CN114103357B - 一种高阻隔材料复合膜及其无溶剂复合工艺 - Google Patents
一种高阻隔材料复合膜及其无溶剂复合工艺 Download PDFInfo
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Abstract
本发明公开了一种高阻隔材料复合膜及其无溶剂复合工艺,一种高阻隔材料复合膜的无溶剂复合工艺包括以下步骤:A、将外层和中间层放置在无溶剂复合机;B、将加热后的无溶剂胶水一涂布在外层表面;C、将涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h;D、通过无溶剂复合机将固化后的外层和中间层进行复合并收卷;E、将收卷后的外层和中间层进行熟化,得到高阻隔材料复合膜。本技术方案提出的一种高阻隔材料复合膜及其无溶剂复合工艺,步骤简单,操作方便,在确保高阻隔材料复合膜的外层与中间层之间具有一定剥离强度的前提下,有效消除高阻隔材料复合膜的外层与中间层之间出现的白点和气泡。
Description
技术领域
本发明涉及多层复合膜结构的复合工艺领域,尤其涉及一种高阻隔材料复合膜及其无溶剂复合工艺。
背景技术
软包装因具有阻隔性能好、重量轻、耐冲击、成本低、方便使用、包装设计选择余地大等优点,极大地延长了商品的保质期,方便流通、促进销售、提高了商品附加值,强有力地推动了食品、日化及医药等行业的进步,是世界经济发展中必不可少的一部分。当前在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。在我国循环经济建设的大背景下,开发绿色包装对食品安全的意义重大,对减少社会资源的浪费也具有积极的意义。
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技术,以满足市场对新型、高档复合软包装功能材料的需求。而无溶剂复合膜的研究正好满足国内包装绿色制造的需求。
无溶剂复合工艺是一种新型的复合工艺,具有环保、安全、成本节约等诸多优点,但由于无溶剂胶水在复合后的初粘力几乎为零,因此无溶剂胶水在复合过程中的控制难度较大,尤其是对于多层复合膜结构中的高阻隔材料外层与中间层的复合,极容易令复合膜产生外观与剥离强度等的问题。
发明内容
本发明的目的在于提出一种高阻隔材料复合膜的无溶剂复合工艺,步骤简单,操作方便,在确保高阻隔材料复合膜的外层与中间层之间具有一定剥离强度的前提下,有效消除高阻隔材料复合膜的外层与中间层之间出现的白点和气泡,解决现有无溶剂复合工艺中高阻隔材料复合膜的外层与中间层的复合极容易产生外观与剥离强度的技术问题。
本发明的另一个目的在于提出一种高阻隔材料复合膜,其外观平整,外层白点气泡现象得到有效消除,且外层剥离强度较大,具有耐高温性能。
为达此目的,本发明采用以下技术方案:
一种高阻隔材料复合膜的无溶剂复合工艺,包括以下步骤:
A、将外层和中间层放置在无溶剂复合机;
B、将加热后的无溶剂胶水一涂布在外层表面;其中,所述无溶剂胶水一为双组份聚氨酯胶黏剂,且所述无溶剂胶水一的粘度范围为3500~5000mPa.s;
C、将涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h;
D、通过无溶剂复合机将固化后的外层和中间层进行复合并收卷;
E、将收卷后的外层和中间层进行熟化,得到高阻隔材料复合膜。
优选的,步骤B中,加热后的所述无溶剂胶水一的温度为70~75℃。
优选的,步骤C中,将涂布无溶剂胶水一后的外层在20~22℃的温度和50~60%的湿度下固化2~3h。
优选的,步骤E中,将收卷后的外层和中间层在50~60℃的温度下熟化70~75h。
优选的,步骤A具体还包括以下步骤:将循环冷却水输入至无溶剂复合机中的复合压辊和冷却导辊。
优选的,所述中间层包括过渡中间层和多个复合中间层,步骤D具体包括以下步骤:
D1、通过无溶剂复合机将固化后的外层和过渡中间层进行复合;
D2、将无溶剂胶水二涂布在过渡中间层表面,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合;
D3、将无溶剂胶水二涂布在所述复合中间层表面,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合;
D4、重复步骤D3,直至所有复合中间层均已复合后收卷。
7.根据权利要求6所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于:步骤D2中,将加热后的无溶剂胶水二涂布在过渡中间层表面,将涂布有无溶剂胶水二的过渡中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合。
优选的,步骤D3中,将加热后的无溶剂胶水二涂布在所述复合中间层表面,将涂布有无溶剂胶水二的所述复合中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合。
一种高阻隔材料复合膜,使用上述的高阻隔材料复合膜的无溶剂复合工艺制备而成。
本申请实施例提供的技术方案可以包括以下有益效果:
1、使用粘度范围为3500~5000mPa.s的双组份聚氨酯胶黏剂对外层和中间层进行复合,有利于令高阻隔材料复合膜符合产品所需要剥离强度要求。
2、由于无溶剂胶水一的粘度较高,为了确保胶水在外层表面上的有效附着,首先将无溶剂胶水一进行加热,从而可以提升其流动性,便于胶水在涂布过程中具有较好的流平性,且有利于胶水的均匀涂布。
3、为了提升无溶剂胶水一的初粘力,令涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h,使无溶剂胶水一迅速降温定性,有利于提升无溶剂胶水一的交联度,从而提升其初粘力的剥离强度。利用初粘力上升后的无溶剂胶水一将外层和中间层进行复合,能有效降低无溶剂胶水在复合过程中的控制难度,便于无溶剂胶水一与中间层之间的有效复合,进一步降低高阻隔材料复合膜中间层与无溶剂胶水一之间出现外观问题的可能,步骤简单,操作方便,有效地解决了现有无溶剂复合工艺中高阻隔材料复合膜的外层与中间层的复合极容易产生外观与剥离强度的技术问题。
具体实施方式
一种高阻隔材料复合膜的无溶剂复合工艺,包括以下步骤:
A、将外层和中间层放置在无溶剂复合机;
B、将加热后的无溶剂胶水一涂布在外层表面;其中,所述无溶剂胶水一为双组份聚氨酯胶黏剂,且所述无溶剂胶水一的粘度范围为3500~5000mPa.s;
C、将涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h;
D、通过无溶剂复合机将固化后的外层和中间层进行复合并收卷;
E、将收卷后的外层和中间层进行熟化,得到高阻隔材料复合膜。
普通材料复合膜结构,即普通食品包装袋,如塑塑结构、普通塑铝结构和镀铝结构等,其对剥离强度的要求不高,因此,使用一般的常规无溶剂胶水则可以达到其所需要的剥离强度要求,且上述常规无溶剂胶水的粘度较低,流动性较好,在复合时很少会出现白点、气泡等现象。
而高阻隔材料复合膜指的是可以耐受高温蒸煮、高温灭菌,耐乙基麦芽酚、耐辣油等具有高阻隔性能的食品包装袋,例如PET印刷膜和铝箔的双层结构复合膜,PET印刷膜、铝箔和聚丙烯膜的三层结构复合膜,PET印刷膜、铝箔、尼龙膜和聚丙烯膜的四层结构复合膜等。高阻隔材料复合膜对剥离强度的要求较高,因此,需要使用高粘度的特定无溶剂胶水进行复合,才能达到高要求的剥离强度,同时,由于上述特定无溶剂胶水的粘度较高,流动性较差,所述,利用上述高粘度的特定无溶剂胶水对高阻隔材料复合膜进行复合时,极容易出现白点、气泡等现象,引起复合膜的外观问题。由于利用无溶剂胶水对高阻隔材料复合膜进行复合时,极容易出现白点、气泡等现象,因此,现有复合膜的生产厂家一般只使用溶剂型胶水进行高阻隔材料外层结构的复合。
因了,为了确保高阻隔材料复合膜的外层与中间层之间具有一定剥离强度的前提下,有效消除高阻隔材料复合膜的外层与中间层之间出现的白点和气泡,本技术方案提出了一种高阻隔材料复合膜的无溶剂复合工艺,包括以下步骤:
A、将外层和中间层放置在无溶剂复合机;
B、将加热后的无溶剂胶水一涂布在外层表面;其中,所述无溶剂胶水一为双组份聚氨酯胶黏剂,且所述无溶剂胶水一的粘度范围为3500~5000mPa.s;为了令高阻隔材料复合膜符合产品所需要剥离强度要求,本方案使用粘度范围为3500~5000mPa.s的双组份聚氨酯胶黏剂对外层和中间层进行复合;由于本方案采用的无溶剂胶水一的粘度较高,为了确保胶水在外层表面上的有效附着,本方案首先将无溶剂胶水一进行加热,从而可以提升其流动性,便于胶水在涂布过程中具有较好的流平性,且有利于胶水的均匀涂布。
C、将涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h;胶水涂布完成后,这时胶水在外层表面进行固化反应,为了提升无溶剂胶水一的初粘力,本方案令涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h,使无溶剂胶水一迅速降温定性,有利于提升无溶剂胶水一的交联度,从而提升其初粘力的剥离强度。若步骤C的固化温度太低,固化过程太慢,不利于无溶剂胶水一的反应交联及初粘力的有效上升;若步骤C的固化温度太高,无溶剂胶水一的固化速度过快,未能使无溶剂胶水一快速定性,同样不利于无溶剂胶水一初粘力的有效上升。
D、通过无溶剂复合机将固化后的外层和中间层进行复合并收卷;E、将收卷后的外层和中间层进行熟化,得到高阻隔材料复合膜。本方案利用初粘力上升后的无溶剂胶水一将外层和中间层进行复合,能有效降低无溶剂胶水在复合过程中的控制难度,便于无溶剂胶水一与中间层之间的有效复合,进一步降低高阻隔材料复合膜中间层与无溶剂胶水一之间出现外观问题的可能,步骤简单,操作方便,有效地解决了现有无溶剂复合工艺中高阻隔材料复合膜的外层与中间层的复合极容易产生外观与剥离强度的技术问题。
需要说明的是,本方案中的外层指的是高阻隔材料复合膜中最外层层次结构,可以为PET印刷膜等,中间层指的是与最外层进行直接复合的层次结构,可以为铝箔等。本方案使用的无溶剂复合机为复合胶膜技术领域常规的无溶剂复合机,无溶剂胶水一的低温固化过程可以在无溶剂复合机安装常规的冷却装置实现,但不限制于此。
更进一步说明,步骤B中,加热后的所述无溶剂胶水一的温度为70~75℃。
在本技术方案的一个实施例中,将加热至70~75℃的无溶剂胶水一涂布在外层表面,更有利于保证无溶剂胶水一的高温流动性,降低高阻隔材料复合膜外层与无溶剂胶水一之间出现外观问题的可能。
更进一步说明,步骤C中,将涂布无溶剂胶水一后的外层在20~22℃的温度和50~60%的湿度下固化2~3h。
在本技术方案的一个优选实施例中,还对低温固化过程中的湿度进行了进一步的限定,若低温固化过程中的湿度过低,则不利于固化过程的稳定进行,若低温固化过程中的湿度过高,那么双组份聚氨酯胶黏剂在双组份(即主剂和固化剂)进行混合时,空气中的水分可能会消耗少量的固化剂组份生成缩脲,从而会影响复合膜的剥离强度。
更进一步说明,步骤E中,将收卷后的外层和中间层在50~60℃的温度下熟化70~75h。
在本技术方案的一个实施例中,将收卷后的外层和中间层在50~60℃的温度下熟化70~75h,令复合膜进一步固化,使复合膜不会产生收缩和皱纹,进一步提高了粘合效果。
更进一步说明,步骤A具体还包括以下步骤:将循环冷却水输入至无溶剂复合机中的复合压辊和冷却导辊。
在本技术方案的一个实施例中,可以在步骤A中将循环冷却水输入至无溶剂复合机中的复合压辊和冷却导辊,有利于对无溶剂胶水一进行冷却降温,便于提升无溶剂胶水一的初始粘合力。
更进一步说明,所述中间层包括过渡中间层和多个复合中间层,步骤D具体包括以下步骤:
D1、通过无溶剂复合机将固化后的外层和过渡中间层进行复合;
D2、将无溶剂胶水二涂布在过渡中间层表面,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合;
D3、将无溶剂胶水二涂布在所述复合中间层表面,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合;
D4、重复步骤D3,直至所有复合中间层均已复合后收卷。
在本技术方案的一个实施例中,当高阻隔材料复合膜具有两层以上的层次结构时,中间层包括过渡中间层和多个复合中间层,由于复合膜的外观问题主要由复合膜的外层结构引起,即由复合膜的外层、无溶剂胶水一和与外层进行复合的中间层(即本实施例中的过渡中间层)引起。因此,复合膜中外层结构之外的层次结构可进行快速连续涂布,便于提升高阻隔材料复合膜的生产效率。
需要说明的是,本实施例中的无溶剂胶水二的种类可与无溶剂胶水一的种类一致,也可根据实际需求选取合适的无溶剂胶水,在此不作限定。
更进一步说明,步骤D2中,将加热后的无溶剂胶水二涂布在过渡中间层表面,将涂布有无溶剂胶水二的过渡中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合。
更进一步说明,步骤D3中,将加热后的无溶剂胶水二涂布在所述复合中间层表面,将涂布有无溶剂胶水二的所述复合中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合。
在本技术方案的一个优选实施例中,在进行外层结构之外的层次结构的复合过程时,也可利用低温固化的方法令无溶剂胶水二初粘力上升,更有利于降低无溶剂胶水在复合过程中的控制难度,更进一步地提升高阻隔材料复合膜外观和剥离强度。
一种高阻隔材料复合膜,使用上述高阻隔材料复合膜的无溶剂复合工艺制备而成。
本技术方案还提出了一种使用上述高阻隔材料复合膜的无溶剂复合工艺制备而成的高阻隔材料复合膜,其外观平整,外层白点气泡现象得到有效消除,且外层剥离强度较大,具有耐高温性能。
下面通过具体实施方式来进一步说明本发明的技术方案。
实施例1-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将加热至70℃的双组份聚氨酯胶黏剂涂布在PET印刷膜表面;其中,双组份聚氨酯胶黏剂的粘度为3500mPa.s;
C、将涂布有双组份聚氨酯胶黏剂的PET印刷膜在20℃的温度和50%的湿度下固化2h;
D、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合并收卷;
E、将收卷后的PET印刷膜和铝箔在50℃的温度下熟化70h,得到高阻隔材料复合膜。
实施例2-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将加热至73℃的双组份聚氨酯胶黏剂涂布在PET印刷膜表面;其中,双组份聚氨酯胶黏剂的粘度为4000mPa.s;
C、将涂布有双组份聚氨酯胶黏剂的PET印刷膜在21℃的温度和55%的湿度下固化2.5h;
D、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合并收卷;
E、将收卷后的PET印刷膜和铝箔在55℃的温度下熟化72h,得到高阻隔材料复合膜。
实施例3-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将加热至75℃的双组份聚氨酯胶黏剂涂布在PET印刷膜表面;其中,双组份聚氨酯胶黏剂的粘度为5000mPa.s;
C、将涂布有双组份聚氨酯胶黏剂的PET印刷膜在22℃的温度和60%的湿度下固化3h;
D、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合并收卷;
E、将收卷后的PET印刷膜和铝箔在60℃的温度下熟化75h,得到高阻隔材料复合膜。
实施例4-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将加热至75℃的双组份聚氨酯胶黏剂涂布在PET印刷膜表面;其中,双组份聚氨酯胶黏剂的粘度为5000mPa.s;
C、将涂布有双组份聚氨酯胶黏剂的PET印刷膜在22℃的温度和60%的湿度下固化3h;
D、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合;
将加热至75℃、粘度为5000mPa.s的双组份聚氨酯胶黏剂涂布在铝箔表面,将涂布有双组份聚氨酯胶黏剂的铝箔在22℃的温度和60%的湿度下固化3h,通过无溶剂复合机将聚丙烯膜和铝箔进行复合并收卷;
E、将收卷后的PET印刷膜、铝箔和聚丙烯膜在60℃的温度下熟化75h,得到高阻隔材料复合膜。
实施例5-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将加热至75℃的双组份聚氨酯胶黏剂涂布在PET印刷膜表面;其中,双组份聚氨酯胶黏剂的粘度为5000mPa.s;
C、将涂布有双组份聚氨酯胶黏剂的PET印刷膜在22℃的温度和60%的湿度下固化3h;
D、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合;
将加热至75℃、粘度为5000mPa.s的双组份聚氨酯胶黏剂涂布在铝箔表面,将涂布有双组份聚氨酯胶黏剂的铝箔在22℃的温度和60%的湿度下固化3h,通过无溶剂复合机将尼龙膜和铝箔进行复合;
将加热至75℃、粘度为5000mPa.s的双组份聚氨酯胶黏剂涂布在尼龙膜表面,将涂布有双组份聚氨酯胶黏剂的尼龙膜在22℃的温度和60%的湿度下固化3h,通过无溶剂复合机将聚丙烯膜和尼龙膜进行复合;
E、将收卷后的PET印刷膜、铝箔、尼龙膜和聚丙烯膜在60℃的温度下熟化75h,得到高阻隔材料复合膜。
对比例1-一种高阻隔材料复合膜的无溶剂复合工艺
A、将PET印刷膜和铝箔放置在无溶剂复合机;
B、将双组份聚氨酯胶黏剂涂布在PET印刷膜表面;
C、通过无溶剂复合机将固化后的PET印刷膜和铝箔进行复合并收卷;
D、将收卷后的PET印刷膜和铝箔在55℃的温度下熟化72h,得到高阻隔材料复合膜。
分别取上述实施例和对比例中经过一次复合的PET印刷膜和铝箔复合膜,进行复合胶膜技术领域常规的初粘力测试;观察上述实施例和对比例中高阻隔材料复合膜成品的外观,并对复合膜进行剥离强度测试,然后将上述成品进行高温处理,再对高温处理后的复合膜进行剥离强度测试,其结果如下表所示。
各测试项目的具体实验步骤如下:
初粘力测试:将经过一次复合的PET印刷膜和铝箔复合膜裁剪成15mm×200mm的实验样条,在BLD电脑式剥离测试仪上测试复合层的剥离强度;
高温处理:将复合膜成品制成食品包装袋(内容物:肉制品),放入A型立式压力蒸汽灭菌器内做高温蒸煮测试(135℃、30min),高温灭菌结束后,用冷水冲洗食品包装袋;
剥离强度测试:将复合膜成品裁剪成15mm×200mm的实验样条,在BLD电脑式剥离测试仪上测试各复合层的剥离强度。
表1高阻隔材料复合膜的性能测试结果
从实施例1-5和对比例1的性能测试结果可以得知,使用本方案的无溶剂复合工艺制备而成的高阻隔材料复合膜,其外观平整,外层白点气泡现象得到有效消除,且外层剥离强度较大,具有耐高温性能。
以上结合具体实施例描述了本发明的技术原理。这些描述只是为了解释本发明的原理,而不能以任何方式解释为对本发明保护范围的限制。基于此处的解释,本领域的技术人员不需要付出创造性的劳动即可联想到本发明的其它具体实施方式,这些方式都将落入本发明的保护范围之内。
Claims (7)
1.一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于,包括以下步骤:
A、将外层和中间层放置在无溶剂复合机;
B、将加热后的无溶剂胶水一涂布在外层表面;其中,所述无溶剂胶水一为双组份聚氨酯胶黏剂,且所述无溶剂胶水一的粘度范围为3500~5000mPa.s;
C、将涂布有无溶剂胶水一的外层在20~22℃的温度下固化2~3h;
D、通过无溶剂复合机将固化后的外层和中间层进行复合并收卷;
E、将收卷后的外层和中间层进行熟化,得到高阻隔材料复合膜;
其中,步骤B中,加热后的所述无溶剂胶水一的温度为70~75℃;步骤C中,将涂布无溶剂胶水一后的外层在20~22℃的温度和50~60%的湿度下固化2~3h。
2.根据权利要求1所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于:步骤E中,将收卷后的外层和中间层在50~60℃的温度下熟化70~75h。
3.根据权利要求1所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于,步骤A具体还包括以下步骤:将循环冷却水输入至无溶剂复合机中的复合压辊和冷却导辊。
4.根据权利要求1所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于,所述中间层包括过渡中间层和多个复合中间层,步骤D具体包括以下步骤:
D1、通过无溶剂复合机将固化后的外层和过渡中间层进行复合;
D2、将无溶剂胶水二涂布在过渡中间层表面,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合;
D3、将无溶剂胶水二涂布在所述复合中间层表面,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合;
D4、重复步骤D3,直至所有复合中间层均已复合后收卷。
5.根据权利要求4所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于:步骤D2中,将加热后的无溶剂胶水二涂布在过渡中间层表面,将涂布有无溶剂胶水二的过渡中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将一复合中间层和涂布有无溶剂胶水二的过渡中间层进行复合。
6.根据权利要求5所述的一种高阻隔材料复合膜的无溶剂复合工艺,其特征在于:步骤D3中,将加热后的无溶剂胶水二涂布在所述复合中间层表面,将涂布有无溶剂胶水二的所述复合中间层在20~22℃的温度下固化2~3h,通过无溶剂复合机将下一复合中间层和涂布有无溶剂胶水二的所述复合中间层进行复合。
7.一种高阻隔材料复合膜,其特征在于:使用权利要求1~6任意一项所述的高阻隔材料复合膜的无溶剂复合工艺制备而成。
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