食品包装膜，由三层复合得到，从上到下依次为抗拉层、抗撕层和抗菌层。其中，所述抗拉层的厚度为0.12mm，所述抗撕层的厚度为0.14mm，所述抗菌层的厚度为0.06mm。
所述抗拉层为以聚己内酯-聚三亚甲基碳酸酯共聚物、聚乳酸-聚己内酯共聚物、聚羟基丁酸酯和羟磷灰石为主料，加入少量防水剂、抗氧剂、润滑剂复配挤出而成。其中，聚己内酯-聚三亚甲基碳酸酯共聚物的质量份数为56份，聚乳酸-聚己内酯共聚物的质量份数为38份，聚羟基丁酸酯的质量份数为14份，羟磷灰石的质量份数为7.5份。防水剂的质量份数为4份，抗氧剂的质量份数为2.5份，润滑剂的质量份数为4份。
所述防水剂为水溶性丙烯酸酯类共聚物。
所述抗氧剂为抗氧剂 BHT。
所述抗拉层中，聚己内酯-聚三亚甲基碳酸酯共聚物的分子量介于180000-240000之间，其中聚己内酯和聚三亚甲基碳酸酯的摩尔比例为60：40。
所述聚乳酸-聚己内酯共聚物的分子量介于250000-350000之间，其中聚乳酸和聚己内酯的摩尔比例为70：30。
所述聚羟基丁酸酯的分子量介于120000-160000之间。
所述抗撕层为以羟基丁酸戊酸共聚酯、端羟基超支化聚酯为主料，加入少量催化剂辛酸亚锡、纳米片层蒙脱土、加工助剂复配挤出而成。其中，羟基丁酸戊酸共聚酯的质量份数为80份，端羟基超支化聚酯的质量份数为15份，催化剂辛酸亚锡的质量份数为1.2份，纳米片层蒙脱土的质量份数为5份，加工助剂的质量份数为3.5份。
所述羟基丁酸戊酸共聚酯的分子量介于80000-150000之间。
所述端羟基超支化聚酯为长链脂肪族超支化聚酯，其羟值为40/mol，羟值为520，酸值小于30，分子量为5000-5200，分子量分布为1.15。
所述加工助剂为液体石蜡。
所述抗菌层为部分醇解PVA、PVA接枝聚甲基丙烯酸酯、羧甲基壳聚糖为主料，加入少量增塑剂、表面活性剂、纤维素类增稠剂复配流延成膜。其中，部分醇解PVA的质量份数为64份，PVA接枝聚甲基丙烯酸酯的质量份数为36份，羧甲基壳聚糖的质量份数为14份，增塑剂的质量份数为3.6份，表面活性剂的质量份数为5.2份，纤维素类增稠剂的质量份数为1份。
所述抗菌层中部分醇解PVA的醇解度为82%，聚合度为2800。
所述PVA接枝聚甲基丙烯酸酯的接枝度按质量比为12%，分子量介于15000-20000之间。所述羧甲基壳聚糖为N，O-羧甲基壳聚糖，其取代度为1.3。
所叙述表面活性剂为阴离子聚丙烯酰胺。
所述纤维素类增稠剂为甲基纤维素。
所述三层复合膜的制备方式为：其中抗拉层、抗撕层采用熔融双层共挤成膜，抗菌层为通过以抗拉层、抗撕层复合层为基膜，在其上进行流延成膜。
所述抗拉层的挤出加工温度介于215-230℃之间，抗撕层的挤出加工温度介于210-220℃之间，抗菌层的流延加工温度为85℃。
具体性能如表1所示。
表1：实施例1、2的膜性能
复合材料性能 实施例1 实施例2
断裂延伸率（%） 187.2±6.5 209.2±7.2
拉伸强度（Mpa） 28.5±2.6 30.6±3.2
横向直角撕裂强度（KN/ m） 89.3±2.4 87.5±3.2
纵向直角撕裂强度（KN/ m） 73.5±3.1 79.5±4.6

Claims (6)

1.一种全降解抗拉抗撕食品包装膜，由3层复合得到，从上到下依次为抗拉层、抗撕层和抗菌层。其特征在于：所述抗拉层为以聚己内酯-聚三亚甲基碳酸酯共聚物、聚乳酸-聚己内酯共聚物、聚羟基丁酸酯和羟磷灰石为主料，加入少量防水剂、抗氧剂、润滑剂复配挤出而成；其中，聚己内酯-聚三亚甲基碳酸酯共聚物的质量份数介于35-65份之间，聚乳酸-聚己内酯共聚物的质量份数介于25-45份之间，聚羟基丁酸酯的质量份数介于10-20份之间，羟磷灰石的质量份数介于5-10份之间，防水剂的质量份数介于3-6份之间，抗氧剂的质量份数介于2-4份之间，润滑剂的质量介于3-6份之间；
其特征还在于：
所述抗撕层为以羟基丁酸戊酸共聚酯、端羟基超支化聚酯为主料，加入少量催化剂辛酸亚锡、纳米片层蒙脱土、加工助剂复配挤出而成；其中，羟基丁酸戊酸共聚酯的质量份数介于65-85份之间，端羟基超支化聚酯的质量份数介于10-20份之间，催化剂辛酸亚锡的质量份数介于0.8-1.6份之间，纳米片层蒙脱土的质量份数介于3-6份之间，加工助剂的质量份数介于3-6份之间；
其特征还在于：
所述抗菌层为部分醇解PVA、PVA接枝聚甲基丙烯酸酯、羧甲基壳聚糖为主料，加入少量增塑剂、表面活性剂、纤维素类增稠剂复配流延成膜；其中，部分醇解PVA的质量份数介于50-75份之间，PVA接枝聚甲基丙烯酸酯的质量份数介于20-45份之间，羧甲基壳聚糖的质量份数介于10-20份之间，增塑剂的质量份数介于3-6份之间，表面活性剂的质量份数介于4-8份之间，纤维素类增稠剂的质量份数介于0.5-1.2份之间。
2.如权利要求1所述的一种全降解抗拉抗撕食品包装膜，其特征在于：所述三层复合膜的制备方式为：其中抗拉层、抗撕层采用熔融双层共挤成膜，抗菌层为通过以抗拉层、抗撕层复合层为基膜，在其上进行流延成膜。
3.如权利要求1所述的一种全降解抗拉抗撕食品包装膜，其特征在于：所述抗拉层中，聚己内酯-聚三亚甲基碳酸酯共聚物的分子量介于150000-300000之间，其中聚己内酯和聚三亚甲基碳酸酯的摩尔比例介于30：70-70：30之间；聚乳酸-聚己内酯共聚物的分子量介于200000-400000之间，其中聚乳酸和聚己内酯的摩尔比例介于80：20-50：50之间。
4.如权利要求1所述的一种全降解抗拉抗撕食品包装膜，其特征在于：所述抗撕层中，羟基丁酸戊酸共聚酯的分子量介于150000-300000之间，端羟基超支化聚酯为长链脂肪族超支化聚酯，其羟值为20-50/mol，羟值为500-650，酸值小于30，分子量介于2000-5500之间，分子量分布介于1-1.3之间。
5.如权利要求1所述的一种全降解抗拉抗撕食品包装膜，其特征在于：所述抗菌层中部分醇解PVA的醇解度为60%-88%之间，聚合度介于1500-4000之间，PVA接枝聚甲基丙烯酸酯的接枝度按质量比介于5-15%之间，分子量介于10000-25000之间，羧甲基壳聚糖为N，O-羧甲基壳聚糖，其取代度介于1-1.5之间。
6.如权利要求1所述的一种全降解抗拉抗撕食品包装膜，其特征在于：所述抗拉层的厚度介于0.05-0.15mm之间，所述抗撕层的厚度介于0.08-0.16mm之间，所述抗菌层的厚度介于0.05-0.1mm之间。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108724879A (zh) * 2018-05-04 2018-11-02 山东商业职业技术学院 一种可降解保鲜包装材料及其制备方法和应用
CN113085319A (zh) * 2021-03-16 2021-07-09 晋江市新迪新材料科技有限公司 一种餐具用全生物降解复合材料与使用该复合材料的餐具

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0909640A1 (en) * 1996-07-19 1999-04-21 Kureha Kagaku Kogyo Kabushiki Kaisha Gas-barrier composite film
EP1182142A1 (en) * 1999-09-10 2002-02-27 Ishida Co., Ltd. Food-packaging bag, method of food packaging, and use of laminated film as food-packaging bag
CN101318392A (zh) * 2008-07-03 2008-12-10 大连华诺塑料科技有限公司 三层共挤热收缩树脂膜、生产方法及应用方法
CN104943306A (zh) * 2015-06-23 2015-09-30 湖南工业大学 一种高强度多层共挤生物质复合包装膜
CN105440611A (zh) * 2015-05-03 2016-03-30 湖南工业大学 一种具有抗菌阻隔性的高强韧聚乳酸复合膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0909640A1 (en) * 1996-07-19 1999-04-21 Kureha Kagaku Kogyo Kabushiki Kaisha Gas-barrier composite film
EP1182142A1 (en) * 1999-09-10 2002-02-27 Ishida Co., Ltd. Food-packaging bag, method of food packaging, and use of laminated film as food-packaging bag
CN101318392A (zh) * 2008-07-03 2008-12-10 大连华诺塑料科技有限公司 三层共挤热收缩树脂膜、生产方法及应用方法
CN105440611A (zh) * 2015-05-03 2016-03-30 湖南工业大学 一种具有抗菌阻隔性的高强韧聚乳酸复合膜
CN104943306A (zh) * 2015-06-23 2015-09-30 湖南工业大学 一种高强度多层共挤生物质复合包装膜

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108724879A (zh) * 2018-05-04 2018-11-02 山东商业职业技术学院 一种可降解保鲜包装材料及其制备方法和应用
CN108724879B (zh) * 2018-05-04 2020-06-05 山东商业职业技术学院 一种可降解保鲜包装材料及其制备方法和应用
CN113085319A (zh) * 2021-03-16 2021-07-09 晋江市新迪新材料科技有限公司 一种餐具用全生物降解复合材料与使用该复合材料的餐具

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