CN115464947B - 一种可降解保温彩虹膜及其制备方法 - Google Patents
一种可降解保温彩虹膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种可降解保温彩虹膜及其制备方法,属于包装材料技术领域,彩虹膜包括镭射层、铝箔纸和保护膜,制备方法包括如下步骤:第一步、将镭射转移涂料涂布在PET薄膜上,烘干后进行模压,得到转移镭射膜;第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与保护膜进行贴合,得到可降解保温彩虹膜。以脂肪族和芳香族共聚酯作为保护膜的原料,保留生物可降解性,为水性聚氨酯作为镭射转移涂料的原料,赋予镭射转移涂料一定的抗菌性,通过对彩虹膜制备的原料进行调整,提高彩虹膜的可降解性,满足包装材料的绿色化要求。
Description
技术领域
本发明属于包装材料技术领域,具体地,涉及一种可降解保温彩虹膜及其制备方法。
背景技术
彩虹膜在不同距离、不同角度光效应会呈现出完全不同的幻彩效果,主要用于软包装塑料袋、面膜袋化妆品包装、软包装面膜袋用烟包、包装糖果、包装礼品、包装花束等;
随着环境污染问题的加剧,人们的环保意识越来越强,对于包装材料的绿色化要求也越来越高,因此,在保证包装材料具有幻彩效果的同时还要求其可自然降解性能,进一步维护地球的可持续发展。
发明内容
为了解决背景技术中提到的技术问题,本发明提供一种可降解保温彩虹膜及其制备方法。
本发明的目的可以通过以下技术方案实现:
一种可降解保温彩虹膜,包括镭射层、铝箔纸和保护膜,所述镭射层贴附于铝箔纸上,所述保护膜贴附于镭射层表面;
所述保护膜通过如下步骤制备:
将1,4-丁二醇和二酸混合单体混合,加热至90-100℃,加入催化剂升温至190℃反应2h,升温至200℃反应1h,升温至230℃反应1h,然后在真空条件下,升温至245℃缩聚反应2h,反应结束后,加入氯仿混合,用甲醇沉淀后在过滤,在80℃条件下真空干燥至恒重,用氯仿溶解后浇筑在玻璃板上,待溶剂挥发后,得到保护膜。
进一步地,催化剂为钛酸异丙酯,1,4-丁二醇和二酸混合单体的质量比为2:1.5;二酸混合单体为丁二酸、对苯二甲酸和二羧基单体;其中,丁二酸、对苯二甲酸和二羧基单体的质量比3:11:1-1.1。
进一步地,二羧基单体通过如下步骤制备:
将氨基酸和2-吡咯烷酮加入甲醛水溶液中,设置温度为20℃,搅拌反应9-10h,反应结束后,将得到的反应液的减压浓缩除去溶剂,得到二羧基单体。氨基酸、2-吡咯烷酮和甲醛发生曼尼希反应,氨基酸上的氨基与2-吡咯烷酮反应,得到二羧基单体。二羧基单体属于一种亲水性单体,引入保护膜中用于改变其表面的亲水性。
进一步地,甲醛水溶液的质量分数为37%,氨基酸和2-吡咯烷酮的用量摩尔比为1:1;氨基酸为天冬氨酸和谷氨酸中的一种。
一种可降解保温彩虹膜的制备方法,包括如下步骤:
第一步、将镭射转移涂料涂布在PET薄膜上,涂布速度为18-20m/min,然后在165-170℃条件下烘干,烘干车速为22-25m/min;烘干后进行模压,得到转移镭射膜;
第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与保护膜进行贴合,得到可降解保温彩虹膜。
进一步地,热压复合条件为:温度180-190℃,压力0.4MPa,辊速20-22m/min。
进一步地,镭射转移涂料为水性聚氨酯、助溶剂、水、变色组合物和消泡剂混合后得到,水性聚氨酯、助溶剂、水、变色组合物和消泡剂的质量比为40:5:40:2:0.1。
进一步地,所述变色组合物包括螺吡喃、甲基紫和三芳基甲烷;螺吡喃、甲基紫和三芳基甲烷的质量比为3:3:1;助溶剂为乙醇、异丙醇中的一种;消泡剂为有机硅硅氧烷类消泡剂。
进一步地,水性聚氨酯通过如下步骤制备:
步骤一、将丙交酯加热至110℃,真空脱水30min,在氮气保护条件下,N-甲基二乙醇胺和异辛酸亚锡,升温至140℃,反应8h,得到改性聚乳酸;丙交酯和N-甲基二乙醇胺在异辛酸亚锡的催化作用下,发生开环聚合制备得到含有双端羟基的改性聚乳酸,聚乳酸具有良好的环境相容性和生物相容性,最终可降解成二氧化碳和水,对环境污染小。
步骤二、将甲苯二异氰酸酯和改性聚乳酸混合,在温度为85℃条件下搅拌3h,得到预聚体,降温至60℃,加入1,4-丁二醇,搅拌30min,冷却至室温,加入乙酸和去离子水中和,搅拌30min,得到水性聚氨酯。以改性聚乳酸作为高分子二元醇,与甲苯二异氰酸酯反应得到水性聚氨酯,在制备过程中加入酸进行中和时得到阳离子,会使聚氨酯的结构中引入具有抗菌效果的季铵盐结构,赋予镭射转移涂料一定的抗菌性,提高储存稳定性。
进一步地,丙交酯、N-甲基二乙醇胺和异辛酸亚锡的用量质量比为20g:1g:20mg;甲苯二异氰酸酯、改性聚乳酸和1,4-丁二醇的用量质量比为20:22:1。
进一步地,镭射转移涂料的涂布量为0.6±0.1g/m2。
进一步地,所述胶粘剂为单组份无溶剂聚氨酯复膜胶。
本发明的有益效果:
本发明制备了一种可降解保温彩虹膜,该彩虹膜包括镭射层、铝箔纸和保护膜,镭射层贴附于铝箔纸上,保护膜贴附于镭射层表面,通过对彩虹膜制备的原料进行调整,提高彩虹膜的可降解性,满足包装材料的绿色化要求。具体的,保护膜的原料为脂肪族和芳香族共聚酯,具有良好的生物降解性,二酸混合单体中的1,4-丁二醇可与丁二酸、对苯二甲酸和二羧基单体发生聚合,在维持较好的力学性能的前提下保留生物可降解性,同时,二酸混合单体中的二羧基单体属于氨基酸衍生物,二羧基单体中保留了2-吡咯烷酮的部分结构,提高成膜后的膜表面的亲水性,疏水性的污染物如油污等容易去除,保护膜表面与水的相互作用强,可以形成紧密的水化层,消除静电作用,提高保护膜的保护效果。
镭射转移涂料为水性聚氨酯、助溶剂、水、变色组合物和消泡剂混合后得到,其中以改性聚乳酸作为高分子二元醇,与甲苯二异氰酸酯反应得到,在制备过程中引入具有抗菌效果的季铵盐结构,赋予镭射转移涂料一定的抗菌性,提高储存稳定性。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
制备保护膜:
将天冬氨酸和2-吡咯烷酮加入质量分数为37%的甲醛水溶液中,设置温度为20℃,搅拌反应9h,反应结束后,将得到的反应液的减压浓缩除去溶剂,得到二羧基单体。其中,甲醛水溶液的,天冬氨酸和2-吡咯烷酮的用量摩尔比为1:1;
将1,4-丁二醇和二酸混合单体混合,加热至90℃,加入钛酸异丙酯,升温至190℃反应2h,升温至200℃反应1h,升温至230℃反应1h,然后在真空条件下,升温至245℃缩聚反应2h,反应结束后,加入氯仿混合,用甲醇沉淀后在过滤,在80℃条件下真空干燥至恒重,用氯仿溶解后浇筑在玻璃板上,待溶剂挥发后,得到保护膜。其中,1,4-丁二醇和二酸混合单体的质量比为2:1.5;二酸混合单体为丁二酸、对苯二甲酸和二羧基单体;其中,丁二酸、对苯二甲酸和二羧基单体的质量比3:11:1.1。
实施例2
制备保护膜:
将谷氨酸和2-吡咯烷酮加入质量分数为37%的甲醛水溶液中,设置温度为20℃,搅拌反应10h,反应结束后,将得到的反应液的减压浓缩除去溶剂,得到二羧基单体。其中,甲醛水溶液的,谷氨酸和2-吡咯烷酮的用量摩尔比为1:1;
将1,4-丁二醇和二酸混合单体混合,加热至100℃,加入钛酸异丙酯,升温至190℃反应2h,升温至200℃反应1h,升温至230℃反应1h,然后在真空条件下,升温至245℃缩聚反应2h,反应结束后,加入氯仿混合,用甲醇沉淀后在过滤,在80℃条件下真空干燥至恒重,用氯仿溶解后浇筑在玻璃板上,待溶剂挥发后,得到保护膜。其中,1,4-丁二醇和二酸混合单体的质量比为2:1.5;二酸混合单体为丁二酸、对苯二甲酸和二羧基单体;其中,丁二酸、对苯二甲酸和二羧基单体的质量比3:11:1。
对比例1
将1,4-丁二醇和二酸混合单体混合,加热至100℃,加入钛酸异丙酯,升温至190℃反应2h,升温至200℃反应1h,升温至230℃反应1h,然后在真空条件下,升温至245℃缩聚反应2h,反应结束后,加入氯仿混合,用甲醇沉淀后在过滤,在80℃条件下真空干燥至恒重,用氯仿溶解后浇筑在玻璃板上,待溶剂挥发后,得到保护膜。其中,1,4-丁二醇和二酸混合单体的质量比为2:1.5;二酸混合单体为丁二酸和对苯二甲酸;其中,丁二酸和对苯二甲酸的质量比3:11。
对实施例1-实施例2和对比例1制备的保护膜样品进行测试;
采用光学接触角测量仪测量复合膜的水接触角。每个样品进行5次试验,取平均值。生物降解测试方法:参考ISO14855的测试方法,以材料的60天堆肥后CO2释放量为降解性指标。
测试结果如下表1所示:
表1
实施例1 | 实施例2 | 对比例1 | |
水接触角/O | 73 | 73 | 80 |
CO2释放量 | 75% | 75% | 60% |
对制备的样品测试后,可知,本发明中实施例1-实施例2制备的保护膜亲水性强,耐污性好,且对其进行降解实验可知,相对于常规方法制备的膜材料,本发明制备的样品降解性好。
实施例3
制备镭射转移涂料:
步骤一、将丙交酯加热至110℃,真空脱水30min,在氮气保护条件下,N-甲基二乙醇胺和异辛酸亚锡,升温至140℃,反应8h,得到改性聚乳酸;其中,丙交酯、N-甲基二乙醇胺和异辛酸亚锡的用量质量比为20g:1g:20mg;
步骤二、将甲苯二异氰酸酯和改性聚乳酸混合,在温度为85℃条件下搅拌3h,得到预聚体,降温至60℃,加入1,4-丁二醇,搅拌30min,冷却至室温,加入乙酸和去离子水中和,搅拌30min,得到水性聚氨酯;其中,甲苯二异氰酸酯、改性聚乳酸和1,4-丁二醇的用量质量比为20:22:1。
步骤三、将水性聚氨酯、助溶剂、水、变色组合物和消泡剂按照质量比40:5:40:2:0.1混合得到镭射转移涂料。其中,变色组合物包括螺吡喃、甲基紫和三芳基甲烷;螺吡喃、甲基紫和三芳基甲烷的质量比为3:3:1;助溶剂为乙醇;消泡剂为有机硅硅氧烷类消泡剂。
对比例2
与实施例3相比,将N-甲基二乙醇胺换成1,4-丁二醇,其余原料及制备过程与实施例3保持相同。
对实施例3和对比例2制备的样品进行测试,采用AATCC100—2012标准的抗菌性能检测方法来评价其抑制微生物的作用效用,将镭射转移涂料干燥固化后剪成2cm×2cm的样品,在水中浸泡24h后取出,吸干膜表面的水分,进行称重,计算吸水率,测试结果如下表2所示:
表2
抗大肠杆菌率/% | 吸水率/% | |
实施例3 | 84 | 42.8 |
对比例2 | - | 41.1 |
从测试结果可知,实施例3制备的镭射转移涂料具有抗菌性,且吸水性好,且加入了改性聚乳酸作为原料具有一定的可降解性。
实施例4
一种可降解保温彩虹膜的制备方法,包括如下步骤:
第一步、将实施例3制备的镭射转移涂料涂布在PET薄膜上,涂布速度为18m/min,然后在165℃条件下烘干,烘干车速为22m/min;烘干后进行模压,得到转移镭射膜,镭射转移涂料的涂布量为0.6±0.1g/m2;
第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合条件为:温度180℃,压力0.4MPa,辊速20m/min,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与实施例1制备的保护膜进行贴合,得到可降解保温彩虹膜。胶粘剂为单组份无溶剂聚氨酯复膜胶。
实施例5
一种可降解保温彩虹膜的制备方法,包括如下步骤:
第一步、将实施例3制备的镭射转移涂料涂布在PET薄膜上,涂布速度为20m/min,然后在-170℃条件下烘干,烘干车速为25m/min;烘干后进行模压,得到转移镭射膜,镭射转移涂料的涂布量为0.6±0.1g/m2;
第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合条件为:温度185℃,压力0.4MPa,辊速22m/min,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与实施例1制备的保护膜进行贴合,得到可降解保温彩虹膜。胶粘剂为单组份无溶剂聚氨酯复膜胶。
实施例6
一种可降解保温彩虹膜的制备方法,包括如下步骤:
第一步、将实施例3制备的镭射转移涂料涂布在PET薄膜上,涂布速度为20m/min,然后在170℃条件下烘干,烘干车速为25m/min;烘干后进行模压,得到转移镭射膜,镭射转移涂料的涂布量为0.6±0.1g/m2;
第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合条件为:温度190℃,压力0.4MPa,辊速22m/min,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与实施例2制备的保护膜进行贴合,得到可降解保温彩虹膜。胶粘剂为单组份无溶剂聚氨酯复膜胶。
在说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。以上内容仅仅是对本发明所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (5)
1.一种可降解保温彩虹膜,包括镭射层、铝箔纸和保护膜,所述镭射层贴附于铝箔纸上,所述保护膜贴附于镭射层表面;其特征在于,所述保护膜通过如下步骤制备:
将1,4-丁二醇和二酸混合单体混合,加热至90-100℃,加入催化剂升温至190℃反应2h,升温至200℃反应1h,升温至230℃反应1h,然后在真空条件下,升温至245℃缩聚反应2h,反应结束后,加入氯仿混合,用甲醇沉淀后在过滤,在80℃条件下真空干燥至恒重,用氯仿溶解后浇筑在玻璃板上,待溶剂挥发后,得到保护膜;二酸混合单体为丁二酸、对苯二甲酸和二羧基单体混合得到;所述二羧基单体通过如下步骤制备:
将氨基酸和2-吡咯烷酮加入甲醛水溶液中,设置温度为20℃,搅拌反应9-10h,反应结束后,将得到的反应液的减压浓缩除去溶剂,得到二羧基单体;所述氨基酸和2-吡咯烷酮的用量摩尔比为1:1;氨基酸为天冬氨酸和谷氨酸中的一种;
镭射层由转移镭射膜与铝箔纸热压复合后形成,转移镭射膜由镭射转移涂料烘干后模压形成,所述镭射转移涂料为水性聚氨酯、助溶剂、水、变色组合物和消泡剂按照质量比为40:5:40:2:0.1混合后得到;
所述变色组合物为螺吡喃、甲基紫和三芳基甲烷按照质量比为3:3:1混合得到;助溶剂为乙醇、异丙醇中的一种;消泡剂为有机硅硅氧烷类消泡剂;
所述水性聚氨酯通过如下步骤制备:
步骤一、将丙交酯加热至110℃,真空脱水30min,在氮气保护条件下,加入N-甲基二乙醇胺和异辛酸亚锡,升温至140℃,反应8h,得到改性聚乳酸;步骤二、将甲苯二异氰酸酯和改性聚乳酸混合,在温度为85℃条件下搅拌3h,得到预聚体,降温至60℃,加入1,4-丁二醇,搅拌30min,冷却至室温,加入乙酸和去离子水中和,搅拌30min,得到水性聚氨酯。
2.根据权利要求1所述的一种可降解保温彩虹膜,其特征在于,所述催化剂为钛酸异丙酯,1,4-丁二醇和二酸混合单体的质量比为2:1.5;丁二酸、对苯二甲酸和二羧基单体的质量比3:11:1-1.1。
3.根据权利要求1所述的一种可降解保温彩虹膜的制备方法,其特征在于,包括如下步骤:
第一步、将镭射转移涂料涂布在PET薄膜上,然后在165-170℃条件下烘干,烘干后进行模压,得到转移镭射膜;
第二步,将在铝箔纸表面涂布胶粘剂,将转移镭射膜与铝箔纸贴合,进行热压复合,热压复合后将PET薄膜揭去,形成镭射层,在镭射层表面涂覆胶粘剂,然后与保护膜进行贴合,得到可降解保温彩虹膜。
4.根据权利要求3所述的一种可降解保温彩虹膜的制备方法,其特征在于,所述热压复合的条件为:温度180-190℃,压力0.4MPa,辊速20-22m/min。
5.根据权利要求3所述的一种可降解保温彩虹膜的制备方法,其特征在于,镭射转移涂料的涂布量为0.6±0.1g/m2。
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