CN107686715A - 一种速冻食品软包装用pet复合薄膜及其制备方法 - Google Patents

一种速冻食品软包装用pet复合薄膜及其制备方法 Download PDF

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CN107686715A
CN107686715A CN201710629287.8A CN201710629287A CN107686715A CN 107686715 A CN107686715 A CN 107686715A CN 201710629287 A CN201710629287 A CN 201710629287A CN 107686715 A CN107686715 A CN 107686715A
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pet
compound
parts
aqueous polyurethane
polyurethane adhesives
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李书堂
魏风军
张春健
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HENAN DAYOU PLASTICS INDUSTRY DEVELOPMENT Co Ltd
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HENAN DAYOU PLASTICS INDUSTRY DEVELOPMENT Co Ltd
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Abstract

本发明属于软包装材料技术领域，具体涉及一种速冻食品软包装用PET复合薄膜，该复合薄膜由表至里依次为PET层、铝箔层和线性低密度聚乙烯即LLDPE层，层间采用干式复合，干式复合所采用的黏结剂为水性聚氨酯胶黏剂，所述的水性聚氨酯胶黏剂包括封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚、氨水、去离子水、乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物和复合助剂。本发明采用PET层/铝箔层/LLDPE三层复合膜具有高阻隔、防渗透、不易分层、耐酸碱，满足当今社会对健康、安全、环保要求，且工艺简单。

Description

一种速冻食品软包装用PET复合薄膜及其制备方法
技术领域
本发明属于包装材料技术领域，具体涉及一种速冻食品软包装用PET复合薄膜及其制备方法。
背景技术
塑料软包装具有屏蔽、可印刷和热封等功能，当前已广泛应用于食品、医药、化妆品等。软包装绝大部分用于食品包装, 尤其是速成或即食食品，还可用于农药、化肥、洗涤剂等化学产品、卫生保健产品等的包装。在当前环境保护浪潮的冲击下，绿色包装是国际环保发展趋势的需要，同时也代表了各国包装的发展潮流。与此相适应，塑料软包装绿色制造就成了重要的发展趋势。
随着社会以及国家战略性新兴产业（新材料产业）的发展，对软包装提出了新的要求，其中环保的需求格外的迫切。目前采用的塑料软包装生产工艺都是针对一定的产品和一定的性能，有自身的局限性，同时也普遍存在生产工艺复杂、原材料用量多浪费大、生产周期长、劳动强度大、有机溶剂污染、作业环境差的问题，有待开发符合绿色、安全、环保要求的绿色制造工艺，以满足市场对新型、高档复合软包装功能材料的需求。
发明内容
针对现有技术中存在的不足，本发明提供一种速冻食品软包装用PET复合薄膜及其制备方法，其不仅满足实际使用，同时满足当今社会对健康、安全、环保要求，且工艺简单。
为实现上述发明的目的，本发明采用的技术方案如下：
一种用于PET复合薄膜干式复合选用的黏结剂，干式复合选用的黏结剂为水性聚氨酯胶黏剂；以重量份数计，所述的水性聚氨酯胶黏剂包括110－120份封闭型脂环族多异氰酸酯、40－55份聚醚二元醇、8－10份二羟甲基丙酸、30－40份聚丙二醇、15－20份聚四亚甲基乙二醇醚、5－10份氨水、70－90份去离子水、15－20份乙二胺基乙磺酸钠、5－8份改性环氧树脂、3－5份活性基团化合物和1－3份复合助剂。
具体的，所述的改性环氧树脂由重量比为3：1的双酚A型环氧树脂和脂肪族环氧树脂混合而成。
具体的，所述的活性基团化合物为聚醚胺，分子量800－1000，伯胺值>95%总胺。
具体的，所述的复合助剂由偶联剂、流平剂和催化剂按重量比1:1:1.5复配而成；所述的偶联剂为磷酸酯钛偶联剂，所述的催化剂由重量比为2:1的辛酸亚锡和二甲基苯胺混合而成。
具体的，所述的水性聚氨酯胶黏剂还添加有10－20份水性聚丙烯酸酯。
具体的，所述的水性聚氨酯胶黏剂还添加有5－8份改性增粘乳液，所述的改性增粘乳液为液态氢化松香酯。
进一步的，上述的水性聚氨酯胶黏剂还添加有3份－5份改性增强剂，该改性增强剂由气相二氧化硅和钛酸酯偶联剂按重量比10:0.1混合而成，气相二氧化硅粒径为7－12nm。
上述用于PET复合薄膜干式复合选用的黏结剂的制备方法，具体包括如下步骤：按比例将封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚置于反应釜中，加热至70－80℃并搅拌4－6h，然后向反应釜中加入氨水并继续搅拌0.5－1h后，加入去离子水搅拌均匀，然后降温至40－50℃，再加入乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物、水性聚丙烯酸酯、改性增粘乳液、改性增强剂和复合助剂，搅拌反应1－1.5h即得。
一种利用上述黏结剂制备得到的速冻食品软包装用PET复合薄膜，该复合薄膜由表至里依次为PET层、铝箔层和LLDPE层（线性低密度聚乙烯层），层与层之间采用干式复合，其中，干式复合选用的黏结剂为水性聚氨酯胶黏剂。
上述速冻食品软包装用PET复合薄膜的制备方法，其包括以下工序：印刷工序、干式复合工序、热压复合、收卷和熟化，其中，印刷工序为：在PET层印刷；干式复合工序为：将印刷后的PET层利用水性聚氨酯胶黏剂与铝箔层进行干式复合形成PET/铝箔复合膜，然后将PET/铝箔复合膜再次利用水性聚氨酯胶黏剂与LLDPE层进行干式复合形成PET/铝箔/LLDPF复合膜；最后将PET/铝箔/LLDPF复合膜经热压复合、收卷和熟化工序得到最终速冻食品软包装用PET复合薄膜。
本发明中，所述氨水浓度为5%-8%（指质量百分比），所述PET层的厚度为10－20μm；铝箔层的厚度为7－9μm；LLDPF层的厚度为6－20μm。PET层主要用作承印物，可以依据要求印刷各种彩色图案，同时还具有耐高温、能够适应高速印刷的要求。铝箔层能够阻隔空气中水蒸气、氧气、光线进入PET复合膜中，但可以快速将冷源传递到包装膜内，使食物快速速冻。LLDPE层具有良好的粘结性能，在干式复合中能够与铝箔膜在聚氨酯胶黏剂的作用下进行良好的复合，并且对食物不会造成污染。
与现有技术相比，本发明具有以下有益效果：
1）本发明采用PET层/铝箔层/LLDPE三层复合膜具有高阻隔、防渗透、不易分层、耐酸碱的特点；满足当今社会对健康、安全、环保要求，且工艺简单。
2）本发明PET层/铝箔层/LLDPE复合膜采用水性聚氨酯胶黏剂干式复合法制成，对环境无污染，没有溶剂型聚氨酯的游离TDI 等问题，也不存在水解后产生芳香族伯胺这种致癌物质的问题，可以满足FDA 和欧盟规定的溶剂残留、蒸发残渣、迁移量、极限迁移量、芳香族伯胺等各种要求，并且耐低温性能良好；
3）本发明工艺简单，可利用现有设备进行加工生产，适合许多彩印厂急于生产高卫生标准的产品、降低生产成本而不需要做新设备投入的要求。
具体实施方式
以下结合实施例对本发明的技术方案作进一步地详细介绍，但本发明的保护范围并不局限于此。
下述实施例中，氨水浓度为7%；液态氢化松香酯（美国Eastman伊士曼）：酸值8 mgKOH/g，粘度指数（100℃ SUS）385，购自深圳市新志和化工原料有限公司。其它原料如无特殊说明，均为普通市售产品。
实施例1
一种速冻食品软包装用PET复合薄膜，该复合薄膜由表至里依次为PET层、铝箔层和LLDPE层，层与层间采用干式复合，干式复合所采用的黏结剂为水性聚氨酯胶黏剂；按重量份数计，所述的水性聚氨酯胶黏剂由110份封闭型脂环族多异氰酸酯、40份聚醚二元醇、8份二羟甲基丙酸、30份聚丙二醇、15份聚四亚甲基乙二醇醚、5份氨水、70份去离子水、15份乙二胺基乙磺酸钠、5份改性环氧树脂、3份活性基团化合物、1份复合助剂、10份水性聚丙烯酸酯、5份改性增粘乳液和3份改性增强剂制成。
所述的改性环氧树脂由重量比为3：1的双酚A型环氧树脂和脂肪族环氧树脂混合而成；所述的活性基团化合物为聚醚胺，分子量800，伯胺值>95%总胺。所述的复合助剂由偶联剂、流平剂、催化剂按重量比1:1:1.5复配而成，所述的偶联剂为磷酸酯钛偶联剂,所述的催化剂由重量比为2:1的辛酸亚锡和二甲基苯胺混合而成。所述的改性增粘乳液为液态氢化松香酯。所述改性增强剂由气相二氧化硅和钛酸酯偶联剂按照重量比10:0.1混合而成，气相二氧化硅粒径为7nm。
所述的水性聚氨酯胶黏剂其制备方法为：按比例将封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚置于反应釜中，加热至70℃，搅拌4h，然后向反应釜中加入氨水，继续搅拌0.5h后，加入去离子水搅拌均匀，然后降温至40℃，再加入乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物、水性聚丙烯酸酯、改性增粘乳液、改性增强剂和复合助剂，搅拌均匀，反应1h后制得水性聚氨酯胶黏剂。
上述速冻食品软包装用PET复合薄膜的制备方法，包括以下工序：印刷工序、干式复合工序、热压复合、收卷和熟化，其中，印刷工序为：在PET层印刷；干式复合工序为：将印刷后的PET层利用水性聚氨酯胶黏剂与铝箔层进行干式复合（涂覆量2-2.2 g/m2，干燥温度为50-70℃，熟化温度50℃-60℃，熟化4-5h）形成PET/铝箔复合膜，然后将PET/铝箔复合膜再次利用水性聚氨酯胶黏剂与LLDPE层进行干式复合形成PET/铝箔/LLDPF复合膜；最后将PET/铝箔/LLDPF复合膜经热压复合、收卷和熟化工序（参照本领域常规技术即可）得到最终速冻食品软包装用PET复合薄膜。
实施例2
一种速冻食品软包装用PET复合薄膜，该复合薄膜由表至里依次为PET层、铝箔层和LLDPE层，层与层间采用干式复合，干式复合所采用的黏结剂为水性聚氨酯胶黏剂；按重量份数计，所述的水性聚氨酯胶黏剂由120份封闭型脂环族多异氰酸酯、55份聚醚二元醇、10份二羟甲基丙酸、40份聚丙二醇、20份聚四亚甲基乙二醇醚、10份氨水、90份去离子水、20份乙二胺基乙磺酸钠、8份改性环氧树脂、5份活性基团化合物、3份复合助剂、20份水性聚丙烯酸酯、8份改性增粘乳液和4份改性增强剂制成。
所述的改性环氧树脂由重量比为3：1的双酚A型环氧树脂和脂肪族环氧树脂混合而成；所述的活性基团化合物为聚醚胺，分子量1000，伯胺值>95%总胺。所述的复合助剂由偶联剂、流平剂、催化剂按重量比1:1:1.5复配而成，所述的偶联剂为磷酸酯钛偶联剂,所述的催化剂由重量比为2:1的辛酸亚锡和二甲基苯胺混合而成。所述的改性增粘乳液为液态氢化松香酯。所述的改性增强剂由气相二氧化硅和钛酸酯偶联剂按照重量比10:0.1混合而成，气相二氧化硅粒径为12nm。
所述的水性聚氨酯胶黏剂其制备方法为：按比例将封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚置于反应釜中，加热至80℃，搅拌6h，然后向反应釜中加入氨水，继续搅拌1h后，加入去离子水搅拌均匀，然后降温至50℃，再加入乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物、水性聚丙烯酸酯、改性增粘乳液、改性增强剂和复合助剂，搅拌均匀，反应1.5h后制得水性聚氨酯胶黏剂。
上述速冻食品软包装用PET复合薄膜的制备方法，包括以下工序：印刷工序、干式复合工序、热压复合、收卷和熟化，其中，印刷工序为：在PET层印刷；干式复合工序为：将印刷后的PET层利用水性聚氨酯胶黏剂与铝箔层进行干式复合形成PET/铝箔复合膜，然后将PET/铝箔复合膜再次利用水性聚氨酯胶黏剂与LLDPE层进行干式复合形成PET/铝箔/LLDPF复合膜；最后将PET/铝箔/LLDPF复合膜经热压复合、收卷和熟化工序得到最终速冻食品软包装用PET复合薄膜。
实施例3
一种速冻食品软包装用PET复合薄膜，该复合膜由表至里依次为PET层、铝箔层和LLDPE层，层与层间采用干式复合，干式复合所采用的黏结剂为水性聚氨酯胶黏剂；按重量份数计，所述的水性聚氨酯胶黏剂由115份封闭型脂环族多异氰酸酯、48份聚醚二元醇、9份二羟甲基丙酸、35份聚丙二醇、17份聚四亚甲基乙二醇醚、8份氨水、80份去离子水、17份乙二胺基乙磺酸钠、7份改性环氧树脂、4份活性基团化合物、2份复合助剂、15份水性聚丙烯酸酯、7份改性增粘乳液和5份改性增强剂制成。
所述的改性环氧树脂由重量比为3：1的双酚A型环氧树脂和脂肪族环氧树脂混合而成；所述的活性基团化合物为聚醚胺，分子量900，伯胺值>95%总胺。所述的复合助剂由偶联剂、流平剂、催化剂按重量比1:1:1.5复配而成，所述的偶联剂为磷酸酯钛偶联剂,所述的催化剂由重量比为2:1的辛酸亚锡和二甲基苯胺混合而成。所述的改性增粘乳液为液态氢化松香酯。
所述的改性增强剂由气相二氧化硅和钛酸酯偶联剂按照重量比10:0.1混合而成，气相二氧化硅粒径为8nm。
所述的水性聚氨酯胶黏剂其制备方法为：按上述比例将封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚置于反应釜中，加热至75℃，搅拌4-6h，然后向反应釜中加入氨水，继续搅拌1h后，加入去离子水搅拌均匀，然后降温至45℃，再加入乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物、水性聚丙烯酸酯、改性增粘乳液、改性增强剂和复合助剂，搅拌均匀，反应1.5h后制得水性聚氨酯胶黏剂。
上述速冻食品软包装用PET复合薄膜的制备方法，包括以下工序：印刷工序、干式复合工序、热压复合、收卷和熟化，其中，印刷工序为：在PET层印刷；干式复合工序为：将印刷后的PET层利用水性聚氨酯胶黏剂与铝箔层进行干式复合形成PET/铝箔复合膜，然后将PET/铝箔复合膜再次利用水性聚氨酯胶黏剂与LLDPE层进行干式复合形成PET/铝箔/LLDPF复合膜；最后将PET/铝箔/LLDPF复合膜经热压复合、收卷和熟化工序得到最终速冻食品软包装用PET复合薄膜。
在相同条件下对以上实施例产品进行测定，测试参照GB/T 21302-2007包装用复合膜进行，测试结果如下。从下表中可以看出，本发明PET复合薄膜在断裂伸长率、拉断力、剥离力、热合强度、水蒸气透过率、氧气透过率等性能方面表现良好，比现有技术中同类产品性能高10－15%。
以上所述仅为本发明的优选实施例而已 ，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种用于PET复合薄膜干式复合选用的黏结剂，其特征在于，干式复合选用的黏结剂为水性聚氨酯胶黏剂；以重量份数计，所述的水性聚氨酯胶黏剂包括110－120份封闭型脂环族多异氰酸酯、40－55份聚醚二元醇、8－10份二羟甲基丙酸、30－40份聚丙二醇、15－20份聚四亚甲基乙二醇醚、5－10份氨水、70－90份去离子水、15－20份乙二胺基乙磺酸钠、5－8份改性环氧树脂、3－5份活性基团化合物和1－3份复合助剂。
2.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的改性环氧树脂由重量比为3：1的双酚A型环氧树脂和脂肪族环氧树脂混合而成。
3.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的活性基团化合物为聚醚胺，分子量800－1000，伯胺值>95%总胺。
4.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的复合助剂由偶联剂、流平剂和催化剂按重量比1:1:1.5复配而成；所述的偶联剂为磷酸酯钛偶联剂，所述的催化剂由重量比为2:1的辛酸亚锡和二甲基苯胺混合而成。
5.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的水性聚氨酯胶黏剂还添加有10－20份水性聚丙烯酸酯。
6.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的水性聚氨酯胶黏剂还添加有5－8份改性增粘乳液，所述的改性增粘乳液为液态氢化松香酯。
7.根据权利要求1所述的用于PET复合薄膜干式复合选用的黏结剂，其特征在于，所述的水性聚氨酯胶黏剂还添加有3份－5份改性增强剂，该改性增强剂由气相二氧化硅和钛酸酯偶联剂按重量比10:0.1混合而成，气相二氧化硅粒径为7－12nm。
8.权利要求1至7任一所述用于PET复合薄膜干式复合选用的黏结剂的制备方法，其特征在于，包括如下步骤：按比例将封闭型脂环族多异氰酸酯、聚醚二元醇、二羟甲基丙酸、聚丙二醇、聚四亚甲基乙二醇醚置于反应釜中，加热至70－80℃并搅拌4－6h，然后向反应釜中加入氨水并继续搅拌0.5－1h后，加入去离子水搅拌均匀，然后降温至40－50℃，再加入乙二胺基乙磺酸钠、改性环氧树脂、活性基团化合物、水性聚丙烯酸酯、改性增粘乳液、改性增强剂和复合助剂，搅拌反应1－1.5h即得。
9.利用权利要求1至8任一所述黏结剂制备得到的速冻食品软包装用PET复合薄膜，其特征在于，该复合薄膜由表至里依次为PET层、铝箔层和LLDPE层，层与层之间采用干式复合，干式复合选用的黏结剂为水性聚氨酯胶黏剂。
10.权利要求9所述速冻食品软包装用PET复合薄膜的制备方法，其特征在于：包括以下工序：印刷工序、干式复合工序、热压复合、收卷和熟化，其中，印刷工序为：在PET层印刷；干式复合工序为：将印刷后的PET层利用水性聚氨酯胶黏剂与铝箔层进行干式复合形成PET/铝箔复合膜，然后将PET/铝箔复合膜再次利用水性聚氨酯胶黏剂与LLDPE层进行干式复合形成PET/铝箔/LLDPF复合膜；最后将PET/铝箔/LLDPF复合膜经热压复合、收卷和熟化工序得到最终速冻食品软包装用PET复合薄膜。
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