CN108638680A - 一种改进型pet烫金膜 - Google Patents
一种改进型pet烫金膜 Download PDFInfo
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Abstract
本发明公开了一种改进型PET烫金膜,包括依次设置的PET基膜层、水氧复合阻隔层、EVA胶粘层和烫金层;所述PET基膜层的上表面涂覆有PVOH涂层,所述PVOH涂层的上表面设置有镀银铜粉复合导电涂层,所述烫金层的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层。本发明设置的水氧复合阻隔层中,设置了乙烯‑乙烯醇共聚物层和聚乙烯胺‑聚乙烯醇共聚物层,由于上述聚合物是将乙烯聚合物的加工性和乙烯醇聚合物的阻隔作用相结合,使得乙烯‑乙烯醇共聚物不仅表现出极好的加工性能,而且也对气体、气味、香料、溶剂等呈现出优异的阻断作用。
Description
技术领域
本发明涉及一种改进型PET烫金膜。
背景技术
PET膜又名耐高温聚酯薄膜。它具有优异的物理性能、化学性能及尺寸稳定性、透明性、可回收性,可广泛的应用于磁记录、感光材料、电子、电气绝缘、工业用膜、包装装饰、屏幕保护、光学级镜面表面保护等领域。
其中,烫金膜又称电化铝(电化铝的叫法在印刷行业用得更多),是一种在薄膜片基上经涂料和真空蒸镀复加一层金属箔而制成的烫印材料。
虽然PET本身对于水、氧气以及二氧化碳气体以及具有较高的阻隔性能,但是对于一些对阻隔性有特殊要求的场合,如番茄制品、对微量氧气敏感的熟产品等等,仅用PET作为包装材料就不能满足要求了。作为包装材料,可热封性是一种基本的性能,PET由于分子链本身是刚性的,加之生产过程中的热定型使得其结晶度高而导致熔点比较高,因此,PET薄膜自身不能热封结合,很大程度上限制了包装材料的使用。
现有的PET烫金膜中,由PET烫金膜受到摩擦产生静电现象,常会引起包装材料的表面粘灰、受到污染,影响包装效果和美观。因此,需要对PET烫金膜进行抗静电处理。
另外,还要求所使用的PET烫金膜具有更高的阻气防潮等阻隔性能,以延长PET烫金膜以及其保护的电子产品的寿命和保质期。
发明内容
本发明目的是针对现有技术存在的缺陷提供一种改进型PET烫金膜。
本发明为实现上述目的,采用如下技术方案:一种改进型PET烫金膜,其特征在于:包括依次设置的PET基膜层、水氧复合阻隔层、EVA胶粘层和烫金层;所述PET基膜层的上表面涂覆有PVOH涂层,所述PVOH涂层的上表面设置有镀银铜粉复合导电涂层,所述烫金层的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层;
其中,所述水氧复合阻隔层包括设置在上部上层的氮化硼纳米层,设置在中间上层的乙烯-乙烯醇共聚物层,设置在中间中层的水溶性聚合物层,设置在中间下层的聚乙烯胺-聚乙烯醇共聚物层,以及设置在下部下层的石墨烯纳米层;其中,所述氮化硼纳米层的厚度为100-180nm,所述乙烯-乙烯醇共聚物层的厚度为50-70nm,所述水溶性聚合物层的厚度为50-80nm,所述聚乙烯胺-聚乙烯醇共聚物层的厚度为40-60nm,所述石墨烯纳米层的厚度为150-180nm;
其中,所述氮化硼纳米层中的氮化硼纳米材料制备方法是:将一维硼酸盐前驱物在含氮气氛中加热至2200~2500℃并保温反应,之后在保护气体中降温至零下十度,获得粗产物,再对所述粗产物进行后处理,获得所示氮化硼纳米材料;
其中,所述聚乙烯胺-聚乙烯醇共聚物层由如下物质共聚合而形成:(a)60到2mol%的N-乙烯基甲酰胺和(b)2到66mol%的一种或多种乙烯基C1-C10烷基酯,然后从共聚单元(a)水解50到70mol%的甲酰基来形成氨基,从共聚单元(b)水解到60到90mol%的C1-C10烷基酯基来形成羟基,其中共聚物具有单一的组成分布,其由凝胶渗透梯度洗脱色谱分析中的基本上单一峰证明;
其中,所述乙烯-乙烯醇共聚物层中的乙烯-乙烯醇共聚物以溶剂、醋酸乙烯酯单体、引发剂及乙烯单体为原料,经包括釜内置换、初始加料、聚合反应、吹出残单及皂化步骤制备乙烯-乙烯醇共聚物;在进行釜内置换之前还进行原料除氧步骤,所述原料除氧是将醋酸乙烯单体、溶剂和引发剂加入混合槽中搅拌,边搅拌边通入氮气混合均匀,进行置换,使得体系内氧含量小于3.0×10-3mol/L;
其中,所述石墨烯纳米层中的石墨烯纳米材料的制备方法是:(1)将可膨胀石墨放置在坩埚内进行微波处理后加入到分散剂中进行超声处理得到浆料,然后对浆料进行离心处理,浆料分为上下两层,去掉上层清液,制备得到氧化石墨烯;(2)将对氨基苯磺酸分散到酸性溶液中得到混合溶液,将混合溶液放入到冰水浴中搅拌,然后将亚硝酸水溶液滴入混合溶液中,得到白色沉淀,过滤清洗得到对氨基苯磺酸重氮盐;(3)将氧化石墨烯与对氨基苯磺酸重氮盐混合,在冰水浴下搅拌清洗过滤,得到磺酸基修饰的氧化石墨烯浆料;然后将磺酸基修饰的氧化石墨烯浆料烘烤直至浆液干燥;最后对磺酸基修饰的氧化石墨烯进行粉碎处理,得到磺酸基修饰的氧化石墨烯。
进一步的:所述镀银铜粉复合导电涂层的上表面设置有氧化锑锡粒子和碳粒子复合层。
进一步的:所述氧化锑锡粒子和碳粒子复合层中的氧化锡粒子的粒径在10-20nm之间。
本发明的有益效果:本发明PET烫金膜中由于在上PET基膜层的上表面设置了PVOH涂层,可以大大提高烫金膜的整体强度。本申请的水氧复合阻隔层中,设置了乙烯-乙烯醇共聚物层和聚乙烯胺-聚乙烯醇共聚物层,由于上述聚合物是将乙烯聚合物的加工性和乙烯醇聚合物的阻隔作用相结合,使得乙烯-乙烯醇共聚物不仅表现出极好的加工性能,而且也对气体、气味、香料、溶剂等呈现出优异的阻断作用。由于在PVOH涂层上设置了镀银铜粉复合导电涂层,可以很好的消除PET烫金膜上的静电,在用于产品包装时更容易操作,能够防止静电累积导致的PET烫金膜表面污染,产生灰尘等,提高产品的包装效果和美观。需要注意的是,将PVOH涂层设置在PET基膜层和复合导电涂层之间,可以避免PVOH涂层直接暴露在空气中而受到潮湿,避免PVOH的氧气阻隔性降低。在烫金层的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层,增加了烫金膜表面的张力,热封时,将薄膜的可热封涂层相对设置,直接热封即可,自粘性好,成本低。
附图说明
图1为本发明的结构示意图;
图2为本发明的水氧复合阻隔层结构示意图。
具体实施方式
图1所示,涉及一种改进型PET烫金膜,包括依次设置的PET基膜层1、水氧复合阻隔层2、EVA胶粘层3和烫金层4;所述PET基膜层1的上表面涂覆有PVOH涂层11,所述PVOH涂层11的上表面设置有镀银铜粉复合导电涂层12,所述烫金层4的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层41。
本发明PET烫金膜中由于在上PET基膜层的上表面设置了PVOH涂层,可以大大提高烫金膜的整体强度。
图2中,所述水氧复合阻隔层2包括设置在上部上层的氮化硼纳米层21,设置在中间上层的乙烯-乙烯醇共聚物层22,设置在中间中层的水溶性聚合物层23,设置在中间下层的聚乙烯胺-聚乙烯醇共聚物层24,以及设置在下部下层的石墨烯纳米层25;其中,所述氮化硼纳米层的厚度为100-180nm,所述乙烯-乙烯醇共聚物层的厚度为50-70nm,所述水溶性聚合物层的厚度为50-80nm,所述聚乙烯胺-聚乙烯醇共聚物层的厚度为40-60nm,所述石墨烯纳米层的厚度为150-180nm。
其中,所述氮化硼纳米层中的氮化硼纳米材料制备方法是:将一维硼酸盐前驱物在含氮气氛中加热至2200~2500℃并保温反应,之后在保护气体中降温至零下十度,获得粗产物,再对所述粗产物进行后处理,获得所示氮化硼纳米材料;
其中,所述聚乙烯胺-聚乙烯醇共聚物层由如下物质共聚合而形成:(a)60到2mol%的N-乙烯基甲酰胺和(b)2到66mol%的一种或多种乙烯基C1-C10烷基酯,然后从共聚单元(a)水解50到70mol%的甲酰基来形成氨基,从共聚单元(b)水解到60到90mol%的C1-C10烷基酯基来形成羟基,其中共聚物具有单一的组成分布,其由凝胶渗透梯度洗脱色谱分析中的基本上单一峰证明;
其中,所述乙烯-乙烯醇共聚物层中的乙烯-乙烯醇共聚物以溶剂、醋酸乙烯酯单体、引发剂及乙烯单体为原料,经包括釜内置换、初始加料、聚合反应、吹出残单及皂化步骤制备乙烯-乙烯醇共聚物;在进行釜内置换之前还进行原料除氧步骤,所述原料除氧是将醋酸乙烯单体、溶剂和引发剂加入混合槽中搅拌,边搅拌边通入氮气混合均匀,进行置换,使得体系内氧含量小于3.0×10-3mol/L;
其中,所述石墨烯纳米层中的石墨烯纳米材料的制备方法是:(1)将可膨胀石墨放置在坩埚内进行微波处理后加入到分散剂中进行超声处理得到浆料,然后对浆料进行离心处理,浆料分为上下两层,去掉上层清液,制备得到氧化石墨烯;(2)将对氨基苯磺酸分散到酸性溶液中得到混合溶液,将混合溶液放入到冰水浴中搅拌,然后将亚硝酸水溶液滴入混合溶液中,得到白色沉淀,过滤清洗得到对氨基苯磺酸重氮盐;(3)将氧化石墨烯与对氨基苯磺酸重氮盐混合,在冰水浴下搅拌清洗过滤,得到磺酸基修饰的氧化石墨烯浆料;然后将磺酸基修饰的氧化石墨烯浆料烘烤直至浆液干燥;最后对磺酸基修饰的氧化石墨烯进行粉碎处理,得到磺酸基修饰的氧化石墨烯。
本申请的阻隔层中,利用石墨烯纳米层和氮化硼纳米层的不可透过性及其合规的纳米尺度,对制得PET烫金膜具有对气体高的阻隔性能和PET烫金膜异的机械性能,可显著地提高PET烫金膜的阻隔性能,大大提高了电子产品的保质期。
另一个关键技术在于,本申请的水氧复合阻隔层2中,设置了乙烯-乙烯醇共聚物层和聚乙烯胺-聚乙烯醇共聚物层,由于上述聚合物是将乙烯聚合物的加工性和乙烯醇聚合物的阻隔作用相结合,使得乙烯-乙烯醇共聚物不仅表现出极好的加工性能,而且也对气体、气味、香料、溶剂等呈现出优异的阻断作用。并且,在已知可利用的聚合物中,聚乙烯醇(PVOH)的气体渗透率最低。目前,乙烯-乙烯醇共聚物(EVOH)共聚物是目前现有工艺中是这样制取的:首先是乙烯和醋酸乙烯共聚,然后是水解该共聚物得到乙烯-乙烯醇。因此,仍然保留了高度的阻隔作用,而且在防潮和加工性能方面有明显改善。
从性质上来说,EVOH共聚物是高度结晶体,它的性质主要取决于其共聚单体的相对浓度。一般地说,当乙烯含量增加时,气体阻隔性能下降,防潮性能改进,且树脂更易于加工。
另外,由于在PVOH涂层上设置了镀银铜粉复合导电涂层,可以很好的消除PET烫金膜上的静电,在用于产品包装时更容易操作,能够防止静电累积导致的PET烫金膜表面污染,产生灰尘等,提高产品的包装效果和美观。需要注意的是,将PVOH涂层设置在PET基膜层和复合导电涂层之间,可以避免PVOH涂层直接暴露在空气中而受到潮湿,避免PVOH的氧气阻隔性降低。在烫金层的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层,增加了烫金膜表面的张力,热封时,将薄膜的可热封涂层相对设置,直接热封即可,自粘性好,成本低。其中,为了达到最佳性能,所述氧化锑锡粒子和碳粒子复合层中的氧化锡粒子的粒径在10-20nm之间。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,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 (3)
1.一种改进型PET烫金膜,其特征在于:包括依次设置的PET基膜层(1)、水氧复合阻隔层(2)、EVA胶粘层(3)和烫金层(4);所述PET基膜层(1)的上表面涂覆有PVOH涂层(11),所述PVOH涂层(11)的上表面设置有镀银铜粉复合导电涂层(12),所述烫金层(4)的下表面设有由热塑弹性烯烃聚合物制成的可热封涂层(41);
其中,所述水氧复合阻隔层(2)包括设置在上部上层的氮化硼纳米层,设置在中间上层的乙烯-乙烯醇共聚物层,设置在中间中层的水溶性聚合物层,设置在中间下层的聚乙烯胺-聚乙烯醇共聚物层,以及设置在下部下层的石墨烯纳米层;其中,所述氮化硼纳米层的厚度为100-180nm,所述乙烯-乙烯醇共聚物层的厚度为50-70nm,所述水溶性聚合物层的厚度为50-80nm,所述聚乙烯胺-聚乙烯醇共聚物层的厚度为40-60nm,所述石墨烯纳米层的厚度为150-180nm;
其中,所述氮化硼纳米层中的氮化硼纳米材料制备方法是:将一维硼酸盐前驱物在含氮气氛中加热至2200~2500℃并保温反应,之后在保护气体中降温至零下十度,获得粗产物,再对所述粗产物进行后处理,获得所示氮化硼纳米材料;
其中,所述聚乙烯胺-聚乙烯醇共聚物层由如下物质共聚合而形成:(a)60到2mol%的N-乙烯基甲酰胺和(b)2到66mol%的一种或多种乙烯基C1-C10烷基酯,然后从共聚单元(a)水解50到70mol%的甲酰基来形成氨基,从共聚单元(b)水解到60到90mol%的C1-C10烷基酯基来形成羟基,其中共聚物具有单一的组成分布,其由凝胶渗透梯度洗脱色谱分析中的基本上单一峰证明;
其中,所述乙烯-乙烯醇共聚物层中的乙烯-乙烯醇共聚物以溶剂、醋酸乙烯酯单体、引发剂及乙烯单体为原料,经包括釜内置换、初始加料、聚合反应、吹出残单及皂化步骤制备乙烯-乙烯醇共聚物;在进行釜内置换之前还进行原料除氧步骤,所述原料除氧是将醋酸乙烯单体、溶剂和引发剂加入混合槽中搅拌,边搅拌边通入氮气混合均匀,进行置换,使得体系内氧含量小于3.0×10-3mol/L;
其中,所述石墨烯纳米层中的石墨烯纳米材料的制备方法是:(1)将可膨胀石墨放置在坩埚内进行微波处理后加入到分散剂中进行超声处理得到浆料,然后对浆料进行离心处理,浆料分为上下两层,去掉上层清液,制备得到氧化石墨烯;(2)将对氨基苯磺酸分散到酸性溶液中得到混合溶液,将混合溶液放入到冰水浴中搅拌,然后将亚硝酸水溶液滴入混合溶液中,得到白色沉淀,过滤清洗得到对氨基苯磺酸重氮盐;(3)将氧化石墨烯与对氨基苯磺酸重氮盐混合,在冰水浴下搅拌清洗过滤,得到磺酸基修饰的氧化石墨烯浆料;然后将磺酸基修饰的氧化石墨烯浆料烘烤直至浆液干燥;最后对磺酸基修饰的氧化石墨烯进行粉碎处理,得到磺酸基修饰的氧化石墨烯。
2.如权利要求1所述的一种改进型PET烫金膜,其特征在于:所述镀银铜粉复合导电涂层(12)的上表面设置有氧化锑锡粒子和碳粒子复合层。
3.如权利要求2所述的一种改进型PET烫金膜,其特征在于:所述氧化锑锡粒子和碳粒子复合层中的氧化锡粒子的粒径在10-20nm之间。
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